Coating compositions for application to steel for thermal insulation and Anti-corrosion, and methods of coating steel

Abstract

This disclosure relates to methods of coating a steel substrate with a coating composition. Tire disclosure further relates to articles of manufacture prepared by the disclosed methods. Uris disclosure further relates to polymers and polymer composites prepared by the disclosed methods.

Description

COATING COMPOSITIONS FOR APPLICATION TO STEEL FOR THERMAL INSULATION AND ANTI-CORROSION, AND METHODS OF COATING STEEL CROSS REFERENCE TO RELATED APPLICATIONS

[0001] The application claims the benefit of U.S. Provisional Patent Application No. 63 / 698,773, filed September 25, 2024, the disclosure of which is incorporated herein by reference. TECHNICAL FIELD

[0002] This disclosure relates to compositions suitable for use in coating steel. More particularly, this disclosure relates to compositions suitable for use as dual-purpose thermal insulative and anti-corrosion coatings and protective coatings, particularly for application to steel, and especially for direct application to steel in exemplary embodiments, such as but not limited to coating steel pipes of pipelines and for field joints, including but not limited to subsea oil and gas pipelines.

[0003] The coating compositions of the disclosure may be utilized for a wide range of steel substrates, especially ones used in petrochemical and chemical production operations and in pipelines. The disclosure has utility in the fields of, for example, pipeline production, onsite treatment and maintenance, forming and repairing pipeline field joints, and retrofitting pipelines and pipeline field joints. BACKGROUND

[0004] According to the National Association of Corrosion Engineers International, corrosion is a naturally occurring phenomenon commonly defined as the deterioration of a material (usually a metal such as steel) that results from a chemical or electrochemical reaction with its environment. Corrosion causes severe damage and is very costly to repair. Protective coatings are an effective means of protecting against corrosion. In a broader sense, materials deteriorate resulting from interaction with the environment in mechanisms other than corrosion, e.g., erosion and other processes. Protective coatings can, in addition to protecting against corrosion, also protect against deterioration caused by ice, acid rain, salt water, and weathering and UV light.

[0005] Corrosion of metals such as steel occurs through either chemical or electrochemical reactions. Electrochemical corrosion is the most common form of metal corrosion. For metals such as iron and / or steel, corrosion occurs when the metals come into contact with oxygen and moisture (e.g., humidity, vapour, immersion), and rust begins to form.

[0006] Exposure to water (e.g., ground water, sea water, atmospheric water, etc.), corrosive chemicals, ultraviolet radiation, ozone, and other harmful factors can cause the unprotected surfaces of objects such as, e.g., pipelines, automobiles, buses, boats, trains, other vehicles, aircrafts, bridges, signage, buildings, sidewalks, roads, subterranean pipelines and equipment, and petrochemical and chemical production equipment, to suffer from changes in quality over time leading to deterioration or failure of the object.

[0007] Corrosion is so widespread and costly to repair that it is recommended to take effective precautionary measures when it comes to corrosion prevention. One of the best ways to prevent corrosion is to apply a protective coating. Such a protective coating protects its substrate by preventing contact between the substrate and harsh environments (atmospheric, chemical, etc.).

[0008] Therefore, over the years, there has been an ongoing need for coating compositions (e.g., anti- corrosion coating compositions) that provide surface protection to objects from corrosive materials or damaging environmental conditions.

[0009] Most pipelines used in petrochemical and chemical production operations are constructed of metal, typically some grade of steel, and many are jacketed in insulation. If, during installation of the pipe or pipeline, the insulation material covering the pipe or pipeline becomes damaged or degrades over time, the underlying surface of the pipeline becomes at risk of being in direct contact with the atmospheric environment, which may lead to a host of problems including premature failure of the pipe or pipeline resulting in increased repair and / or replacement costs.

[0010] Therefore, there is a need for an underlying coating applied to the pipeline surface, between the pipeline surface and the insulation material, which will act as an anti-corrosion barrier in case the insulation material is damaged or degrades. This need has led to the introduction of a number of coating compositions for the purpose of protecting steel pipelines and structures. Epoxy-, polyamide-, and polyurethane-based coating compositions have been used extensively to prevent corrosion of steel pipelines and structures. However, the preparation of coated steel pipelines for offshore subsea applications is an involved, multi- step process when utilizing these materials.

[0011] For example, the pipes of a pipeline are typically first coated with an anti-corrosion coating such as a fusion-bonded epoxy (FBE) and secondly, with a thicker thermal-insulative coating such as multiple layers of extruded polypropylene (PP). The FBE coating provides corrosion protection to the pipeline, whereas the PP insulative coating is intended to provide flow assurance for the pipeline, enabling the efficient flow of hydrocarbons from the wellhead to the host platform by preventing blockages caused by the buildup of thermally driven hydrates or waxes that can form as the hydrocarbon mixture cools down.The FBE coating application process itself is laborious and involves various steps. The making of field joints involves the process of joining individual pipe sections together via a weld and then coating the jointed pipe section in the field, often on the lay barge (S- and J-lay methods). Another problem is that the industry has largely relied on 2K epoxies. However, liquid 2-part epoxies typically require long cure cycles and are not as conducive to rapid coating operations that facilitate manufacturing. Further, the use of epoxy coating operations involves additional steps and equipment. In the case of subsea pipelines, e.g., oil and gas pipelines, the additional equipment must be transported by ship for on-site installation and / or repair of the subsea pipelines.

[0012] The above-described known field-joint methods can cost upwards of $600,000 per day. The additional equipment required for conventional coating materials adds to this expense, especially in the context of subsea pipeline installation and repair. Reducing the number of steps and hence the time required to complete the coating operations brings value across the project. A single-step, dual-purpose, anti- corrosion, and insulative coating using suitable resin could lead to a 4-5 minute reduction in field joint operation time, which can translate into savings of several days and multiple millions of dollars for a 1000 field joint pipeline. The number of field joints required for a full project can range from the hundreds to thousands. Thus, the single-step coating process can have a significant impact on the overall project cost. A single-step coating is also beneficial as its implementation relates to the individual flowline pipe sections as well. Reducing operational complexity yields economic benefits by streamlining project scope and accelerating the schedule.

[0013] Notwithstanding the advances made in the art with respect to coating compositions, particularly anti-corrosion and thermally insulating coating compositions for coating pipelines and structures, a continuing need exists for further improvements, particularly in the field of steel substrate coatings, especially for in-field coating of steel pipelines. BRIEF SUMMARY OF THE DISCLOSURE

[0014] This Summary is provided to introduce a selection of representative concepts in a simplified form, which representative concepts are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it or the objects and benefits described herein intended to be used to limit the scope of the claimed subject matter.

[0015] Exemplary embodiments are directed to addressing one or more of the aforementioned concerns and relate to coating compositions and methods for coating steel substrates with the coating compositions disclosed herein. The coating compositions disclosed herein may be used for a variety of purposes, including, without limitation, protection of substrate materials of various steel grades, including but notlimited to carbon steel, from time wise degradation in quality, or deterioration, due to environmental exposure, as well as providing excellent thermal insulation properties. The coating compositions disclosed herein may be applied directly to steel substrate surfaces to provide thermal insulation and protection, including anti-corrosion protection, against deterioration of the steel substrate material and / or steel substrate surface, especially steel pipelines and steel pipeline surfaces, due to environmental exposure, in conjunction with excellent insulating properties, including in certain embodiments thermal insulation sufficient to overcome the problems described above in the Background.

[0016] Coating compositions disclosed herein may also be used as adhesives for attaching other coatings to steel substrates, especially steel pipelines.

[0017] Aspects of the disclosure provide coating compositions for coating steel pipelines, as well as steel structures used in petrochemical and chemical production operations to provide excellent thermal insulation in conjunction with an anti-corrosion barrier against deterioration of the underlying pipe, pipeline, equipment, structure, or object due to environmental exposure and other corrosive materials. The coatings of exemplary embodiments provide a constant protective lining that helps save pipes from the damaging effects of corrosion and ensure reliable corrosion prevention. The coatings of exemplary embodiments are especially useful in connection with subsea pipelines, such as those used for transporting oil and gas.

[0018] The coating compositions disclosed herein offer several advantages over the prior art materials used for providing a protective coating on steel pipes, steel pipelines, steel equipment, steel structures, and steel objects used in petrochemical and chemical production operations. The coating compositions disclosed herein may be formulated to meet a wide variety of application conditions and needs.

[0019] As an example of one advantage, the coating compositions disclosed herein are designed to provide long-term thermal insulation, as well as corrosion inhibition by serving as an impermeable barrier to oxygen, water, ions, etc. Certain embodiments of the coating compositions disclosed herein are non-porous, and / or can be applied and cured in high humidity conditions and at colder temperatures.

[0020] Another advantage of certain embodiments of the coating compositions disclosed herein, including those incorporated by reference, is tunable cure times, i.e., the ability to be formulated to have a wide range of cure times. For example, in certain embodiments, the coating compositions may be formulated to cure quickly (“fast cure”) so that they are dry to the touch seconds after being applied to the substrate surface. In comparison, liquid epoxies typically take many hours to cure.

[0021] Another advantage of certain embodiments of the coating compositions disclosed herein is that the coating compositions are solvent-free.

[0022] Another advantage of certain embodiments of the coating compositions disclosed herein is that the coating compositions are resistant to cracking and delamination in hot / wet aqueous environments.

[0023] Another advantage of certain embodiments of the coating compositions disclosed herein is that the coating compositions can be prepared by different chemical transformations and can be processed by a variety of methods.

[0024] Aspects of this disclosure further relate to methods of applying the coating compositions disclosed herein in articles of manufacture produced by the methods, and related kits.

[0025] The first aspect of this disclosure relates to methods of coating a steel substrate with a coating composition, comprising, consisting essentially of, or consisting of: contacting the coating composition with at least a portion of at least one surface of the steel substrate; and optionally, subjecting the coating composition to conditions effective to polymerize the coating composition to form a polymer (e.g., a ROMP polymer) or a polymer composite (e.g., a ROMP polymer composite); wherein the method does not include a fusion bonded epoxy (FBE) and / or a chemically modified polypropylene (CMPP) application; and wherein the coating composition comprises, consists essentially of, or consists of any one or more of the compositions of the embodiments disclosed herein.

[0026] A second aspect of this disclosure relates to articles of manufacture prepared by any one of the disclosed methods herein.

[0027] A third aspect of this disclosure relates to ROMP polymers and ROMP polymer composites prepared from any one of the methods disclosed herein.

[0028] A fourth aspect of this disclosure, relates to coating pipeline field joints with any one of the coating compositions and methods disclosed herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The drawing referenced herein forms a part of the specification. Features shown in the drawings are meant as illustrative of only some embodiments, and not of all embodiments, unless otherwise explicitly indicated.

[0030] FIG. 1 shows a process, apparatus, and system for formulating and blending cyclic olefin compositions.

[0031] FIG.2 is a comparison upper flow chart setting forth steps for a field joint process with a fusion- bonded epoxy (FBE) anti-corrosion coating and a lower flow chart setting forth steps for a field joint process according to embodiments disclosed herein.

[0032] FIG. 3 is a schematic demonstrating pipe location nomenclature for reporting of direct-to-steel adhesion test data.

[0033] FIG.4 is a schematic showing field joint nomenclature. DETAILED DESCRIPTION OF THE DISCLOSURE

[0034] This application incorporates herein in its entireties the complete disclosures, including drawing, of each of the following: (1) co-pending U.S. Application No. 19 / 167,630 filed in the U.S. Patent & Trademark Application on September 22, 2025 entitled “ROMP and Thermal Insulation Compositions and Materials and Use Thereof” along with its corresponding PCT International Application PCT / US2024 / 020862 filed in the U.S. Receiving Office on March 21, 2024, which claims the benefit of priority to U.S. Provisional Application No.63 / 491,437, (2) co-pending U.S. Application No.17 / 311,495 filed in the U.S. Patent & Trademark Office on June 7, 2021 entitled “Coating Compositions” corresponding to PCT International Application PCT / US2019 / 066239 filed in the U.S. Receiving Office on December 13, 2019, which claims the benefit of priority to U.S. Provisional Application Nos.62 / 778,901 and 62 / 845,052. Terminology and Definitions

[0035] Unless otherwise indicated, the disclosure is not limited to specific reactants, substituents, catalysts, catalyst compositions, resin compositions, cyclic olefins, reaction conditions, or the like, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not to be interpreted as being limiting.

[0036] As used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a substituent” encompasses a single substituent as well as two or more substituents, and the like.

[0037] As used in the specification and the appended claims, the terms “for example,” “for instance,” “such as,” or “including” are meant to introduce examples that further clarify more general subject matter. Unless otherwise specified, these examples are provided only as an aid for understanding the disclosure, and are not meant to be limiting in any fashion.

[0038] In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings:

[0039] The term “alkyl” as used herein refers to a linear, branched, or cyclic saturated hydrocarbon group typically although not necessarily containing 1 to about 24 carbon atoms, such as 1 to about 12 carbonatoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl, and the like. Generally, although again not necessarily, alkyl groups herein contain 1 to about 12 carbon atoms. The term “lower alkyl” refers to an alkyl group of 1 to 6 carbon atoms, and the specific term “cycloalkyl” refers to a cyclic alkyl group, typically having 4 to 8, such as 5 to 7, carbon atoms. The term “substituted alkyl” refers to alkyl substituted with one or more substituent groups, and the terms “heteroatom-containing alkyl” and “heteroalkyl” refer to alkyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, substituted, and / or heteroatom-containing alkyl and lower alkyl, respectively.

[0040] The term “alkylene” as used herein refers to a difunctional linear, branched, or cyclic alkyl group, where “alkyl” is as defined above.

[0041] The term “alkenyl” as used herein refers to a linear, branched, or cyclic hydrocarbon group of 2 to about 24 carbon atoms (e.g., 2 to about 12 carbon atoms) containing at least one double bond, such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like. The term “lower alkenyl” refers to an alkenyl group of 2 to 6 carbon atoms, and the specific term “cycloalkenyl” refers to a cyclic alkenyl group, such as 5 to 8 carbon atoms. The term “substituted alkenyl” refers to alkenyl substituted with one or more substituent groups, and the terms “heteroatom-containing alkenyl” and “heteroalkenyl” refer to alkenyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkenyl” and “lower alkenyl” include linear, branched, cyclic, unsubstituted, substituted, and / or heteroatom-containing alkenyl and lower alkenyl, respectively.

[0042] The term “alkenylene” as used herein refers to a difunctional linear, branched, or cyclic alkenyl group, where “alkenyl” is as defined above.

[0043] The term “alkynyl” as used herein refers to a linear or branched hydrocarbon group of 2 to about 24 carbon atoms (e.g., 2 to about 12 carbon atoms) containing at least one triple bond, such as ethynyl, n-propynyl, and the like. The term “lower alkynyl” refers to an alkynyl group of 2 to 6 carbon atoms. The term “substituted alkynyl” refers to alkynyl substituted with one or more substituent groups, and the terms “heteroatom-containing alkynyl” and “heteroalkynyl” refer to alkynyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkynyl” and “lower alkynyl” include linear, branched, unsubstituted, substituted, and / or heteroatom-containing alkynyl and lower alkynyl, respectively.

[0044] The term “alkoxy” as used herein refers to an alkyl group bound through a single, terminal ether linkage; that is, an “alkoxy” group may be represented as -O-alkyl where alkyl is as defined above. A “lower alkoxy” group refers to an alkoxy group containing 1 to 6 carbon atoms. Analogously, “alkenyloxy”and “lower alkenyloxy” respectively refer to an alkenyl and lower alkenyl group bound through a single, terminal ether linkage, and “alkynyloxy” and “lower alkynyloxy” respectively refer to an alkynyl and lower alkynyl group bound through a single, terminal ether linkage.

[0045] The term “aryl” as used herein, and unless otherwise specified, refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety). Aryl groups may contain 5 to 24 carbon atoms (e.g., 5 to 14 carbon atoms). Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl, naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, and the like. “Substituted aryl” refers to an aryl moiety substituted with one or more substituent groups, and the terms “heteroatom-containing aryl” and “heteroaryl” refer to aryl substituents in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail infra.

[0046] The term “aryloxy” as used herein refers to an aryl group bound through a single, terminal ether linkage, wherein “aryl” is as defined above. An “aryloxy” group may be represented as -O-aryl where aryl is as defined above. Aryloxy groups may contain 5 to 24 carbon atoms (e.g., 5 to 14 carbon atoms). Examples of aryloxy groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy, phalo- phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4dimethoxy-phenoxy, 3,4,5- trimethoxy-phenoxy, and the like.

[0047] The term “alkaryl” refers to an aryl group with an alkyl substituent, and the term “aralkyl” refers to an alkyl group with an aryl substituent, wherein “aryl” and “alkyl” are as defined above. Alkaryl and aralkyl groups may contain 6 to 24 carbon atoms (e.g., 6 to 16 carbon atoms). Alkaryl groups include, without limitation, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7dimethylnaphthyl, 7- cyclooctylnaphthyl, 3-ethyl-cyclopenta-1,4-diene, and the like. Examples of aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4- phenylcyclohexyl, 4-benzylcyclohexyl, 4phenylcyclohexylmethyl, 4benzylcyclohexylmethyl, and the like. The terms “alkaryloxy” and “aralkyloxy” refer to substituents of the formula -OR wherein R is alkaryl or aralkyl, respectively, as just defined.

[0048] The term “acyl” refers to substituents having the formula -(CO)-alkyl, -(CO)-aryl, (CO)- aralkyl, -(CO)-alkaryl, -(CO)-alkenyl, or -(CO)-alkynyl, and the term “acyloxy” refers to substituents having the formula O(CO)-alkyl, O(CO)-aryl, -O(CO)-aralkyl, -O(CO)-alkaryl, -O(CO)-alkenyl, -O(CO)- alkynyl wherein “alkyl,” “aryl,” “aralkyl”, alkaryl, alkenyl, and alkynyl are as defined above.

[0049] The terms “cyclic” and “ring” refer to alicyclic or aromatic groups that may or may not be substituted and / or heteroatom containing, and that may be monocyclic, bicyclic, or polycyclic. The term“alicyclic” is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic, or polycyclic.

[0050] The terms “halo” and “halogen” are used in the conventional sense to refer to a chloro, bromo, fluoro, or iodo substituent.

[0051] “Hydrocarbyl” refers to univalent hydrocarbyl radicals containing 1 to about 30 carbon atoms, such as 1 to about 24 carbon atoms, such as 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated, and unsaturated species, such as alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and the like. The term “lower hydrocarbyl” intends a hydrocarbyl group of 1 to 6 carbon atoms, such as 1 to 4 carbon atoms, and the term “hydrocarbylene” refers to a divalent hydrocarbyl moiety containing 1 to about 30 carbon atoms, such as 1 to about 24 carbon atoms, such as 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated, and unsaturated species. The term “lower hydrocarbylene” refers to a hydrocarbylene group of 1 to 6 carbon atoms. “Substituted hydrocarbyl” refers to hydrocarbyl substituted with one or more substituent groups, and the terms “heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom. Similarly, “substituted hydrocarbylene” refers to hydrocarbylene substituted with one or more substituent groups, and the terms “heteroatom-containing hydrocarbylene” and “heterohydrocarbylene” refer to hydrocarbylene in which at least one carbon atom is replaced with a heteroatom. Unless otherwise indicated, the term “hydrocarbyl” and “hydrocarbylene” are to be interpreted as including substituted and / or heteroatom-containing hydrocarbyl and heteroatom-containing hydrocarbylene moieties, respectively.

[0052] The term “heteroatom-containing” as in a “heteroatom-containing hydrocarbyl group” refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus, or silicon, typically nitrogen, oxygen, or sulfur. Similarly, the term “heteroalkyl” refers to an alkyl substituent that is heteroatom-containing, the term “heterocyclic” refers to a cyclic substituent that is heteroatom-containing, the terms “heteroaryl” and “heteroaromatic” respectively refer to “aryl” and “aromatic” substituents that are heteroatom-containing, and the like. It should be noted that a “heterocyclic” group or compound may or may not be aromatic, and further that “heterocycles” may be monocyclic, bicyclic, or polycyclic as described above with respect to the term “aryl.” Examples of heteroalkyl groups include without limitation alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the like. Examples of heteroaryl substituents include without limitation pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc., and examples of heteroatom-containing alicyclic groups include without limitation pyrrolidino, morpholino, piperazino, piperidino, etc.

[0053] By “substituted” as in “substituted hydrocarbyl,” “substituted alkyl,” “substituted aryl,” and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, alkyl,aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents. Examples of such substituents include, without limitation: functional groups referred to herein as “Fn,” such as halo, hydroxyl, sulfhydryl, C1-C24alkoxy, C2-C24alkenyloxy, C2- C24alkynyloxy, C5-C24aryloxy, C6-C24aralkyloxy, C6-C24alkaryloxy, acyl (including C2-C24alkylcarbonyl (-CO-alkyl) and C6-C24arylcarbonyl (-CO-aryl)), acyloxy (-O-acyl, including C2-C24alkylcarbonyloxy (- O-CO-alkyl) and C6-C24arylcarbonyloxy (-O-CO-aryl)), C2-C24alkoxycarbonyl (-(CO)-O-alkyl), C6-C24aryloxycarbonyl (-(CO)-O-aryl), halocarbonyl (-CO)-X where X is halo), C2-C24alkylcarbonato (-O-(CO)- O-alkyl), C6-C24arylcarbonato (-O-(CO)-O-aryl), carboxy (-COOH), carboxylato (COO‾), carbamoyl (- (CO)-NH2), mono-(C1-C24alkyl)-substituted carbamoyl ((CO)-NH(C1-C24alkyl)), di-(C1-C24alkyl)- substituted carbamoyl (-(CO)-N(C1-C24alkyl)2), mono-(C1-C24haloalkyl)-substituted carbamoyl (-(CO)- NH(C1-C24haloalkyl)), di-(C1-C24haloalkyl)-substituted carbamoyl (-(CO)-N(C1-C24haloalkyl)2), mono- (C5-C24aryl)-substituted carbamoyl ((CO)-NH-aryl), di-( C5-C24aryl)-substituted carbamoyl (-(CO)-N(C5- C24aryl)2), di-N-(C1-C24alkyl),N-(C5-C24aryl)-substituted carbamoyl (-(CO)-N(C1-C24alkyl)(C5-C24aryl), thiocarbamoyl (-(CS)-NH2), mono-(C1-C24alkyl)-substituted thiocarbamoyl (-(CS)-NH(C1-C24alkyl)), di- (C1-C24alkyl)-substituted thiocarbamoyl (-(CS)-N(C1-C24alkyl)2), mono-(C5-C24aryl)-substituted thiocarbamoyl (-(CS)-NH-aryl), di(C5-C24aryl)-substituted thiocarbamoyl (-(CS)-N(C5-C24aryl)2), di-N- (C1-C24alkyl), N-(C5-C24aryl)-substituted thiocarbamoyl (-(CS)-N(C1-C24alkyl)(C5-C24aryl), carbamido (-NH-(CO)-NH2), cyano (-C≡N), cyanato (-O-C≡N), thiocyanato (-S-C≡N), isocyanate (–N=C=O), thioisocyanate (–N=C=S), formyl (-(CO)-H), thioformyl ((CS)-H), amino (-NH2), mono-(C1-C24alkyl)- substituted amino (-NH(C1-C24alkyl), di-(C1-C24alkyl)-substituted amino (-N(C1-C24alkyl)2), mono-(C5- C24aryl)-substituted amino (-NH(C5-C24aryl), di-(C5-C24aryl)-substituted amino (-N(C5-C24aryl)2), C2-C24 alkylamido (-NH-(CO)-alkyl), C6-C24arylamido (-NH-(CO)-aryl), imino (-CR=NH where R includes without limitation hydrogen, C1-C24alkyl, C5-C24aryl, C6C24alkaryl, C6-C24aralkyl, etc.), C2-C20alkylimino (CR=N(alkyl), where R includes without limitation hydrogen, C1C24alkyl, C5-C24aryl, C6-C24alkaryl, C6- C24aralkyl, etc.), arylimino (-CR=N(aryl), where R includes without limitation hydrogen, C1-C20alkyl, C5- C24aryl, C6-C24alkaryl, C6-C24aralkyl, etc.), nitro (-NO2), nitroso (NO), sulfo (-SO2-OH), sulfonato (-SO2- O‾), C1-C24alkylsulfanyl (-S-alkyl; also termed “alkylthio”), C5-C24arylsulfanyl (-S-aryl; also termed “arylthio”), C1-C24alkylsulfinyl (-(SO)-alkyl), C5-C24arylsulfinyl (-(SO)-aryl), C1-C24alkylsulfonyl (SO2- alkyl), C1-C24monoalkylaminosulfonyl (-SO2-N(H) alkyl), C1-C24dialkylaminosulfonyl (-SO2-N(alkyl)2), C5-C24arylsulfonyl (-SO2-aryl), boryl (-BH2), borono (-B(OH)2), boronato (-B(OR)2 where R includes without limitation alkyl or other hydrocarbyl), phosphono (-P(O)(OH)2), phosphonato (-P(O)(O‾)2), phosphinato (P(O)(O‾)), phospho (-PO2), and phosphino (-PH2); and the hydrocarbyl moieties C1-C24alkyl (e.g., C1-C12 alkyl, C1-C6 alkyl), C2-C24alkenyl (e.g., C2-C12 alkenyl, C2-C6 alkenyl), C2-C24alkynyl (e.g.,C2-C12alkynyl, C2-C6alkynyl), C5-C24aryl (e.g., C5-C14aryl), C6-C24alkaryl (e.g., C6-C16alkaryl), and C6- C24aralkyl (e.g., C6-C16aralkyl).

[0054] By “functionalized” as in “functionalized hydrocarbyl,” “functionalized alkyl,” “functionalized olefin,” “functionalized cyclic olefin,” and the like, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more functional groups such as those described hereinabove. The term “functional group” is meant to include any functional species that is suitable for the uses described herein. In particular, as used herein, a functional group would necessarily possess the ability to react with or bond to corresponding functional groups on a substrate surface.

[0055] In addition, the aforementioned functional groups may, if a particular group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically mentioned above. Analogously, the above-mentioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties as noted above.

[0056] “Optional” or “optionally” means that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not. For example, the phrase “optionally substituted” means that a nonhydrogen substituent may or may not be present on a given atom, and, thus, the description includes structures wherein a non-hydrogen substituent is present and structures wherein a nonhydrogen substituent is not present.

[0057] The term “substrate material” as used herein, is intended to generally mean any material that the ROMP composition of the disclosure may be contacted with, applied to, or have the substrate material incorporated into the ROMP composition. Without limitation, such materials include reinforcing materials, such as filaments, fibers, rovings, mats, weaves, fabrics, knitted material, cloth or other known structures, glass fibers and fabrics, carbon fibers and fabrics, aramid fibers and fabrics, and polyolefin or other polymer fibers or fabrics. Other suitable substrate materials include metallic density modulators, microparticulate density modulators, such as microspheres, glass microspheres, ceramic microspheres, microballons, cenospheres, and macroparticulate density modulators, such as glass or ceramic beads. A ROMP polymer composite may be comprised of one substrate material or a mixture of different substrate materials.

[0058] The term “polymer backbone” is intended to mean the chains of atoms in a polymer that comprise the main chain and any crosslinks, if it is a crosslinked polymer.

[0059] The term “field joint” as used herein, is intended to generally mean a connection between adjoining members or parts, made at the time of installation (i.e., in the field). The term “field joint” is a term of art often used to describe the welded ends of individual lengths of pipe. For example, pipelines used to transport oil and / or gas is most often formed from many individual pieces of pipe, for example steel pipe. During the manufacturing of individual pieces of pipe, an anti-corrosion coating is often applied to theexterior surface of the pipe in such a manner that the exterior surface of the pipe ends remains uncoated. Furthermore, the pipe may be subsequently coated with an insulation material; however, the exterior surface of the pipe ends still remains uncoated. The pipeline is formed by connecting the individual pieces of pipe by welding together the uncoated pipe ends. At least part of this welding process may take place at an onshore facility prior to loading the pipe on a lay barge or reel ship, with the remainder of the connections made offshore prior to the pipeline being deployed in offshore use. In the alternative, during the manufacturing of individual pieces of pipe, an anti-corrosion coating may be applied to the exterior surface of the pipe in such a manner that the exterior surface of the pipe ends are also coated. In this instance, the anti-corrosion coating must be removed from the pipe ends prior to welding.

[0060] The term “sulfhydryl” as used herein, represents a group of formula “-SH.”

[0061] The term “hydroxyl” as used herein, represents a group of formula “-OH.”

[0062] The term “carbonyl” as used herein, represents a group of formula “-C(O)-.”

[0063] The term “ketone” as used herein, represents an organic compound having a carbonyl group linked to a carbon atom such as –C(O)Rx1, wherein Rx1can be alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.

[0064] The term “ester” as used herein, represents an organic compound having a carbonyl group linked to a carbon atom such as –C(O)ORx1wherein Rx1can be alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.

[0065] The term “amine” as used herein, represents a group of formula “-NRxRy,” wherein Rxand Rycan be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.

[0066] The term “carboxyl” as used herein, represents a group of formula “-C(O)O-.”

[0067] The term “sulfonyl” as used herein, represents a group of formula “-SO2-.”

[0068] The term “sulfate” as used herein, represents a group of formula “-O-S(O)2-O-.”

[0069] The term “sulfonate” as used herein, represents a group of the formula “-S(O)2-O-.”

[0070] The term “amide” as used herein, represents a group of formula “-C(O)NRxRy,” wherein Rxand Rycan be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.

[0071] The term “sulfonamide” as used herein, represents a group of formula “-S(O)2NRxRy” wherein Rxand Rycan be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.

[0072] The term “sulfoxide” as used herein, represents a group of formula “-S(O)-.”

[0073] The term “phosphonic acid” as used herein, represents a group of formula “-P(O)(OH)2.”

[0074] The term “phosphonate ester” as used herein, represents a group of formula “-P(O)(ORx1)2,” wherein Rx1can be alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.

[0075] The term “phosphoric acid” as used herein, represents a group of formula “-OP(O)(OH)2.”

[0076] The term “phosphate ester” as used herein, represents a group of formula “-OP(O)(ORx1)2,” wherein Rx1can be alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.

[0077] The term “sulphonic acid” as used herein, represents a group of formula “-S(O)2OH.”

[0078] The formula “H” as used herein, represents a hydrogen atom.

[0079] The formula “O” as used herein, represents an oxygen atom.

[0080] The formula “N” as used herein, represents a nitrogen atom.

[0081] The formula “S” as used herein, represents a sulfur atom.

[0082] Functional groups may be protected in cases where the functional group interferes with the metal carbene olefin metathesis catalyst, and any of the protecting groups commonly used in the art may be employed. Acceptable protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 5th Ed. (New York: Wiley, 2014). Examples of protecting groups include acetals, cyclic acetals, boronate esters (boronates), cyclic boronate esters (cyclic boronates), carbonates, or the like. Examples of protecting groups include cyclic acetals or cyclic boronate esters.

[0083] The terms “coating” as used herein, refers to a substance temporarily or permanently applied to a surface or substrate for decorative purpose, to impart a function on a surface or substrate such as electrical passivity or conductivity, or to protect the surface or substrate from deterioration or degradation as a result of its reaction with the environment or corrosive agents. In particular, the coatings in this disclosure are suitable for industrial coatings such as protective coatings and particularly anti-corrosion coatings. Coatings may be applied as liquids, gases (vapor deposition) or solids.

[0084] The term “adhesive” or “adhesive coating composition” as used herein refers to a substance applied between two substrates to create a bond or joint.

[0085] The term “adhesion promoter” as used herein, refers to an additive or a primer which promotes adhesion of coatings to the substrate of interest. An adhesion promoter usually has an affinity for the substrate and the applied coating.

[0086] The term “dispersant” as used herein, refers to agents able to prevent settling or clump and is used interchangeably with “dispersing agent.”

[0087] The term “antioxidant” is used herein interchangeably with the terms “antiozonant” and is one type of a“stabilizer.”

[0088] As is known in the art, weight percent (wt.%) can be represented by gas chromatography (GC) percent area (area %). Hence, GC area% obtained from the GC was reported as wt.%. Weight percent (wt.%) and percent by weight are used interchangeably herein. Mol percent (mol%) was calculated from the weight percent (wt.%) as is known in the art.Cyclic Olefin Compositions

[0089] In general, any cyclic olefin suitable for the metathesis reactions disclosed herein may be used in the cyclic olefin composition. Such cyclic olefins may be optionally substituted, optionally heteroatom- containing, mono-unsaturated, di-unsaturated, or poly-unsaturated C5to C24hydrocarbons that may be mono-, di-, or poly-cyclic. When the cyclic olefin comprises more than one ring, the rings may or may not be fused. The cyclic olefin may generally be any strained or unstrained cyclic olefin, provided the cyclic olefin is able to participate in a ROMP reaction either individually or as part of the ROMP composition. While certain unstrained cyclic olefins such as cyclohexene are generally understood to not undergo ROMP reactions by themselves, under appropriate circumstances, such unstrained cyclic olefins may nonetheless be ROMP active. For example, when present as a co-monomer in a ROMP composition, unstrained cyclic olefins may be ROMP active. Accordingly, as used herein and as would be appreciated by the skilled artisan, the term “unstrained cyclic olefin” is intended to refer to those unstrained cyclic olefins that may undergo a ROMP reaction under any conditions, or in any ROMP composition, provided the unstrained cyclic olefin is ROMP active.

[0090] In general, the cyclic olefin may be represented by the structure of formula (A)wherein J, RA1, and RA2are as follows: RA1and RA2is selected independently from the group consisting of hydrogen, hydrocarbyl (e.g., C1-C20alkyl, C5-C20aryl, C5-C30 aralkyl, or C5-C30 alkaryl), substituted hydrocarbyl (e.g., substituted C1- C20alkyl, C5-C20aryl, C5-C30 aralkyl, or C5-C30 alkaryl), heteroatom-containing hydrocarbyl (e.g., C1-C20heteroalkyl, C5-C20heteroaryl, heteroatom-containing C5-C30 aralkyl, or heteroatom-containing C5-C30 alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g., substituted C1-C20heteroalkyl, C5-C20heteroaryl, heteroatom-containing C5-C30 aralkyl, or heteroatom-containing C5-C30 alkaryl) and, if substituted hydrocarbyl or substituted heteroatom-containing hydrocarbyl, wherein the substituents may be functional groups (Fn) such as phosphonato, phosphoryl, phosphanyl, phosphino, sulfonato, C1-C20alkylsulfanyl, C5-C20arylsulfanyl, C1-C20alkylsulfonyl, C5-C20arylsulfonyl, C1-C20alkylsulfinyl, C5-C20arylsulfinyl, sulfonamido, amino, amido, imino, nitro, nitroso, hydroxyl, C1-C20alkoxy, C5-C20aryloxy, C2- C20alkoxycarbonyl, C5-C20aryloxycarbonyl, carboxyl, carboxylato, mercapto, formyl, C1-C20thioester, cyano, cyanato, thiocyanato, isocyanate, thioisocyanate, carbamoyl, epoxy, styrenyl, silyl, silyloxy, silanyl, siloxazanyl, boronato, boryl, or halogen, or a metal-containing or metalloid-containing group (wherein the metal may be, for example, Sn or Ge). RA1and RA2may itself be one of the aforementioned groups, suchthat the Fn moiety is directly bound to the olefinic carbon atom indicated in the structure. In the latter case, however, the functional group will generally not be directly bound to the olefinic carbon through a heteroatom containing one or more lone pairs of electrons, e.g., an oxygen, sulfur, nitrogen, or phosphorus atom, or through an electron-rich metal or metalloid such as Ge, Sn, As, Sb, Se, Te, etc. With such functional groups, there will normally be an intervening linkage Z*, such that RA1and / or RA2then has the structure -(Z*)n-Fn wherein n is 0 or 1, Fn is the functional group, and Z*is a hydrocarbylene linking group such as an alkylene, substituted alkylene, heteroalkylene, substituted heteroalkene, arylene, substituted arylene, heteroarylene, or substituted heteroarylene linkage. J is a saturated or unsaturated hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene linkage, wherein when J is substituted hydrocarbylene or substituted heteroatom-containing hydrocarbylene, the substituents may include one or more -(Z*)n-Fn groups, wherein n is 0 or 1, and Fn and Z*are as defined previously. Additionally, two or more substituents attached to ring carbon (or other) atoms within J may be linked to form a bicyclic or polycyclic olefin. J will generally contain in the range of approximately 5 to 14 ring atoms, typically 5 to 8 ring atoms, for a monocyclic olefin, and, for bicyclic and polycyclic olefins, each ring will generally contain 4 to 8, typically 5 to 7, ring atoms.

[0091] Mono-unsaturated cyclic olefins encompassed by structure (A) may be represented by the structure (B)wherein b is an integer generally although not necessarily in the range of 1 to 10, typically 1 to 5, RA1and RA2are as defined above for structure (A), and RB1, RB2, RB3, RB4, RB5, and RB6are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom- containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl and -(Z*)n-Fn where n, Z*, and Fn are as defined previously, and wherein if any of the RB1through RB6moieties is substituted hydrocarbyl or substituted heteroatom-containing hydrocarbyl, the substituents may include one or more -(Z*)n-Fn groups. Accordingly, RB1, RB2, RB3, RB4, RB5, and RB6may be, for example, hydrogen, hydroxyl, C1-C20alkyl, C5- C20aryl, C1-C20alkoxy, C5-C20aryloxy, C2-C20alkoxycarbonyl, C5-C20aryloxycarbonyl, amino, amido, nitro, etc.

[0092] Furthermore, any of the RB1, RB2, RB3, RB4, RB5, and RB6moieties can be linked to any of the other RB1, RB2, RB3, RB4, RB5, and RB6moieties to provide a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms or combinations thereof and the linkage may include heteroatoms or functional groups, e.g., the linkage may include without limitation an ether, ester, thioether, amino, alkylamino, imino, or anhydride moiety. The alicyclic group can be monocyclic, bicyclic, or polycyclic. When unsaturated the cyclic group can contain monounsaturation or multiunsaturation. When substituted, the rings contain monosubstitution or multisubstitution wherein the substituents are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z*)n-Fn where n is 0 or 1, Z*and Fn are as defined previously, and functional groups (Fn) provided above.

[0093] Examples of monounsaturated, monocyclic olefins encompassed by structure (B) include, without limitation, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, tricyclodecene, tetracyclodecene, octacyclodecene, and cycloeicosene, and substituted versions thereof such as 1-methylcyclopentene, 1ethylcyclopentene, 1isopropylcyclohexene, l- chloropentene, 1-fluorocyclopentene, 4methylcyclopentene, 4-methoxy-cyclopentene, 4-ethoxy- cyclopentene, cyclopent-3-ene-thiol, cyclopent-3-ene, 4-methylsulfanyl-cyclopentene, 3- methylcyclohexene, 1-methylcyclooctene, 1,5-dimethylcyclooctene, etc.

[0094] Monocyclic diene reactants encompassed by structure (A) may be generally represented by the structure (C)wherein c and d are independently integers in the range of 1 to about 8, typically 2 to 4, such as 2 (such that the reactant is a cyclooctadiene), RA1and RA2are as defined above for structure (A), and RC1, RC2, RC3, RC4, RC5, and RC6are defined as for RB1through RB6. In this case, RC3and RC4may be non-hydrogen substituents, in which case the second olefinic moiety is tetrasubstituted. Examples of monocyclic diene reactants include, without limitation, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 5-ethyl-l,3- cyclohexadiene, 1,3-cycloheptadiene, cyclohexadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, and substituted analogs thereof. Triene reactants are analogous to the diene structure (C), and will generally contain at least one methylene linkage between any two olefinic segments.

[0095] Bicyclic and polycyclic olefins encompassed by structure (A) may be generally represented by the structure (D)wherein RA1and RA2are as defined above for structure (A), RD1, RD2, RD3, and RD4are as defined for RB1through RB6, e is an integer in the range of 1 to 8 (typically 2 to 4) f is generally 1 or 2; T is lower alkylene or alkenylene (generally substituted or unsubstituted methyl or ethyl), CHRG1, C(RG1)2, O, S, N-RG1, P-RG1, O=P-RG1, Si(RG1)2, B-RG1, or As-RG1where RG1is alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl, or alkoxy. Furthermore, any of the RD1, RD2, RD3, and RD4moieties can be linked to any of the other RD1, RD2, RD3, and RD4moieties to provide a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms or combinations thereof and the linkage may include heteroatoms or functional groups, e.g., the linkage may include without limitation an ether, ester, thioether, amino, alkylamino, imino, or anhydride moiety.

[0096] The cyclic group can be monocyclic, bicyclic, or polycyclic. When unsaturated the cyclic group can contain monounsaturation or multiunsaturation. When substituted, the rings contain monosubstitution or multisubstitution wherein the substituents are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z*)n-Fn where n is 0 or 1, Z*and Fn are as defined previously, and functional groups (Fn) provided above.

[0097] Cyclic olefins encompassed by structure (D) are in the norbornene family. As used herein, norbornene means any compound that includes at least one norbornene or substituted norbornene moiety, including without limitation norbornene, substituted norbornene(s), norbornadiene, substituted norbornadiene(s), polycyclic norbornenes, and substituted polycyclic norbornene(s). Norbornenes within this group may be generally represented by the structure (E)wherein RA1and RA2are as defined above for structure (A), T is as defined above for structure (D), RE1,RE5, RE6, RE7, and RE8are as defined for RB1through RB6, and “a” represents a single bond or a double bond, f is generally 1 or 2, “g” is an integer from 0 to 5, and when “a” is a double bond one of RE5, RE6and one of RE7, RE8is not present.

[0098] Furthermore, any of the RE5, RE6, RE7, and RE8moieties can be linked to any of the other RE5, RE6, RE7, and RE8moieties to provide a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms or combinations thereof and the linkage may include heteroatoms or functional groups, e.g., the linkage may include without limitation an ether, ester, thioether, amino, alkylamino, imino, or anhydride moiety. The cyclic group can be monocyclic, bicyclic, or polycyclic. When unsaturated the cyclic group can contain monounsaturation or multiunsaturation. When substituted, the rings contain monosubstitution or multisubstitution wherein the substituents are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z*)n-Fn where n is 0 or 1, Z*and Fn are as defined previously, and functional groups (Fn) provided above.

[0099] Cyclic olefins possessing at least one norbornene moiety have the structure (F):wherein RF1, RF2, RF3, and RF4, are as defined for RB1through RB6, and “a” represents a single bond or a double bond, “g” is an integer from 0 to 5, and when “a” is a double bond one of RF1, RF2and one of RF3, RF4is not present.

[0100] Furthermore, any of the RF1, RF2, RF3, and RF4moieties can be linked to any of the other RF1, RF2, RF3, and RF4moieties to provide a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms or combinations thereof and the linkage may include heteroatoms or functional groups, e.g., the linkage may include without limitation an ether, ester, thioether, amino, alkylamino, imino, or anhydride moiety. The alicyclic group can be monocyclic, bicyclic, or polycyclic. When unsaturated the cyclic group can contain monounsaturation or multiunsaturation. When substituted, the rings contain monosubstitution or multisubstitution wherein the substituents are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z*)n-Fn where n is 0 or 1, Z*and Fn are as defined previously, and functional groups (Fn) provided above.

[0101] One route for the preparation of hydrocarbyl substituted and functionally substituted norbornenes employs the Diels-Alder cycloaddition reaction in which cyclopentadiene or substituted cyclopentadiene is reacted with a suitable dienophile at elevated temperatures to form the substituted norbornene adduct generally shown by the following reaction Scheme 1: SCHEME 1wherein RF1to RF4are as previously defined for structure (F).

[0102] Other norbornene adducts can be prepared by the thermal pyrolysis of dicyclopentadiene in the presence of a suitable dienophile. The reaction proceeds by the initial pyrolysis of dicyclopentadiene to cyclopentadiene followed by the Diels-Alder cycloaddition of cyclopentadiene and the dienophile to give the adduct shown below in Scheme 2: SCHEME 2wherein “g” is an integer from 0 to 5, and RF1to RF4are as previously defined for structure (F).

[0103] Norbornadiene and higher Diels-Alder adducts thereof similarly can be prepared by the thermal reaction of cyclopentadiene and dicyclopentadiene in the presence of an acetylenic reactant as shown below in Scheme 3:wherein “g” is an integer from 0 to 5, RF1and RF4are as previously defined for structure (F)

[0104] Examples of bicyclic and polycyclic olefins thus include, without limitation, dicyclopentadiene (DCPD); trimer and other higher order oligomers of cyclopentadiene including without limitation tricyclopentadiene (cyclopentadiene trimer), cyclopentadiene tetramer, and cyclopentadiene pentamer; ethylidenenorbornene; dicyclohexadiene; norbornene; 5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5- isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5-phenylnorbornene; 5-benzylnorbornene; 5- acetylnorbornene; 5-methoxycarbonylnorbornene; 5-ethyoxycarbonyl-1-norbornene; 5-methyl-5- methoxy-carbonylnorbornene; 5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene; cyclo- hexenylnorbornene; endo, exo-5,6-dimethoxynorbornene; endo, endo-5,6-dimethoxynorbornene; endo, exo-5,6-dimethoxycarbonylnorbornene; endo,endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene; norbornadiene; tricycloundecene; tetracyclododecene; 8- methyltetracyclododecene; 8-ethyltetracyclododecene; 8-methoxycarbonyltetracyclododecene; 8-methyl- 8-tetracyclododecene; 8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene; and the like, and their structural isomers, stereoisomers, and mixtures thereof. Additional examples of bicyclic and polycyclic olefins include, without limitation, C2-C12hydrocarbyl substituted norbornenes such as 5-butyl- 2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, 5-dodecyl-2- norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2- norbornene, and 5-butenyl-2-norbornene, and the like. It is well understood by one in the art that bicyclic and polycyclic olefins as disclosed herein may consist of a variety of structural isomers and / or stereoisomers, any and all of which are suitable for use in the disclosure. Any reference herein to such bicyclic and polycyclic olefins unless specifically stated includes mixtures of any and all such structural isomers and / or stereoisomers.

[0105] Cyclic olefins may include C5to C24 unsaturated hydrocarbons, as well as C5to C24 cyclic hydrocarbons that contain one or more (typically 2 to 12) heteroatoms such as O, N, S, or P. For example, crown ether cyclic olefins may include numerous O heteroatoms throughout the cycle, and these are within the scope of the disclosure. In addition, cyclic olefins may be C5to C24 hydrocarbons that contain one or more (typically 2 or 3) olefins. For example, the cyclic olefin may be mono-, di-, or tri-unsaturated. Examples of cyclic olefins include without limitation cyclooctene, cyclododecene, and (c,t,t)-1,5,9- cyclododecatriene.

[0106] The cyclic olefins may also comprise multiple (typically 2 or 3) rings. For example, the cyclic olefin may be mono-, di-, or tri-cyclic. When the cyclic olefin comprises more than one ring, the rings may or may not be fused. Examples of cyclic olefins that comprise multiple rings include norbornene, dicyclopentadiene, tricyclopentadiene, and 5-ethylidene-2-norbornene.

[0107] The cyclic olefin may also be substituted, for example, a C5to C24 cyclic hydrocarbon wherein one or more (typically 2, 3, 4, or 5) of the hydrogens are replaced with non-hydrogen substituents. Suitable non-hydrogen substituents may be chosen from the substituents described hereinabove. For example, functionalized cyclic olefins, i.e., C5to C24 cyclic hydrocarbons wherein one or more (typically 2, 3, 4, or 5) of the hydrogens are replaced with functional groups, are within the scope of the disclosure. Suitable functional groups may be chosen from the functional groups described hereinabove. For example, a cyclic olefin functionalized with an alcohol group may be used to prepare a telechelic polymer comprising pendent alcohol groups. Functional groups on the cyclic olefin may be protected in cases where the functional group interferes with the metathesis catalyst, and any of the protecting groups commonly used in the art may be employed. Acceptable protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3rd Ed. (New York: Wiley, 1999). Examples of functionalized cyclic olefins includewithout limitation 2-hydroxymethyl-5-norbornene, 2-[(2-hydroxyethyl)carboxylate]-5-norbornene, cydecanol, 5-n-hexyl-2-norbornene, 5-n-butyl-2-norbornene.

[0108] Cyclic olefins incorporating any combination of the abovementioned features (i.e., heteroatoms, substituents, multiple olefins, multiple rings) are suitable for the methods disclosed herein. Additionally, cyclic olefins incorporating any combination of the abovementioned features (i.e., heteroatoms, substituents, multiple olefins, multiple rings) are suitable for the disclosure disclosed herein.

[0109] The cyclic olefins useful in the methods disclosed herein may be strained or unstrained. It will be appreciated that the amount of ring strain varies for each cyclic olefin compound, and depends upon a number of factors including the size of the ring, the presence and identity of substituents, and the presence of multiple rings. Ring strain is one factor in determining the reactivity of a molecule towards ring-opening olefin metathesis reactions. Highly strained cyclic olefins, such as certain bicyclic compounds, readily undergo ring opening reactions with olefin metathesis catalysts. Less strained cyclic olefins, such as certain unsubstituted hydrocarbon monocyclic olefins, are generally less reactive. In some cases, ring opening reactions of relatively unstrained (and therefore relatively unreactive) cyclic olefins may become possible when performed in the presence of the olefinic compounds disclosed herein. Additionally, cyclic olefins useful in the disclosure disclosed herein may be strained or unstrained.

[0110] The ROMP compositions and / or cyclic olefin compositions of the disclosure may comprise a plurality of cyclic olefins. A plurality of cyclic olefins may be used to prepare metathesis polymers from the olefinic compound. For example, two cyclic olefins selected from the cyclic olefins described hereinabove may be employed to form metathesis products that incorporate both cyclic olefins. Where two or more cyclic olefins are used, one example of a second cyclic olefin is a cyclic alkenol, i.e., a C5-C24 cyclic hydrocarbon wherein at least one of the hydrogen substituents is replaced with an alcohol or protected alcohol moiety to yield a functionalized cyclic olefin.

[0111] The use of a plurality of cyclic olefins, and in particular when at least one of the cyclic olefins is functionalized, allows for further control over the positioning of functional groups within the products. For example, the density of cross-linking points can be controlled in polymers and macromonomers prepared using the methods disclosed herein. Control over the quantity and density of substituents and functional groups also allows for control over the physical properties (e.g., melting point, tensile strength, glass transition temperature, etc.) of the products. Control over these and other properties is possible for reactions using only a single cyclic olefin, but it will be appreciated that the use of a plurality of cyclic olefins further enhances the range of possible metathesis products and polymers formed.

[0112] Non-limiting examples of cyclic olefins include dicyclopentadiene; tricyclopentadiene; dicyclohexadiene; norbornene; 5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5-tolyl-2-norbornene; 5-phenyl-2-norbornene; 5-benzylnorbornene; 5-acetylnorbornene; 5-methoxycarbonylnorbornene; 5-ethoxycarbonyl-1-norbornene; 5-methyl-5-methoxy- carbonylnorbornene; 5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene; cyclo-hexenylnorbornene; endo, exo-5,6-dimethoxynorbornene; endo, endo-5,6-dimethoxynorbornene; endo, exo-5-6- dimethoxycarbonylnorbornene; endo, endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene; norbornadiene; tricycloundecene; tetracyclododecene; 8-methyltetracyclododecene; 8-ethyl- tetracyclododecene; 8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclo-dodecene; 8- cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene; higher order oligomers of cyclopentadiene such as cyclopentadiene tetramer, cyclopentadiene pentamer, and the like; and C2-C12hydrocarbyl substituted norbornenes such as 5-butyl-2-norbornene; 5-hexyl-2-norbornene; 5-octyl-2- norbornene; 5-decyl-2-norbornene; 5-dodecyl-2-norbornene; 5-vinyl-2-norbornene; 5-ethylidene-2- norbornene; 5-isopropenyl-2-norbornene; 5-propenyl-2-norbornene; and 5-butenyl-2-norbornene, and the like.

[0113] Cyclic olefins include dicyclopentadiene, tricyclopentadiene, and higher order oligomers of cyclopentadiene, such as cyclopentadiene tetramer, cyclopentadiene pentamer, and the like, 5-tolyl-2- norbornene, 5-phenyl-2-norbornene, C2-C12 hydrocarbyl substituted norbornenes, such as 5-hexyl-2- norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, 5-dodecyl-2-norbornene, and the like.

[0114] Cyclic that contain multiunsaturation include dicyclopentadiene, tricyclopentadiene, and higher order oligomers of cyclopentadiene, such as cyclopentadiene tetramer, cyclopentadiene pentamer, and the like, and 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5- propenyl-2-norbornene, 5-butenyl-2-norbornene, and the like.

[0115] Cyclic olefins that contain multiunsaturation include dicyclopentadiene, tricyclopentadiene, and higher order oligomers of cyclopentadiene, such as cyclopentadiene tetramer, cyclopentadiene pentamer, and the like, and 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, 5-butenyl-2-norbornene, and the like.

[0116] Cyclic olefins that contain multiunsaturation include dicyclopentadiene, tricyclopentadiene, and higher order oligomers of cyclopentadiene, such as cyclopentadiene tetramer, and the like.

[0117] Cyclic olefins that contain multiunsaturation include dicyclopentadiene, tricyclopentadiene, and higher order oligomers of cyclopentadiene, such as cyclopentadiene tetramer, cyclopentadiene pentamer, and the like.

[0118] Cyclic olefins that contain multiunsaturation include dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene.

[0119] In one embodiment, multiunsaturated cyclic olefins include dicyclopentadiene, tricyclopentadiene, and 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5- propenyl-2-norbornene, 5-butenyl-2-norbornene, and the like.

[0120] In another embodiment, multiunsaturated cyclic olefins include dicyclopentadiene, tricyclopentadiene, and 5-ethylidene-2-norbornene.

[0121] An example of a multiunsaturated cyclic olefin is dicyclopentadiene.

[0122] An example of a multiunsaturated cyclic olefin is tricyclopentadiene.

[0123] An example of a multiunsaturated cyclic olefin is tetracyclopentadiene

[0124] An example of a multiunsaturated cyclic olefin is 5-ethylidene-2-norbornene.

[0125] The cyclic olefin composition may comprise multiunsaturated cyclic olefins selected from dicyclopentadiene, tricyclopentadiene, 5-ethylidene-2-norbornene, and mixtures thereof, wherein the dicyclopentadiene may be present in an amount of 90 wt.% or greater (e.g., 91 wt.% or greater, 92 wt.% or greater, 93 wt.% or greater, 94 wt.% or greater, 95 wt.% or greater, 96 wt.% or greater, 97 wt.% or greater, 98 wt.% or greater, 99 wt.% or greater, 99.9 wt.% or greater), and the tricyclopentadiene and / or 5- ethylidene-2-norbornene may be present in an amount of 0.1 wt.% or greater (e.g., 1 wt.% or greater, 2 wt.% or greater, 3 wt.% or greater, 4 wt.% or greater, 5 wt.% or greater, 6 wt.% or greater, 7 wt.% or greater, 8 wt.% or greater, 9 wt.% or greater), based on the total weight of the cyclic olefin composition. For example, cyclic olefin compositions may comprise 90 to 100 wt.% dicyclopentadiene (e.g., 91 to 99.9 wt.% dicyclopentadiene, 92 to 99 wt.%, 93 to 98 wt.%, 94 to 97 wt.%, 95 to 96 wt.%) and 0 to 10 wt.% tricyclopentadiene and / or 5-ethylidene-2-norbornene (e.g., 0.1 to 9 wt.%, 1 to 8 wt.%, 2 to 7 wt.%, 3 to 6 wt.%, 4 to 5 wt.%), based on the total weight of the cyclic olefin composition.

[0126] Cyclic olefins that contain monounsaturation include 5-tolyl-2-norbornene, 5-phenyl-2- norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, 5- dodecyl-2-norbornene.

[0127] Cyclic olefins that contain monounsaturation include 5-tolyl-2-norbornene, 5-phenyl-2- norbornene.

[0128] Cyclic olefins that contain monounsaturation include 5-butyl-2-norbornene, 5-hexyl-2- norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, 5-dodecyl-2-norbornene Cyclic olefins that contain monounsaturation include 5-hexyl-2-norbornene, 5-octyl-2 norbornene, 5-decyl-2-norbornene.

[0129] Cyclic olefins that contain monounsaturation include 5-hexyl-2-norbornene, 5-octyl-2- norbornene, 5-decyl-2-norbornene, and 5-tolyl-2-norbornene.

[0130] Cyclic olefins that contain monounsaturation include 5-hexyl-2-norbornene, 5-octyl-2- norbornene, 5-decyl-2-norbornene, 5-tolyl-2-norbornene, and 5-phenyl-2-norbornene.

[0131] Cyclic olefins that contain monounsaturation include 5-octyl-2-norbornene and 5-decyl-2- norbornene.

[0132] Cyclic olefins that contain monounsaturation include C2-C12 hydrocarbyl substituted norbornenes.

[0133] Cyclic olefins that contain monomunsaturation include C4-C12 hydrocarbyl substituted norbornenes.

[0134] Cyclic olefins that contain monounsaturation include C6-C12 hydrocarbyl substituted norbornenes.

[0135] Cyclic olefins that contain monomunsaturation include C6-C10 hydrocarbyl substituted norbornenes.

[0136] An example of a cyclic olefin that contains monounsaturation is 5-octyl-2-norbornene.

[0137] An example of a cyclic olefin that contains monounsaturation is 5-decyl-2-norbornene.

[0138] An example of a cyclic olefin that contains monounsaturation is 5-hexyl-2-norbornene.

[0139] An example of a cyclic olefin that contains monounsaturation is 5-phenyl-2-norbornene.

[0140] An example of a cyclic olefin that contains monounsaturation is 5-tolyl-2-norbornene.

[0141] An example of a cyclic olefin that contains monounsaturation is 5-butyl-2-norbornene.

[0142] An example of a cyclic olefin that contains monounsaturation is 5-dodecyl-2-norbornene.

[0143] The cyclic olefin compositions of the invention comprise, consist essentially of, or consist of at least one cyclic olefin containing multiunsaturation and at least one cyclic olefin containing monounsaturation.

[0144] Monounsaturated cyclic olefins, if present, include C2-C12 hydrocarbyl substituted norbornenes (e.g., C4-C12 hydrocarbyl substituted norbornenes, C6-C12 hydrocarbyl substituted norbornenes, C6-C10 hydrocarbyl substituted norbornenes). Monounsaturated cyclic olefins include, for example, 5-tolyl-2- norbornene, 5-phenyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, 5-dodecyl-2-norbornene.

[0145] The at least one cyclic olefin containing multiunsaturation and the at least one cyclic olefin containing monounsaturation may be, independent of one another, substituted or unsubstituted.

[0146] The at least one cyclic olefin containing multiunsaturation and the at least one cyclic olefin containing monounsaturation may be, independent of one another, substituted by hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z*)n-Fn wherein n is 0 or 1, Fn is the functional group, and Z* is a hydrocarbylene linking group such as an alkylene, substituted alkylene, heteroalkylene, substituted heteroalkene, arylene, substituted arylene, heteroarylene, or substituted heteroarylene linkage, or functional groups (Fn).

[0147] The at least one cyclic olefin containing multiunsaturation may be present in the cyclic olefin composition in an amount ranging from 80.1 mol% to 99.9 mol% (e.g., 81.0 mol% to 99.0 mol%, 82.0 mol% to 98.0 mol%, 83.0 mol% to 97.0 mol%, 84.0 mol% to 96.0 mol%, 85.0 mol% to 97.0 mol%, 86.0 mol% to 96.0 mol%, 87.0 mol% to 95.0 mol%, 88.0 mol% to 94.0 mol%, 89.0 mol% to 95.0 mol%, 90.0mol% to 94.0 mol%, 91.0 mol% to 93.0 mol%), and the at least one cyclic olefin containing monounsaturation may be present in the cyclic olefin composition in an amount up to 19.9 mol% (e.g., 0.1 mol% to 19.9 mol%, 1.0 mol% to 19.0 mol%, 2.0 mol% to 18.0 mol%, 3.0 mol% to 17.0 mol%, 4.0 mol% to 16.0 mol%, 5.0 mol% to 15.0 mol%, 6.0 mol% to 14.0 mol%, 7.0 mol% to 13.0 mol%, 8.0 mol% to 12.0 mol%, 9.0 mol% to 11.0 mol%).

[0148] The cyclic olefin compositions used in the ROMP compositions disclosed herein may comprise, consist essentially of, or consist of at least one multiunsaturated cyclic olefin, and wherein the cyclic olefin composition does not contain, or is substantially free of (e.g., 10 wt.% or less, 9 wt.% or less, 8 wt.% or less, 7 wt.% or less, 6 wt.% or less, 5 wt.% or less, 4 wt.% or less, 3 wt.% or less, 2 wt.% or less, 1 wt.% or less, 0.5 wt.% or less, 0.1 wt.% or less, 0.01 wt.% or less; based on the total weight of the cyclic olefin composition), a monounsaturated cyclic olefin, wherein the monounsaturated cyclic olefin is selected from 5-octyl-2-norbornene (ONB). For example, the cyclic olefin composition may comprise, consist essentially of, or consist of at least one multiunsaturated cyclic olefin, and wherein the cyclic olefin composition does not contain a monounsaturated cyclic olefin, wherein the monounsaturated cyclic olefin is selected from ONB. For example, the cyclic olefin composition may comprise, consist essentially of, or consist of at least one multiunsaturated cyclic olefin, and wherein the cyclic olefin composition is substantially free of (e.g., 10 wt.% or less, 9 wt.% or less, 8 wt.% or less, 7 wt.% or less, 6 wt.% or less, 5 wt.% or less, 4 wt.% or less, 3 wt.% or less, 2 wt.% or less, 1 wt.% or less, 0.5 wt.% or less, 0.1 wt.% or less, 0.01 wt.% or less; based on the total weight of the cyclic olefin composition), a monounsaturated cyclic olefin, wherein the monounsaturated cyclic olefin is selected from ONB.

[0149] The cyclic olefin compositions used in the ROMP compositions disclosed herein may also comprise, consist essentially of, or consist of at least one multiunsaturated cyclic olefin, and wherein the cyclic olefin composition does not contain, or is substantially free of (e.g., 10 wt.% or less, 9 wt.% or less, 8 wt.% or less, 7 wt.% or less, 6 wt.% or less, 5 wt.% or less, 4 wt.% or less, 3 wt.% or less, 2 wt.% or less, 1 wt.% or less, 0.5 wt.% or less, 0.1 wt.% or less, 0.01 wt.% or less; based on the total weight of the cyclic olefin composition), a monounsaturated cyclic olefin, wherein the monounsaturated cyclic olefin is selected from at least one substituted norbornene, including, but not limited to, the monounsaturated substituted norbornenes encompassed by cyclic olefin structures (D), (E), or (F) (as defined below). For example, the cyclic olefin composition may comprise, consist essentially of, or consist of at least one multiunsaturated cyclic olefin, and wherein the cyclic olefin composition does not contain a monounsaturated cyclic olefin, wherein the monounsaturated cyclic olefin is selected from at least one substituted norbornene, including, but not limited to, the monounsaturated substituted norbornenes encompassed by cyclic olefin structures (D), (E), or (F) (as defined below). For example, the cyclic olefin composition may comprise, consistessentially of, or consist of at least one multiunsaturated cyclic olefin, and wherein the cyclic olefin composition is substantially free of (e.g., 10 wt.% or less, 9 wt.% or less, 8 wt.% or less, 7 wt.% or less, 6 wt.% or less, 5 wt.% or less, 4 wt.% or less, 3 wt.% or less, 2 wt.% or less, 1 wt.% or less, 0.5 wt.% or less, 0.1 wt.% or less, 0.01 wt.% or less; based on the total weight of the cyclic olefin composition), a monounsaturated cyclic olefin, wherein the monounsaturated cyclic olefin is selected from at least one substituted norbornene, including, but not limited to, the monounsaturated substituted norbornenes encompassed by cyclic olefin structures (D), (E), or (F) (as defined below).

[0150] The cyclic olefin compositions used in the ROMP compositions disclosed herein may also comprise, consist essentially of, or consist of at least one multiunsaturated cyclic olefin, and wherein the cyclic olefin composition does not contain, or is substantially free of (e.g., 10 wt.% or less, 9 wt.% or less, 8 wt.% or less, 7 wt.% or less, 6 wt.% or less, 5 wt.% or less, 4 wt.% or less, 3 wt.% or less, 2 wt.% or less, 1 wt.% or less, 0.5 wt.% or less, 0.1 wt.% or less, 0.01 wt.% or less; based on the total weight of the cyclic olefin composition), a monounsaturated cyclic olefin. For example, the cyclic olefin composition may comprise, consist essentially of, or consist of at least one multiunsaturated cyclic olefin, and wherein the cyclic olefin composition does not contain a monounsaturated cyclic olefin. For example, the cyclic olefin composition may comprise, consist essentially of, or consist of at least one multiunsaturated cyclic olefin, and wherein the cyclic olefin composition is substantially free of (e.g., 10 wt.% or less, 9 wt.% or less, 8 wt.% or less, 7 wt.% or less, 6 wt.% or less, 5 wt.% or less, 4 wt.% or less, 3 wt.% or less, 2 wt.% or less, 1 wt.% or less, 0.5 wt.% or less, 0.1 wt.% or less, 0.01 wt.% or less; based on the total weight of the cyclic olefin composition), a monounsaturated cyclic olefin.

[0151] The at least one multiunsaturated cyclic olefin and the at least one monounsaturated cyclic olefin, if present, may be, independent of one another, substituted or unsubstituted.

[0152] The at least one multiunsaturated cyclic olefin and the at least one monounsaturated cyclic olefin, if present, may be, independent of one another, substituted by hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z*)n-Fn wherein n is 0 or 1, Fn is the functional group, and Z*is a hydrocarbylene linking group such as an alkylene, substituted alkylene, heteroalkylene, substituted heteroalkene, arylene, substituted arylene, heteroarylene, or substituted heteroarylene linkage, and functional groups (Fn).

[0153] The cyclic olefin composition may contain at least one multiunsaturated cyclic olefin in an amount ranging from 90 to 100 wt.% (e.g., 91 to 99.9 wt.%, 92 to 99 wt.%, 93 to 98 wt.%, 94 to 97 wt.%, 95 to 96 wt.%), and the at least one monounsaturated cyclic olefin in an amount of 10 wt.% or less (e.g., 9 wt.% or less, 8 wt.% or less, 7 wt.% or less, 6 wt.% or less, 5 wt.% or less, 4 wt.% or less, 3 wt.% or less, 2 wt.% or less, 1 wt.% or less, 0.5 wt.% or less, 0.1 wt.% or less, 0.01 wt.% or less, 0 wt.%), based on the total weight of the cyclic olefin composition.

[0154] The ROMP composition disclosed herein also may not contain, or may be substantially free of (e.g., 10 wt.% or less, 9 wt.% or less, 8 wt.% or less, 7 wt.% or less, 6 wt.% or less, 5 wt.% or less, 4 wt.% or less, 3 wt.% or less, 2 wt.% or less, 1 wt.% or less, 0.5 wt.% or less, 0.1 wt.% or less, 0.01 wt.% or less; based on the total weight of the ROMP composition), a monounsaturated cyclic olefin. The monounsaturated cyclic olefin may be selected from ONB. Alternatively, the monounsaturated cyclic olefin may be selected from at least one substituted norbornene, including, but not limited to, the monounsaturated substituted norbornenes encompassed by cyclic olefin structures (D), (E), or (F) (as defined below). Alternatively, the monounsaturated cyclic olefin may be selected from any monounsaturated cyclic olefin. For example, the ROMP composition of the disclosure may not contain a monounsaturated cyclic olefin, wherein the monounsaturated cyclic olefin is selected from ONB, or wherein the monounsaturated cyclic olefin is selected from at least one substituted norbornene, including, but not limited to, the monounsaturated substituted norbornenes encompassed by cyclic olefin structures (D), (E), or (F) (as defined below), or wherein the monounsaturated cyclic olefin is selected from any monounsaturated cyclic olefin. For example, the ROMP composition of the disclosure may be substantially free of (e.g., 10 wt.% or less, 9 wt.% or less, 8 wt.% or less, 7 wt.% or less, 6 wt.% or less, 5 wt.% or less, 4 wt.% or less, 3 wt.% or less, 2 wt.% or less, 1 wt.% or less, 0.5 wt.% or less, 0.1 wt.% or less, 0.01 wt.% or less; based on the total weight of the ROMP composition), a monounsaturated cyclic olefin, wherein the monounsaturated cyclic olefin is selected from ONB, or wherein the monounsaturated cyclic olefin is selected from at least one substituted norbornene, including, but not limited to, the monounsaturated substituted norbornenes encompassed by cyclic olefin structures (D), (E), or (F) (as defined below), or wherein the monounsaturated cyclic olefin is selected from any monounsaturated cyclic olefin.

[0155] In other embodiments, the cyclic olefin compositions used in the ROMP compositions of the disclosure disclosed herein may comprise, consist essentially of, or consist of 70 to 90 wt.% (e.g., 72 to 88 wt.%, 74 to 86 wt.%, 76 to 84 wt.%, 78 to 82 wt.%) of at least one multiunsaturated cyclic olefin, and 25 wt.% or less (e.g., 20 wt.% or less, 15 wt.% or less, 10 wt.% or less, 9 wt.% or less, 8 wt.% or less, 7 wt.% or less, 6 wt.% or less, 5 wt.% or less, 4 wt.% or less, 3 wt.% or less, 2 wt.% or less, 1 wt.% or less, 0.5 wt.% or less, 0.1 wt.% or less, 0.01 wt.% or less, 0 wt.%) of a monounsaturated cyclic olefin, wherein the monounsaturated cyclic olefin is selected from ONB, or wherein the monounsaturated cyclic olefin is selected from at least one substituted norbornene, including, but not limited to, the monounsaturated substituted norbornenes encompassed by cyclic olefin structures (D), (E), or (F) (as defined below), or wherein the monounsaturated cyclic olefin is selected from any monounsaturated cyclic olefin. For example, the cyclic olefin composition may also comprise, consist essentially of, or consist of 70 to 80 wt.% dicyclopentadiene (e.g., 70 wt.%, 71 wt.%, 72 wt.%, 73 wt.%, 74 wt.%, 75 wt.%, 76 wt.%, 77 wt.%, 78 wt.%, 79 wt.%, 80 wt.%), 0.1 to 10 wt.% tricyclopentadiene (e.g., 0.1 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 4wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%), and 25 wt.% or less of the monounsaturated cyclic olefin (e.g., 20 wt.% or less, 15 wt.% or less, 10 wt.% or less, 9 wt.% or less, 8 wt.% or less, 7 wt.% or less, 6 wt.% or less, 5 wt.% or less, 4 wt.% or less, 3 wt.% or less, 2 wt.% or less, 1 wt.% or less, 0.5 wt.% or less, 0.1 wt.% or less, 0.01 wt.% or less, 0 wt.%), based on the total weight of the cyclic olefin composition, wherein the monounsaturated cyclic olefin is selected from ONB, or wherein the monounsaturated cyclic olefin is selected from at least one substituted norbornene, including, but not limited to, the monounsaturated substituted norbornenes encompassed by cyclic olefin structures (D), (E), or (F) (as defined below), or wherein the monounsaturated cyclic olefin is selected from any monounsaturated cyclic olefin.

[0156] As still another example, in certain embodiments the coating compositions comprises, consists essentially of, or consists of at least one cyclic olefin selected from the group consisting of Formulae (I), (II), and (III); optionally at least one linear olefin of Formula (IV); at least one coating additive; and at least one curing agent selected from an organometallic complex, a free radical initiator and a cationic initiator, preferably at least one metal carbene metathesis catalyst curing agent. The cyclic olefin of Formulae (I), (II), and (III), and the linear olefin of Formula (IV) have the following structures:, , , .cyclic olefins of Formulae (I), (II), and (III), and the linear olefins of Formula (IV), including Ra, Rb, Rst, Rc, and Rd, z and other features are defined below. According to an embodiment of this example, the coating composition comprises at least one cyclic olefin represented by Formula (I), by Formula (II), by Formula (III), and at least one metal carbene olefin metathesis catalyst represented by Formula (1), wherein Formulae (I), (II), (III), and (1) are as defined below. According to an embodiment of this example, the coating composition comprises at least one cyclic olefin represented by Formula (I), and by Formula (II) and at least one metal carbene olefin metathesis catalyst represented by Formula (1), wherein Formulae (I), (II) and (1) are as defined below. According to an embodiment of this example, the coating composition comprises at least one cyclic olefin represented by Formula (I), and by Formula (III), and at least one metal carbene olefin metathesis catalyst represented by Formula (1), wherein Formulae (I), (III) and (1) are as defined below. According to an embodiment of this example, the coating composition comprises at least one cyclic olefin represented by Formula (II), and by Formula (III) and at least one metal carbeneolefin metathesis catalyst represented by Formula (1), wherein Formulae (II), (III) and (1) are as defined below.

[0157] Cyclic Olefins

[0158] Such cyclic olefins may be optionally substituted, optionally heteroatom-containing, mono- unsaturated, di-unsaturated, or poly-unsaturated C5to C24hydrocarbons, that may be mono-, di-, or poly- cyclic. When the cyclic olefin comprises more than one ring, the rings may or may not be fused.

[0159] The cyclic olefin may generally be any strained or unstrained cyclic olefin, provided the cyclic olefin is able to participate in a polymerization reaction either individually or as part of a cyclic olefin composition.

[0160] In one embodiment of the disclosure, the cyclic olefin is represented by the structure of Formula (I):Formula (I) wherein: Rais H, optionally substituted linear or branched C1-24alkyl, optionally substituted linear or branched C2-24alkenyl, halogen, - C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, -CN, -NO2, -CF3, -P(O)(ORh)2, -OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, an optionally substituted spiro heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C3-10cycloalkyl, -CH2- (optionally substituted C3-10cycloalkyl), optionally substituted C5-24aryl, -CH2-(optionally substituted C5-24aryl), optionally substituted C3-12cycloalkenyl, -CH2-(optionally substituted C3-12cycloalkenyl),each Rsis independently optionally substituted linear or branched C1-24 alkyl, optionally substituted linear or branched C2-24 alkenyl, halogen, - C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, -CN, NO2, -CF3, - P(O)(ORh)2, -OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C3-10 cycloalkyl, -CH2-(optionally substituted C3-10 cycloalkyl), optionally substituted C5-24 aryl, -CH2-(optionally substituted C5-24 aryl), optionally substituted C3-12 cycloalkenyl, -CH2-(optionally substituted C3-12 cycloalkenyl), C(Rh)(Ri)COORj, -C(Rh)(Ri)C(O)H, - C(Rh)(Ri)C(O)Rk, -C(Rh)(Ri)CRl(ORm)(ORn), -C(Rh)(Ri)C(O)NRoRp, -C(Rh)(Ri)C(O)NRoORn;t is 0, 1, 2, 3, 4, 5 or 6; Rfis OH, ORk, NRgRh, optionally substituted linear or branched C1-24alkyl, optionally substituted C3-10cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl or optionally substituted C3-12cycloalkenyl; Rgis H, optionally substituted linear or branched C1-24alkyl, optionally substituted C3-10cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl, optionally substituted linear or branched C2-24alkenyl, -C(O)-(optionally substituted C5-24aryl), -C(O)-(optionally substituted linear or branched C2-24alkenyl), or optionally substituted C3-12cycloalkenyl; Rhis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl; Riis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl; Rjis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl; Rkis optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl; Rlis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl; Rmis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl; Rnis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl; Rois H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl or optionally substituted C3-12cycloalkenyl; andRpis H, optionally substituted linear or branched C1-24alkyl, optionally substituted C3-10cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl or optionally substituted C3-12cycloalkenyl.

[0161] In one embodiment of the disclosure, the cyclic olefin is represented by Formula (I) wherein: Rais H, optionally substituted linear or branched C1-12alkyl, optionally substituted linear or branched C2-12alkenyl, halogen, - C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, CN, NO2, -CF3, -P(O)(ORh)2, - OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, -CH2-(optionally substituted heterocycle), an optionally substituted spiro heterocycle, optionally substituted C5-7cycloalkyl, -CH2- (optionally substituted C5-7 cycloalkyl), optionally substituted C6-10 aryl, -CH2-(optionally substituted C6-10 aryl), optionally substituted C5-12 cycloalkenyl, -CH2-(optionally substituted C5-12 cycloalkenyl), C(Rh)(Ri)COORj, -C(Rh)(Ri)C(O)H, -C(Rh)(Ri)C(O)Rk, -C(Rh)(Ri)CRl(ORm)(ORn), -C(Rh)(Ri)C(O)NRoRp, -C(Rh)(Ri)C(O)NRoORn,each Rsis independently optionally substituted linear or branched C1-12 alkyl, optionally substituted linear or branched C2-12 alkenyl, halogen, - C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, CN, NO2, -CF3, - P(O)(ORh)2, -OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C5-7 cycloalkyl, -CH2-(optionally substituted C5-7 cycloalkyl), optionally substituted C6-10 aryl, -CH2-(optionally substituted C6-10 aryl), optionally substituted C5-12cycloalkenyl, -CH2-(optionally substituted C5-12cycloalkenyl), C(Rh)(Ri)COORj, -C(Rh)(Ri)C(O)H, - C(Rh)(Ri)C(O)Rk, -C(Rh)(Ri)CRl(ORm)(ORn), -C(Rh)(Ri)C(O)NRoRp, -C(Rh)(Ri)C(O)NRoORn; t is 0, 1, 2, 3 or 4; Rfis OH, ORk, NRgRh, optionally substituted linear or branched C1-12 alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl; Rgis H, optionally substituted linear or branched C1-12alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl, optionally substituted linear or branched C2-12alkenyl, -C(O)-(optionally substituted C6-10aryl), -C(O)-(optionally substituted linear or branched C2-12alkenyl), or optionally substituted C5-12cycloalkenyl; Rhis H, optionally substituted linear or branched C1-12alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl; Riis H, optionally substituted linear or branched C1-12alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl;Rjis H, optionally substituted linear or branched C1-12alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl; Rkis optionally substituted linear or branched C1-12alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl; Rlis H, optionally substituted linear or branched C1-12alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl; Rmis H, optionally substituted linear or branched C1-12 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl; Rnis H, optionally substituted linear or branched C1-12 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl; Rois H, optionally substituted linear or branched C1-12 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl; and Rpis H, optionally substituted linear or branched C1-12 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl.

[0162] In one embodiment of the disclosure, the cyclic olefin is represented by Formula (I) wherein: Rais H, optionally substituted linear or branched C1-6 alkyl, optionally substituted linear or branched C2-6 alkenyl, halogen, - C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, CN, NO2, -CF3, -P(O)(ORh)2, - OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, an optionally substituted spiro heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C5-7 cycloalkyl, -CH2- (optionally substituted C5-7 cycloalkyl), optionally substituted C6-10 aryl, -CH2-(optionally substituted C6-10 aryl), optionally substituted C5-12cycloalkenyl, -CH2-(optionally substituted C5-7cycloalkenyl), or; t is 0; Rfis OH, ORk, NRgRh, optionally substituted linear or branched C1-6alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl;Rgis H, optionally substituted linear or branched C1-6alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl, optionally substituted linear or branched C2-6alkenyl, -C(O)-(optionally substituted C6-10aryl), -C(O)-(optionally substituted linear or branched C2-6alkenyl), or optionally substituted C5-12cycloalkenyl; Rhis H, optionally substituted linear or branched C1-6alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl; and Rkis optionally substituted linear or branched C1-6alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl.

[0163] Depending on the position of Rson the tetracyclododeca-3-ene moiety, the cyclic olefin of Formula (I), can be of structure, wherein: t is 1, Raand Rsare as defined herein; and Raand Rscan form an optionally substituted polycyclic ring with the rest of the molecule.

[0164] In one embodiment of the disclosure, the cyclic olefin is represented by Formula (I) wherein: Ra,.

[0166] In one embodiment of the disclosure, the cyclic olefin is represented by the structure of Formula (II):Formula (II) wherein: Rbis H, optionally substituted linear or branched C1-24alkyl, optionally substituted linear or branched C2-24alkenyl, halogen, - C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, CN, NO2, -CF3, -P(O)(ORh)2, - OP(O)(ORh)2, -Si(ORk)3, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, an optionally substituted spiro heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C3-10cycloalkyl, -CH2-(optionally substituted C3-10cycloalkyl), optionally substituted C5-24aryl, -CH2- (optionally substituted C5-24aryl), optionally substituted C3-12cycloalkenyl, -CH2-(optionally substituted C3-12cycloalkenyl), C(Rh)(Ri)COORj, -C(Rh)(Ri)C(O)H, -C(Rh)(Ri)C(O)Rk, -C(Rh)(Ri)CRl(ORm)(ORn), -each Rsis independently optionally substituted linear or branched C1-24alkyl, optionally substituted linear or branched C2-24 alkenyl, halogen, - C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, CN, NO2, -CF3, - P(O)(ORh)2, -OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C3-10cycloalkyl, -CH2-(optionally substituted C3-10cycloalkyl), optionally substituted C5-24aryl, -CH2-(optionally substituted C5-24aryl), optionally substituted C3-12cycloalkenyl, -CH2-(optionally substituted C3-12cycloalkenyl), C(Rh)(Ri)COORj, -C(Rh)(Ri)C(O)H, - C(Rh)(Ri)C(O)Rk, -C(Rh)(Ri)CRl(ORm)(ORn), -C(Rh)(Ri)C(O)NRoRp, -C(Rh)(Ri)C(O)NRoORn; t is 0, 1, 2, 3, 4, 5 or 6; Rfis OH, ORk, NRgRh, optionally substituted linear or branched C1-24alkyl, optionally substituted C3-10cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl or optionally substituted C3-12cycloalkenyl; Rgis H, optionally substituted linear or branched C1-24alkyl, optionally substituted C3-10cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl, optionally substituted linear or branched C2-24alkenyl, -C(O)-(optionally substituted C5-24aryl), -C(O)-(optionally substituted linear or branched C2-24alkenyl), or optionally substituted C3-12cycloalkenyl; Rhis H, optionally substituted linear or branched C1-24alkyl, optionally substituted C3-10cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl or optionally substituted C3-12cycloalkenyl;Riis H, optionally substituted linear or branched C1-24alkyl, optionally substituted C3-10cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl or optionally substituted C3-12cycloalkenyl; Rjis H, optionally substituted linear or branched C1-24alkyl, optionally substituted C3-10cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl or optionally substituted C3-12cycloalkenyl; Rkis optionally substituted linear or branched C1-24alkyl, optionally substituted C3-10cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl or optionally substituted C3-12cycloalkenyl; Rlis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl; Rmis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl; Rnis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl; Rois H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl; and Rpis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl.

[0167] In one embodiment of the disclosure, the cyclic olefin is represented by the structure of Formula (II) wherein: Rbis H, optionally substituted linear or branched C1-12 alkyl, optionally substituted linear or branched C2-12 alkenyl, halogen, - C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, CN, NO2, -CF3, -P(O)(ORh)2, - OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, an optionally substituted spiro heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C5-7 cycloalkyl, -CH2- (optionally substituted C5-7cycloalkyl), optionally substituted C6-10aryl, -CH2-(optionally substituted C6-10aryl), optionally substituted C5-12cycloalkenyl, -CH2-(optionally substituted C5-12cycloalkenyl),C(Rh)(Ri)COORj, -C(Rh)(Ri)C(O)H, -C(Rh)(Ri)C(O)Rk, -C(Rh)(Ri)CRl(ORm)(ORn), -C(Rh)(Ri)C(O)NRoRp,each Rsis independently optionally substituted linear or branched C1-12 alkyl, optionally substituted linear or branched C2-12 alkenyl, halogen, - C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, CN, NO2, -CF3, - P(O)(ORh)2, -OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C5-7 cycloalkyl, -CH2-(optionally substituted C5-7 cycloalkyl), optionally substituted C6-10 aryl, -CH2-(optionally substituted C6-10 aryl), optionally substituted C5-12 cycloalkenyl, -CH2-(optionally substituted C5-12 cycloalkenyl), C(Rh)(Ri)COORj, -C(Rh)(Ri)C(O)H, - C(Rh)(Ri)C(O)Rk, -C(Rh)(Ri)CRl(ORm)(ORn), -C(Rh)(Ri)C(O)NRoRp, -C(Rh)(Ri)C(O)NRoORn; t is 0, 1, 2, 3 or 4; Rfis OH, ORk, NRgRh, optionally substituted linear or branched C1-12 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl; Rgis H, optionally substituted linear or branched C1-12 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl, optionally substituted linear or branched C2-12 alkenyl, -C(O)-(optionally substituted C6-10 aryl), -C(O)-(optionally substituted linear or branched C2- 12 alkenyl), or optionally substituted C5-12 cycloalkenyl; Rhis H, optionally substituted linear or branched C1-12alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl; Riis H, optionally substituted linear or branched C1-12 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl; Rjis H, optionally substituted linear or branched C1-12alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl; Rkis optionally substituted linear or branched C1-12alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl; Rlis H, optionally substituted linear or branched C1-12alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl;Rmis H, optionally substituted linear or branched C1-12alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl; Rnis H, optionally substituted linear or branched C1-12alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl; Rois H, optionally substituted linear or branched C1-12alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl; and Rpis H, optionally substituted linear or branched C1-12 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl.

[0168] In one embodiment of the disclosure, the cyclic olefin is represented by Formula (II) wherein: Rbis H, optionally substituted linear or branched C1-6 alkyl, optionally substituted linear or branched C2-6 alkenyl, halogen, - C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, CN, NO2, -CF3, -P(O)(ORh)2, - OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, an optionally substituted spiro heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C5-7 cycloalkyl, -CH2- (optionally substituted C5-7 cycloalkyl), optionally substituted C6-10 aryl, -CH2-(optionally substituted C6-10 aryl), optionally substituted C5-12cycloalkenyl, -CH2-(optionally substituted C5-12cycloalkenyl), or; t is 0; Rfis OH, ORk, NRgRh, optionally substituted linear or branched C1-6alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl; Rgis H, optionally substituted linear or branched C1-6alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl, optionally substituted linear or branched C2-6alkenyl, -C(O)-(optionally substituted C6-10aryl), -C(O)-(optionally substituted linear or branched C2-6alkenyl), or optionally substituted C5-12cycloalkenyl; Rhis H, optionally substituted linear or branched C1-6alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl; andRkis optionally substituted linear or branched C1-6alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl.

[0169] Depending on the position of Rson the 2-norbornene moiety, the cyclic olefin of structure Formula (II), can be represented bywherein: t =1, Rsand Rbare as defined herein; and Rsand Rbcan form together an optionally substituted polycyclic structure with the rest of the molecule.

[0170] In one embodiment of the disclosure, the cyclic olefin is represented by Formula (II) wherein: , , , , ,

[0171] Non-limiting examples of monomers of Formula (II) can be represented by,

[0172] In one embodiment of the disclosure, the cyclic olefin is represented by the structure of FormulaFormula (III) wherein z is 0, 1, 2 or 3.

[0173] In one embodiment of the disclosure, the cyclic olefin is represented by the structure of Formula (III), wherein z is 1 or 2.

[0174] In one embodiment of the disclosure, the cyclic olefin is represented by the structure of Formula (III), wherein z is 2.

[0175] Non-limiting examples of monomers of Formula (III) can be represented by,

[0176] Examples of cyclic olefins thus include, without limitation, dicyclopentadiene; tricyclopentadiene, tetracyclopentadiene; norbornene; 5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5-phenyl-2- norbornene; 5-benzyl-2-norbornene; 5-acetyl-2-norbornene; 5-methoxycarbonyl-2-norbornene; 5- ethoxycarbonyl-2-norbornene; 5-methyl-5-methoxycarbonyl-2-norbornene; 5-cyano-2-norbornene; 5,5,6- trimethyl-2-norbornene; endo,exo-5,6-dimethoxy-2-norbornene; endo,endo-5,6-dimethoxy-2-norbornene; endo,exo-5-6-dimethoxycarbonyl-2-norbornene; endo,endo-5,6-dimethoxycarbonyl-2-norbornene; norbornadiene; tricycloundecene; tetracyclododecene; 8-methoxycarbonyl-tetracyclododecene; 8- cyanotetracyclododecene; C1-C12hydrocarbyl substituted norbornenes such as 5-methyl-2-norbornene; 5- ethyl-2-norbornene; 5-butyl-2-norbornene; 5-hexyl-2-norbornene; 5-octyl-2-norbornene; 5-decyl-2- norbornene; 5-dodecyl-2-norbornene; 5-vinyl-2-norbornene; 5-ethylidene-2-norbornene; 5-isopropenyl-2- norbornene; 5-propenyl-2-norbornene; and 5-butenyl-2-norbornene, and the like; C2-C12hydrocarbyl substituted tetracyclododecenes such as 8-methyl-tetracyclododeca-3-ene; 8-ethyl-tetracyclododeca-3-ene; 8-butyl-tetracyclododeca-3-ene; 8-hexyl-tetracyclododeca-3-ene; 8-octyl-2-tetracyclododeca-3-ene; 8- decyl-2-tetracyclododeca-3-ene; 8-dodecyl-2-tetracyclododeca-3-ene; 8-vinyl-tetracyclododeca-3-ene; 8- ethylidene-2-tetracyclododeca-3-ene; 8-isopropenyl-tetracyclododeca-3-ene; 5-propenyl- tetracyclododeca-3-ene; 5-butenyl-tetracyclododeca-3-ene.

[0177] It is well understood by one of skill in the art that bicyclic and polycyclic olefins as disclosed herein may consist of a variety of structural isomers and / or stereoisomers, any and all of which are suitable for use in the present disclosure. Any reference herein to such bicyclic and polycyclic olefins unless specifically stated, includes mixtures of any and all such structural isomers and / or stereoisomers.

[0178] Linear Olefins

[0179] The linear olefins used in the disclosure, may be optionally substituted, optionally heteroatom- containing, mono-unsaturated, or multi-unsaturated.

[0180] In one embodiment of the disclosure, the linear olefin is represented by the structure of Formula (IV) in which Rcand Rdmay be in a cis or trans configuration:wherein: Rcis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted linear or branched C2-24 alkenyl, halogen, - C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, CN, NO2, -CF3, -P(O)(ORh)2, - OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C3-10 cycloalkyl, -CH2-(optionally substituted C3-10 cycloalkyl), optionally substituted C5-24 aryl, -CH2-(optionally substituted C5-24 aryl), optionally substituted C3-12 cycloalkenyl, -CH2-(optionally substituted C3-12 cycloalkenyl), C(Rh)(Ri)COORj, -C(Rh)(Ri)C(O)H, - C(Rh)(Ri)C(O)Rk, -C(Rh)(Ri)CRl(ORm)(ORn), -C(Rh)(Ri)C(O)NRoRp, -C(Rh)(Ri)C(O)NRoORn; Rdis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted linear or branched C2-24 alkenyl, halogen, - C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, CN, NO2, -CF3, -P(O)(ORh)2, - OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C3-10 cycloalkyl, -CH2-(optionally substituted C3-10 cycloalkyl), optionally substituted C5-24 aryl, -CH2-(optionally substituted C5-24 aryl), optionally substituted C3-12 cycloalkenyl, -CH2-(optionally substituted C3-12 cycloalkenyl), C(Rh)(Ri)COORj, -C(Rh)(Ri)C(O)H, - C(Rh)(Ri)C(O)Rk, -C(Rh)(Ri)CRl(ORm)(ORn), -C(Rh)(Ri)C(O)NRoRp, -C(Rh)(Ri)C(O)NRoORn; Rfis OH, ORk, NRgRh, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl; Rgis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl, optionally substituted linear or branched C2-24alkenyl, -C(O)-(optionally substituted C5-24aryl), -C(O)-(optionally substituted linear or branched C2-24alkenyl), or optionally substituted C3-12cycloalkenyl; Rhis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl; Riis H, optionally substituted linear or branched C1-24alkyl, optionally substituted C3-10cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl or optionally substituted C3-12cycloalkenyl;Rjis H, optionally substituted linear or branched C1-24alkyl, optionally substituted C3-10cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl or optionally substituted C3-12cycloalkenyl; Rkis optionally substituted linear or branched C1-24alkyl, optionally substituted C3-10cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl or optionally substituted C3-12cycloalkenyl; Rlis H, optionally substituted linear or branched C1-24alkyl, optionally substituted C3-10cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl or optionally substituted C3-12cycloalkenyl; Rmis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl; Rnis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl; Rois H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl; and Rpis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl or optionally substituted C3-12 cycloalkenyl.

[0181] In one embodiment of the disclosure, the linear olefins are represented by the structure of Formula (IV) wherein: Rcis H, optionally substituted linear or branched C1-12 alkyl, optionally substituted linear or branched C2-12 alkenyl, halogen, - C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, CN, NO2, -CF3, -P(O)(ORh)2, - OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C5-7 cycloalkyl, -CH2-(optionally substituted C5-7 cycloalkyl), optionally substituted C6-10 aryl, -CH2-(optionally substituted C6-10 aryl), optionally substituted C5-12 cycloalkenyl, -CH2-(optionally substituted C5-12 cycloalkenyl), C(Rh)(Ri)COORj, -C(Rh)(Ri)C(O)H, - C(Rh)(Ri)C(O)Rk, -C(Rh)(Ri)CRl(ORm)(ORn), -C(Rh)(Ri)C(O)NRoRp, -C(Rh)(Ri)C(O)NRoORn; Rdis H, optionally substituted linear or branched C1-12alkyl, optionally substituted linear or branched C2-12alkenyl, halogen, - C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, CN, NO2, -CF3, -P(O)(ORh)2, - OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C5-7cycloalkyl, -CH2-(optionally substituted C5-7cycloalkyl),optionally substituted C6-10aryl, -CH2-(optionally substituted C6-10aryl), optionally substituted C5-12cycloalkenyl, -CH2-(optionally substituted C5-12cycloalkenyl), C(Rh)(Ri)COORj, -C(Rh)(Ri)C(O)H, - C(Rh)(Ri)C(O)Rk, -C(Rh)(Ri)CRl(ORm)(ORn), -C(Rh)(Ri)C(O)NRoRp, -C(Rh)(Ri)C(O)NRoORn; Rfis OH, ORk, NRgRh, optionally substituted linear or branched C1-12alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl; Rgis H, optionally substituted linear or branched C1-12alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl, optionally substituted linear or branched C2-12 alkenyl, -C(O)-(optionally substituted C6-10 aryl), -C(O)-(optionally substituted linear or branched C2- 12 alkenyl), or optionally substituted C5-12 cycloalkenyl; Rhis H, optionally substituted linear or branched C1-12 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl; Riis H, optionally substituted linear or branched C1-12 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl; Rjis H, optionally substituted linear or branched C1-12 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl; Rkis optionally substituted linear or branched C1-12 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl; Rlis H, optionally substituted linear or branched C1-12 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl; Rmis H, optionally substituted linear or branched C1-12 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl; Rnis H, optionally substituted linear or branched C1-12 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl; Rois H, optionally substituted linear or branched C1-12alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl; andRpis H, optionally substituted linear or branched C1-12alkyl, optionally substituted C5-7cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl or optionally substituted C5-12cycloalkenyl.

[0182] In one embodiment of the disclosure, the linear olefins are represented by Formula (IV) wherein: Rcis H, optionally substituted linear or branched C1-6alkyl, optionally substituted linear or branched C2-6alkenyl, halogen, - C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, CN, NO2, -CF3, -P(O)(ORh)2, - OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C5-7cycloalkyl, -CH2-(optionally substituted C5-7cycloalkyl), optionally substituted C6-10 aryl, -CH2-(optionally substituted C6-10 aryl), optionally substituted C5-12 cycloalkenyl, - CH2-(optionally substituted C5-12 cycloalkenyl); Rdis H, optionally substituted linear or branched C1-6 alkyl, optionally substituted linear or branched C2-6 alkenyl, halogen, -C(O)Rf, -CH2-C(O)Rf, -ORg, -CH2-ORg, CN, NO2, -CF3, -P(O)(ORh)2, - OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C5-7 cycloalkyl, -CH2-(optionally substituted C5-7 cycloalkyl), optionally substituted C6-10 aryl, -CH2-(optionally substituted C6-10 aryl), optionally substituted C5-12 cycloalkenyl, - CH2-(optionally substituted C5-12 cycloalkenyl); Rfis OH, ORk, NRgRh, optionally substituted linear or branched C1-6 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl; Rgis H, optionally substituted linear or branched C1-6 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl, optionally substituted linear or branched C2-6 alkenyl, -C(O)-(optionally substituted C6-10 aryl), -C(O)-(optionally substituted linear or branched C2-6 alkenyl), or optionally substituted C5-7 cycloalkenyl; Rhis H, optionally substituted linear or branched C1-6 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl; and Rkis optionally substituted linear or branched C1-6 alkyl, optionally substituted C5-7 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl or optionally substituted C5-12 cycloalkenyl.

[0183] In one embodiment of the disclosure, the linear olefins are represented by Formula (IV) wherein:a.

[0185] In separate embodiments, a coating composition of the disclosure, composition may as its olefinic component may comprise, consist essentially or, or consist of, at least one cyclic olefin represented selected from the group consisting of Formulae (I) and (II); at least one cyclic olefin selected from the group consisting of Formulae (I) and (III), or at least one cyclic olefin selected from the group consisting of Formulae (II) and (III). A coating composition of the disclosure may contain only cyclic monomers of Formula (I), (II) and (III) or mixtures thereof, or as just mentioned, may contain at least one particular cyclic olefin selected from one of Formula (I), (II) and (III), but not contain a linear olefin of Formula (IV). In a coating composition of the disclosure, the olefinic component may comprise, consist essentially or, or consist of, 0-100%, preferably 25-100%, most preferably 50-100% or 70-85% of at least one cyclic olefin of Formula (I); 0-100%, preferably 20-80% or 15-50% of at least one cyclic olefin of Formula (II); 0-100%, preferably 10-80% or 20-75% of at least one cyclic olefin of Formula (III); and 0-20%, preferably 0-10% or 1-5% of at least one linear olefin of Formula (IV), such the olefins making up the olefinic component add to 100% of that component of a coating composition of the disclosure.

[0186] As yet another example, one or more embodiments of the resin composition described herein comprises, consists essentially of, or consists of a cyclic olefin composition, and a catalyst composition comprising at least one metal carbene olefin metathesis catalyst, wherein the cyclic olefin composition comprises 80.1 mol% to 99.9 mol% of at least one cyclic olefin containing multiunsaturation, and 0.1 mol% to 19.9 mol% of at least one cyclic olefin containing monounsaturation, wherein the at least one cyclicolefin containing multiunsaturation may be substituted or unsubstituted, and wherein the at least one cyclic olefin containing monounsaturation may be substituted or unsubstituted. Exemplary Catalysts

[0187] The catalyst compositions used in the ROMP composition of the disclosure disclosed herein comprise, consist essentially of, or consist of at least one metal carbene olefin metathesis catalyst.

[0188] A metal carbene olefin metathesis catalyst that may be used in the catalyst composition of the disclosure disclosed herein is a Group 8 transition metal complex having the structure of formula (1) (1)wherein: M is a Group 8 transition metal; L1, L2, and L3are neutral electron donor ligands; n is 0 or 1, such that L3may or may not be present; m is 0, 1, or 2; k is 0 or 1; X1and X2are anionic ligands; and R1and R2are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, wherein any two or more of X1, X2, L1, L2, L3, R1, and R2can be taken together to form one or more cyclic groups, and further wherein any one or more of X1, X2, L1, L2, L3, R1, and R2may be attached to a support.

[0189] Additionally, in formula (1), one or both of R1and R2may have the structure –(W)n-U+V-, wherein W is selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene; U is a positively charged Group 15 or Group 16 element substituted with hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; V is a negatively charged counterion; and n is 0 or 1. Furthermore, R1and R2may be taken together to form an indenylidene moiety.

[0190] Catalysts may contain Ru or Os as the Group 8 transition metal, with Ru preferred.

[0191] Numerous embodiments of the catalysts useful in the reactions disclosed herein are described in more detail infra. For the sake of convenience, the catalysts are described in groups, but it should beemphasized that these groups are not meant to be limiting in any way. That is, any of the catalysts useful in the disclosure may fit the description of more than one of the groups described herein.

[0192] A first group of catalysts, then, are commonly referred to as First Generation Grubbs-type catalysts, and have the structure of formula (1). For the first group of catalysts, M is a Group 8 transition metal, m is 0, 1, or 2, and n, X1, X2, L1, L2, L3, R1, and R2are described as follows.

[0193] For the first group of catalysts, n is 0, and L1and L2are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, (including cyclic ethers), amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine, imidazole, substituted imidazole, pyrazine, substituted pyrazine and thioether. Exemplary ligands are trisubstituted phosphines. Trisubstituted phosphines may be of the formula PRH1RH2RH3, where RH1, RH2, and RH3are each independently substituted or unsubstituted aryl or C1-C10 alkyl, particularly primary alkyl, secondary alkyl, or cycloalkyl. L1and L2may be independently selected from the group consisting of trimethylphosphine (PMe3), triethylphosphine (PEt3), tri-n-butylphosphine (PBu3), tri(ortho-tolyl)phosphine (P-o-tolyl3), tri- tert-butylphosphine (P-tert-Bu3), tricyclopentylphosphine (PCyclopentyl3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), trioctylphosphine (POct3), triisobutylphosphine, (P-i-Bu3), triphenylphosphine (PPh3), tri(pentafluorophenyl)phosphine (P(C6F5)3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph). Alternatively, L1and L2may be independently selected from phosphabicycloalkane (e.g., monosubstituted 9- phosphabicyclo-[3.3.1]nonane, or monosubstituted 9-phosphabicyclo[4.2.1]nonane] such as cyclohexylphoban, isopropylphoban, ethylphoban, methylphoban, butylphoban, pentylphoban and the like).

[0194] X1and X2are anionic ligands, and may be the same or different, or are linked together to form a cyclic group, typically although not necessarily a five- to eight-membered ring. X1and X2may be each independently hydrogen, halide, or one of the following groups: C1-C20alkyl, C5-C24 aryl, C1-C20alkoxy, C5-C24 aryloxy, C2-C20alkoxycarbonyl, C6-C24 aryloxycarbonyl, C2-C24 acyl, C2-C24 acyloxy, C1-C20alkylsulfonato, C5C24 arylsulfonato, C1-C20alkylsulfanyl, C5-C24 arylsulfanyl, C1-C20alkylsulfinyl, NO3, - N=C=O, -N=C=S, or C5-C24 arylsulfinyl. Optionally, X1and X2may be substituted with one or more moieties selected from C1-C12 alkyl, C1-C12 alkoxy, C5-C24 aryl, and halide, which may, in turn, with the exception of halide, be further substituted with one or more groups selected from halide, C1-C6 alkyl, C1- C6 alkoxy, and phenyl. X1and X2may be halide, benzoate, C2-C6 acyl, C2-C6 alkoxycarbonyl, C1-C6 alkyl, phenoxy, C1-C6alkoxy, C1-C6alkylsulfanyl, aryl, or C1-C6alkylsulfonyl. X1and X2may each be halide, CF3CO2, CH3CO2, CFH2CO2, (CH3)3CO, (CF3)2(CH3)CO, (CF3)(CH3)2CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethane-sulfonate. X1and X2may each be chloride.

[0195] R1and R2are independently selected from hydrogen, hydrocarbyl (e.g., C1-C20alkyl, C2-C20alkenyl, C2-C20alkynyl, C5-C24aryl, C6-C24alkaryl, C6-C24aralkyl, etc.), substituted hydrocarbyl (e.g., substituted C1-C20alkyl, C2-C20alkenyl, C2-C20alkynyl, C5-C24aryl, C6-C24alkaryl, C6-C24aralkyl, etc.), heteroatom-containing hydrocarbyl (e.g., heteroatom-containing C1-C20alkyl, C2-C20alkenyl, C2-C20alkynyl, C5-C24aryl, C6-C24alkaryl, C6-C24aralkyl, etc.), and substituted heteroatom-containing hydrocarbyl (e.g., substituted heteroatom-containing C1C20alkyl, C2-C20alkenyl, C2-C20alkynyl, C5-C24aryl, C6-C24alkaryl, C6-C24aralkyl, etc.), and functional groups. R1and R2may also be linked to form a cyclic group, which may be aliphatic or aromatic, and may contain substituents and / or heteroatoms. Generally, such a cyclic group will contain 4 to 12, such as 5, 6, 7, or 8 ring atoms.

[0196] In certain catalysts, R1is hydrogen and R2is selected from C1-C20alkyl, C2-C20alkenyl, and C5-C24 aryl, such as C1-C6 alkyl, C2-C6 alkenyl, and C5-C14 aryl. R2may be phenyl, vinyl, methyl, isopropyl, or t- butyl, optionally substituted with one or more moieties selected from C1-C6 alkyl, C1-C6 alkoxy, phenyl, and a functional group Fn as defined earlier herein. R2may be phenyl or vinyl substituted with one or more moieties selected from methyl, ethyl, chloro, bromo, iodo, fluoro, nitro, dimethylamino, methyl, methoxy, and phenyl. R2may be phenyl or -CH=C(CH3)2.

[0197] Any two or more (typically two, three, or four) of X1, X2, L1, L2, L3, R1, and R2can be taken together to form a cyclic group, including bidentate or multidentate ligands, as disclosed, for example, in U.S. Patent No.5,312,940, the disclosure of which is incorporated herein by reference. When any of X1, X2, L1, L2, L3, R1, and R2are linked to form cyclic groups, those cyclic groups may contain 4 to 12, such as 4, 5, 6, 7 or 8 atoms, or may comprise two or three of such rings, which may be either fused or linked. The cyclic groups may be aliphatic or aromatic, and may be heteroatom-containing and / or substituted. The cyclic group may, in some cases, form a bidentate ligand or a tridentate ligand. Examples of bidentate ligands include, but are not limited to, bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates.

[0198] A second group of catalysts, commonly referred to as Second Generation Grubbs-type catalysts, have the structure of formula (1), wherein L1is a carbene ligand having the structure of formula (2) (2)such that the complex may have the structure of formula (3)(3)wherein M, m, n, X1, X2, L2, L3, R1, and R2are as defined for the first group of catalysts, and the remaining substituents are as follows: X and Y are heteroatoms typically selected from N, O, S, and P. Since O and S are divalent, p is necessarily 0 when X is O or S, q is necessarily 0 when Y is O or S, and k is 0 or 1. However, when X is N or P, then p is 1, and when Y is N or P, then q is 1. Both X and Y may be N; Q1, Q2, Q3, and Q4are linkers, e.g., hydrocarbylene (including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene, such as substituted and / or heteroatom-containing alkylene) or -(CO)-, and w, x, y, and z are independently 0 or 1, meaning that each linker is optional. w, x, y, and z may all be 0. Further, two or more substituents on adjacent atoms within Q1, Q2, Q3, and Q4may be linked to form an additional cyclic group; and R3, R3A, R4, and R4Aare independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl. In addition, X and Y may be independently selected from carbon and one of the heteroatoms mentioned above, no more than one of X or Y may be carbon. Also, L2and L3may be taken together to form a single bindentate electron-donating heterocyclic ligand. Furthermore, R1and R2may be taken together to form an indenylidene moiety. Moreover, X1, X2, L2, L3, X and Y may be further coordinated to boron or to a carboxylate.

[0199] In addition, any two or more of X1, X2, L1, L2, L3, R1, R2, R3, R3A, R4, R4A, Q1, Q2, Q3, and Q4can be taken together to form a cyclic group, and any one or more of X1, X2, L2, L3, Q1, Q2, Q3, Q4, R1, R2, R3, R3A, R4, and R4Amay be attached to a support. Any two or more of X1, X2, L1, L2, L3, R1, R2, R3, R3A, R4, and R4Acan also be taken to be –A-Fn, wherein “A” is a divalent hydrocarbon moiety selected from alkylene and arylalkylene, wherein the alkyl portion of the alkylene and arylalkylene groups can be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the of arylalkylene can be substituted or unsubstituted, and wherein hetero atoms and / or functional groups may be present in either the aryl or the alkyl portions of the alkylene and arylalkylenegroups, and Fn is a functional group, or together to form a cyclic group, and any one or more of X1, X2, L2, L3, Q1, Q2, Q3, Q4, R1, R2, R3, R3A, R4, and R4Amay be attached to a support.

[0200] A particular class of carbene ligands having the structure of formula (II), where R3Aand R4Aare linked to form a cyclic group and at least one of X or Y is a nitrogen, or at least one of Q3or Q4is a heteroatom-containing hydrocarbylene or substituted heteroatom-containing hydrocarbylene, where at least one heteroatom is a nitrogen, are commonly referred to as N-heterocyclic carbene (NHC) ligands.

[0201] R3Aand R4Amay be linked to form a cyclic group so that the carbene ligand has the structure of formula (4) (4)wherein R3and R4are as defined for the second group of catalysts above, with at least one of R3and R4, such as both R3and R4, being alicyclic or aromatic of one to about five rings, and optionally containing one or more heteroatoms and / or substituents. Q is a linker, typically a hydrocarbylene linker, including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene linkers, wherein two or more substituents on adjacent atoms within Q may also be linked to form an additional cyclic structure, which may be similarly substituted to provide a fused polycyclic structure of two to about five cyclic groups. Q is often, although not necessarily, a two-atom linkage or a three-atom linkage.

[0202] Examples of N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands suitable as L1thus include, but are not limited to, the following where DIPP or DiPP is diisopropylphenyl and Mes is 2,4,6trimethylphenyl:

[0203] Additional examples of N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands suitable as L1thus include, but are not limited to the following:wherein RW1, RW2, RW3, RW4are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, or heteroatom containing hydrocarbyl, and where one or both of RW3and RW4may be in independently selected from halogen, nitro, amido, carboxyl, alkoxy, aryloxy, sulfonyl, carbonyl, thio, or nitroso groups.

[0204] Additional examples of N-heterocyclic carbene (NHC) ligands suitable as L1are further described in U.S. Pat. Nos.7,378,528; 7,652,145; 7,294,717; 6,787,620; 6,635,768; and 6,552,139, the disclosure of each of which is incorporated herein by reference.

[0205] Additionally, thermally activated N-Heterocyclic Carbene Precursors as disclosed in U.S. Pat. No. 6,838,489, the disclosure of which is incorporated herein by reference, may also be used with the disclosure.

[0206] When M is ruthenium, then, the complexes may have the structure of formula (5)wherein n, X1, X2, L2, L3, R1, and R2are as defined for the first group of catalysts, and k, R3, R4, and Q are as defined for the second group of catalysts.

[0207] More perferably, Q is a two-atom linkage having the structure -CR11R12-CR13R14- or -CR11=CR13- , such as -CR11R12-CR13R14-, wherein R11, R12, R13, and R14are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom- containing hydrocarbyl, and functional groups. Examples of functional groups here include without limitation carboxyl, C1-C20alkoxy, C5-C24aryloxy, C2-C20alkoxycarbonyl, C5-C24alkoxycarbonyl, C2-C24acyloxy, C1-C20alkylthio, C5-C24arylthio, C1C20alkylsulfonyl, and C1-C20alkylsulfinyl, optionally substituted with one or more moieties selected from C1-C12alkyl, C1-C12alkoxy, C5-C14aryl, hydroxyl, sulfhydryl, formyl, and halide. R11, R12, R13, and R14may be independently selected from hydrogen, C1-C12alkyl, substituted C1-C12alkyl, C1-C12heteroalkyl, substituted C1-C12heteroalkyl, phenyl, and substituted phenyl. Alternatively, any two of R11, R12, R13, and R14may be linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., a C4-C12 alicyclic group or a C5or C6 aryl group, which may itself be substituted, e.g., with linked or fused alicyclic or aromatic groups, or with other substituents. In one further aspect, any one or more of R11, R12, R13, and R14comprises one or more of the linkers. Additionally, R3and R4may be unsubstituted phenyl or phenyl substituted with one or more substituents selected from C1-C20alkyl, substituted C1-C20alkyl, C1-C20heteroalkyl, substituted C1-C20heteroalkyl, C5-C24 aryl, substituted C5-C24 aryl, C5-C24 heteroaryl, C6-C24 aralkyl, C6-C24 alkaryl, or halide. Furthermore, X1and X2may be halogen.

[0208] When R3and R4are aromatic, they are typically although not necessarily composed of one or two aromatic rings, which may or may not be substituted, e.g., R3and R4may be phenyl, substituted phenyl, biphenyl, substituted biphenyl, or the like. R3and R4may be the same and are each unsubstituted phenyl or phenyl substituted with up to three substituents selected from C1-C20alkyl, substituted C1-C20alkyl, C1-C20heteroalkyl, substituted C1-C20heteroalkyl, C5-C24aryl, substituted C5-C24aryl, C5-C24heteroaryl, C6-C24aralkyl, C6-C24alkaryl, or halide. Any substituents present may be hydrogen, C1-C12alkyl, C1-C12alkoxy, C5-C14aryl, substituted C5-C14aryl, or halide. As an example, R3and R4are mesityl (i.e., Mes as defined herein).

[0209] In a third group of catalysts having the structure of formula (1), M, m, n, X1, X2, R1, and R2are as defined for the first group of catalysts, L1is a strongly coordinating neutral electron donor ligand such as any of those described for the first and second group of catalysts, and L2and L3are weakly coordinating neutral electron donor ligands in the form of optionally substituted heterocyclic groups. Again, n is 0 or 1, such that L3may or may not be present. Generally, in the third group of catalysts, L2and L3are optionally substituted five- or six-membered monocyclic groups containing 1 to 4 (e.g., 1 to 3, 1 to 2) heteroatoms, or are optionally substituted bicyclic or polycyclic structures composed of 2 to 5 such five- or six-membered monocyclic groups. If the heterocyclic group is substituted, it should not be substituted on a coordinating heteroatom, and any one cyclic moiety within a heterocyclic group will generally not be substituted with more than 3 substituents.

[0210] For the third group of catalysts, examples of L2and L3include, without limitation, heterocycles containing nitrogen, sulfur, oxygen, or a mixture thereof.

[0211] Examples of nitrogen-containing heterocycles appropriate for L2and L3include pyridine, bipyridine, pyridazine, pyrimidine, bipyridamine, pyrazine, 1,3,5-triazine, 1,2,4triazine, 1,2,3-triazine, pyrrole, 2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1,2,3triazole, 1,2,4-triazole, indole, 3H-indole, 1H-isoindole, cyclopenta(b)pyridine, indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, cinnoline, quinazoline, naphthyridine, piperidine, piperazine, pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolylimine, purine, benzimidazole, bisimidazole, phenazine, acridine, and carbazole. Additionally, the nitrogen-containing heterocycles may be optionally substituted on a non-coordinating heteroatom with a non-hydrogen substitutent.

[0212] Examples of sulfur-containing heterocycles appropriate for L2and L3include thiophene, 1,2- dithiole, 1,3-dithiole, thiepin, benzo(b)thiophene, benzo(c)thiophene, thionaphthene, dibenzothiophene, 2H-thiopyran, 4H-thiopyran, and thioanthrene.

[0213] Examples of oxygen-containing heterocycles appropriate for L2and L3include 2Hpyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,2-dioxin, 1,3-dioxin, oxepin, furan, 2H1benzopyran, coumarin, coumarone,chromene, chroman-4-one, isochromen-1-one, isochromen-3-one, xanthene, tetrahydrofuran, 1,4-dioxan, and dibenzofuran.

[0214] Examples of mixed heterocycles appropriate for L2and L3include isoxazole, oxazole, thiazole, isothiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxatriazole, 1,2,3,5-oxatriazole, 3H-1,2,3-dioxazole, 3H-1,2-oxathiole, 1,3-oxathiole, 4H-1,2-oxazine, 2H1,3-oxazine, 1,4-oxazine, 1,2,5- oxathiazine, o-isooxazine, phenoxazine, phenothiazine, pyrano[3,4-b]pyrrole, indoxazine, benzoxazole, anthranil, and morpholine.

[0215] L2and L3ligands may be aromatic nitrogen-containing and oxygen-containing heterocycles, such as monocyclic N-heteroaryl ligands that are optionally substituted with 1 to 3 (e.g., 1 or 2) substituents. Specific examples of L2and L3ligands are pyridine and substituted pyridines, such as 3bromopyridine, 4- bromopyridine, 3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6dibromopyridine, 3-chloropyridine, 4- chloropyridine, 3,5-dichloropyridine, 2,4,6trichloropyridine, 2,6-dichloropyridine, 4-iodopyridine, 3,5- diiodopyridine, 3,5-dibromo-4-methylpyridine, 3,5-dichloro-4-methylpyridine, 3,5-dimethyl-4- bromopyridine, 3,5dimethylpyridine, 4-methylpyridine, 3,5-diisopropylpyridine, 2,4,6-trimethylpyridine, 2,4,6triisopropylpyridine, 4-(tert-butyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine, 3,5dichloro-4- phenylpyridine, and the like.

[0216] In general, any substituents present on L2and / or L3are selected from halo, C1-C20alkyl, substituted C1-C20alkyl, C1-C20heteroalkyl, substituted C1-C20heteroalkyl, C5-C24 aryl, substituted C5-C24 aryl, C5-C24 heteroaryl, substituted C5-C24 heteroaryl, C6-C24 alkaryl, substituted C6-C24 alkaryl, C6-C24 heteroalkaryl, substituted C6-C24 heteroalkaryl, C6-C24 aralkyl, substituted C6-C24 aralkyl, C6-C24 heteroaralkyl, substituted C6-C24 heteroaralkyl, and functional groups, with suitable functional groups including, without limitation, C1-C20alkoxy, C5-C24 aryloxy, C2-C20alkylcarbonyl, C6-C24 arylcarbonyl, C2-C20alkylcarbonyloxy, C6-C24 arylcarbonyloxy, C2-C20alkoxycarbonyl, C6-C24 aryloxycarbonyl, halocarbonyl, C2-C20alkylcarbonato, C6- C24 arylcarbonato, carboxy, carboxylato, carbamoyl, mono-(C1-C20alkyl)-substituted carbamoyl, di-(C1- C20alkyl)-substituted carbamoyl, di-N-(C1-C20alkyl), N-(C5-C24 aryl)-substituted carbamoyl, mono-(C5- C24 aryl)-substituted carbamoyl, di-(C6-C24 aryl)-substituted carbamoyl, thiocarbamoyl, mono-(C1-C20alkyl)-substituted thiocarbamoyl, di(C1C20alkyl)-substituted thiocarbamoyl, di-N-(C1-C20alkyl)-N-(C6-C24 aryl)-substituted thiocarbamoyl, mono-(C6-C24 aryl)-substituted thiocarbamoyl, di-(C6-C24 aryl)-substituted thiocarbamoyl, carbamido, formyl, thioformyl, amino, mono-(C1-C20alkyl)-substituted amino, di-(C1-C20alkyl)-substituted amino, mono-(C5-C24 aryl)-substituted amino, di-(C5-C24 aryl)-substituted amino, di-N- (C1-C20alkyl),N-(C5-C24aryl)-substituted amino, C2-C20alkylamido, C6C24arylamido, imino, C1-C20alkylimino, C5-C24arylimino, nitro, and nitroso. In addition, two adjacent substituents may be taken together to form a ring, generally a five- or six-membered alicyclic or aryl ring, optionally containing 1 to 3 heteroatoms and 1 to 3 substituents as above.

[0217] Substituents on L2and L3include, without limitation, halo, C1-C12alkyl, substituted C1-C12alkyl, C1-C12heteroalkyl, substituted C1-C12heteroalkyl, C5-C14aryl, substituted C5-C14aryl, C5-C14heteroaryl, substituted C5-C14heteroaryl, C6-C16alkaryl, substituted C6-C16alkaryl, C6-C16heteroalkaryl, substituted C6-C16heteroalkaryl, C6-C16aralkyl, substituted C6-C16aralkyl, C6-C16heteroaralkyl, substituted C6-C16heteroaralkyl, C1-C12alkoxy, C5-C14aryloxy, C2-C12alkylcarbonyl, C6-C14arylcarbonyl, C2-C12alkylcarbonyloxy, C6-C14arylcarbonyloxy, C2-C12alkoxycarbonyl, C6-C14aryloxycarbonyl, halocarbonyl, formyl, amino, mono-(C1-C12alkyl)-substituted amino, di-(C1-C12alkyl)-substituted amino, mono-(C5-C14aryl)-substituted amino, di-(C5-C14aryl)-substituted amino, and nitro.

[0218] In another embodiment, the substituents are halo, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, phenyl, substituted phenyl, formyl, N,N-di(C1-C6 alkyl)amino, nitro, and nitrogen heterocycles as described above (including, for example, pyrrolidine, piperidine, piperazine, pyrazine, pyrimidine, pyridine, pyridazine, etc.).

[0219] L2and L3may also be taken together to form a bidentate or multidentate ligand containing two or more, generally two, coordinating heteroatoms such as N, O, S, or P, such as diimine ligands of the Brookhart type. One representative bidentate ligand has the structure of formula (6) (6)wherein R15, R16, R17, and R18hydrocarbyl (e.g., C1-C20alkyl, C2-C20alkenyl, C2-C20alkynyl, C5-C24aryl, C6-C24 alkaryl, or C6-C24 aralkyl), substituted hydrocarbyl (e.g., substituted C1-C20alkyl, C2-C20alkenyl, C2-C20alkynyl, C5-C24 aryl, C6-C24 alkaryl, or C6-C24 aralkyl), heteroatom-containing hydrocarbyl (e.g., C1- C20heteroalkyl, C5-C24heteroaryl, heteroatom-containing C6-C24aralkyl, or heteroatom-containing C6-C24alkaryl), or substituted heteroatom-containing hydrocarbyl (e.g., substituted C1-C20heteroalkyl, C5-C24 heteroaryl, heteroatom-containing C6-C24 aralkyl, or heteroatom-containing C6-C24 alkaryl), or (1) R15and R16, (2) R17and R18, (3) R16and R17, or (4) both R15and R16, and R17and R18, may be taken together to form a ring, i.e., an N-heterocycle. Cyclic groups in such a case may be five-and six-membered rings, typically aromatic rings.

[0220] In a fourth group of catalysts that have the structure of formula (1), two of the substituents are taken together to form a bidentate ligand or a tridentate ligand. Examples of bidentate ligands include, but are not limited to, bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates. Specific examples include P(Ph)2CH2CH2P(Ph)2-, As(Ph)2CH2CH2As(Ph2)-, -P(Ph)2CH2CH2C(CF3)2O-, binaphtholate dianions,pinacolate dianions, -P(CH3)2(CH2)2P(CH3)2-, and -OC(CH3)2(CH3)2CO-. Bidentate ligands may be P(Ph)2CH2CH2P(Ph)2- and P(CH3)2(CH2)2P(CH3)2-. Tridentate ligands include, but are not limited to, (CH3)2NCH2CH2P(Ph)CH2CH2N(CH3)2. Other tridentate ligands are those in which any three of X1, X2, L1, L2, L3, R1, and R2(e.g., X1, L1, and L2) are taken together to be cyclopentadienyl, indenyl, or fluorenyl, each optionally substituted with C2-C20alkenyl, C2C20alkynyl, C1-C20alkyl, C5-C20aryl, C1-C20alkoxy, C2- C20alkenyloxy, C2-C20alkynyloxy, C5C20aryloxy, C2-C20alkoxycarbonyl, C1-C20alkylthio, C1-C20alkylsulfonyl, or C1-C20alkylsulfinyl, each of which may be further substituted with C1-C6alkyl, halide, C1-C6alkoxy or with a phenyl group optionally substituted with halide, C1-C6alkyl, or C1-C6alkoxy. In compounds of this type, X, L1, and L2may be taken together to be cyclopentadienyl or indenyl, each optionally substituted with vinyl, C1-C10 alkyl, C5-C20aryl, C1-C10 carboxylate, C2-C10 alkoxycarbonyl, C1- C10 alkoxy, or C5-C20aryloxy, each optionally substituted with C1-C6 alkyl, halide, C1-C6 alkoxy or with a phenyl group optionally substituted with halide, C1-C6 alkyl or C1C6 alkoxy. X, L1and L2may be taken together to be cyclopentadienyl, optionally substituted with vinyl, hydrogen, methyl, or phenyl. Tetradentate ligands include, but are not limited to O2C(CH2)2P(Ph)(CH2)2P(Ph)(CH2)2CO2, phthalocyanines, and porphyrins.

[0221] Complexes wherein Y is coordinated to the metal are examples of a fifth group of catalysts, and are commonly called “Grubbs-Hoveyda” catalysts. Grubbs-Hoveyda metathesis-active metal carbene complexes may be described by the formula (7) (7)wherein: M is a Group 8 transition metal, particularly Ru or Os, or, more particularly, Ru; X1, X2, and L1are as previously defined herein for the first and second groups of catalysts; Y is a heteroatom selected from N, O, S, and P; for example, Y is O or N; R5, R6, R7, and R8are each, independently, selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl,perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or –A-Fn, wherein “A” and Fn have been defined above; and any combination of Y, Z, R5, R6, R7, and R8can be linked to form one or more cyclic groups; n is 0, 1, or 2, such that n is 1 for the divalent heteroatoms O or S, and n is 2 for the trivalent heteroatoms N or P; and Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, functionalized aryl where the functional group(s) may independently be one or more or the following: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl and trimethylsilyl; and wherein any combination or combinations of X1, X2, L1,Y, Z, R5, R6, R7, and R8may be linked to a support. Additionally, R5, R6, R7, R8, and Z may independently be thioisocyanate, cyanato, or thiocyanato.

[0222] Examples of complexes comprising Grubbs-Hoveyda ligands suitable in the disclosure include:wherein L1, X1, X2, and M are as described for any of the other groups of catalysts. Suitable chelating carbenes and carbene precursors are further described by Pederson et al. (U.S. Pat. Nos. 7,026,495 and 6,620,955, the disclosure of both of which is incorporated herein by reference) and Hoveyda et al. (U.S. Pat. No.6,921,735 and WO0214376, the disclosure of both of which is incorporated herein by reference).

[0223] Other useful complexes include structures wherein L2and R2according to formulae (I), (III), or (V) are linked, such as styrenic compounds that also include a functional group for attachment to a support. Examples in which the functional group is a trialkoxysilyl functionalized moiety include, but are not limited to, the following:

[0224] Further examples of complexes having linked ligands include those having linkages between a neutral NHC ligand and an anionic ligand, a neutral NHC ligand and an alkylidine ligand, a neutral NHC ligand and an L2ligand, a neutral NHC ligand and an L3ligand, an anionic ligand and an alkylidine ligand,and any combination thereof. While the possible structures are too numerous to list herein, some suitable structures based on formula (III) include:

[0225] In addition to the catalysts that have the structure of formula (1), as described above, other transition metal carbene complexes include, but are not limited to:neutral ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, have an electron count of 16, are penta-coordinated, and are of the general formula (9); neutral ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, have an electron count of 18, are hexa-coordinated, and are of the general formula (10); cationic ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, have an electron count of 14, are tetra-coordinated, and are of the general formula (11); and cationic ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, have an electron count of 14 or 16, are tetra-coordinated or penta-coordinated, respectively, and are of the general formula (12)wherein: M, X1, X2, L1, L2, L3, R1, and R2are as defined for any of the previously defined four groups of catalysts;r and s are independently 0 or 1; t is an integer in the range of 0 to 5; k is an integer in the range of 0 to 1; Y is any non-coordinating anion (e.g., a halide ion, BF4-, etc.); Z1and Z2are independently selected from -O-, -S-, -NR2-, -PR2-, -P(=O)R2-, -P(OR2)- , -P(=O)(OR2)-, -C(=O)-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, -S(=O)-, -S(=O)2-, -, and an optionally substituted and / or optionally heteroatom –containing C1-C20hydrocarbylene linkage; Z3is any cationic moiety such as -P(R2)3+or -N(R2)3+; and any two or more of X1, X2, L1, L2, L3, Z1, Z2, Z3, R1, and R2may be taken together to form a cyclic group, e.g., a multidentate ligand, and wherein any one or more of X1, X2, L1, L2, L3, Z1, Z2, Z3, R1, and R2may be attached to a support.

[0226] Additionally, another group of metal carbene olefin metathesis catalysts that may be used in the catalyst composition of the disclosure disclosed herein, is a Group 8 transition metal complex having the structure of formula (13):wherein: M is a Group 8 transition metal, particularly ruthenium or osmium, or more particularly, ruthenium; X1, X2, L1and L2are as defined for the first and second groups of catalysts defined above; and RG1, RG2, RG3, RG4, RG5, and RG6are each independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, thioisocyanate, cyanato, thiocyanato, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or – A-Fn, wherein “A” is a divalent hydrocarbon moiety selected from alkylene and arylalkylene, wherein the alkyl portion of the alkylene and arylalkylene groups can be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the arylalkylene can besubstituted or unsubstituted, and wherein hetero atoms and / or functional groups may be present in either the aryl or the alkyl portions of the alkylene and arylalkylene groups, and Fn is a functional group, or any one or more of the RG1, RG2, RG3, RG4, RG5, and RG6may be linked together to form a cyclic group, or any one or more of the RG1, RG2, RG3, RG4, RG5, and RG6may be attached to a support.

[0227] Additionally, one Group 8 transition metal complex of formula (13) is a Group 8 transition metal complex of formula (14): (14) wherein: M, X1, X2, L1, L2, are as defined above for Group 8 transition metal complex of formula (13); and RG7, RG8, RG9, RG10, RG11, RG12, RG13, RG14, RG15, and RG16are as defined above for RG1, RG2, RG3, RG4, RG5, and RG6for Group 8 transition metal complex of formula (13) or any one or more of the RG7, RG8, RG9, RG10, RG11, RG12, RG13, RG14, RG15, and RG16may be linked together to form a cyclic group, or any one or more of the RG7, RG8, RG9, RG10, RG11, RG12, RG13, RG14, RG15, and RG16may be attached to a support.

[0228] Additionally, another Group 8 transition metal complex of formula (13) is a Group 8 transition metal complex of formula (15):wherein M, X1, X2, L1, and L2are as defined above for Group 8 transition metal complex of formula (13) .

[0229] Additionally, another group of olefin metathesis catalysts that may be used in the catalyst composition of the disclosure disclosed herein, is a Group 8 transition metal complex comprising a Schiff base ligand having the structure of formula (16):wherein: M is a Group 8 transition metal, particularly ruthenium or osmium, or more particularly, ruthenium; X1and L1are as defined for the first and second groups of catalysts defined above; Z is selected from the group consisting of oxygen, sulfur, selenium, NRJ11, PRJ11, AsRJ11, and SbRJ11; and RJ1, RJ2, RJ3, RJ4, RJ5, RJ6, RJ7, RJ8, RJ9, RJ10, and RJ11are each independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, thioisocyanate, cyanato, thiocyanato, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide, halogen- substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or –A-Fn, wherein “A” is a divalent hydrocarbon moiety selected from alkylene and arylalkylene, wherein the alkyl portion of the alkylene and arylalkylene groups can be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the arylalkylene can be substituted or unsubstituted, and wherein hetero atoms and / or functional groups may be present in either the aryl or the alkyl portions of the alkylene and arylalkylene groups, and Fn is a functional group, or any one or more of the RJ1, RJ2, RJ3, RJ4, RJ5, RJ6, RJ7, RJ8, RJ9, RJ10, and RJ11may be linked together to form a cyclic group, or any one or more of the RJ1, RJ2, RJ3, RJ4, RJ5, RJ6, RJ7, RJ8, RJ9, RJ10, and RJ11may be attached to a support.

[0230] Additionally, one Group 8 transition metal complex of formula (16) is a Group 8 transition metal complex comprising a Schiff base ligand having the structure of formula (17):(17)wherein: M, X1, L1, Z, RJ7, RJ8, RJ9, RJ10, and RJ11are as defined above for Group 8 transition metal complex of formula 16; and RJ12, RJ13, RJ14, RJ15, RJ16, RJ17, RJ18, RJ19, RJ20, and RJ21are as defined above for RJ1, RJ2, RJ3, RJ4, RJ5, and RJ6for Group 8 transition metal complex of formula 16, or any one or more of the RJ7, RJ8, RJ9, RJ10, RJ11, RJ12, RJ13, RJ14, RJ15, RJ16, RJ17, RJ18, RJ19, RJ20, and RJ21may be linked together to form a cyclic group, or any one or more of the RJ7, RJ8, RJ9, RJ10, RJ11, RJ12, RJ13, RJ14, RJ15, RJ16, RJ17, RJ18, RJ19, RJ20, and RJ21may be attached to a support.

[0231] Additionally, another Group 8 transition metal complex of formula (16) is a Group 8 transition metal complex comprising a Schiff base ligand having the structure of formula (18): (18)wherein M, X1, L1, Z, RJ7, RJ8, RJ9, RJ10, and RJ11are as defined above for Group 8 transition metal complex of formula (16).

[0232] Additionally, another group of olefin metathesis catalysts that may be used in the catalyst composition of the disclosure disclosed herein, is a Group 8 transition metal complex comprising a Schiff base ligand having the structure of formula (19):wherein: M is a Group 8 transition metal, particularly ruthenium or osmium, or more particularly, ruthenium; X1, L1, R1, and R2are as defined for the first and second groups of catalysts defined above; Z is selected from the group consisting of oxygen, sulfur, selenium, NRK5, PRK5, AsRK5, and SbRK5; m is 0, 1, or 2; and RK1, RK2, RK3, RK4, and RK5are each independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, thioisocyanate, cyanato, thiocyanato, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or – A-Fn, wherein “A” is a divalent hydrocarbon moiety selected from alkylene and arylalkylene, wherein the alkyl portion of the alkylene and arylalkylene groups can be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the arylalkylene can be substituted or unsubstituted, and wherein hetero atoms and / or functional groups may be present in either the aryl or the alkyl portions of the alkylene and arylalkylene groups, and Fn is a functional group, or any one or more of the RK1, RK2, RK3, RK4, and RK5may be linked together to form a cyclic group, or any one or more of the RK1, RK2, RK3, RK4, and RK5may be attached to a support.

[0233] In addition, catalysts of formulas (16) to (19) may be optionally contacted with an activating compound, where at least partial cleavage of a bond between the Group 8 transition metal and at least one Schiff base ligand occurs, wherein the activating compound is either a metal or silicon compound selected from the group consisting of copper (I) halides; zinc compounds of the formula Zn(RY1)2, wherein RY1is halogen, C1-C7 alkyl or aryl; tin compounds represented by the formula SnRY2RY3RY4RY5wherein each ofRY2, RY3, RY4and RY5is independently selected from the group consisting of halogen, C1-C20alkyl, C3-C10cycloalkyl, aryl, benzyl and C2-C7alkenyl; and silicon compounds represented by the formula SiRY6RY7RY8RY9wherein each of RY6, RY7, RY8, RY9is independently selected from the group consisting of hydrogen, halogen, C1-C20alkyl, halo, C1-C7alkyl, aryl, heteroaryl, and vinyl. In addition, catalysts of formulas (XVI) to (XIX) may be optionally contacted with an activating compound where at least partial cleavage of a bond between the Group 8 transition metal and at least one Schiff base ligand occurs, wherein the activating compound is an inorganic acid such as hydrogen iodide, hydrogen bromide, hydrogen chloride, hydrogen fluoride, sulfuric acid, nitric acid, iodic acid, periodic acid, perchloric acid, HOClO, HOClO2 and HOIO3. In addition, catalysts of formulas (16) to (19) may be optionally contacted with an activating compound where at least partial cleavage of a bond between the Group 8 transition metal and at least one Schiff base ligand occurs, wherein the activating compound is an organic acid such as sulfonic acids including but not limited to methanesulfonic acid, aminobenzenesulfonic acid, benzenesulfonic acid, napthalenesulfonic acid, sulfanilic acid and trifluoromethanesulfonic acid; monocarboxylic acids including but not limited to acetoacetic acid, barbituric acid, bromoacetic acid, bromobenzoic acid, chloroacetic acid, chlorobenzoic acid, chlorophenoxyacetic acid, chloropropionic acid, cis-cinnamic acid, cyanoacetic acid, cyanobutyric acid, cyanophenoxyacetic acid, cyanopropionic acid, dichloroacetic acid, dichloroacetylacetic acid, dihydroxybenzoic acid, dihydroxymalic acid, dihydroxytartaric acid, dinicotinic acid, diphenylacetic acid, fluorobenzoic acid, formic acid, furancarboxylic acid, furoic acid, glycolic acid, hippuric acid, iodoacetic acid, iodobenzoic acid, lactic acid, lutidinic acid, mandelic acid, α-naphtoic acid, nitrobenzoic acid, nitrophenylacetic acid, o-phenylbenzoic acid, thioacetic acid, thiophene-carboxylic acid, trichloroacetic acid, and trihydroxybenzoic acid; and other acidic substances such as but not limited to picric acid and uric acid.

[0234] In addition, other examples of catalysts that may be used in the catalyst composition of the disclosure are located in the following disclosures, the disclosure of each of which is incorporated herein by reference, U.S. Pat. Nos. 7,687,635; 7,671,224; 6,284,852; 6,486,279; and 5,977,393; International Publication Number WO2010 / 037550; and U.S. Pat. App. Nos. 12 / 303,615; 10 / 590,380; 11 / 465,651 (Publication No.: US 2007 / 0043188); and 11 / 465,651 (Publication No.: US 2008 / 0293905 Corrected Publication); and European Pat. Nos. EP1757613B1 and EP1577282B1.

[0235] Non-limiting examples of catalysts that may be used to prepare supported complexes and in the reactions disclosed herein include the following, some of which for convenience are identified throughout this disclosure by reference to their molecular weight:

[0236] In the foregoing molecular structures and formulae, Ph represents phenyl, Cy represents cyclohexyl, Cp represents cyclopentyl, Me represents methyl, Bu represents n-butyl, t-Bu represents tert- butyl, i-Pr represents isopropyl, py represents pyridine (coordinated through the N atom), Mes represents mesityl (i.e., 2,4,6trimethylphenyl), DiPP and DIPP represents 2,6-diisopropylphenyl, and MiPP respresents 2isopropylphenyl.

[0237] Further examples of catalysts useful to prepare supported complexes and in the reactions disclosed herein include the following: ruthenium (II) dichloro (3-methyl-2-butenylidene) bis(tricyclopentylphosphine) (C716); ruthenium (II) dichloro (3-methyl-2butenylidene) bis(tricyclohexylphosphine) (C801); ruthenium (II) dichloro(phenylmethylene)bis(tricyclohexylphosphine) (C823); ruthenium (II) (1,3-bis-(2,4,6-trimethylphenyl)-2- imidazolidinylidene) dichloro (phenylmethylene) (triphenylphosphine) (C830); ruthenium (II) dichloro (phenylvinylidene) bis(tricyclohexylphosphine) (C835); ruthenium (II) dichloro (tricyclohexylphosphine) (o-isopropoxyphenylmethylene) (C601); ruthenium (II) (1,3-bis-(2, 4,6-trimethylphenyl)-2- imidazolidinylidene) dichloro (phenylmethylene) bis(3bromopyridine) (C884); [1,3-bis-(2,4,6- trimethylphenyl)-2-imidazolidinylidene]dichloro(o-isopropoxyphenylmethylene)ruthenium(II) (C627); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro (benzylidene) (triphenylphosphine) ruthenium(II) (C831); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro (benzylidene)(methyldiphenylphosphine)ruthenium(II) (C769);[1,3-bis-(2,4,6-trimethylphenyl)-2- imidazolidinylidene]dichloro(benzylidene)(tricyclohexylphosphine)ruthenium(II) (C848);[1,3-bis-(2,4,6- trimethylphenyl)-2-imidazolidinylidene] dichloro(benzylidene) (diethylphenylphosphine) ruthenium(II) (C735);[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylidene)(tri-n- butylphosphine)ruthenium(II) (C771);[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3- methyl-2-butenylidene)(triphenylphosphine)ruthenium(II) (C809); [1,3-bis-(2,4,6-trimethylphenyl)-2- imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(methyldiphenylphosphine)ruthenium(II) (C747);[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene) (tricyclohexylphosphine) ruthenium(II) (C827);[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro(3-methyl-2-butenylidene)(diethylphenylphosphine)ruthenium(II) (C713); [1,3-bis-(2,4,6- trimethylphenyl)-2-imidazolidinylidene] dichloro (3-methyl-2-butenylidene) (tri-n- butylphosphine)ruthenium(II) (C749); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro(phenylindenylidene)(triphenylphosphine)ruthenium(II) (C931); [1,3-bis-(2,4,6-trimethylphenyl)- 2-imidazolidinylidene] dichloro (phenylindenylidene) (methylphenylphosphine) ruthenium(II) (C869); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro (phenylindenylidene) (tricyclohexylphosphine) ruthenium(II) (C949); [1,3-bis-(2,4,6-trimethylphenyl)-2- imidazolidinylidene]dichloro(phenylindenylidene)(diethylphenylphosphine)ruthenium(II) (C835); and [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylindenylidene)(tri-n- butylphosphine)ruthenium(II) (C871).

[0238] Still further catalysts useful in ROMP reactions, and / or in other metathesis reactions, such as ring- closing metathesis, cross metathesis, ring-opening cross metathesis, self-metathesis, ethenolysis, alkenolysis, acyclic diene metathesis polymerization, and combinations thereof, include the following structures:

[0239] In general, the transition metal complexes used as catalysts herein can be prepared by several different methods, such as those described by Schwab et al. (1996) J. Am. Chem. Soc.118:100-110, Scholl et al. (1999) Org. Lett. 6:953-956, Sanford et al. (2001) J. Am. Chem. Soc. 123:749-750, U.S. Pat. No. 5,312,940, and U.S. Pat. No. 5,342,909, the disclosure of each of which are incorporated herein by reference. Also see U.S. Pat. Pub. No.2003 / 0055262 to Grubbs et al., WO 02 / 079208, and U.S. Pat. No. 6,613,910 to Grubbs et al., the disclosure of each of which are incorporated herein by reference. Synthetic methods are described in WO 03 / 11455A1 to Grubbs et al., the disclosure of which is incorporated herein by reference.

[0240] Metal carbene olefin metathesis catalysts may be Group 8 transition metal complexes having the structure of formula (1) commonly called “First Generation Grubbs” catalysts, formula (III) commonly called “Second Generation Grubbs” catalysts, or formula (7) commonly called “Grubbs-Hoveyda” catalysts.

[0241] Metal carbene olefin metathesis catalysts may have the structure of formula (1)(1)wherein: M is a Group 8 transition metal; L1, L2, and L3are neutral electron donor ligands; n is 0 or 1; m is 0, 1, or 2; k is 0 or 1; X1and X2are anionic ligands; R1and R2are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, wherein any two or more of X1, X2, L1, L2, L3, R1, and R2can be taken together to form one or more cyclic groups, and further wherein any one or more of X1, X2, L1, L2, L3, R1, and R2may be attached to a support; and formula (7) (7)wherein: M is a Group 8 transition metal; L1is a neutral electron donor ligand; X1and X2are anionic ligands; Y is a heteroatom selected from O or N; R5, R6, R7, and R8are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups;n is 0,1, or 2; and Z is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, wherein any combination of Y, Z, R5, R6, R7, and R8can be linked to form one or more cyclic groups, and further wherein any combination of X1, X2, L1, Y, Z, R5,R6, R7, and R8may be attached to a support.

[0242] Metal carbene olefin metathesis catalysts may have the structure of formula (1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3- bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes independently selected from the group consisting of 1,3- bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3- bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2- ylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2or thienyl; or R1and R2are taken together to form 3-phenyl-1H-indene;and formula (7) (7)wherein: M is ruthenium; L1is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn- Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2- ylidene; X1and X2are chloride; Y is oxygen; R5, R6, R7, and R8are each hydrogen; n is 1; and Z is isopropyl.

[0243] An example of metal carbene olefin metathesis catalysts having the structure of formula (1) (1)wherein: M is ruthenium; n is 0; m is 0;k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3- bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes independently selected from the group consisting of 1,3- bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3- bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2- ylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2 or thienyl; or R1and R2are taken together to form an indenylidene moiety.

[0244] An example of metal carbene olefin metathesis catalysts having the structure of formula (1) (1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes independently selected from the group consisting of 1,3- bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3- bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2- ylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2 or thienyl; or R1and R2are taken together to form an indenylidene moiety, where the indenylidene moiety is phenylindenylidene.

[0245] An example of metal carbene olefin metathesis catalysts having the structure of formula (1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3- bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3- bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2- ylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2; or R1and R2are taken together to form an indenylidene moiety.

[0246] An example of metal carbene olefin metathesis catalysts having the structure of formula (1) (1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3- bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes independently selected from the group consisting of 1,3- bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3- bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2- ylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2; or R1and R2are taken together to form an indenylidene moiety, where the indenylidene moiety is phenylindenylidene.

[0247] An example of metal carbene olefin metathesis catalysts having the structure of formula (1) (1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes independently selected from the group consisting of 1,3- bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2; or R1and R2are taken together to form an indenylidene moiety.

[0248] An example of metal carbene olefin metathesis catalysts having the structure of formula (1) (1)wherein: M is ruthenium; n is 0; m is 0;k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes independently selected from the group consisting of 1,3- bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2; or R1and R2are taken together to form an indenylidene moiety, where the indenylidene moiety is phenylindenylidene.

[0249] An example of metal carbene olefin metathesis catalysts having the structure of formula (1) (1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine(PEt2Ph); or L1and L2are N-heterocyclic carbenes selected from 1,3-bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2; or R1and R2are taken together to form an indenylidene moiety.

[0250] An example of metal carbene olefin metathesis catalysts having the structure of formula (1) (1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes selected from 1,3-bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2; or R1and R2are taken together to form an indenylidene moiety, where the indenylidene moiety is phenylindenylidene.

[0251] An example of metal carbene olefin metathesis catalysts having the structure of formula (1) (1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes selected from 1,3-bis(2,4,6-trimethylphenyl)imidazol- 2-ylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2 or thienyl; or R1and R2are taken together to form an indenylidene moiety.

[0252] An example of metal carbene olefin metathesis catalysts having the structure of formula (1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, and L2is a trisubstitutedphosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes selected from 1,3-bis(2,4,6-trimethylphenyl)imidazol- 2-ylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2or thienyl; or R1and R2are taken together to form an indenylidene moiety, where the indenylidene moiety is phenylindenylidene.

[0253] An example of metal carbene olefin metathesis catalysts having the structure of formula (1) (1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes selected from 1,3-bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2or thienyl; or R1and R2are taken together to form an indenylidene moiety.

[0254] An example of metal carbene olefin metathesis catalysts having the structure of formula (1)(1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes selected from 1,3-bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2 or thienyl; or R1and R2are taken together to form an indenylidene moiety, where the indenylidene moiety is phenylindenylidene.

[0255] An example of metal carbene olefin metathesis catalysts having the structure of formula (7)L1is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn- Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2- ylidene; X1and X2are chloride; Y is oxygen; R5, R6, R7, and R8are each hydrogen; n is 1; and Z is isopropyl.

[0256] An example of metal carbene olefin metathesis catalysts having the structure of formula (1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3- bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3- bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2- ylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2or thienyl.

[0257] An example of metal carbene olefin metathesis catalysts having the structure of formula (1) (1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes independently selected from the group consisting of 1,3- bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2or thienyl.

[0258] An example of metal carbene olefin metathesis catalysts having the structure of formula (1) (1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes selected from 1,3-bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2 or thienyl.

[0259] An example of metal carbene olefin metathesis catalysts having the structure of formula (1) (1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine(PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes selected from 1,3-bis(2,4,6-trimethylphenyl)imidazol- 2-ylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2or thienyl.

[0260] An example of metal carbene olefin metathesis catalysts having the structure of formula (1) (1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3- bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes independently selected from the group consisting of 1,3- bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3- bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2- ylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2.

[0261] An example of metal carbene olefin metathesis catalysts having the structure of formula (1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes independently selected from the group consisting of 1,3- bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2.

[0262] An example of metal carbene olefin metathesis catalysts having the structure of formula (1) (1)wherein: M is ruthenium; n is 0; m is 0; k is 1;L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes selected from 1,3-bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene; X1and X2are chloride; and R1is hydrogen and R2is phenyl or –CH=C(CH3)2.

[0263] An example of metal carbene olefin metathesis catalysts having the structure of formula (1)wherein: M is ruthenium; n is 0; m is 0; k is 1; L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes selected from 1,3-bis(2,4,6-trimethylphenyl)imidazol- 2-ylidene; X1and X2are chloride; andR1is hydrogen and R2is phenyl or –CH=C(CH3)2.

[0264] An example of a metal carbene olefin metathesis catalyst having the structure of formula (15): (15)wherein: M is ruthenium; X1and X2are chloride; and L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3- bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes independently selected from the group consisting of 1,3- bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3- bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazol-2- ylidene.

[0265] An example of a metal carbene olefin metathesis catalyst having the structure of formula (15):(15)wherein: M is ruthenium; X1and X2are chloride; and L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes independently selected from the group consisting of 1,3- bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene.

[0266] An example of a metal carbene olefin metathesis catalyst having the structure of formula (15): (15)wherein: M is ruthenium; X1and X2are chloride; andL1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes selected from 1,3-bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene.

[0267] An example of a metal carbene olefin metathesis catalyst having the structure of formula (15): (15)wherein: M is ruthenium; X1and X2are chloride; and L1and L2are trisubstituted phosphines independently selected from the group consisting of tri-n- butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, and L2is a trisubstituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes selected from 1,3-bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene.

[0268] In one embodiment, the disclosure provides coating compositions comprising ring opening metathesis polymerization compositions, which comprise at least one cyclic olefin, and at least one metalcarbene olefin metathesis catalyst. In a fast-cure coating composition of the disclosure the at least one metal carbene olefin metathesis catalysts is preferably a catalyst of Formula (1) where L1is, as defined above, and L2is a triarylphosphine and / or a catalyst of Formula (7) where L1is. Preferred embodiments of L1and L2and catalyst containing them are described above and shown in the Examples.

[0269] The coating composition comprises at least one cyclic olefin represented by Formula (I), by Formula (II), and by Formula (III); may optionally contain a linear olefin represented by Formula (IV); and at least one metal carbene olefin metathesis catalyst represented by Formula (1), wherein Formulae (I), (II), (III), (IV) and (1) are as defined herein.

[0270] The coating composition comprises at least one cyclic olefin represented by Formula (I), by Formula (II), by Formula (III), and at least one metal carbene olefin metathesis catalyst represented by Formula (1), wherein Formulae (I), (II), (III), and (1) are as defined herein.

[0271] The coating composition comprises at least one cyclic olefin represented by Formula (I), and by Formula (II) and at least one metal carbene olefin metathesis catalyst represented by Formula (1), wherein Formulae (I), (II) and (1) are as defined herein.

[0272] The coating composition comprises at least one cyclic olefin represented by Formula (I), and by Formula (III), and at least one metal carbene olefin metathesis catalyst represented by Formula (1), wherein Formulae (I), (III) and (1) are as defined herein.

[0273] The coating composition comprises at least one cyclic olefin represented by Formula (II), and by Formula (III) and at least one metal carbene olefin metathesis catalyst represented by Formula (1), wherein Formulae (II), (III) and (1) are as defined herein.

[0274] The coating composition comprises at least one cyclic olefin represented by Formula (I), by Formula (II), and by Formula (III); may optionally contain a linear olefin represented by Formula (IV); and at least one metal carbene olefin metathesis catalyst represented by Formula (7), wherein Formulae (I), (II), (III), (IV) and (7) are as defined herein.

[0275] The coating composition comprises at least one cyclic olefin represented by Formula (I), by Formula (II), by Formula (III), and at least one metal carbene olefin metathesis catalyst represented by Formula (7), wherein Formulae (I), (II), (III), and (7) are as defined herein.

[0276] The coating composition comprises at least one cyclic olefin represented by Formula (I), and by Formula (II) and at least one metal carbene olefin metathesis catalyst represented by Formula (7), wherein Formulae (I), (II) and (7) are as defined herein.

[0277] The coating composition comprises at least one cyclic olefin represented by Formula (I), and by Formula (III), and at least one metal carbene olefin metathesis catalyst represented by Formula (7), wherein Formulae (I), (III) and (7) are as defined herein.

[0278] The coating composition comprises at least one cyclic olefin represented by Formula (II), and by Formula (III) and at least one metal carbene olefin metathesis catalyst represented by Formula (7), wherein Formulae (II), (III) and (7) are as defined herein.

[0279] The coating composition comprises at least one cyclic olefin represented by Formula (I), by Formula (II), and by Formula (III); may optionally contain a linear olefin represented by Formula (IV); and at least one metal carbene olefin metathesis catalyst represented by Formula (1) and Formula (7), wherein Formulae (I), (II), (III), (IV), (1) and (7) are as defined herein.

[0280] The coating composition comprises at least one cyclic olefin represented by Formula (I), by Formula (II), by Formula (III), and at least one metal carbene olefin metathesis catalyst represented by Formula (1) and Formula (7), wherein Formulae (I), (II), (III), (1), and (7) are as defined herein.

[0281] The coating composition comprises at least one cyclic olefin represented by Formula (I), and by Formula (II) and at least one metal carbene olefin metathesis catalyst represented by Formula (1) and Formula (7), wherein Formulae (I), (II), (1), and (7) are as defined herein.

[0282] The coating composition comprises at least one cyclic olefin represented by Formula (I), and by Formula (III), and at least one metal carbene olefin metathesis catalyst represented by Formula (1) and Formula (7), wherein Formulae (I), (III), (1), and (7) are as defined herein.

[0283] The coating composition comprises at least one cyclic olefin represented by Formula (II), and by Formula (III) and at least one metal carbene olefin metathesis catalyst represented by Formula (1) and Formula (7), wherein Formulae (II), (III), (1), and (7) are as defined herein.

[0284] Suitable supports for any of the catalysts described herein may be of synthetic, semi-synthetic, or naturally occurring materials, which may be organic or inorganic, e.g., polymeric, ceramic, or metallic. Attachment to the support will generally, although not necessarily, be covalent, and the covalent linkage may be direct or indirect. Indirect covalent linkages are typically, though not necessarily, through a functional group on a support surface. Ionic attachments are also suitable, including combinations of one or more anionic groups on the metal complexes coupled with supports containing cationic groups, orcombinations of one or more cationic groups on the metal complexes coupled with supports containing anionic groups.

[0285] When utilized, suitable supports may be selected from silicas, silicates, aluminas, aluminum oxides, silica-aluminas, aluminosilicates, zeolites, titanias, titanium dioxide, magnetite, magnesium oxides, boron oxides, clays, zirconias, zirconium dioxide, carbon, polymers, cellulose, cellulosic polymers amylose, amylosic polymers, or a combination thereof. The support may comprise silica, a silicate, or a combination thereof.

[0286] It is also possible to use a support that has been treated to include functional groups, inert moieties, and / or excess ligands. Any of the functional groups described herein are suitable for incorporation on the support, and may be generally accomplished through techniques known in the art. Inert moieties may also be incorporated on the support to generally reduce the available attachment sites on the support, e.g., to control the placement, or amount, of a complex linked to the support.

[0287] The catalyst compositions comprising at least one metal carbene olefin metathesis catalyst may be utilized in olefin metathesis reactions according to techniques known in the art. The catalyst compositions of the disclosure are typically added to the ROMP composition as a solid, a solution, or as a suspension. When the catalyst composition of the disclosure is added to the ROMP composition as a suspension, the at least one metal carbene olefin metathesis catalyst is suspended in a dispersing carrier such as mineral oil, paraffin oil, soybean oil, tri-isopropylbenzene, or any hydrophobic liquid which has a sufficiently high viscosity so as to permit effective dispersion of the catalyst(s), and which is sufficiently inert and which has a sufficiently high boiling point so that is does not act as a low-boiling impurity in the olefin metathesis reaction. It will be appreciated that the amount of catalyst that is used (i.e., the “catalyst loading”) in the reaction is dependent upon a variety of factors such as the identity of the reactants and the reaction conditions that are employed. It is therefore understood that catalyst loading may be optimally and independently chosen for each reaction. In general, however, the catalyst will be present in an amount that ranges from a low of about 0.1 ppm, 1 ppm, or 5 ppm, to a high of about 10 ppm, 15 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, or 1000 ppm relative to the amount of an olefinic substrate.

[0288] The catalyst will generally be present in an amount that ranges from a low of about 0.00001 mol%, 0.0001 mol%, or 0.0005 mol%, to a high of about 0.001 mol%, 0.0015 mol%, 0.0025 mol%, 0.005 mol%, 0.01 mol%, 0.02 mol%, 0.05 mol%, or 0.1 mol% relative to the cyclic olefin(s) present in the cyclic olefin composition.

[0289] When expressed as the molar ratio of monomer to catalyst, the catalyst (the “monomer to catalyst ratio”), loading will generally be present in an amount that ranges from a low of about 10,000,000:1, 1,000,000:1, or 200,00:1, to a high of about 100,000:166,667:1, 40,000:1, 20,000:1, 10,000:1, 5,000:1, or 1,000:1.

[0290] The metathesis reactions disclosed herein may be carried out under a dry, inert atmosphere. Such an atmosphere may be created using any inert gas, including such gases as nitrogen and argon. The use of an inert atmosphere is optimal in terms of promoting catalyst activity, and reactions performed under an inert atmosphere typically are performed with relatively low catalyst loading. The reactions disclosed herein may also be carried out in an oxygen-containing and / or a water-containing atmosphere, and the reactions may be carried out under ambient conditions. The presence of oxygen or water in the reaction may, however, necessitate the use of higher catalyst loadings as compared with reactions performed under an inert atmosphere. Where the vapor pressure of the reactants allows, the reactions disclosed herein may also be carried out under reduced pressure.

[0291] The reactions disclosed herein may be carried out in a solvent, and any solvent that is inert towards cross-metathesis may be employed. Generally, solvents that may be used in the metathesis reactions include organic, protic, or aqueous solvents, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof. Example solvents include benzene, toluene, p-xylene, methylene chloride, 1,2-dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, methanol, ethanol, water, or mixtures thereof. The reactions disclosed herein may be carried out neat, i.e., without the use of a solvent.

[0292] It will be appreciated that the temperature at which a metathesis reaction according to methods disclosed herein is conducted can be adjusted as needed, and may be at least about 78 ºC, 40 ºC, -10 ºC, 0 ºC, 10 ºC, 20 ºC, 25 ºC, 35 ºC, 50 ºC, 70 ºC, 100 ºC, or 150 ºC, or the temperature may be in a range that has any of these values as the upper or lower bounds. The reactions may be carried out at a temperature of at least about 35 ºC, or the reactions are carried out at a temperature of at least about 50 ºC. Coating Additives

[0293] In one or more embodiments, the coating compositions disclosed herein and in the accompanying appendices incorporated herein by reference contain at least one coating additives, including but not limited to those known in the art. Suitable coating additives may include, but are not limited to, gel modifiers, hardness modulators, impact modifiers, fillers, binders, thixotropes, rheology modifiers, dispersants, wetting agents, plasticizers, pigments, flame retardants, dyes, fibers, reinforcement materials, coupling agents, adhesion promoters, film formers, lubricants, and stabilizers such as, for example, antioxidants, antiozonants, UV absorbers, and UV light stabilizers and other stabilizers, including those known in the art. Furthermore, the amount of an additive added to the resin compositions may vary, depending on the particular type of additive. The coating additive and the coating additive loading should not interfere with curing the coating composition. Care should be taken when using chemistries that are known to inhibit ring- opening polymerization. In one or more embodiments, the concentration of the coating additives in thecoating compositions ranges from, for example, 0.001-95 percent by weight, particularly, from 0.1-75 percent by weight, or even more particularly, from 1-60 percent by weight, 5-70 percent by weight, 10-60 percent by weight, or from 20-60 percent by weight.

[0294] The plasticizer compound used in the ROMP composition of the disclosure disclosed herein may comprise, consist essentially of, or consist of any compound or substance that improves the flexibility, workability, or distensibility of a plastic or elastomer.

[0295] For example, the plasticizer compound may be selected from the group consisting of a polyisobutylene or polybutene (PB) oil , a polyalphaolefin oil, a hydrocarbon resin, and mixtures thereof. The plasticizer compound may be a PB oil.

[0296] PB oil is an oligomer or polymer made from butene monomers, such as 1-butene and isobutene, or a mixture of butene monomers. PB oils possess the general repeat unit structure of (C4H8)n. PB oil made from isobutene monomer may be referred to as polyisobutene or polyisobutylene. PB oil made from 1- butene may be referred to as poly(1-butene). Commercial sources of polybutene oil that may be used in the disclosure include, for example, Indopol® H-15, H-25, H-50, H-100, H-300, H-1200, H-1500, H-1900, H- 2100). Higher molecular weight polybutene oils may be semi solid at room temperature.

[0297] The polyalphaolefin oil may comprise oligomers of C5to C18 olefins (e.g., C6 to C14, C8 to C12, C10); having a kinematic viscosity of 3 to 30 cSt or more at 100 °C. (e.g., 20 cSt or less, 4 cSt or more at 100 °C.); and a pour point of -10 °C. or less (e.g., -20 °C. or less, -30 °C. or less). For example, the polyalphaolefin oil may be Group IV hydrocarbon oil basestocks, polyisobutenes, wax isomerate lubricant oil basestocks, ethylene / butene copolymers, or mixtures thereof. For example, the polyalphaolefin oil may be Group IV hydrocarbon basestocks, such as those derived from linear alpha olefins. For example, polyalphaolefin oils derived from oligomerization of linear alpha olefins such as, but not limited to, C8, C10, C12, C14, C16, and C18. Typical molecular weights, as defined by number average molecular weight, Mn, defining polyalphaolefin oil are 250 g / mol to 10000 g / mol (e.g., 300 g / mol, 500 g / mol, 1000 g / mol, 2000 g / mol, 4000 g / mol, 6000 g / mol, 7000 g / mol, 9000 g / mol, 9500 g / mol). Commercial polyalphaolefin oils include SpectraSyn 100, SpectraSyn 40, SpectraSyn 10, SpectraSyn 8, SpectraSyn 6, SpectraSyn 5, SpectraSyn 4, SpectraSyn 2, and SpectraSyn Elite 300.

[0298] The at least one plasticizer compound may be present in the ROMP composition in an amount ranging from 1 to 40 wt.% (e.g., 5 to 45 wt.%, 10 to 40 wt.%, 25 to 35 wt.%), based on the total weight of the ROMP composition.

[0299] Suitable impact modifiers or elastomers include without limitation rubber toughener compounds. Suitable impact modifiers or elastomers include without limitation natural rubber, butyl rubber, polyisoprene, polybutadiene, polyisobutylene, ethylene-propylene copolymer, styrene-butadienestyrene triblock rubber, random styrene-butadiene rubber, styrene-isoprene-styrene triblock rubber, styrene- ethylene / butylene-styrene copolymer, styrene-ethylene / propylene-styrene copolymer, ethylenepropylene- diene terpolymers, ethylene-vinyl acetate and nitrile rubbers. Preferred impact modifiers or elastomers are polybutadiene Diene 55AC10 (Firestone), polybutadiene Diene 55AM5 (Firestone), EPDM Royalene 301T, EPDM Buna T9650 (Bayer), styrene-ethylene / butylene-styrene copolymer Kraton G1651H, Polysar Butyl 301 (Bayer), polybutadiene Taktene 710 (Bayer), styrene-ethylene / butylene-styrene Kraton G1726M, Ethylene-Octene Engage 8150 (DuPont-Dow), styrene-butadiene Kraton D1184, EPDM Nordel 1070 (DuPont-Dow), and polyisobutylene Vistanex MML-140 (Exxon). Such materials are normally employed in the resin composition at levels of about 0.10 phr to 10 phr, but more preferably at levels of about 0.1 phr to 5 phr. Various polar impact modifiers or elastomers can also be used.

[0300] The rubber tougher compound (also referred to herein as impact modifiers or elastomers) used in the ROMP composition of the disclosure disclosed herein, include, without limitation, butyl rubber, polyisobutylene, ethylene-propylene copolymer, styrene-ethylene / butylene-styrene copolymer, styrene- ethylene / propylene-styrene copolymer, ethylene-propylene-diene terpolymers, ethylene-vinyl acetate, and nitrile rubbers. Impact modifiers or elastomers may be polybutadiene Diene 55AC10 (Firestone), polybutadiene Diene 55AM5 (Firestone), EPDM Royalene 301T, EPDM Buna T9650 (Bayer), styrene- ethylene / butylene-styrene copolymer Kraton G1651H, Polysar Butyl 301 (Bayer), polybutadiene Taktene 710 (Bayer), styrene-ethylene / butylene-styrene Kraton G1726M, styrene-ethylene / butylene-styrene Kraton G1650, Ethylene-Octene Engage 8150 (DuPont-Dow), styrene-butadiene Kraton D1184, EPDM Nordel 1070 (DuPont-Dow), and polyisobutylene Vistanex MML-140 (Exxon). Various polar impact modifiers or elastomers can also be used.

[0301] The at least one rubber toughener compound may be selected from the group consisting of a poly(styrene-ethylene-butylene-styrene), an ethylene-propylene copolymer, an ethylene-propylene diene terpolymer, and mixtures thereof. The rubber toughener compound may be an ethylene-propylene copolymer (e.g., Vistalon 501, Vistalon 3702). The rubber toughener compound may be a poly(styrene- ethylene-butylene-styrene (e.g., Kraton 1650, Kraton 1651, Taipol 6151).

[0302] The at least one rubber toughener compound may be present in an amount ranging from 0.01 to 30 wt.% (e.g., 0.1 to 25 wt.%, 1 to 20 wt.%, 5 to 15 wt.%, 7 to 12 wt.%), based on the total weight of the ROMP composition.

[0303] Antioxidants and antiozonants include any antioxidant or antiozonant used in the rubber or plastics industry. An “Index of Commercial Antioxidants and Antiozonants, Fourth Edition” is available from Goodyear Chemicals, The Goodyear Tire and Rubber Company, Akron, Ohio 44316. Suitable stabilizers (i.e., antioxidants or antiozonants) include without limitation: 2,6-di-tert-butyl-4-methylphenol (BHT); styrenated phenol, such as Wingstay®S (Goodyear); 2- and 3-tert-butyl-4-methoxyphenol; alkylated hindered phenols, such as Wingstay C (Goodyear); 4-hydroxymethyl-2,6-di-tert-butylphenol; 2,6-di-tert- butyl-4-sec-butylphenol; 2,2′-methylenebis(4-methyl-6-tert-butylphenol); 2,2′-methylenebis(4-ethyl-6- tert-butylphenol); 4,4′-methylenebis(2,6-di-tert-butylphenol); miscellaneous bisphenols, such as Cyanox®53 (Cytec Industries Inc.) and Permanax WSO; 2,2′-ethylidenebis(4,6-di-tert-butylphenol); 2,2′- methylenebis(4-methyl-6-(1-methylcyclohexyl)phenol); 4,4′-butylidenebis(6-tert-butyl-3-methylphenol); polybutylated Bisphenol A; 4,4′-thiobis(6-tert-butyl-3-methylphenol); 4,4′-methylenebis(2,6- dimethylphenol); 1,1′-thiobis(2-naphthol); methylene bridged polyalkylphenol, such as Ethyl antioxidant 738; 2,2′-thiobis(4-methyl-6-tert-butylphenol); 2,2′-isobutylidenebis(4,6-dimethylphenol); 2,2′- methylenebis(4-methyl-6-cyclohexylphenol); butylated reaction product of p-cresol and dicyclopentadiene, such as Wingstay L; tetrakis(methylene-3,5-di-tert-butyl-4-hydroxyhydrocinnamate )methane, i.e., Irganox®1010 (BASF); 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl )benzene, e.g., Ethanox®330 (Albemarle Corporation);tylphenol), e.g., Ethanox 4702 or Ethanox 4710; 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, i.e., Good-rite®3114 (Emerald Performance Materials), 2,5-di-tert-amylhydroquinone, tert-butylhydroquinone, tris(nonylphenylphosphite), bis(2,4-di-tert-butyl)pentaerythritol)diphosphite, distearyl pentaerythritol diphosphite, phosphited phenols and bisphenols, such as Naugard®492 (Chemtura Corporation), phosphite / phenolic antioxidant blends, such as Irganox B215; di-n-octadecyl(3,5-di-tert-butyl-4- hydroxybenzyl)phosphonate, such as Irganox 1093; 1,6-hexamethylene bis(3-(3,5-di-tert-butyl-4- hydroxyphenylpropionate), such as Irganox 259, and octadecyl-3,5-di-tert-butyl-4- hydroxyhydrocinnamate, i.e., Irganox 1076, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylylenediphosp honite, diphenylamine, and 4,4′-diemthoxydiphenylamine. Such materials are normally employed in the resin composition at levels of about 0.10 phr to 10 phr, but more preferably at levels of about 0.1 phr to 5 phr.

[0304] Suitable antioxidants or antiozonants include without limitation: primary antioxidants such as 2,6- di-tert-butyl-4-methylphenol (BHT); styrenated phenols, such as Wingstay®S (Goodyear); 2- and 3-tert- butyl-4-methoxyphenol; alkylated hindered phenols, such as Wingstay C (Goodyear); 4-hydroxymethyl- 2,6-di-tert-butylphenol; 2,6-di-tert-butyl-4-sec-butylphenol; 2,2′-methylenebis(4-methyl-6-tert- butylphenol); 2,2′-methylenebis(4-ethyl-6-tert-butylphenol); 4,4′-methylenebis(2,6-di-tert-butylphenol);miscellaneous bisphenols, such as Cyanox®53 and Permanax WSO; 2,2′-ethylidenebis(4,6-di-tert- butylphenol); 2,2′-methylenebis(4-methyl-6-(1-methylcyclohexyl)phenol); 4,4′-butylidenebis(6-tert-butyl- 3-methylphenol); polybutylated Bisphenol A; 4,4′-thiobis(6-tert-butyl-3-methylphenol); 4,4′- methylenebis(2,6-dimethylphenol); 1,1′-thiobis(2-naphthol); methylene bridged polyaklylphenols, such as Ethyl antioxidant 738; 2,2′-thiobis(4-methyl-6-tert-butylphenol); 2,2′-isobutylidenebis(4,6- dimethylphenol); 2,2′-methylenebis(4-methyl-6-cyclohexylphenol); butylated reaction products of p-cresol and dicyclopentadiene, such as Wingstay L; tetrakis(methylene-3,5-di-tert-butyl-4- hydroxyhydrocinnamate)methane, i.e., Irganox 1010; 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4- hydroxybenzyl)benzene, e.g., Ethanox 330; 4,4ʹ-methylenebis(2,6-di-tertiary-butylphenol), e.g., Ethanox 4702 or Ethanox 4710; 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, i.e., Good-rite 3114; 2,5- di-tert-amylhydroquinone; tert-butylhydroquinone; 1,6-hexamethylene bis(3-(3,5-di-tert-butyl-4- hydroxyphenylpropionate), such as Irganox 259; octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, i.e., Irganox 1076; diphenylamine; 4,4′-diemthoxydiphenylamine; secondary antioxidants such as tris(nonylphenylphosphite); bis(2,4-di-tert-butyl)pentaerythritol)diphosphate; distearyl pentaerythritol diphosphite; phosphited phenols and bisphenols, such as Naugard 492; phosphite / phenolic antioxidant blends, such as Irganox B215; di-n-octadecyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, such as Irganox 1093; tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylylenediphosphonite; esters of thiodipropionic acid such as Irganox PS 802, Irganox PS 800, and Cyanox MTDP. Such materials are normally employed in the compositions of the disclosure at levels of about 0.10%-10% percent by weight, or more preferably at levels of about 0.1%-5% percent by weight.

[0305] As mentioned above, UV absorbers and UV light stabilizers are two examples of the type of stabilizers which may be used in a coating composition of the disclosure. Suitable UV absorbers include nickel quenchers, benzophenones, benzotriazoles, benzyldene malonates, triazines, etc. Suitable UV light stabilizers include hindered amines, etc. The blend of various UV absorbers and UV light stabilizers are also suitable to provide protection against UV. Some suitable UV absorbers include 2-(2H-benzotriazol-2- yl)-p-cresol, 2-tert-Butyl-6-(5-chloro-2H-benzotriazol-2-yl)-4-methylphenol, and 2,2′-Methylenebis[6- (2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-hydroxy-4-methoxybenzophenone and 2- hydroxy-4-octyloxybenzophenone, as 2-(4,6-Diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol; oxanilide UV absorbers such as N-(2-ethoxyphenyl)-N'-(2-ethylphenyl)oxamide, Dimethyl 2-(4- Methoxybenzylidene)malonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6- pentamethyl-4-piperidyl sebacate, bis(1,2,2,6,6-pentamethyl-4-pperidyl)sebacate, bis(1-octyloxy-2,2,6,6- tetramethyl-4-piperidyl) sebacate, LOWILITE® Q84 and POLYBATCH® LLUVS 110, Tinuvin 1130, Tinuvin 171, Tinuvin 328, Tinuvin 384-2, Tinuvin 900, Tinuvin 928, Tinuvin 99, Tinuvin 5050, Tinuvin5060, Tinuvin 5151, Tinuvin 5248, Tinuvin 5251, Tinuvin 5350, Tinuvin 123, Tinuvin 144, Tinuvin 152, Tinuvin 249, Tinuvin 292, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479 (BASF), Chimassorb 81, Chimassorb 944, Chimassorb 2020 (BASF), KEMISORB 10, KEMISORB 11, KEMISORB 111 (Chemipro Kasei Ksisha), BP-2, BP-3, BP-6, BP-9 (Dalian Richfortune Chemicals), Ultra V 301 (Dover, ICI Industries), Grandsorb BP-1, Grandsorb BP-2, Grandsorb BP-4, Grandsorb BP-6 (Hongkun Group), SpeedBlock UV-6 (Lamsson), Maxgard 1000, Maxgard 300, Maxgard 400, Maxgard 500, Maxgard 600, Maxgard 700 (Lycus), Cyasorb UV-3346, Hostavin N 30 and the like. Such stabilizers can be used as individual components or in combination with other stabilizers known in the art for coating compositions. Such materials are normally employed in the compositions of the disclosure at levels of about 0.10wt% to 10wt%, but more preferably at levels of about 0.1wt% to 5wt%.

[0306] Suitable fillers include, for example, microparticulate density modulators, such as, microspheres, or macroparticulate density modulators, for example: glass or ceramic beads. Other suitable fillers are inorganic fillers such as, for example, aluminum powder, aluminum flakes (e.g., aluminum flake paste), glass flakes, micaceous iron oxide, calcium carbonate, dolomite, silicas, silicates, talc, kaolin, mica, feldspar, barium sulfate and wollastonites, carbon nanotubes, graphene. Preferred inorganic fillers include aluminum powder, aluminum flakes, micaceous iron oxide, mica, glass fibers, wollastonite, calcium carbonate, silica and mixtures thereof, with flake-like fillers also being preferred. Preferably, the filler is aluminum powder or aluminum flakes (e.g., aluminum flake paste), or alloys thereof. The aluminum powder or aluminum flake may be used alone or in combination with other fillers, such as those mentioned previously. For example, aluminum flake paste may be used alone or in combination with micaceous iron oxide. The fillers, particularly the preferred fillers, may be present in the coating compositions of the disclosure in any suitable amount, such as about 0.01 to about 95 percent by weight, about 1 to about 95 percent by weight, about 5 to about 95 percent by weight, about 1 to about 30 percent by weight, preferably about 0.01 to about 25 percent by weight, preferably about 10 about 80 percent by weight, preferably about 5 about 70 percent by weight, preferably about 10 about 60 percent by weight, preferably about 20 about 50 percent by weight, and most preferably about 15 to about 40 percent by weight. The aluminum flakes may have a particle size ranging from about 2 to about 50 microns, preferably about 5 to about 30 microns, most preferably about 10 to about 20 microns. Metallic flakes such as zinc, aluminum, magnesium, nickel, etc. can be added as inorganic fillers to coatings as sacrificial anodes to provide cathodic protection. They can also be used in combination with electrically conducting fillers as taught in US patent 7,794,626 to provide galvanic anti-corrosion protection to the substrates.

[0307] Suitable dyes or pigments include MO 02294 black, MO-80406BV-Yellow from Chromaflo, and white pigment powder TI-PURE from Dupont.

[0308] Suitable rheology modifiers and anti-settling agents include inorganic and organic rheology modifiers. Inorganic rheology modifiers include clays and organoclays of hectorite, bentonite, attapulgite, kaoline, pyrophilite and talc; minerals such as fumed silica, precipitated silica, precipitated calcium carbonate, and montmorillonite, metal organic gellants such as zirconates, aluminates. Organic rheology modifiers include castor oil derivatives, modified polyurea, polyamides, calcium sulfonates, cellulose, shydrophobic ethoxylated urethane resins, Examples of suitable rheology modifiers include fumed silica such as Cab-O-Sil TS610, TS720 from Cabot Corp and AEROSIL 972, AEROSIL 974 from Evonik, organoclay such as BENTOLITE L-10, BENTOLITE-WH, CLAYTONE 40, CLAYTONE AF, MINERAL COLLOID BP, Garamite 7303 from BYK Chemie, USA; Bentonite 149, Bentonite 329, Bentonite 331, Bentonite 344 from Brentag Specialities, Attagel from BASF and the like, polyaminoamide phosphate, high molecular weight carboxylic acid salts of polyamine amides, and alkylene amine salts of an unsaturated fatty acid, all available from BYK Chemie USA as ANTI TERRA™, polyamide modified castor oil derivatives such as Luvotix ZH5, Luvitix ZH50 from Lehmann & Voss; micronized amide wax such as Crayvallac SUPER from Arkema.

[0309] A coating composition of the disclosure may contain additives such as dispersants / dispersing agents (surfactants) known in the art. Examples of dispersing agents and surfactants include sodium bis(tridecyl) sulfosuccinnate, di(2-ethylhexyl) sodium sulfosuccinnate, sodium dihexylsulfosuccinnate, sodium dicyclohexyl sulfosuccinnate, diamyl sodium sulfosuccinnate, sodium diisobutyl sulfosuccinate, disodium isodecyl sulfosuccinnate, disodium ethoxylated alcohol half ester of sulfosuccinnic acid, disodium alkyl amido polyethoxy sulfosuccinnate, tetrasodium N-(1,2-dicarboxy-ethyl)-N-oxtadecyl sulfosuccinnamate, disodium N-octasulfosuccinnamate, sulfated ethoxylated nonylphenol, 2-amino-2- methyl-1-propanol, and the like.

[0310] The compositions of this disclosure containing functional monomers may be optionally formulated with other reactive chemistries to form co-cured coatings. The co-curing process may form interpenetrating polymer networks; for example, a co-cured polyurethane can form from a polyol and a diisocyanate; a co- cured epoxy can form from a bisepoxide and a hardener such as an anhydride, amine, or thiol. Care should be taken when using chemistries that are known to inhibit ring-opening polymerization. Copolymeric coatings may be formed if bifunctional monomers are incorporated; for example, isocyanate- or alcohol- containing olefinic comonomers can copolymerize urethanes with the compositions of the disclosure, and epoxide-containing comonomers can copolymerize epoxies with the compositions of the disclosure. Otherpolymers such as polysiloxanes, polyureas, and acrylics can be incorporated into the compositions of the disclosure.

[0311] The resin composition of the disclosure may additionally comprise an exogenous inhibitor. Exogenous inhibitors or “gel modification additives”, for use in the disclosure are disclosed in U.S. Pat. No. 5,939,504, the contents of which are incorporated herein by reference. The resin composition of the disclosure may additionally comprise a hydroperoxide gel modifier. Hydroperoxide gel modifiers (e.g., cumene hydroperoxide) for use in the disclosure are disclosed in International Pat. App. No. PCT / US2012 / 042850.

[0312] The resin composition of the disclosure may be optionally formulated with additives. Suitable additives include, but are not limited to, gel modifiers, hardness modulators, antioxidants, antiozonants, stabilizers, crosslinkers, fillers, binders, coupling agents, thixotropes, wetting agents, biocides, plasticizers, pigments, flame retardants, dyes, fibers and reinforcement materials, including sized reinforcements and substrates, such as those treated with finishes, coatings, coupling agents, film formers and / or lubricants. Furthermore, the amount of additives present in the resin compositions may vary depending on the particular type of additive used. The concentration of the additives in the resin compositions typically ranges from, for example, 0.001-85 percent by weight, particularly, from 0.1-75 percent by weight, or even more particularly, from 2-60 percent by weight.

[0313] The resin composition of the disclosure may be optionally formulated with or without a crosslinker, for example, a crosslinker selected from dialkyl peroxides, diacyl peroxides, and peroxyacids.

[0314] Suitable reinforcing materials include those that add to the strength or stiffness of a polymer composite when incorporated with the polymer. Reinforcing materials can be in the form of filaments, fibers, rovings, mats, weaves, fabrics, knitted material, cloth, or other known structures. Suitable reinforcement materials include glass fibers and fabrics, carbon fibers and fabrics, aramid fibers and fabrics, polyolefin fibers or fabrics (including ultrahigh molecular weight polyethylene fabrics such as those produced by Honeywell under the Spectra®trade name), and polyoxazole fibers or fabrics (such as those produced by the Toyobo Corporation under the Zylon®trade name). Reinforcing materials containing surface finishes, sizings, or coatings are particularly suitable for the described disclosure including Ahlstrom glass roving (R338-2400), Johns Manville glass roving (Star ROV®-086), Owens Corning rovings (OCV 366-AG-207, R25H-X14-2400, SE1200-207, SE1500-2400, SE2350-250), PPG glass rovings (Hybon®2002, Hybon®2026), Toho Tenax®carbon fiber tow (HTR-40), and Zoltek carbon fiber tow (Panex®35). Furthermore, any fabrics prepared using reinforcing materials containing surface finishes,sizings or coatings are suitable for the disclosure. Advantageously, the disclosure does not require the expensive process of removing of surface finishes, sizings, or coatings from the reinforcing materials. Additionally, glass fibers or fabrics may include without limitation A-glass, E-glass or S-glass, S-2 glass, C-glass, R-glass, ECR-glass, M-glass, D-glass, and quartz, and silica / quartz. Preferred glass fiber reinforcements are those with finishes formulated for use with epoxy, vinyl ester, and / or polyurethane resins. When formulated for use with a combination of these resin types, the reinforcements are sometimes described as “multi-compatible.” Such reinforcements are generally treated during their manufacture with organosilane coupling agents comprising vinyl, amino, glycidoxy, or methacryloxy functional groups (or various combinations thereof) and are coated with a finish to protect the fiber surface and facilitate handling and processing (e.g., spooling and weaving). Finishes typically comprise a mixture of chemical and polymeric compounds such as film formers, surfactants, and lubricants. Especially preferred glass reinforcements are those containing some amount of amino-functionalized silane coupling agent. Especially preferred finishes are those comprising and epoxy-based and / or polyurethane-based film formers. Examples of preferred glass-fiber reinforcements are those based on Hybon®2026, 2002, and 2001 (PPG) multi- compatible rovings; Ahlstrom R338 epoxysilane-sized rovings; StarRov®086 (Johns Manville) soft silane sized multi-compatible rovings; OCV™ 366, SE 1200, and R25H (Owens Corning) multi-compatible rovings; OCV™ SE 1500 and 2350 (Owens Corning) epoxy-compatible rovings; and Jushi Group multi- compatible glass rovings (752 type, 396 type, 312 type, 386 type). Additional suitable polymer fibers and fabrics may include without limitation one or more of polyester, polyamide (for example, NYLON polamide available from E.I. DuPont, aromatic polyamide (such as KEVLAR aromatic polyamide available from E.I. DuPont, or P84 aromatic polyamide available from Lenzing Aktiengesellschaft), polyimide (for example KAPTON polyimide available from E.I. DuPont, polyethylene (for example, DYNEEMA polyethylene from Toyobo Co., Ltd.). Additional suitable carbon fibers may include without limitation AS2C, AS4, AS4C, AS4D, AS7, IM6, IM7, IM9, and PV42 / 850 from Hexcel Corporation; TORAYCA T300, T300J, T400H, T600S, T700S, T700G, T800H, T800S, T1000G, M35J, M40J, M46J, M50J, M55J, M60J, M30S, M30G and M40 from Toray Industries, Inc.; HTS12K / 24K, G30-5003k / 6K / 12K, G30-500 12K, G30-70012K, G30-700024K F402, G40-80024K, STS 24K, HTR 40 F2224K 1550tex from Toho Tenax, Inc.; 34-700, 34-700WD, 34-600, 34-600WD, and 34-600 unsized from Grafil Inc.; T-300, T- 650 / 35, T-300C, and T-650 / 35C from Cytec Industries. Additionally suitable carbon fibers may include without limitation AKSACA (A42 / D011), AKSACA (A42 / D012), Blue Star Starafil (10253512-90), Blue Star Starafil (10254061-130), SGL Carbon (C30 T050 1.80), SGL Carbon (C50 T024 1.82), Grafil (347R1200U), Grafil (THR 6014A), Grafil (THR 6014K), Hexcel Carbon (AS4C / EXP 12K), Mitsubishi (Pyrofil TR 50S 12L AF), Mitsubishi (Pyrofil TR 50S 12L AF), Toho Tenax (T700SC 12000-50C), Toray (T700SC 12000-90C), Zoltek (Panex 3550K, sizing 11), Zoltek (Panex 3550K, sizing 13). Additionalsuitable carbon fabrics may include without limitation Carbon fabrics by Vectorply (C-L 1800) and Zoltek (Panex 35 UD Fabic-PX35UD0500-1220). Additionally suitable glass fabrics may include without limitation glass fabrics as supplied by Vectorply (E-LT 3500-10) based on PPG Hybon®2026; Saertex (U14EU970-01190-T2525-125000) based on PPG Hybon®2002; Chongqing Polycomp Internation Corp. (CPIC®Fiberglass) (EKU 1150(0) / 50-600); and Owens Corning (L1020 / 07A06 Xweft 200tex).

[0315] Other suitable fillers include, for example, metallic density modulators, microparticulate density modulators, such as, for example, microspheres, and macroparticulate density modulators, such as, for example, glass or ceramic beads. Metallic density modulators include, but are not limited to, powdered, sintered, shaved, flaked, filed, particulated, or granulated metals, metal oxides, metal nitrides, and / or metal carbides, and the like. Preferred metallic density modulators include, among others, tungsten, tungsten carbide, aluminum, titanium, iron, lead, silicon oxide, aluminum oxide, boron carbide, and silicon carbide. Microparticulate density modulators include, but are not limited to, glass, metal, thermoplastic (either expandable or pre-expanded) or thermoset, and / or ceramic / silicate microspheres. Macroparticulate density modulators include, but are not limited to, glass, plastic, or ceramic beads; metal rods, chunks, pieces, or shot; hollow glass, ceramic, plastic, or metallic spheres, balls, or tubes; and the like.

[0316] Adhesion promoters that may be used in the coating compositions disclosed herein may include, for example, compounds containing at least two isocyanate groups (such as, for example, methylene diphenyl diisocyanate and hexamethylene diisocyanate). The adhesion promoter may be a diisocyanate, triisocyanate, or polyisocyanate (i.e., containing four or more isocyanate groups). The adhesion promoter may be a mixture of at least one diisocyanate, triisocyanate, or polyisocyanate. In a more particular embodiment, the adhesion promoter comprises, or is limited to, a diisocyanate compound, or mixtures of diisocyanate compounds. Adhesion promoters that may be used may be an alkyl diisocyanate. Adhesion promoters that may be used also include aryl diisocyanate. Aryl diisocyanates refers to aromatic diisocyanates containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety). Preferred aryl diisocyanates contain 5 to 24 carbon atoms, and particularly preferred aryl diisocyanates contain 5 to 14 carbon atoms. Adhesion promoters that may be used include a polymer-containing isocyanate, such as, for example, diisocyanates. Polymer-containing isocyanates refers to a polymer-containing two or more terminal and / or pendant alkyl or aryl isocyanate groups. Adhesion promoters that may be used include a trimer of alkyl diisocyanates and aryl diisocyanates. Additional adhesion promoters suitable for use comprise functionalized silanes of the formula Fn-(A)n-Si(Y*)3, wherein Y* is selected from halide (preferably chloride) or OR; Fn is a functional group selected fromacrylate, methacrylate, allyl, vinyl, alkene, cycloalkene, or norbornene; A is a divalent linking group selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene; n is 0 or 1; and R is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl, preferably lower alkyl, more preferably methyl, ethyl, or isopropyl; and a peroxide selected from dialkyl and diaryl peroxides. For example, adhesion promoters that may be used may be an acid- functionalized polyolefin, such as a polyolefin comprising maleic anhydride. The polyolefin may be unsaturated, comprising alkene moieties, such as polybutadiene. An exemplary acid-functionalized polyolefin that may be used as an adhesion promoter is polybutadiene comprising maleic anhydride. Any concentration of adhesion promoter which improves the mechanical properties of the olefin composite (e.g., ROMP polymer composite) is sufficient. In general, suitable amounts of adhesion promoter range from 0.001-50 phr, particularly 0.05-10 phr, more particularly 0.1-10 phr, or even more particularly 0.5-4.0 phr.

[0317] The optional adhesion promoter used in the ROMP composition of the disclosure disclosed herein may be an acid-functionalized polyolefin.

[0318] The acid-functionalized polyolefin that may be used as the adhesion promoter includes those disclosed in US 7,465,773, the disclosure of which is incorporated herein by reference. For example, adhesion promoters that may be used in the disclosure may be an acid-functionalized polyolefin, such as a polyolefin comprising maleic anhydride. The polyolefin may be unsaturated, comprising alkene moieties, such as polybutadiene. The polyolefin may have a vinyl content of no greater than 40, 35, or 30 wt.%. The polyolefin may have an average anhydride equivalent weight ranging from 200-5000 g / mole per anhydride group (e.g., no greater than 4000, 3000, 2000, 1000, or 500 g / mole per anhydride group). The polyolefin comprising maleic anhydride is a liquid, typically having a viscosity at 20 or 25 °C of at least 2000, 3000, 4000, or 5000 mPas. (DIN EN ISO 3219). The viscosity at 20 or 25 °C may be no greater than 75,000 mPas (e.g., no greater than 30,000, 25,000, 20,000, or 15,000 or 10,000 mPas; less than 1000 or 500 mPas). The polyolefin may have a viscosity of at least 50,000; 75,000; 100,000; 125,000; or 150,000 mPas at 45, 50, or 55 °C. The viscosity is indicative of the molecular weight. The polyolefin may have a molecular weight (Mn) of no greater than 10,000; 9,000; 8,000; 7,000; 6,000; 5,000; 4,500; 4,000; 3,500; or 3,000 g / mole. The polyolefin may have a molecular weight (Mn) of at least 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,600, 1,700, 1,800, 1,900, or 2,000 g / mole. An acid-functionalized polyolefin that may be used as an adhesion promoter is polybutadiene comprising maleic anhydride (e.g., Ricobond 1731, Polyvest EP MA 100, Ricon 130MA8, Ricon 130MA20, Ricon 131MA5, Ricon 131MA10, Ricon 131MA20, Ricon 184MA6, Ricobond 1731, Ricobond 1756 from Cray Valley, Polyvest EP MA 100, MA 75, EP MV MA60 from Evonik, Lithene Ultra PM4-7.5MA, N4-B-10MA, N4-5000-10 MA, AL-15MA from Synthomer (polybutadiene modified with maleic anhydride)).

[0319] Other adhesion promoters that may be used in the disclosure may be any compound having at least two isocyanate groups. The compound containing at least two isocyanate groups may be selected from the group consisting of at least one diisocyanate, at least one triisocyanate, or at least one polyisocyanate (i.e., containing four or more isocyanate groups), and mixtures thereof. In a more particular aspect of the disclosure, the adhesion promoter comprises, or is limited to, a diisocyanate compound, or mixtures of diisocyanate compounds.

[0320] The compounds of the isocyanate compounds comprising at least two isocyanate groups may be selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functionalized hydrocarbyl compounds. As described above, suitable hydrocarbyl adhesion promoter compounds generally include alkyl, cycloalkyl, alkylene, alkenyl, alkynyl, aryl, cycloalkyl, alkaryl, and aralkyl compounds. Substituted heteroatom-containing, and functionalized hydrocarbyl adhesion promoter compounds include the aforementioned hydrocarbyl compounds, as well as the variations thereof noted hereinabove.

[0321] Adhesion promoters that may be used in the disclosure may be an alkyl diisocyanate. An alkyl diisocyanate refers to a linear, branched, or cyclic saturated or unsaturated hydrocarbon group typically although not necessarily containing 1 to about 24 carbon atoms, such as a diisocyanate containing 2 to about 12 carbon atoms (e.g., 6 to 12 carbon atoms such as hexamethylene diisocyanate (HDI), octamethylene diisocyanate, decamethylene diisocyanate, and the like). Cycloalkyl diisocyanates contain cyclic alkyl group, typically having 4 to 16 carbon atoms. A cycloalkyl diisocyanate containing 6 to about 12 carbon atoms are cyclohexyl, cyclooctyl, cyclodecyl, and the like. A cycloalkyl diisocyanate may originate as a condensation product of acetone called 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethyl-cyclohexane, commonly known as Isophorone diisocyanate (IPDI) and the isomers of isocyanato- [(isocyanatocyclohexyl)methyl]cyclohexane (H12MDI). H12MDI is derived from the hydrogenated form of the aryl diisocyanate methylene diphenyl diisocyanate (MDI).

[0322] Adhesion promoters that may be used in the disclosure may be an aryl diisocyanate. Aryl diisocyanates refers to aromatic diisocyanates containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety). Aryl diisocyanates may contain 5 to 24 carbon atoms (e.g., 5 to 14 carbon atoms). Exemplary aryl diisocyanates contain one aromatic ring or two fused orlinked aromatic rings, e.g., phenyl, tolyl, xylyl, naphthyl, biphenyl, diphenylether, benzophenone, and the like. Aromatic diisocyanates include toluene diisocyanates, tetramethylxylene diisocyanate (TMXDI), and methylene diphenyl diisocyanate (MDI), which may comprise any mixture of its three isomers, 2.2’-MDI, 2,4’-MDI, and 4,4’-MDI.

[0323] Adhesion promoters that may be used in the disclosure may be a polymer-containing isocyanate, such as, for example, diisocyanates. Polymer-containing isocyanates refers to a polymer-containing two or more terminal and / or pendant alkyl or aryl isocyanate groups. The polymer-containing isocyanates generally have a minimal solubility in the ROMP composition to provide improved mechanical properties. Polymer-containing isocyanates include, but are not limited to, PM200 (poly MDI), Lupranate®(poly MDI from BASF), Krasol®isocyanate terminated polybutadiene prepolymers, such as, for example, Krasol®LBD2000 (TDI based), Krasol®LBD3000 (TDI based), Krasol®NN-22 (MDI based), Krasol®NN-23 (MDI based), Krasol®NN-25 (MDI based), and the like. Krasol®isocyanate terminated polybutadiene prepolymers are available from Cray Valley.

[0324] Adhesion promoters that may be used in the disclosure may be a trimer of alkyl diisocyanates and aryl diisocyanates. In its simplest form, any combination of polyisocyanate compounds may be trimerized to form an isocyanurate ring containing isocyanate functional groups. Trimers of alkyl diisocyanate and aryl diisocyanates may also be referred to as isocyanurates of alkyl diisocyanate or aryl diisocyanate. Alkyl diisocyanate and aryl diisocyanate trimers include, but are not limited to, hexamethylene diisocyanate trimer (HDIt), isophorone diisocyanate trimer, toluene diisocyanate trimer, tetramethylxylene diisocyanate trimer, methylene diphenyl diisocyanate trimers, and the like. Adhesion promoters include, but are not limited to, toluene diisocyanates, tetramethylxylene diisocyanate (TMXDI), and methylene diphenyl diisocyanate (MDI) including any mixture of its three isomers 2.2’-MDI, 2,4’-MDI and 4,4’-MDI; liquid MDI; solid MDI; hexamethylenediisocyanatetrimer (HDIt); hexamethylenediisocyanate (HDI); isophorone diisocyanate (IPDI); 4,4’-methylene bis(cyclohexyl isocyanate) (H12MDI); polymeric MDI (PM200); MDI prepolymer (Lupranate®5080); liquid carbodiimide modified 4,4’-MDI (Lupranate®MM103); liquid MDI (Lupranate®MI); liquid MDI (Mondur®ML); and liquid MDI (Mondur®MLQ). Adhesion promoters may be methylene diphenyl diisocyanate (MDI) including any mixture of its three isomers 2,2’-MDI, 2,4’-MDI and 4,4’-MDI; liquid MDI; solid MDI; hexamethylenediisocyanatetrimer (HDIt); hexamethylene diisocyanate (HDI); isophorone diisocyanate (IPDI); 4,4’-methylene bis(cyclohexyl isocyanate) (H12MDI); polymeric MDI (PM200); MDI prepolymer (Lupranate®5080); liquid carbodiimide modified 4,4’-MDI (Lupranate®MM103); liquid MDI) (Lupranate®MI); liquid MDI (Mondur®ML); liquid MDI (Mondur®MLQ).

[0325] Additional adhesion promoters that may be used in the disclosure include compositions comprising at least one compound containing at least two isocyanate groups (e.g., methylene diphenyl diisocyanate, hexamethylene diisocyanate) and at least one compound comprising a heteroatom-containing functional group with a metathesis active olefin (e.g., 2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate (HENB), 2-hydroxyethyl acrylate (HEA), oleyl alcohol, 9-decen-1-ol), where the compounds may be combined in various ratios to form a pre-reacted mixture, For example, the pre-reacted mixtures include liquid MDI (Mondur® MLQ) and 2-hydroxyethyl bicycle[2.2.1]hept-2-ene-carboxylate (HENB); pre- reacted mixtures of liquid MDI (Mondur® MLQ) and 2-hydroxyethyl acrylate (HEA); pre-reacted mixtures of liquid MDI (Mondur® MLQ) and oleyl alcohol; and pre-reacted mixtures of liquid MDI (Mondur® MLQ) and 9-decen-1-ol. The pre-reacted mixture may be used as the adhesion promoter in the disclosure. Further examples of such adhesion promoters are described in US 9,527,982, the disclosure of which is incorporated herein by reference. It is also possible to use a mixture of HENB-MDI and excess, unreacted MDI as the adhesion promoter in the disclosure.

[0326] In some embodiments, such as when a polyolefin comprising maleic anhydride is used as the adhesion promoter, the adhesion promoter may not comprise any isocyanate moieties. Furthermore, in some embodiments, the adhesion promoter does not contain any compound containing at least two isocyanate groups. And in other embodiments, the ROMP composition does not contain any compound containing at least two isocyanate groups.

[0327] Additional adhesion promoters suitable for use in the disclosure comprise functionalized silanes of the formula Fn-(A)n-Si(Y*)3, wherein Y* is selected from halide (e.g., chloride) or OR; Fn is a functional group selected from acrylate, methacrylate, allyl, vinyl, alkene, cycloalkene, or norbornene; A is a divalent linking group selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene; n is 0 or 1; and R is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom- containing hydrocarbyl, such as lower alkyl (e.g., methyl, ethyl, or isopropyl); and a peroxide selected from dialkyl and diaryl peroxides.

[0328] Additional adhesion promoters for use in the disclosure include those disclosed in International Pat. App. Nos. PCT / US2012 / 042850 and PCT / US2016 / 017449 and U.S. Pat. Nos. 7,465,773 and 9,527,982, the contents of which are incorporated herein by reference.

[0329] An additional adhesion promoter that may be used in the disclosure is at least one polyoctenamer, such as Vestenamer® (e.g., Vestenamer 8012, Vestenamer CS10). Polyoctenamers may be present in theROMP composition in an amount ranging from 0.1 to 3 phr (e.g., 0.5 to 2 phr, 0.75 to 1.5 phr), for example 1 phr.

[0330] One or more of any of the aforementioned adhesion promoters, in any combination, may be used in the ROMP composition of the disclosure. For example, at least one acid-functionalized polyolefin may be used in combination with at least one polyoctenamer.

[0331] Suitable adhesion promoters include isocyantes and their derivatives; phosphorous containing compounds such as phosphoric acids and phosphate ester containing compounds; sulfonic acid, sulfonate and sulfate containing compounds; carboxylic acid and carboxylate containing compounds; maleic- modified esters; organofunctional silanes; organometallic compounds such as zirconates, zircono aluminates and titanates; chlorinated olefins, etc. Some suitable adhesion promoters are carbamic acid [3- (triethoxysilyl)propyl]-bicyclo[2.2.1]hept-5-en-2-ylmethyl ester (NBCbSi), 3-(trimethoxysilyl)propyl methacrylate, [(5-bicyclo[2.2.1]hept-2-enyl)ethyl]trimethoxysilane, 5-bicyclo[2.2.1]hept-2- enyl)methyldichlorosilane, (5-bicyclo[2.2.1]hept-2-enyl)triethoxysilane, (5-bicyclo[2.2.1]hept-2- enyl)methyldiethoxysilane, (5-bicyclo[2.2.1]hept-2-enyl)dimethylethoxysilane, (3- acryloxypropyl)trimethoxysilane, n-(2-aminoethyl)-3-aminopropyltrimethoxysilane, (3- triethoxysilyl)propylsuccinic anhydride, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, ((chloromethyl)phenylethyl)trimethoxysilane, 3-(guanidinyl)propyltrimethoxysilane, n,n-bis(2- hydroxyethyl)-3-aminopropyltriethoxysilane, styrylethyltrimethoxysilane, methacryloxymethyltrimethoxysilane, vinyltriethoxysilane, ureidopropyltriethoxysilane, 3- isocyanatopropyltriethoxysilane, triethoxysilyl modified poly-1,2-butadiene, bis(methyldiethoxysilylpropyl)amine, [2-(3-cyclohexenyl)ethyl]triethoxysilane, hexadecafluorododec-11- en-1-yltrimethoxysilane or mixtures of 2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate (HENB). Other typical adhesion promoters include coupling agents such as organosilanes (3-isocyanatopropyl triethoxysilane, bicyclo[2.2.1]hept-5-en-2-yl)ethyltrimethoxysilane), organozirconates, organotitanates (Manchem® products (Manchem® Zircoaluminates) (FedChem, LLC) (e.g., Manchem® A, Manchem® APG-X, Manchem® APG-1, Manchem®APG-2, Manchem® APG-3, Manchem® C, Manchem® CPG, Manchem® CPM, Manchem® F, Manchem® FPM, Manchem® M, Manchem® S, Manchem® 376, Manchem® 441) and Kenrich Petrochemicals products such as KR 55 (Titanium IV tetrakis(bis 2- propenolato methyl)-1-butanolato adduct 2 moles (di-tridecyl)hydrogen phosphite), KZ® TPPJ (Zirconium IV (2-ethyl, 2-propenolatomethyl)1,3-propanediolato, cyclo bis 2-dimethylamino pyrophosphato-O, adduct with 2 moles of methanesulfonic acid), KZ® 55 (Zirconium IV tetrakis 2,2(bis-2 propenolatomethyl)butanolato, adduct with 2 moles of di-tridecyl, hydrogen phosphite); phosphate andphosphate esters-containing resins (Sipomer PAM products from Solvay) (e.g., Sipomer PAM-100 (Phosphate esters of polyethylene glycol monomethacrylate), Sipomer PAM-200). Also other Sipomer products from Solvay containing other polar functional groups such as Sipomer WAM products, Sipomer WAM II products, Sipomer COPS-1 products, Sipomer β-CEA, Sipomer BEM, Sipomer IBOA, Sipomer IBOMA, Sipomer SEM-25); carboxylic acid and anhydride-containing resins (Nucrel from DuPont (ethylene acrylic acid copolymer), Escor EAA copolymers from ExxonMobil Chemicals, POLYBOND (acrylic acid grafted polypropylene) from Addivant. Anhydride-containing resins such as FG1901, FG1924 (SEBS grafted with maleic anhydride) from Kraton, ROYALTUF 485, ROYALTUF 498 (EPDM polymers modified with maleic anhydride) from Addivant); isocyanate-containing resins (hexamethylene diisocyanate (HDI); 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethyl-cyclohexane (commonly known as isophorone diisocyanate or IPDI); tetramethylxylene diisocyanate (TMXDI), methylene diphenyl diisocyanate (MDI - which may comprise any mixture of its three isomers 2,2'-MDI, 2,4'-MDI, and 4,4'- MDI); 4,4’methylene bis(cyclohexyl isocyanate) (H12MDI); hexamethylene-diisocyanatetrimer (HDIt); toluene diisocyanate (TDI – which may comprise any mixture of 2,4-TDI and 2,6-TDI); 2-biphenylyl isocyanate; 4-benzylphenyl isocyanate; toluene diisocyanates; PM200 (poly MDI), Lupranate®(poly MDI from BASF), Krasol®isocyanate terminated polybutadiene prepolymers, Krasol® LBD2000 (TDI based), Krasol® LBD3000 (TDI based), Krasol® NN-22 (MDI based), Krasol® NN-23 (MDI based), Krasol® NN-25 (MDI based); MDI prepolymer (Lupranate® 5080); liquid carbodiimide modified 4,4’-MDI (Lupranate® MM103); liquid MDI (Lupranate® MI); liquid MDI (e.g., Mondur®ML or Mondur®MLQ, which is a 50 / 50 blend of 4,4'-MDI and 2,4-MDI), or 2-hydroxyethyl acrylate (HEA) and liquid MDI (Mondur®MLQ), or 9-decen-1-ol and liquid MDI (Mondur®MLQ), or oleyl alcohol and liquid MDI (Mondur®MLQ). The ratio between the alcohol and the liquid MDI varies from 1:1 to 1:10.; bicyclo[2.2.1] hept-5-ene-2-carboxylic acid, and 2-[[[[4-[(4-isocyanatophenyl)methyl]phenyl]amino]carbonyl]oxy]ethyl ester); chlorinated polyolefins such as Eastman CP 343-1, CP343-3, CP515-2, CP-164-1 (Eastman Chemical); Hardlen 13LP (Advanced Polymer); KEPRADH 949, 951, 958, 980, 982 (Kito Chemical); Lanco Intercoat VPP 154, 555 (Lubrizol); HARDLEN 15-LP, BS-40, CY-1132, CY-9122P, CY-9124P; TRAPYLEN 112X, 130X, 135X, 137X, 138S (Tramaco); Special-Primer PP 7560 (Worlee).

[0332] The resin composition of the disclosure may additionally comprise an adhesion promoter. Adhesion promoters for use in the disclosure are disclosed in International Pat. App. No. PCT / US2012 / 042850.

[0333] If present, any concentration of adhesion promoter is sufficient for the disclosure. For example, the at least one adhesion promoter may be present in the ROMP composition in an amount ranging from 0.05 to 15 wt.% (e.g., 0.1 to 13 wt.%, 0.5 to 10 wt.%, 1 to 8 wt.%, 2 to 6 wt.%, 3 to 5 wt.%), based on the totalweight of the ROMP composition. For example, the adhesion promoter may comprise 0.1 to 10 wt.% (e.g., 0.5 to 9 wt.%, 1 to 8 wt.%, 2 to 7 wt.%, 3 to 6 wt.%, 4 to 5 wt.%), based on the total weight of the ROMP composition, of the at least one acid-functionalized polyolefin, and 0.05 to 5 wt.% (e.g., 0.1 to 4 wt.%, 0.5 to 3 wt.%, 1 to 2 wt.%), based on the total weight of the ROMP composition, of at least one polyoctenamer.

[0334] Other cyclic olefin resin compositions may be used in the resin composition of the disclosure herein as well. Additionally, the resin composition of the disclosure may also comprise at least one substrate material. Additionally, the resin composition of the disclosure may also comprise at least one adhesion promoter, where the resin composition is combined with the catalyst composition of the disclosure to form the ROMP composition of the disclosure, and the resulting ROMP composition is applied to at least one substrate material. Additionally, the resin composition of the disclosure may also comprise a cyclic olefin composition of the disclosure and at least one adhesion promoter comprising at least one compound containing at least two isocyanate groups and / or at least one acid-functionalized polyolefin, where the resin composition is combined with at least one olefin metathesis catalyst, and the resulting ROMP composition is applied to at least one substrate material, wherein the substrate material may be functionalized substrate material, such as, for example, a heteroatom-functionalized substrate, such as, for example, an amino- functionalized substrate. Additionally, the resin composition of the disclosure may also comprise at least one adhesion promoter comprising at least one compound containing at least two isocyanate groups and / or at least one acid-functionalized polyolefin, where the resin composition is combined with at least olefin metathesis catalyst, and the resulting resin composition is applied to at least one substrate material, such as, for example, a glass substrate material or carbon substrate material. Resin compositions, particularly ROMP compositions of the disclosure comprise at a cyclic olefin composition, at least one olefin metathesis catalyst, at least one adhesion promoter comprising at least one compound containing at least two isocyanate groups, and at least one heteroatom-functionalized substrate material and / or at least one acid- functionalized polyolefin.

[0335] The amounts of the adhesion promoter in the resin composition may vary over a wide range and may vary depending on the manufacturing operation or the particular end-use application. Generally, any level of adhesion promoter which produces a desired increase in mechanical properties is of particular interest. When formulated or combined with a resin composition, the concentration of the adhesion promoter typically ranges from 0.001-50 phr, particularly 0.05-10 phr, more particularly 0.1-10 phr, or even more particularly 0.5-4.0 phr.

[0336] In particular aspects of the disclosure, substrate materials may advantageously comprise an aminosilane-treated substrate.

[0337] Articles of Manufacture

[0338] The disclosure is also directed to articles manufactured from the resin composition of the disclosure and the catalyst composition of the disclosure.

[0339] The disclosure is also directed to articles manufactured from the resin composition of the disclosure and the catalyst composition of the disclosure, wherein the article is a thermal insulation material.

[0340] The disclosure is also directed to articles manufactured from the resin composition of the disclosure, the catalyst composition of the disclosure, and at least one adhesion promoter comprising at least one compound containing at least two isocyanate groups and / or at least one acid-functionalized polyolefin, where the resin composition is combined with at least one olefin metathesis catalyst, and the resulting ROMP composition is applied to at least one substrate material.

[0341] The disclosure is also directed to articles manufactured from the resin composition of the disclosure, at least one olefin metathesis catalyst, at least one adhesion promoter comprising at least one compound containing at least two isocyanate groups and / or at least one acid-functionalized polyolefin, and at least one substrate material, wherein the article is a thermal insulation material. Additionally, the disclosure relates to articles manufactured from the resin composition of the disclosure, at least one olefin metathesis catalyst, and at least one adhesion promoter comprising at least one compound containing at least two isocyanate groups and / or at least one acid-functionalized polyolefin, where the resin composition is combined with at least one olefin metathesis catalyst, and the resulting ROMP composition is applied to at least one substrate material, which may be, for example, a functionalized substrate, such as, for example, a heteroatom-functionalized substrate, such as, for example, an amino-functionalized substrate, wherein the article is a thermal insulation material. ROMP Polymers and ROMP Polymer Composites

[0342] The disclosure also relates to a ROMP polymer or a ROMP polymer composite comprising, consisting essentially of, or consisting of a reaction product of the ROMP composition of the disclosure.

[0343] The disclosure relates to objects at least partially coated with a thermal insulation material, wherein the thermal insulation material is the ROMP polymer or ROMP polymer composite of the disclosure, wherein the ROMP polymer or ROMP polymer composite is a reaction product of the ROMP composition of the disclosure.

[0344] Additionally, the disclosure relates to objects at least partially encased by a thermal insulation material, wherein the thermal insulation material is the ROMP polymer or ROMP polymer composite of the disclosure, wherein the ROMP polymer or ROMP polymer composite is a reaction product of the ROMP composition of the disclosure.

[0345] Additionally, the disclosure relates to a process for a ROMP polymer coating for offshore applications, the process comprising, providing an object surface to be at least partially coated, providing the resin composition of the disclosure, providing the catalyst composition of the disclosure, combining the resin composition and the catalyst composition to form the ROMP composition of the disclosure, contacting the object surface with the ROMP composition, and subjecting the ROMP composition to conditions effective to polymerize the ROMP composition.

[0346] Additionally, the disclosure relates to a process for a ROMP polymer coating for offshore applications, the process comprising, providing an object surface to be at least partially coated, providing a resin composition of the disclosure, providing the catalyst composition of the disclosure, combining the resin composition and the catalyst composition of the disclosure to form the ROMP composition of the disclosure, applying the ROMP composition to the object surface, and subjecting the ROMP composition to conditions effective to polymerize the ROMP composition.

[0347] The application of the ROMP composition of the disclosure to the object surface to be at least partially coated is carried out by methods known in the art, examples include, but are not limited to casting, centrifugal casting, pultrusion, molding, rotational molding, open molding, reaction injection molding (RIM), resin transfer molding (RTM), pouring, vacuum impregnation, surface coating, filament winding, cell casting, dip casting, continuous casting, embedding, potting, encapsulation, film casting or solvent casting, gated casting, mold casting, slush casting, extrusion, mechanical foaming, chemical foaming, physical foaming, compression molding or matched die molding, spray up, spraying, Vacuum Assisted Resin Transfer Molding (VARTM), Seeman’s Composite Resin Infusion Molding Process (SCRIMP), blow molding, in mold coating, in-mold painting or injection, vacuum forming, Reinforced Reaction Injection Molding (RRIM), Structural Reaction Injection Molding (SRIM), thermal expansion transfer molding (TERM), resin injection recirculation molding (RICM), controlled atmospheric pressure resin infusion (CAPRI), hand-layup. For manufacturing techniques requiring the use of a RIM or impingement style mixhead, including without limitation RIM, SRIM, and RRIM, articles of manufacture may be molded using a single mixhead or a plurality of mixheads as well as a plurality of material injection streams (e.g., two resin streams and one catalyst stream).

[0348] The ROMP polymer and / or ROMP polymer composite of the disclosure need not necessarily be molded around an object to be insulated. In the alternative, the ROMP polymer article and / or ROMP polymer composite article may be independently prepared by a variety of methods known in the art and then subsequently affixed to or placed around an object to thermally insulate the object from the surrounding environment. Moreover, the means for affixing the ROMP polymer article and / or ROMP polymer composite article to an object may be by any known means including an adhesive means and / or mechanical means such as fasteners, bolts, screws, etc. For example, the ROMP polymer and / or a ROMP polymercomposite can be pre-made into sections which are shaped to complement the object to be insulated. The pre-made sections may then be secured or affixed to the object using any known means.

[0349] Additionally, the object to be insulated may be pretreated with any known tie coat or primer, which is suitable to improve and / or enhance the adhesion of the ROMP polymer and / or ROMP polymer composite of the disclosure to the object. For example, the tie coat or primer may be first applied to the object to be insulated, then the ROMP composition of the disclosure may be applied to the object, and the ROMP composition is subsequently subjected to conditions effective to polymerize the ROMP composition. Furthermore, the tie coat or primer may be applied to the object to be insulated, and a pre-made ROMP polymer and / or pre-made ROMP polymer composite of the disclosure may be subsequently affixed to the object.

[0350] The invention is also directed to a thermal insulation material comprising, consisting essentially of, or consisting of the ROMP composition, ROMP polymer, or ROMP polymer composite of the invention.

[0351] The ROMP polymer and ROMP polymer composite of the invention offer improved thermal stability and / or improved hydrolytic stability over prior art thermal insulation materials. Thermal insulation materials made from ROMP polymers of the invention offer an advantage over prior art thermal insulation materials made from polypropylene in such ROMP polymers possess improved thermal stability.

[0352] The invention also relates to a thermal insulation material for use in coating, encasing, or insulating (1) an object; (2) at least a portion of an object; and / or (3) at least a portion of at least one surface of an object, wherein the thermal insulation material comprises the ROMP composition, ROMP polymer, or ROMP polymer composite of the invention.

[0353] The invention also relates to the use of a thermal insulation material for coating, encasing, or insulating (1) an object; (2) at least a portion of an object; and / or (3) at least a portion of at least one surface of an object, wherein the thermal insulation material comprises the ROMP composition, ROMP polymer, or ROMP polymer composite of the invention.

[0354] The invention also relates to a method of thermally insulating an object from a surrounding fluid, the method comprising interposing a thermal insulation material between the object and the fluid where the thermal insulation material comprises the ROMP composition, ROMP polymer, or ROMP polymer composite of the invention.

[0355] The invention also relates to a method for coating, encasing, or insulating (1) an object; (2) at least a portion of an object; and / or (3) at least a portion of at least one surface of an object, with a thermal insulation material, wherein the thermal insulation material comprises the ROMP composition, ROMP polymer, or ROMP polymer composite of the invention.

[0356] The invention also relates to a method for coating, encasing, or insulating (1) an object; (2) at least a portion of an object; and / or (3) at least a portion of at least one surface of an object, with a thermal insulation material, comprising: contacting the ROMP composition of the invention with, or applying the ROMP composition of the invention to, (1) the object; (2) at least a portion of the object; and / or (3) at least a portion of at least one surface of the object; and subjecting the ROMP composition to conditions effective to promote a ROMP reaction of the ROMP composition to form the ROMP polymer or ROMP polymer composite of the invention, wherein the thermal insulation material is the ROMP polymer or ROMP polymer composite.

[0357] The invention also relates to a process for applying a thermal insulation material to an object, comprising: placing a mold around an object to define a cavity between an internal surface of the mold and the object; injecting a thermal insulation material in the cavity, wherein the thermal insulation material composition comprises the ROMP composition of the invention; and subjecting the thermal insulation material composition to conditions effective to promote a ROMP reaction of the ROMP composition to form the ROMP polymer or ROMP polymer composite of the invention.

[0358] The invention relates to an object at least partially coated, encased, or insulated with a thermal insulation material of the invention.

[0359] The objects to be encased, coated and / or insulated may be of any configuration, weight, size, thickness, or geometric shape. For example, pipe coated with the ROMP polymer and / or ROMP polymer composite of the invention can have any outer diameter, inner diameter, and length.

[0360] Furthermore, the objects to be encased, coated and / or insulated may be constructed of any material including but not limited to metal, metal alloys, plastic, rubber, polymer, wood, ceramic, glass, carbon, cement, concrete, etc.

[0361] The objects to be encased, coated, and / or insulated may be partially or fully encased, coated, and / or insulated.

[0362] The thermal insulation material may be of any configuration, weight, size, thickness, or geometric shape. Furthermore, the thermal insulation material is not limited to a single polymer layer, but also include multiple polymer layers, where each polymer layer may comprise the same or different composition.

[0363] The invention also relates to a thermal insulation material comprising the ROMP polymer of the invention, where the ROMP polymer has an elongation at break that ranges from at least 20%, from at least 50%, from at least 75%, from at least 100%, from at least 125%, from at least 150%, from at least 175%, from at least 200%, from at least 225%, from at least 250%, from at least 275%, from at least 300%, or from at least 400%.

[0364] The invention also relates to a thermal insulation material comprising the ROMP polymer of the invention, where the ROMP polymer has an elongation at break that ranges from 20% to 400%, 20% to 300%, 20% to 275%, 20% to 250%, 20% to 225%, 20% to 200%, 20% to 175%, 20% to 150%, 20% to 125%, 20% to 100%, 20% to 75%, 20% to 50%, 50% to 300%, 50% to 275%, 50% to 250%, 50% to 225%, 50% to 200%, 50% to 175%, 50% to 150%, 50% to 125%, 50% to 100%, 50% to 75%, 75% to 400%, 75% to 300%, 75% to 275%, 75% to 250%, 75% to 225%, 75% to 200%, 75% to 175%, 75% to 150%, 75% to 125%, 75% to 100%, 100% to 400%, 100% to 300%, 100% to 275%, 100% to 250%, 100% to 225%, 100% to 200%, 100% to 175%, 100% to 150%, 100% to 125%, 125% to 400%, 125% to 300%, 125% to 275%, 125% to 250%, 125% to 225%, 125% to 200%, 125% to 175%, 125% to 150%, 150% to 400%, 150% to 300%, 150% to 275%, 150% to 250%, 150% to 225%, 150% to 200%, 150% to 175%, 175% to 400%, 175% to 300%, 175% to 275%, 175% to 250%, 175% to 225%, 175% to 200%, 200% to 400%, 200% to 300%, 200% to 275%, 200% to 250%, 200% to 225%, 225% to 400%, 225% to 300%, 225% to 275%, 225% to 250%, 250% to 400%, 250% to 300%, 250% to 275%, 275% to 400%, or 275% to 300%.

[0365] Thermal insulation materials made from ROMP polymers of the invention offer an advantage over prior art thermal insulation materials made from polyurethane and epoxy-based materials, including elastomeric amine cured epoxy materials, in that cyclic olefins (cyclic olefin monomers) used to make such ROMP polymers may be selected so that the resultant ROMP polymers do not contain carbon- heteroatom bonds in the polymer backbone. Therefore, ROMP polymers of the invention are generally more hydrolytically stable than polyurethanes and / or epoxy-based polymers, each of which possess carbon-heteroatom bonds in the polymer backbone. Preferentially, ROMP polymers of the invention possess a polymer backbone containing only carbon-carbon single bonds and carbon-carbon double bonds, where the carbon atoms may be substituted or unsubstituted. ROMP polymers of the invention may be optionally hydrogenated by any known method, to provide a hydrogenated ROMP polymer for use as thermal insulation.

[0366] Unexpectedly, the ROMP polymers, ROMP polymer composites, and thermal insulation materials of the invention possessed some or all the desired characteristics and / or properties specified above for thermal insulation materials, in particular thermal insulation materials used in offshore drilling (e.g., subsea applications). As such, the ROMP polymer, ROMP polymer composites, and thermal insulation materials of the invention satisfy this need in the industry.

[0367] It is to be understood that while the invention has been described in conjunction with specific embodiments thereof, the description above as well as the examples that follow are intended to illustrate and not limit the scope of the invention. Other aspects, advantages, and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention pertains

[0368] The thermal insulation and / or thermal insulation coating may be of any configuration, weight, size, thickness, or geometric shape. Furthermore, the thermal insulation and / or thermal insulation coating is not limited to a single polymer layer, but also include multiple polymer layers, where each polymer layer may comprise the same or different composition.

[0369] The objects to be encased, coated and / or insulated may be of any configuration, weight, size, thickness, or geometric shape. Furthermore, the objects to be encased, coated and / or insulated may be constructed of any material including but not limited to metal, metal alloys, plastic, rubber, polymer, wood, ceramic, glass, carbon, cement, concrete, etc.

[0370] The objects to be encased, coated, and / or insulated may be partially or fully encased, coated, and / or insulated.

[0371] In particular, the ROMP polymer and / or ROMP polymer composite of the disclosure are suitable for thermal insulation of objects, such as oil pipelines in cold water (e.g., cold sea water, cold fresh water) and for insulating wellhead equipment. The ROMP polymer and / or ROMP polymer composite of the disclosure may also be used for insulating other objects including, but not limited to, pipes, sub-sea pipes, pipelines, oil pipelines, subsea oil pipelines, subsea pipelines, pipe fittings, hose, hose fitting, tanks, containers, drums, manifolds, risers, field joints, configurations designated as Christmas tree (oil field Christmas tree, subsea Christmas tree), jumpers, spool pieces, configurations designated as pipeline end termination (PLET), configurations designated as pipeline end manifolds (PLEM), and other sub-sea architectures and equipment. The ROMP polymer and / or ROMP polymer composite of the disclosure may also be used to coat other objects such as robotic parts, devices and vehicles used in sub-sea applications. Moreover, the ROMP polymer and / or ROMP polymer composite of the disclosure may be used to construct thermal insulation structures such as configurations designated as subsea dog houses.

[0372] Pipe coated with the ROMP polymer and / or ROMP polymer composite of the disclosure can have any outer diameter, inner diameter, and length.

[0373] While the ROMP polymer and / or ROMP polymer composite of the disclosure are well suited for coating objects or thermally insulating objects which are to be submerged in water (e.g., fresh water, salt water, sea water, etc.) the ROMP polymer and / or ROMP polymer composite may also be used to coat objects or thermally insulate objects which are not exposed to an aqueous environment.

[0374] The resin composition of the disclosure may further comprise a sizing composition, or be used to provide improved adhesion to substrate materials that are sized with certain commercial silanes commonly used in the industry. As is known in the art, glass fibers are typically treated with a chemical solution (e.g., a sizing composition) soon after their formation to reinforce the glass fibers and protect the strands’ mechanical integrity during processing and composite manufacture. Sizing treatments compatible with olefin metathesis catalysts and polydicyclopentadiene composites have been described in U.S. Pat. Nos.6,890,650 and 6,436,476, the disclosures of both of which are incorporated herein by reference. However, these disclosures are based on the use of specialty silane treatments that are not commonly used in industrial glass manufacture. By comparison, the current disclosure may provide improved mechanical properties for polymer-glass composites that are sized with silanes commonly used in the industry.

[0375] Glass sizing formulations typically comprise at least one film former (typically a film forming polymer), at least one silane, and at least one lubricant. Any components of a sizing formulation that do not interfere with or substantially decrease the effectiveness of the metathesis catalyst or olefin polymerization reaction are considered to be compatible with the current disclosure and may generally be used herein.

[0376] Film formers that are compatible with ROMP catalysts include epoxies, polyesters, polyurethanes, polyolefins, and / or polyvinyl acetates. Other common film formers that do not adversely affect the performance of the olefin metathesis catalyst may also be used. Film formers are typically used as nonionic, aqueous emulsions. More than one film former may be used in a given sizing formulation, to achieve a desired balance of glass processability and composite mechanical properties.

[0377] More particularly, the film former may comprise a low molecular weight epoxy emulsion, defined as an epoxy monomer or oligomer with an average molecular weight per epoxide group (EEW) of less than 500, and / or a high molecular weight epoxy emulsion, defined as an epoxy monomer or oligomer with an average molecular weight per epoxide group (EEW) of greater than 500. Examples of suitable low molecular weight products include aqueous epoxy emulsions produced by Franklin International, including Franklin K8-0203 (EEW 190) and Franklin E-102 (EEW 225-275). Other examples of low molecular weight epoxy emulsions are available from Hexion, including EPI-REZ™ 3510-W-60 (EEW 185-215), and EPI-REZ™ 3515-W-60 (EEW 225-275). Further examples of low molecular weight epoxy emulsions are available from COIM, including Filco 309 (EEW 270) and Filco 306 (EEW 330). Further examples of low molecular weight epoxy emulsions are available from DSM, including Neoxil®965 (EEW 220-280) and Neoxil®4555 (EEW 220-260). Examples of suitable high molecular weight epoxy emulsion products include epoxy emulsions produced by Hexion, including EPI-REZ™ 3522-W-60 (EEW 615-715).

[0378] Aqueous emulsions of modified epoxies, polyesters, and polyurethanes may also be used in the film former. Examples of suitable modified epoxy products include emulsions produced by DSM, including Neoxil®2626 (a plasticized epoxy with an EEW of 500-620), Neoxil®962 / D (an epoxy-ester with an EEW of 470-550), Neoxil®3613 (an epoxy-ester with an EEW of 500-800), Neoxil®5716 (an epoxy-novolac with an EEW of 210-290), Neoxil®0035 (a plasticized epoxy-ester with an EEW of 2500), and Neoxil®729 (a lubricated epoxy with an EEW of 200-800). Further examples of modified epoxy emulsions are available from COIM, including Filco 339 (an unsaturated polyester-epoxy with an EEW of 2000) and Filco 362 (an epoxy-ester with an EEW of 530). Examples of suitable polyester products include emulsions produced by DSM, including Neoxil®954 / D, Neoxil®2635, and Neoxil®4759 (unsaturated bisphenolicpolyesters). Additional suitable products from DSM include Neoxil®9166 and Neoxil®968 / 60 (adipate polyesters). Further examples of suitable products include emulsions produced by COIM, including Filco 354 / N (unsaturated bisphenolic polyester), Filco 350 (unsaturated polyester), and Filco 368 (saturated polyester). Examples of suitable polyurethane products include emulsions produced by Bayer Material Science, including Baybond®330 and Baybond®401.

[0379] The film former may also comprise polyolefins or polyolefin-acrylic copolymers, polyvinylacetates, modified polyvinylacetates, or polyolefin-acetate copolymers. Suitable polyolefins include, but are not limited to, polyethylenes, polypropylenes, polybutylenes, and copolymers thereof, and the polyolefins may be oxidized, maleated, or otherwise treated for effective film former use. Examples of suitable products include emulsions produced by Michelman, including Michem®Emulsion 91735, Michem®Emulsion 35160, Michem®Emulsion 42540, Michem®Emulsion 69230, Michem®Emulsion 34040M1, Michem®Prime 4983R, and Michem®Prime 4982SC. Examples of suitable products include emulsions produced by HB Fuller, including PD 708H, PD 707, and PD 0166. Additional suitable products include emulsions produced by Franklin International, including Duracet®637. Additional suitable products include emulsions produced by Celanese, including Vinamul®8823 (plasticized polyvinylacetate), Dur-O- Set®E-200 (ethylene-vinyl acetate copolymer), Dur-O-Set®TX840 (ethylene-vinyl acetate copolymer), and Resyn®1971 (epoxy-modified polyvinylacetate).

[0380] While not limited thereto, preferred film formers include low- and high-molecular weight epoxies, saturated and unsaturated polyesters, and polyolefins, such as Franklin K80-203, Franklin E-102, Hexion 3510-W-60, Hexion 3515-W-60, and Michelman 35160.

[0381] Nonionic lubricants may also be added to the sizing composition. Suitable nonionic lubricants that are compatible with ROMP compositions include esters of polyethylene glycols and block copolymers of ethylene oxide and propylene oxide. More than one nonionic lubricant may be used in a given sizing formulation if desired, e.g., to achieve a desired balance of glass processability and composite mechanical properties.

[0382] Suitable lubricants may contain polyethylene glycol (PEG) units with an average molecular weight between 200 and 2000, preferably between 200-600. These PEG units can be esterified with one or more fatty acids, including oleate, tallate, laurate, stearate, and others. Particularly preferred lubricants include PEG 400 dilaurate, PEG 600 dilaurate, PEG 400 distearate, PEG 600 distearate, PEG 400 dioleate, and PEG 600 dioleate. Examples of suitable products include compounds produced by BASF, including MAPEG®400 DO, MAPEG®400 DOT, MAPEG®600 DO, MAPEG®600 DOT, and MAPEG®600 DS. Additional suitable products include compounds produced by Zschimmer & Schwarz, including Mulsifan 200 DO, Mulsifan 400 DO, Mulsifan 600 DO, Mulsifan 200 DL, Mulsifan 400 DL, Mulsifan 600 DL, Mulsifan 200 DS, Mulsifan 400 DS, and Mulsifan 600 DS. Additional suitable products include compoundsproduced by Cognis, including Agnique®PEG 300 DO, Agnique®PEG 400 DO, and Agnique®PEG 600 DO.

[0383] Suitable nonionic lubricants also include block copolymers of ethylene oxide and propylene oxide. Examples of suitable products include compounds produced by BASF, including Pluronic®L62, Pluronic®L101, Pluronic®P103, and Pluronic®P105.

[0384] Cationic lubricants may also be added to the sizing composition. Cationic lubricants that are compatible with ROMP include modified polyethyleneimines, such as Emery 6760L produced by Pulcra Chemicals.

[0385] Silane coupling agent may optionally be added to the sizing composition, non-limiting examples including, methacrylate, acrylate, amino, or epoxy functionalized silanes along with alkyl, alkenyl, and norbornenyl silanes.

[0386] Optionally, the sizing composition may contain one or more additives for modifying the pH of the sizing resin. One preferred pH modifier is acetic acid.

[0387] The sizing composition may optionally contain other additives useful in glass sizing compositions. Such additives may include emulsifiers, defoamers, cosolvents, biocides, antioxidants, and additives designed to improve the effectiveness of the sizing composition. The sizing composition can be prepared by any method and applied to substrate materials for use herein, such as glass fibers or fabric, by any technique or method.

[0388] Preferably, the metathesis reactions disclosed herein are carried out under a dry, inert atmosphere. Such an atmosphere may be created using any inert gas, including such gases as nitrogen and argon. The use of an inert atmosphere is optimal in terms of promoting catalyst activity, and reactions performed under an inert atmosphere typically are performed with relatively low catalyst loading. The reactions disclosed herein may also be carried out in an oxygen-containing and / or a water-containing atmosphere, and the reactions may be carried out under ambient conditions. The presence of oxygen or water in the reaction may, however, necessitate the use of higher catalyst loadings as compared with reactions performed under an inert atmosphere. Where the vapor pressure of the reactants allows, the reactions disclosed herein may also be carried out under reduced pressure.

[0389] The reactions disclosed herein may be carried out in a solvent, and any solvent that is inert towards cross-metathesis may be employed. Generally, solvents that may be used in the metathesis reactions include organic, protic, or aqueous solvents, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof. Example solvents include benzene, toluene, p-xylene, methylene chloride, 1,2-dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, methanol, ethanol, water, or mixtures thereof. Preferably, the reactions disclosed herein are carried out neat, i.e., without the use of a solvent.

[0390] It will be appreciated that the temperature at which a metathesis reaction according to methods disclosed herein is conducted can be adjusted as needed, and may be at least about -78 ºC, -40 ºC, -10 ºC, 0 ºC, 10 ºC, 20 ºC, 25 ºC, 35 ºC, 50 ºC, 70 ºC, 100 ºC, or 150 ºC, or the temperature may be in a range that has any of these values as the upper or lower bounds. Preferably, the reactions are carried out at a temperature of at least about 35 ºC, or the reactions are carried out at a temperature of at least about 50 ºC. Methods for Formulating the Coating Compositions

[0391] One embodiment, as depicted FIG.1, is directed to a method for formulating a composition comprising cyclic olefin monomers and one or more additives, the method comprising one or more of the following steps, conducted using a formulating system: i) evacuating a vessel; ii) purging the vessel with nitrogen gas, wherein the vessel is subsequently maintained under a nitrogen atmosphere at a pressure ranging from 0 to 20 psig or under vacuum pressure ranging from −1 to −14.5 psig, and wherein the temperature is set within a range of 10°C to 100°C; iii) introducing one or more liquid cyclic olefin monomers into the vessel; iv) introducing one or more additives in an amount ranging from 0.01 wt% to 80 wt% relative to the monomers, optionally added directly into the vessel, into a recirculation loop, or into the final packaging of the formulated composition; v) mixing the contents of the vessel for a duration ranging from 0.1 to 24 hours using one or more of the following: in-line mixers, agitators, pumps in the recirculation loop, or tank agitators; degassing the vessel by applying vacuum pressure ranging from −1 to −14.5 psig to remove dissolved or trapped gases; and vi) offloading the formulated composition from the vessel.

[0392] Some embodiments of the disclosure are directed to a formulating system for preparing a composition comprising cyclic olefin monomers and one or more additives, the system comprising one or more of the following components: i) a supply of cyclic olefin monomers, including but not limited to one or more of dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), norbornene, and their derivatives; ii) one or more additives selected from the group consisting of antioxidants, polymers, and other solid or liquid additives, wherein the additives include, but are not limited to, Butylated Hydroxytoluene (BHT), Styrene-Ethylene-Butylene-Styrene (SEBS), Ethylene Propylene Diene Monomer (EPDM), trans- polyoctenamer rubber (TOR), polybutene (polyisobutylene), methylene diphenyl diisocyanate (MDI), cycloaliphatic hydrocarbon resin, and color-inducing pigments and dyes; iii) a vessel configured to receive one or more cyclic olefin monomers in liquid form and to mix the monomers with one or more additives, the vessel further comprising one or more of the following: a) one or more circulation loops fluidly connected to the vessel and comprising one or more pumps or in-line mixers configured to circulate and homogenize the composition through the vessel, wherein the pumps are arranged in series or in parallel; b) a solid additive introduction system comprising one or more hoppers configured tointroduce solid additives into the vessel or into the circulation loop; c) a mechanical agitation system selected from the group consisting of top-entry agitators, side-entry agitators, bottom-entry agitators, and high-shear disintegrators; d) a system operable under one or more of the following conditions: air, inert atmosphere, or vacuum, and further comprising vapor balancing and emission control features; and e) a temperature control system configured to maintain the system temperature within a predetermined range.

[0393] Unless otherwise indicated, the disclosure is not limited to specific reactants, substituents, catalysts, metal carbene olefin metathesis catalysts, catalyst compositions, olefins, cyclic olefin compositions, coating compositions, reaction conditions, or the like, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not to be interpreted as being limiting. Methods of Applying the Coating Compositions

[0394] The disclosure also relates to applying the coating composition to a substrate material to be coated / protected by several methods. These methods include without limitation: spraying, brushing, dipping, or rolling.

[0395] In one embodiment, the coating composition can be applied on the substrate material to be coated with a paint brush.

[0396] In one embodiment, the coating composition can be sprayed on the substrate material to be coated with a film spray gun, a conventional spray gun, a plural component sprayer, a high volume

[0397] low pressure (HVLP) or an airless applicator.

[0398] It is to be understood that while it has been described in conjunction with specific embodiments thereof, the description above as well as the examples that follow are intended to illustrate and not limit the scope of the invention. Other aspects, advantages, and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention pertains.

[0399] The disclosure also relates to applying the coating composition to a substrate material to be coated / protected by several methods. These methods include without limitation: spraying, brushing, dipping, or rolling. Methods of Applying the Coating Compositions to Steel Substrates

[0400] In exemplary embodiments, the methods disclosed herein serve a dual purpose. First, the methods of said exemplary embodiments disclosed herein serve to coat a steel substrate, such as a steel pipe, pipelines, and field joints, with an anti-corrosion protective and thermal insulation coating for pipes,pipelines, and field joints. Second, the methods of said exemplary embodiments disclosed herein further serve the purpose of eliminating the need for a separate anti-corrosion protective coating process, such as a fusion bonded epoxy coating, and any additional preparation associated with the protective coating process. Eliminating the need for a separate anti-corrosion coating process is especially impactful in reducing the number of overall steps and thus the time required to prepare field joints for service.

[0401] With regard to the second purpose, reference is made to the accompanying figures. As depicted in FIG.2, in a typical field joint process using an fusion bonded epoxy (FBE) anti-corrosion composition, the following steps are practiced: 1) abrasive blast; 2) chamfer prep; 3) FBE / chemically modified polypropylene (CMPP) application; 4) field-joint infill application; and 5) finish and trim. This process can take 22 to 27 minutes. In contrast, a field process using the compositions disclosed herein include the following steps: 1) abrasive blast; 2) chamfer prep; 3) field joint infill application; and 4) finish and trim. The elimination of the FBE / CMPP step results in a process time of 17 to 21 minutes, a savings of 5 to 6 minutes. This savings multiplies when one considers the hundreds if not thousands of field joint processes that are present on a standard pipeline.

[0402] Methods of exemplary embodiments disclosed herein are also beneficial in pipeline preparation. The resin formulations and compositions disclosed herein may contain an adhesion promoter that aids in adhesion of the resin to the steel surface allowing for the efficient application of the dual-purpose anti- corrosion protective and thermal insulation coating.

[0403] Additionally, according to exemplary embodiments compositions without an adhesion promoter can be used in conjunction with an adhesion promoter containing primer.

[0404] According to embodiments, the compositions are cast onto field joints and flowlines to a thickness of 1-4 inches. Thermal conductivity K-values are < 0.175 W / m*K (less than 0.172, less than 0.160).

[0405] Flowline Procedures according to an Embodiment:

[0406] According to an exemplary embodiment, a procedure for coating a flowline involves the following. The steel pipe is first heated above dew-point temperature and then grit blasted with steel shot / grit media to obtain a fresh steel surface with an Anchor profile typically in the 3.0-4.5 mils. (76-114.3 microns) range when measured with Testex Tape. In certain embodiments, the surface is New White (SSPC-SP-10, NACE #2, ISO 8501-1 Sa 2.5) or better. Then the pipe undergoes a secondary induction heating step to bring the pipe up to the desired temperature. Next the pipe is transferred to the clamshell style mold and prepared for the casting-based molding operation. Then the catalyzed resin is introduced to the mold through open topcavity using meter / mix equipment. According to certain exemplary embodiments, the entire length of the pipe is coated. EXEMPLARY EMBODIMENTS

[0407] E1. A method of coating a steel substrate with a coating composition, comprising, consisting essentially of, or consisting of: contacting the coating composition with at least a portion of at least one surface of the steel substrate; and optionally, subjecting the coating composition to conditions effective to polymerize the coating composition to form a polymer (e.g., a ROMP polymer) or a polymer composite (e.g., a ROMP polymer composite); wherein the coating composition comprises, consists essentially of, or consists of: a) a cyclic olefin composition; b) a catalyst composition comprising, consisting essentially of, or consisting of at least one catalyst selected from an organometallic complex, a free radical initiator, a cationic initiator, and mixtures thereof; c) optionally, at least one adhesion promoter; d) optionally, at least one plasticizer compound; e) optionally, at least one rubber toughener compound and f) optionally, at least one coating additive; wherein the method does not include a fusion bonded epoxy (FBE) and / or a chemically modified polypropylene (CMPP) application.

[0408] E2. The method of E1, wherein t...

Claims

The claimed invention is:

1. A method of coating a steel substrate with a coating composition, comprising: contacting the coating composition with at least a portion of at least one surface of the steel substrate; and optionally, subjecting the coating composition to conditions effective to polymerize the coating composition to form a polymer or a polymer composite. wherein the coating composition comprises: a) a cyclic olefin composition; b) a catalyst composition comprising, consisting essentially of, or consisting of at least one catalyst selected from an organometallic complex, a free radical initiator, a cationic initiator, and mixtures thereof; c) optionally, at least one adhesion promoter; d) optionally, at least one plasticizer compound; e) optionally, at least one rubber toughener compound and f) optionally, at least one coating additive; wherein the method does not include a fusion bonded epoxy (FBE) and / or a chemically modified polypropylene (CMPP) application.

2. The method of claim 1, wherein the cyclic olefin composition comprises: at least one cyclic olefin selected from Formulae (I), (II), and (III); optionally at least one linear olefin of Formula (IV); wherein the cyclic olefin of Formulae (I), (II), and (III), and the linear olefin of Formula (IV) have the following structures:, , , and , wherein: Rais H, optionally substituted linear or branched C1-24alkyl, optionally substituted linear or branched C2-24alkenyl, halogen, -C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, -CN, -NO2, -CF3, -P(O)(ORh)2, -OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, -CH2-(optionally substitutedheterocycle), optionally substituted C3-10cycloalkyl, -CH2-(optionally substituted C3-10cycloalkyl), optionally substituted C5-24aryl, -CH2-(optionally substituted C5-24aryl), optionally substituted C3-12cycloalkenyl, -CH2-(optionally substituted C3-12cycloalkenyl), C(Rh)(Ri)COORj, -C(Rh)(Ri)C(O)H, - C(Rh)(Ri)C(O)Rk, -C(Rh)(Ri)CRl(ORm)(ORn), -C(Rh)(Ri)C(O)NRoRp, -C(Rh)(Ri)C(O)NRoORn, or; Rbis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted linear or branched C2-24 alkenyl, halogen, -C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, -CN, -NO2, -CF3, -P(O)(ORh)2, -OP(O)(ORh)2, -Si(ORk)3 -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, spiro optionally substituted heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C3-10 cycloalkyl, - CH2-(optionally substituted C3-10 cycloalkyl), optionally substituted C5-24 aryl, -CH2-(optionally substituted C5-24 aryl), optionally substituted C3-12 cycloalkenyl, -CH2-(optionally substituted C3-12 cycloalkenyl),Rcis H, optionally substituted linear or branched C1-24alkyl, optionally substituted linear or branched C2-24alkenyl, halogen, - C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, CN, NO2, -CF3, -P(O)(ORh)2, - OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C3-10cycloalkyl, -CH2-(optionally substituted C3-10cycloalkyl), optionally substituted C5-24aryl, -CH2-(optionally substituted C5-24aryl), optionally substituted C3-12cycloalkenyl, -CH2-(optionally substituted C3-12cycloalkenyl), C(Rh)(Ri)COORj, -C(Rh)(Ri)C(O)H, - C(Rh)(Ri)C(O)Rk, -C(Rh)(Ri)CRl(ORm)(ORn), -C(Rh)(Ri)C(O)NRoRp, or -C(Rh)(Ri)C(O)NRoORn; Rdis H, optionally substituted linear or branched C1-24alkyl, optionally substituted linear or branched C2-24alkenyl, halogen, - C(O)Rf, -CH2-C(O)Rf, - ORg, -CH2-ORg, CN, NO2, -CF3-P(O)(ORh)2, - OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C3-10cycloalkyl, -CH2-(optionally substituted C3-10cycloalkyl), optionally substituted C5-24aryl, -CH2-(optionally substituted C5-24aryl), optionally substituted C3-12cycloalkenyl, -CH2-(optionally substituted C3-12cycloalkenyl), C(Rh)(Ri)COORj, -C(Rh)(Ri)C(O)H, - C(Rh)(Ri)C(O)Rk, -C(Rh)(Ri)CRl(ORm)(ORn), -C(Rh)(Ri)C(O)NRoRp, or -C(Rh)(Ri)C(O)NRoORn; each Rsis independently optionally substituted linear or branched C1-24alkyl, optionally substituted linear or branched C2-24alkenyl, halogen, -C(O)Rf, -CH2-C(O)Rf, -ORg, -CH2-ORg, -CN, -NO2, -CF3, - P(O)(ORh)2, -OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, -CH2-(optionally substituted heterocycle), optionally substituted C3-10 cycloalkyl, -CH2-(optionally substituted C3-10 cycloalkyl), optionally substituted C5-24 aryl, -CH2-(optionally substituted C5-24 aryl), optionally substituted C3-12 cycloalkenyl, -CH2-(optionally substituted C3-12 cycloalkenyl), C(Rh)(Ri)COORj, -C(Rh)(Ri)C(O)H, - C(Rh)(Ri)C(O)Rk, -C(Rh)(Ri)CRl(ORm)(ORn), -C(Rh)(Ri)C(O)NRoRp, or -C(Rh)(Ri)C(O)NRoORn;t is 0, 1, 2, 3, 4, 5, or 6; Rfis OH, ORk, NRgRh, optionally substituted linear or branched C1-24alkyl, optionally substituted C3-10cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl, or optionally substituted C3-12cycloalkenyl; Rgis H, optionally substituted linear or branched C1-24alkyl, optionally substituted C3-10cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl, optionally substituted linear or branched C2-24alkenyl, -C(O)-(optionally substituted C5-24aryl), -C(O)-(optionally substituted linear or branched C2-24alkenyl), or optionally substituted C3-12cycloalkenyl; Rhis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl, or optionally substituted C3-12 cycloalkenyl; Riis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl, or optionally substituted C3-12 cycloalkenyl; Rjis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl, or optionally substituted C3-12 cycloalkenyl; Rkis optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl, or optionally substituted C3-12 cycloalkenyl; Rlis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl, or optionally substituted C3-12 cycloalkenyl; Rmis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl, or optionally substituted C3-12 cycloalkenyl; Rnis H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24 aryl, or optionally substituted C3-12 cycloalkenyl; Rois H, optionally substituted linear or branched C1-24 alkyl, optionally substituted C3-10 cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl, or optionally substituted C3-12cycloalkenyl;Rpis H, optionally substituted linear or branched C1-24alkyl, optionally substituted C3-10cycloalkyl, optionally substituted heterocycle, optionally substituted C5-24aryl, or optionally substituted C3-12cycloalkenyl; and z is 0, 1, 2, or 3.

3. The method of claim 2, wherein: Rais H, optionally substituted linear or branched C1-12alkyl, optionally substituted linear or branched C2-6alkenyl, halogen, -C(O)Rf, -ORg, -CN, -NO2, -CF3, -P(O)(ORh)2, -OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, optionally substituted C3-10 cycloalkyl, optionally substituted C6 aryl, optionally substituted C cycloalkenyl, or-10 3-12 ; Rbis H, optionally substituted linear or branched C1-12 alkyl, optionally substituted linear or branched C2-6 alkenyl, halogen, -C(O)Rf, -ORg, -CN, -NO2, -CF3, -P(O)(ORh)2, -OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, optionally substituted C3-10 cycloalkyl, optionally substituted C6-10aryl, optionally substituted C3-12cycloalkenyl, or; Rcis H, optionally substituted linear or branched C1-12alkyl, optionally substituted linear or branched C2-6alkenyl, halogen, -C(O)Rf, -ORg, -CN, -NO2, -CF3, -P(O)(ORh)2, -OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, optionally substituted C3-10cycloalkyl, optionally substituted C6-10aryl, optionally substituted C3-12cycloalkenyl; Rdis H, optionally substituted linear or branched C1-12alkyl, optionally substituted linear or branched C2-6alkenyl, halogen, -C(O)Rf, -ORg, -CN, -NO2, -CF3, -P(O)(ORh)2, -OP(O)(ORh)2, -S(O)2ORh, -OS(O)2Rh, optionally substituted heterocycle, optionally substituted C3-10cycloalkyl, optionally substituted C6-10aryl, optionally substituted C3-12cycloalkenyl; t is 0; Rfis OH, ORk, NRgRh, optionally substituted C1-12alkyl, optionally substituted C3-8cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl, or optionally substituted C3-12cycloalkenyl; Rgis H, optionally substituted C1-12alkyl, optionally substituted C3-8cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl, or optionally substituted C3-12cycloalkenyl; Rhis H, optionally substituted C1-12 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl, or optionally substituted C3-12 cycloalkenyl; z is 2; Riis H, optionally substituted C1-12 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl, or optionally substituted C3-12 cycloalkenyl;Rjis H, optionally substituted C1-12alkyl, optionally substituted C3-8cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl, or optionally substituted C3-12cycloalkenyl; Rkis optionally substituted C1-12alkyl, optionally substituted C3-8cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl, or optionally substituted C3-12cycloalkenyl; Rlis H, optionally substituted C1-12alkyl, optionally substituted C3-8cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl, or optionally substituted C3-12cycloalkenyl; Rmis H, optionally substituted C1-12alkyl, optionally substituted C3-8cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10aryl, or optionally substituted C3-12cycloalkenyl; Rnis H, optionally substituted C1-12 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl, or optionally substituted C3-12 cycloalkenyl; Rois H, optionally substituted C1-12 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl, or optionally substituted C3-12 cycloalkenyl; and Rpis H, optionally substituted C1-12 alkyl, optionally substituted C3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C6-10 aryl, or optionally substituted C3-12 cycloalkenyl.

4. The method of claim 2 or claim 3, wherein: the at least one cyclic olefin of Formula (I) is present in an amount ranging from 0 to 100 wt.% , based on the total weight of the cyclic olefin composition; the at least one cyclic olefin of Formula (II) is present in an amount ranging from 0 to 100 wt.% , based on the total weight of the cyclic olefin composition; the at least one cyclic olefin of Formula (III) is present in an amount ranging from 0 to 100 wt.% , based on the total weight of the cyclic olefin composition; and the at least one linear olefin of Formula (IV) is present in an amount ranging from 0 to 20 wt.% , based on the total weight of the cyclic olefin composition.

5. The method of claim 1, wherein the catalyst is the organometallic complex and is a metal carbene olefin metathesis catalyst.

6. The method of claim 5, wherein the metal carbene olefin metathesis catalyst is a Group 8 transition metal complex having the structure of formula (I):wherein: M is a Group 8 transition metal; L1, L2, and L3are neutral electron donor ligands; n is 0 or 1, such that L3may or may not be present; m is 0, 1, or 2; k is 0 or 1; X1and X2are anionic ligands; and R1and R2are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, wherein any two or more of X1, X2, L1, L2, L3, R1, and R2can be taken together to form one or more cyclic groups, and further wherein any one or more of X1, X2, L1, L2, L3, R1, and R2is optionally attached to a support.

7. The method of claim 5, wherein the metal carbene olefin metathesis catalyst is a Group 8 transition metal complex having the structure of formula (VII):wherein: M is a Group 8 transition metal; X1and X2are anionic ligands; L1is a neutral electron donor ligand;Y is a heteroatom selected from N, O, S, and P; R5, R6, R7, and R8are each, independently, selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or -A-Fn, wherein A is a divalent hydrocarbon moiety selected from alkylene and arylalkylene, wherein the alkyl portion of the alkylene and arylalkylene groups can be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the of arylalkylene can be substituted or unsubstituted, and wherein hetero atoms and / or functional groups are optionally present in either the aryl or the alkyl portions of the alkylene and arylalkylene groups, and Fn is a functional group; and any combination of R5, R6, R7, and R8can be linked to form one or more cyclic groups; n is 1 or 2, such that n is 1 for the divalent heteroatoms O or S, and n is 2 for the trivalent heteroatoms N or P; and Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, functionalized aryl where the functional group may independently be one or more or the following: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec- butyl, t-butyl, neopentyl, benzyl, phenyl and trimethylsilyl; and wherein any combination or combinations of X1, X2, L1, V, Z, R5, R6, R7, and R8are optionally linked to a support.

8. The method of any one of claims 1-7, wherein the at least one adhesion promoter is present and is selected from an acid-functionalized polyolefin, a compound containing at least two isocyanate groups, a composition comprising at least one compound containing at least two isocyanate groups and at least one compound comprising a heteroatom-containing functional group with a metathesis active olefin, at least one polyoctenamer, and mixtures thereof.

9. The method of claim 8, wherein the at least one adhesion promoter composition is present in an amount ranging from 0.001 to 50 phr.

10. The method of any one of claims 1-9, wherein the at least one plasticizer compound is present and is selected from a polyisobutylene, polybutene oil, a polyalphaolefin oil, a hydrocarbon resin, and mixtures thereof.

11. The method of claim 10, wherein the at least one plasticizer compound is present in an amount ranging from 1 to 40 wt.%, based on the total weight of the coating composition.

12. The method of any one of claims 1-11, wherein the at least one rubber toughener compound is present and is selected from a poly(styrene-ethylene-butylene-styrene), an ethylene-propylene copolymer, an ethylene-propylene diene terpolymer, and mixtures thereof.

13. The method of claim 12, wherein the at least one rubber toughener compound is present in an amount ranging from 0.01 to 30 wt.%, based on the total weight of the coating composition.

14. The method of any one of claims 1-13, wherein the at least one coating additive is present and is selected from a group consisting of a gel modification additives, impact modifiers, hardness modulators, antioxidants, antiozonants, fillers, binders, coupling agents, thixotropes, rheology modifiers, biocides, dispersants, wetting agents, additional plasticizers, pigments, chain terminating agents, flame retardants, dyes, fibers, reinforcement materials, UV absorbers, UV light stabilizers, film formers, lubricants, additional adhesion promoters, and mixtures thereof.

15. The method of claim 14, wherein the at least one coating additive is present in an amount ranging from 0.0001 to 50 wt.%, based on the total weight of the coating composition.

16. The method of any one of claims 1-15, wherein: the cyclic olefin of Formula (I) is selected from ENB-DDA, HNB-DDA, and mixtures thereofENB-DDA HNB-DDA; the cyclic olefin of Formula (II) is selected from HENB, NBCbSi, ONB, NB-methanol, NB- dimethanol, NB-epoxide, NB-triethoxysilane, NB-Fluorocarbon (1), NB-fluorocarbon (2), NB- fluorocarbon (3), and mixtures thereofNB-fluorocarbon (2) NB-fluorocarbon (3); and the cyclic olefin of Formula (III) is selected from tricyclopentadiene (TCPD), dicyclopentadiene (DCPD), and mixtures thereof.

17. The method of any one of claims 1-16, wherein the at least one coating additive is present and is selected from at least one inorganic filler.

18. The method of claim 17, wherein the inorganic filler is selected from aluminum powder or alloys thereof, aluminum flakes or alloys thereof, micaceous iron oxide, mica, glass fibers, glass flakes, wollastonite calcium carbonate, silica, talc, and mixtures thereof.

19. The method of claim 18, wherein the inorganic filler present in an amount ranging from 0.001 to 95 wt.% , based on the total weight of the coating composition.

20. The method of any one of claims 1-19, wherein the cyclic olefin composition comprises, consists essentially of, or consists of at least one substituted or unsubstituted multiunsaturated cyclic olefin, wherein the at least one multiunsaturated cyclic olefin is substituted or unsubstituted, and wherein the cyclic olefin composition does not contain, or is substantially free of, a monounsaturated cyclic olefin selected from 5-octyl-2-norbornene (ONB).

21. The method of claim 20, wherein the at least one cyclic olefin containing multiunsaturation is selected from dicyclopentadiene, tricyclopentadiene, cyclopentadiene tetramer, cyclopentadiene pentamer, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, 5-butenyl-2-norbornene, and mixtures thereof; and wherein the at least one cyclic olefin containing monounsaturation is selected from 5-tolyl-2- norbornene, 5-phenyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, 5-dodecyl-2-norbornene, and mixtures thereof.

22. The method of any one of claims 1-21, wherein the steel substrate is selected from a carbon steel substrate and a steel pipe.

23. The method of any one of claims 1-22, wherein the method coats a pipeline field joint.

24. The method of any one of claims 1-23, wherein the coating composition is subjected to conditions effective to polymerize the coating composition to form a polymer or a polymer composite.

25. A ROMP polymer, prepared by the method of claim 24.

26. A ROMP polymer composite, prepared by the method of claim 24.

27. A method of coating, encasing, or insulating at least a portion of at least one surface of a steel substrate with the ROMP polymer of claim 25 or the ROMP polymer composite of claim 26, comprising: combining the cyclic olefin composition, the catalyst composition, optionally, the at least one adhesion promoter, optionally, the at least one plasticizer compound, optionally, the at least one rubber toughener compound, and, optionally, the at least one coating additive to form the coating composition; contacting the coating composition with at least a portion of at least one surface of the steel substrate; and subjecting the coating composition to conditions effective to polymerize the coating composition to form the ROMP polymer of claim 25 or the ROMP polymer composite of claim 26.

28. An article of manufacture prepared by the method of any one of claims 1-24 and 27.

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