Coating compositions based on cyclic olefins with adhesion promoters

Abstract

The present invention relates to coating compositions, ROMP polymers, ROMP polymer composites and anti-corrosion materials, and methods for preventing corrosion of pipes and related equipment, structures and objects used in offshore drilling. The present invention relates to an article comprising the coating composition, a ROMP polymer, a ROMP polymer composite, and a corrosion resistant material.

Description

Cross-reference to related applications

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 491,956, filed March 23, 2023, the disclosure of which is incorporated herein by reference. Technical Field

[0002] This invention relates to compositions suitable for use as coatings. More specifically, this invention relates to compositions suitable for use as industrial coatings (e.g., anti-corrosion coatings and protective coatings). This invention also relates to compositions and methods for coating substrates. More specifically, this invention relates to coating compositions and methods for coating substrates, wherein the coating composition comprises polymeric olefins and cyclic olefins obtained through various chemical transformations. This invention also relates to methods for applying coatings to substrates.

[0003] The coating compositions of this invention can be used on a wide range of substrates, especially those used in petrochemical and chemical production operations. This invention has practical applications in the fields of polymers, materials, and manufacturing. Background Technology

[0004] Materials deteriorate due to their interaction with the environment, through mechanisms including corrosion, erosion, and other processes. Protective coatings can provide protection against the degradation of the surface properties of a wide range of substrates. Protective coatings can protect metallic substrates from corrosion, polymer and composite substrates from degradation caused by ice, acid rain, salt water, weathering, and ultraviolet radiation, and wood, concrete, and brick substrates from degradation caused by moisture penetration and degradation.

[0005] According to the National Association of Corrosion Engineers International (NACEI), corrosion is a naturally occurring phenomenon, generally defined as the deterioration of a material (usually a metal) due to a chemical or electrochemical reaction with its environment. Corrosion can cause severe damage and is costly to repair. Protective coatings are an effective means of preventing corrosion. Metal corrosion occurs through chemical or electrochemical reactions. Electrochemical corrosion is the most common form of metal corrosion. For metals (such as iron and / or steel), corrosion occurs and rust begins when they come into contact with oxygen and moisture (e.g., humidity, steam, immersion).

[0006] Exposure to water (such as groundwater, seawater, atmospheric moisture, etc.), corrosive chemicals, ultraviolet radiation, ozone, and other harmful factors can cause the surface of unprotected objects (such as cars, buses, ships, trains, other vehicles, airplanes, bridges, signs, buildings, sidewalks, roads, underground pipes and equipment, and petrochemical and chemical production equipment) to change in quality over time, resulting in deterioration or failure of the objects.

[0007] Corrosion is very common and maintenance costs are very high, so it is recommended to take effective preventive measures when carrying out corrosion prevention.

[0008] One of the best ways to prevent corrosion is to apply a protective coating. This type of coating protects the substrate by preventing it from coming into contact with harsh environments (atmosphere, chemicals, etc.).

[0009] Therefore, there has been a demand for coating compositions (e.g., anti-corrosion coating compositions) that provide surface protection to objects from corrosive materials or destructive environmental conditions for many years.

[0010] Most pipes and pipelines used in petrochemical and chemical production operations are made of metal, typically a certain grade of steel, and many are covered with an insulation layer. If the insulation covering the pipes or pipelines is damaged during installation or deteriorates over time, the lower surface of the pipes or pipelines is at risk of direct contact with the atmospheric environment, leading to a range of problems, including premature pipe or pipeline failure and increased maintenance and / or replacement costs.

[0011] Therefore, it is necessary to apply an undercoat between the pipe or pipeline surface and the insulation material to act as a corrosion barrier in case the insulation material is damaged or degraded. Based on this need, various coating compositions have been developed for protecting steel pipes and structures.

[0012] Epoxy resin-based, polyamide-based, and polyurethane-based coating compositions have been widely used to prevent corrosion of steel pipes and structures.

[0013] The industry typically relies on 2K epoxy resins; however, liquid two-component epoxy resins usually require a long curing period and are not conducive to achieving rapid coating operations that facilitate production.

[0014] Despite advancements in coating compositions, particularly in anti-corrosion coating compositions for coating pipes and structures, there remains a persistent need for further improvements. Summary of the Invention

[0015] This invention aims to solve one or more of the aforementioned problems and relates to coating compositions and methods for coating substrates using the coating compositions of this invention. The coating compositions of this invention can be used for a variety of purposes, including but not limited to decoration, improving the barrier properties of packaging, protecting substrate materials and / or protecting substrate surfaces from quality changes or degradation over time due to environmental exposure; said substrate materials can be: metals (e.g., steel, stainless steel, aluminum, copper, iron, nickel, titanium, silver), or non-metals (e.g., glass, concrete, ceramics, porcelain, brick, stone, plastics, rubber, wood, fabrics), or composite materials (e.g., reinforced plastics, electronic components). In other words, the coating compositions of this invention can be applied to the surface of a substrate to provide protection, including corrosion protection, preventing the substrate material and / or substrate surface from deteriorating due to environmental exposure.

[0016] The coating composition of the present invention can also be used as an adhesive.

[0017] In particular, this invention provides coating compositions for coating pipes, pipelines, and structures used in petrochemical and chemical production operations to provide a corrosion barrier against degradation of the underlying pipes, pipelines, equipment, structures, or objects due to environmental exposure and other corrosive materials. The coatings of this invention form a durable protective lining, helping to protect pipelines from the destructive effects of corrosion. Currently, pipeline coating is one of the most reliable methods of corrosion protection used in industry.

[0018] Compared with existing materials used to provide protective coatings for pipes, pipelines, equipment, structures and objects used in petrochemical and chemical production operations, the coating compositions of the present invention have many advantages.

[0019] In particular, the coating compositions of the present invention can be formulated according to various application conditions and requirements.

[0020] As an example of its advantages, the coating composition of the present invention is designed to provide long-term corrosion inhibition by acting as an impermeable barrier to oxygen, water, ions, etc. The coating composition of the present invention is non-porous. The coating composition of the present invention can be applied and cured under high humidity conditions and at lower temperatures than conventional coatings.

[0021] As another example of an advantage, the coating compositions of the present invention can be formulated to have a wide range of adjustable curing times.

[0022] For example, the coating compositions of the present invention can be formulated as fast-curing (“rapid-curing”) types, so that they quickly reach a dry-to-touch state after being applied to a substrate surface. The rapid-curing coating compositions of the present invention have a rapid dry-to-touch time of less than 20 minutes, preferably less than 10 minutes, more preferably less than 1 minute, and even dry within seconds of application to the surface. Articles coated with the rapid-curing compositions of the present invention reach a workable state and form a durable coating in less than 60 minutes after application, preferably less than 30 minutes, more preferably less than 10 minutes or less. In contrast, liquid epoxy resins typically require several hours to cure.

[0023] As another example of its advantages, the coating compositions of the present invention are solvent-free.

[0024] As another example of its advantages, the coating compositions of the present invention are resistant to cracking and delamination in hot / humid water environments.

[0025] The coating composition of the present invention can be prepared by different chemical conversion methods and can be processed by a variety of methods.

[0026] The coating composition can be cured by ring opening metathesis polymerization (ROMP), which involves reacting at least one cyclic olefin with at least one metal carbene olefin metathesis catalyst.

[0027] More specifically, the present invention relates to a coating composition comprising, substantially comprising, or comprising the following: a) At least one olefin resin composition comprising, substantially comprising, or comprising the following: a.1) At least one olefin component, said olefin component comprising: a.1.1) At least one cyclic olefin, said cyclic olefin being selected from the group consisting of formulas (I), (II) and (III) as defined herein; and a.1.2) Optionally, at least one linear alkene as defined in formula (IV) herein; and a.2) At least one metal carbene olefin metathesis catalyst; and a.3) Optionally, at least one thermoplastic hydrocarbon resin; b) Optionally, at least one inorganic filler; c) At least one adhesion promoter; and d) Optionally, at least one paint additive. The present invention also relates to ROMP polymers or ROMP polymer composites, which include reaction products of the coating compositions of the present invention, are substantially composed of reaction products of the coating compositions of the present invention, or are composed of reaction products of the coating compositions of the present invention.

[0028] The present invention also relates to the use of ROMP polymers and / or ROMP polymer composites for coating or covering objects.

[0029] The present invention also relates to the use of ROMP polymers or ROMP polymer composites for coating or covering objects to isolate them from the surrounding environment.

[0030] The present invention also relates to using the ROMP polymer and / or ROMP polymer composites of the present invention as coating and / or covering materials.

[0031] The present invention also relates to a method for providing a ROMP polymer coating for marine applications, the method comprising the steps of: providing an object surface to be coated; providing the coating composition of the present invention; contacting the object surface with the coating composition or applying the coating composition to the object surface; and subjecting the coating composition to conditions that enable effective polymerization of the coating composition to form a ROMP polymer coating.

[0032] The present invention also relates to a coating or coating material comprising the coating composition of the present invention, a ROMP polymer or a ROMP polymer composite material, substantially composed of the coating composition of the present invention, a ROMP polymer or a ROMP polymer composite material, or composed of the coating composition of the present invention, a ROMP polymer or a ROMP polymer composite material.

[0033] The present invention also relates to a coating or covering material for coating or covering: (1) an object; (2) at least a portion of the object; and / or (3) at least a portion of at least one surface of the object; wherein the coating or covering material comprises the coating composition of the present invention, a ROMP polymer, or a ROMP polymer composite material.

[0034] The present invention also relates to the use of coating or covering materials for coating or covering the following: (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 coating or covering material comprises the coating composition of the present invention, a ROMP polymer, or a ROMP polymer composite material.

[0035] The present invention also relates to a method for coating or covering an object to isolate it from surrounding fluids, the method comprising: placing a coating or covering material between the object and the fluid, wherein the coating or covering material comprises the ROMP polymer or ROMP polymer composite material of the present invention.

[0036] The present invention also relates to a method of coating or covering the following with a coating or covering material: (1) an object; (2) at least a portion of the object; and / or (3) at least a portion of at least one surface of the object; wherein the coating or covering material is a ROMP polymer or a ROMP polymer composite material of the present invention.

[0037] The present invention also relates to a method of coating or covering: (1) an object; (2) at least a portion of the object; and / or (3) at least a portion of at least a surface of the object with a coating or covering material; said method comprising: contacting the coating composition of the present invention with (1) the object; (2) at least a portion of the object; and / or (3) at least a portion of at least a surface of the object, or applying the coating composition of the present invention to (1) the object; (2) at least a portion of the object; and / or (3) at least a portion of at least a surface of the object, and placing the coating composition under conditions that effectively promote the ROMP reaction of the coating composition to form the ROMP polymer or ROMP polymer complex of the present invention; wherein the coating or covering material is a ROMP polymer or ROMP polymer complex.

[0038] The present invention also relates to a method of applying a coating or coating material composition to an object, the method comprising: placing a mold around the object to form a cavity between an inner surface of the mold and the object; injecting a coating or coating material composition into the cavity, wherein the coating or coating material composition comprises the coating composition of the present invention; and subjecting the coating or coating material composition to conditions that effectively promote the ROMP reaction of the coating composition to form the ROMP polymer or ROMP polymer composite of the present invention.

[0039] The present invention also relates to an object, said object being at least partially coated or covered with a coating or covering material; wherein said coating or covering material includes the ROMP polymer or ROMP polymer composite material of the present invention.

[0040] The present invention also relates to an article comprising an object, wherein at least a portion of at least one surface of the object is coated with the ROMP polymer or ROMP polymer composite material of the present invention.

[0041] The present invention also relates to articles prepared by any of the methods described herein.

[0042] The embodiments described herein should not be construed as limiting. Various modifications to the form and details of the embodiments of the invention, as well as other aspects and variations of the invention, will become apparent to those skilled in the art upon consideration of the following detailed description and examples. Detailed Implementation

[0043] Terms and Definitions Unless otherwise stated, the present invention is not limited to specific reactants, substituents, catalysts, catalyst compositions, resin compositions, cycloolefins, reaction conditions, etc., as these can vary. It should also be understood that the terminology used herein is for describing particular embodiments only and should not be construed as limiting the invention.

[0044] As used in the specification and appended claims, the singular forms “a,” “an,” and “the” have a plural meaning unless the context clearly specifies otherwise. Thus, for example, “a substituent” includes a single substituent, as well as two or more substituents, etc.

[0045] As used in the specification and appended claims, the terms "for example," "for instance," "such as," or "comprising" are intended to introduce examples to further illustrate the more general subject matter. Unless otherwise stated, these examples are only for the purpose of helping to understand the invention and are not intended to be limiting in any way.

[0046] In this specification and the following claims, numerous terms will be used, which should be defined to have the following meanings: As used herein, the term "alkyl" refers to a straight-chain, branched, or cyclic saturated hydrocarbon group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, octyl, decyl, etc., and cycloalkyl (e.g., cyclopentyl, cyclohexyl, etc.), which typically, but not necessarily, contains 1 to about 24 carbon atoms, for example, 1 to about 12 carbon atoms. Typically, although not required, alkyl in this document contains 1 to about 12 carbon atoms. The term "lower alkyl" refers to an alkyl group containing 1 to 6 carbon atoms, and the term "cycloalkyl" refers to a cyclic alkyl group, typically containing 4 to 8 carbon atoms, for example, 5 to 7 carbon atoms. The term "substituted alkyl" refers to an alkyl group substituted with one or more substituents, and the terms "heteroatom-containing alkyl" and "heteroalkyl" refer to an alkyl group in which at least one carbon atom is substituted with a heteroatom. Unless otherwise stated, the terms "alkyl" and "lower alkyl" respectively include straight-chain, branched, cyclic, unsubstituted, substituted, and / or heteroatom-containing alkyl and lower alkyl.

[0047] As used herein, the term "alkylene" refers to a bifunctional linear, branched, or cyclic alkyl group, where "alkyl" has the meaning as described above.

[0048] As used herein, the term "alkenyl" refers to a straight-chain, branched, or cyclic hydrocarbon group containing 2 to 24 carbon atoms (e.g., 2 to 12 carbon atoms) and at least one double bond, such as vinyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenoyl, dodecenyl, etc. The term "lower alkenyl" refers to an alkenyl group containing 2 to 6 carbon atoms, and the term "cycloalkenyl" refers to a cyclic alkenyl group, for example, containing 5 to 8 carbon atoms. The term "substituted alkenyl" refers to an alkenyl group substituted by one or more substituents, and the terms "heteroatom-containing alkenyl" and "heteroalkenyl" refer to an alkenyl group in which at least one carbon atom is substituted by a heteroatom. Unless otherwise specified, the terms "alkenyl" and "lower alkenyl" respectively include straight-chain, branched, cyclic, unsubstituted, substituted, and / or heteroatom-containing alkenyl and lower alkenyl groups.

[0049] As used herein, the term "alkenyl" refers to a bifunctional linear, branched, or cyclic alkenyl group, with the meaning of "alkenyl" as described above.

[0050] As used herein, the term "alkynyl" refers to a straight-chain or branched hydrocarbon group containing 2 to 24 carbon atoms (e.g., 2 to 12 carbon atoms) and at least one triple bond, such as ethynyl, n-propynyl, etc. The term "lower alkynyl" refers to an alkynyl group containing 2 to 6 carbon atoms. The term "substituted alkynyl" refers to an alkynyl group substituted by one or more substituents, and the terms "heteroatom-containing alkynyl" and "heteroatom-containing alkynyl" refer to an alkynyl group in which at least one carbon atom is substituted by a heteroatom. Unless otherwise specified, the terms "alkynyl" and "lower alkynyl" include straight-chain, branched, unsubstituted, substituted, and / or heteroatom-containing alkynyl and lower alkynyl groups, respectively.

[0051] As used herein, the term "alkoxy" refers to an alkyl group linked by a single terminal ether bond; that is, "alkoxy" can be represented as -O-alkyl, where the meaning of alkyl is as described above. "Lower alkoxy" refers to an alkoxy group containing 1 to 6 carbon atoms. Similarly, "alkenoxy" and "lower alkenoxy" refer to alkenyl and lower alkenyl groups linked by a single terminal ether bond, respectively, while "alkynyloxy" and "lower alkynyloxy" refer to alkynyl and lower alkynyl groups linked by a single terminal ether bond, respectively.

[0052] As used herein, unless otherwise stated, the term "aryl" refers to an aromatic substituent comprising one or more aromatic rings fused together, directly linked, or indirectly linked (such as attaching different aromatic rings to a common group, such as a methylene or ethylene group). An aryl group may contain 5 to 24 carbon atoms (e.g., 5 to 14 carbon atoms). Exemplary aryl groups comprise one or two fused or linked aromatic rings, such as phenyl, naphthyl, biphenyl, diphenyl ether, diphenylamine, benzophenone, etc. "Substituted aryl" refers to an aryl group substituted by one or more substituents, and the terms "heteroatom-containing aryl" and "heteroaryl" refer to aryl substituents in which at least one carbon atom is substituted by a heteroatom, as will be described in further detail below.

[0053] As used herein, the term "aryloxy group" refers to an aryl group linked by a single terminal ether bond, wherein the definition of "aryl" is as stated above. "Aryloxy group" may be represented as -O-aryl, wherein the meaning of "aryl" is as stated above. An aryloxy group may contain 5 to 24 carbon atoms (e.g., 5 to 14 carbon atoms). Examples of aryloxy groups include, but are not limited to, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, etc.

[0054] The term "alkylaryl" refers to an aryl group having an alkyl substituent, and the term "aralkyl" refers to an alkyl group having an aryl substituent, wherein the meanings of "aryl" and "alkyl" are as described above. Alkaryl and aralkyl groups can contain 6 to 24 carbon atoms (e.g., 6 to 16 carbon atoms). Alkaryl groups include, but are not limited to, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopent-1,4-diene, etc. Examples of aralkyl groups include, but are not limited to, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexylmethyl, 4-benzylcyclohexylmethyl, etc. The terms "alkylaryloxy" and "aralkyloxy" refer to substituents with the chemical formula -OR, where R is either alkylaryl or aralkyl, as defined above.

[0055] The term "acyl" refers to a substituent having the following general formula: -(CO)-alkyl, -(CO)-aryl, (CO)-aralkyl, -(CO)-alkylaryl, -(CO)-alkenyl, or -(CO)-ynyl; the term "acyloxy" refers to a substituent having the following general formula: O(CO)-alkyl, O(CO)-aryl, -O(CO)-aralkyl, -O(CO)-alkylaryl, -O(CO)-alkenyl, -O(CO)-ynyl; wherein, the definitions of "alkyl", "aryl", "aralkyl", "alkylaryl", "alkenyl", and "ynyl" are as described above.

[0056] The terms "cyclic" and "ring" refer to alicyclic or aromatic groups that may or may not be substituted and / or contain heteroatoms, and can be monocyclic, bicyclic, or polycyclic. The term "alicyclic," used in its conventional definition, refers to aliphatic cyclic groups, as opposed to aromatic cyclic groups, and can be monocyclic, bicyclic, or polycyclic.

[0057] The terms “halogenated” and “halogen” are used according to their conventional definitions to refer to chlorine, bromine, fluorine, or iodine substituents.

[0058] "Hydrocarbon group" refers to a monovalent hydrocarbon radical containing 1 to 30 carbon atoms (e.g., 1 to 24 carbon atoms, e.g., 1 to 12 carbon atoms), including straight-chain, branched, cyclic, saturated, and unsaturated types, such as alkyl, alkenyl, alkynyl, aryl, etc. The term "lower hydrocarbon group" refers to a hydrocarbon group containing 1 to 6 carbon atoms (e.g., 1 to 4 carbon atoms); the term "hydrocarbon subgroup" refers to a divalent hydrocarbon group containing 1 to 30 carbon atoms (e.g., 1 to 24 carbon atoms, e.g., 1 to 12 carbon atoms), including straight-chain, branched, cyclic, saturated, and unsaturated types. The term "lower hydrocarbon subgroup" refers to a hydrocarbon subgroup containing 1 to 6 carbon atoms. The term "substituted hydrocarbon group" refers to a hydrocarbon group substituted by one or more substituents; the terms "heteroatom-containing hydrocarbon group" and "heteroatom group" refer to hydrocarbon groups in which at least one carbon atom is substituted by a heteroatom. Similarly, the term "substituted alkylene group" refers to an alkylene group substituted by one or more substituents, and the terms "heteroatom-containing alkylene group" and "heteroalkylene group" refer to an alkylene group in which at least one carbon atom is substituted by a heteroatom. Unless otherwise stated, the terms "alkyl group" and "alkylene group" should be understood to include substituted and / or heteroatom-containing alkyl groups and heteroatom-containing alkylene groups, respectively.

[0059] As used in "heteroatom-containing hydrocarbon group," the term "heteroatom-containing" refers to a hydrocarbon molecule or hydrocarbon group segment in which one or more carbon atoms are replaced by atoms other than carbon, such as nitrogen, oxygen, sulfur, phosphorus, or silicon, typically nitrogen, oxygen, or sulfur. Similarly, the term "heteroalkyl" refers to an alkyl substituent containing a heteroatom, the term "heterocyclic" refers to a cyclic substituent containing a heteroatom, and the terms "heteroaryl" and "heteroaromatic" refer to "aryl" and "aromatic" substituents containing heteroatoms, respectively. It should be noted that a "heterocyclic" group or compound may or may not be aromatic; furthermore, a "heterocyclic" group can be monocyclic, bicyclic, or polycyclic, consistent with the definition of the term "aryl" above. Examples of heteroalkyl groups include, but are not limited to, alkoxyaryl, alkylthio-substituted alkyl, N-alkylated aminoalkyl, etc. Examples of heteroaryl substituents include, but are not limited to, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazoleyl, 1,2,4-triazolyl, tetrazolyl, etc.; examples of alicyclic groups containing heteroatoms include pyrrolidinyl, morpholinyl, piperazineyl, piperidinyl, etc.

[0060] In some of the definitions above, "substituted hydrocarbon group," "substituted alkyl group," "substituted aryl group," etc., "substitution" means that in a hydrocarbon group, alkyl group, aryl group, or other group, at least one hydrogen atom bonded to a carbon (or other) atom is replaced by one or more non-hydrogen substituents. Examples of such substituents include, but are not limited to, functional groups referred to herein as "Fn," such as halogens, hydroxyl groups, mercapto groups, C1-C... 24 Alkoxy, C2-C 24 Alkenyl groups, C2-C 24 Acryloxy group, C5-C 24 Aryloxy group, C6-C 24 Arylalkoxy, C6-C 24 Alkyloxy groups, acyl groups (including C2-C) 24 Alkyl carbonyl (-CO-alkyl) and C6-C 24 aryl carbonyl (-CO-aryl) and acyloxy (-O-acyl, including C2-C) 24 Alkyl carbonyl groups (-O-CO-alkyl) and C6-C 24 aryl carbonyloxy (-O-CO-aryl)), C2-C 24 Alkoxycarbonyl (-(CO)-O-alkyl), C6-C 24 Aryloxycarbonyl (-(CO)-O-aryl), halocarbonyl (-(CO)-X, where X is a halogen), C2-C 24 Alkyl carbonate group (-O-(CO)-O-alkyl), C6-C 24 Aryl carbonate group (-O-(CO)-O-aryl), carboxyl group (-COOH), carboxylate group (-COO) -), carbamoyl (-(CO)-NH2), mono-(C1-C 24 alkyl)-substituted carbamoyl group (-(CO)-NH(C1-C) 24 Alkyl), bis-(C1-C) 24 alkyl)-substituted carbamoyl (-(CO)-N(C1-C) 24 Alkyl)2), mono-(C1-C) 24 Halogenated alkyl) carbamoyl group (-(CO)-NH(C1-C) 24 (halogenated alkyl), bis-(C1-C) 24 Halogenated alkyl) carbamoyl group (-(CO)-N(C1-C) 24 (halogenated alkyl)2), mono-(C5-C) 24 aryl-substituted carbamoyl (-(CO)-NH-aryl), bis-(C5-C 24 aryl)-substituted carbamoyl group (-(CO)-N(C5-C) 24 Aryl)2), bis-N-(C1-C 24 Alkyl), N-(C5-C) 24 aryl)-substituted carbamoyl group (-(CO)-N(C1-C) 24 Alkyl) (C5-C 24 aryl), thiocarbamoyl (-(CS)-NH2), mono-(C1-C 24 alkyl)-substituted thiocarbamoyl (-(CS)-NH(C1-C) 24 Alkyl), bis-(C1-C) 24 alkyl)-substituted thiocarbamoyl (-(CS)-N(C1-C) 24 Alkyl)2), mono-(C5-C) 24 aryl-substituted thiocarbamoyl (-(CS)-NH-aryl), bis-(C5-C 24 aryl)-substituted thiocarbamoyl (-(CS)-N(C5-C) 24 aryl)2), bis-N-(C1-C 24 Alkyl), N-(C5-C) 24 aryl)-substituted thiocarbamoyl (-(CS)-N(C1-C) 24 Alkyl) (C5-C 24Aryl), urea (-NH-(CO)-NH2), cyano (-C≡N), cyanate (cyanato, -OC≡N), thiocyanate (thiocyanato, -SC≡N), isocyanate (-N=C=O), thioisocyanate (thioisocyanate, -N=C=S), formyl (-(CO)-H), thioformyl (-(CS)-H), amino (-NH2), mono-(C1-C) 24 Alkyl) substituted amino (-NH(C1-C) 24 Alkyl), bis-(C1-C) 24 Alkyl) substituted amino (-N(C1-C) 24 Alkyl)2), mono-(C5-C) 24 aryl)-substituted amino group (-NH(C5-C) 24 Aryl), bis-(C5-C) 24 aryl)-substituted amino group (-N(C5-C) 24 Aryl)2), C2-C 24 Alkylamide group (-NH-(CO)-alkyl), C6-C 24 Aryl amide group (-NH-(CO)-aryl), imino group (-CR=NH, where R includes but is not limited to hydrogen, C1-C) 24 Alkyl, C5-C 24 Aryl, C6-C 24 Alkyl, C6-C 24 Aryl alkyl groups, etc., C2-C 20 Alkylimino (-CR=N(alkyl), where R includes, but is not limited to, hydrogen, C1-C) 24 Alkyl, C5-C 24 Aryl, C6-C 24 Alkyl, C6-C 24 Arylalkyl, etc.), arylimino (-CR=N(aryl), where R includes but is not limited to hydrogen, C1-C 20 Alkyl, C5-C 24 Aryl, C6-C 24 Alkyl, C6-C 24 Aryl groups, nitro groups (-NO2), nitroso groups (-NO), sulfonic acid groups (-SO2-OH), and sulfonate groups (-SO2-O) - C1-C 24 Alkylthio (-S-alkyl, also known as "alkoxythio"), C5-C 24 Arylthio (-S-aryl, also known as "arylthio"), C1-C 24 alkylsulfinyl (-(SO)-alkyl), C5-C 24arylsulfinyl (-(SO)-aryl), C1-C 24 alkylsulfonyl (-SO2-alkyl), C1-C 24 Monoalkylaminosulfonyl (-SO2-N(H)alkyl), C1-C 24 Dialkylaminosulfonyl (-SO2-N(alkyl)2), C5-C 24 alkylsulfonyl (-SO2-aryl), boronyl (-BH2), dihydroxyboryl (-B(OH)2), borate ester (-B(OR)2, where R includes, but is not limited to, alkyl or other hydrocarbon groups), phosphonate (-P(O)(OH)2), phosphonate (-P(O)(O)2) - )2) Phosphinate (-P(O)(O) - Phosphate groups (-PO2), phosphine groups (-PH2); and hydrocarbon groups, such as C1-C 24 Alkyl (e.g., C1-C) 12 Alkyl, C1-C6 alkyl), C2-C 24 alkenyl (e.g., C2-C) 12 alkenyl, C2-C6 alkenyl), C2-C 24 alkynyl groups (e.g., C2-C) 12 (C2-C6 ynyl group, C5-C ynyl group) 24 Aryl (e.g., C5-C) 14 Aryl), C6-C 24 Alkyl aryl (e.g., C6-C) 16 (alkylaryl) and C6-C 24 Aryl alkyl groups (e.g., C6-C) 16 Aryl groups).

[0061] In terms such as "functionalized hydrocarbon group," "functionalized alkyl group," "functionalized olefin group," and "functionalized cycloolefin group," "functionalized" means that in a hydrocarbon group, alkyl group, olefin group, cycloolefin group, or other group, at least one hydrogen atom attached to a carbon (or other) atom is replaced by one or more functional groups as described above. The term "functional group" refers to any functional group suitable for the purposes described herein. In particular, as used herein, a functional group should have the ability to react or bind with a corresponding functional group on a matrix surface.

[0062] Furthermore, if permitted by specific groups, the aforementioned functional groups may be further substituted with one or more additional functional groups or one or more hydrocarbon groups, such as those specifically mentioned above. Similarly, as stated above, the aforementioned hydrocarbon groups may be further substituted with one or more functional groups or additional hydrocarbon groups.

[0063] The terms "optional" or "optionally" mean that the following description may or may not occur, and therefore the description includes both scenarios. For example, the phrase "optionally substituted" means that a given atom may or may not have a non-hydrogen substituent, and therefore the description includes both structures with and without non-hydrogen substituents.

[0064] As used herein, the term "substrate material" generally refers to any material that can come into contact with the coating composition of the present invention, any material on which the coating composition of the present invention is coated, or any material into which the substrate material can be incorporated. Such materials include, but are not limited to, reinforcing materials such as filaments, fibers, rovings, pads, weaves, fabrics, woven materials, cloth or other known structures, glass fibers and textiles, carbon fibers and textiles, aramid fibers and textiles, and polyolefin or other polymer fibers or textiles. Other suitable matrix materials include metal density modifiers, particulate density modifiers (e.g., microspheres, glass microspheres, ceramic microspheres, microballoons, hollow microspheres), and macroparticle density modifiers (e.g., glass beads or ceramic beads). ROMP polymer composites may comprise a single matrix material or a mixture of different substrate materials.

[0065] The term "polymer backbone" refers to the atomic chain in a polymer. If it is a cross-linked polymer, the polymer includes the backbone as well as any cross-linking bonds.

[0066] As used herein, the term "field joint" generally refers to a connection between adjacent components or parts during installation (i.e., in the field). The term "field joint" is a term used in this field to describe the welded ends of various pipe sections. For example, pipelines used to transport oil and / or natural gas are typically composed of many individual pipe fittings (e.g., steel pipes) connected together. During the manufacturing process of individual fittings, an anti-corrosion coating is typically applied to the outer surface of the fitting, leaving the outer surface of the pipe ends uncoated. Furthermore, the fitting may be further coated or wrapped with material in subsequent processes, leaving the outer surface of its pipe ends still uncoated. The individual fittings are connected to each other by welding the uncoated ends together, thus forming a pipeline. At least part of the welding process can be carried out onshore before the pipeline is loaded onto a lay barge or reel ship, while the remaining connections are completed at sea before the pipeline is put into service at sea. Additionally, during the manufacturing process of individual fittings, an anti-corrosion coating is typically applied to the outer surface of the pipe, leaving the outer surface of the pipe ends uncoated. In this case, the anti-corrosion coating on the end of the pipe must be removed before welding.

[0067] As is well known in the art, weight percentage (wt%) can be expressed as gas chromatography (GC) area percentage (area%). Therefore, GC area percentage obtained by GC is reported as wt%. In this document, weight percentage (wt%) and percentage by weight are used interchangeably. Mole percentage (mol%) can be calculated from weight percentage (wt%) using conventional methods in the art.

[0068] Olefin resin composition The coating composition of the present invention comprises an olefin resin composition. The olefin resin composition may be present in the coating composition at a content of about 5-99.99 wt% (e.g., 10-99.98 wt%, 15-99.89 wt%, 20-99.88 wt%, 25-99 wt%, 30-95 wt%, 35-90 wt%, 40-85 wt%, 45-80 wt%, 50-75 wt%, 55-70 wt%, or 60-65 wt%), based on the total weight of the coating composition. The olefin resin composition comprises, is substantially composed of, or is composed of: at least one olefin component, at least one metal carbene olefin metathesis catalyst, and optionally at least one thermoplastic hydrocarbon resin.

[0069] olefin components The olefin component used in the olefin resin composition disclosed herein consists of at least one cyclic olefin and at least one linear olefin of formula (IV); wherein the cyclic olefin is selected from the group consisting of formulas (I), (II) and (III), and is present in an amount of about 80-100 wt% (85-99.9 wt%, 90-99 wt%, 91-98 wt%, 92-97 wt%, 93-96 wt% or 94-95 wt%), based on the total weight of the olefin component; the linear olefin is present in an amount of 0-20 wt% (0.1-15 wt%, 1-10 wt%, 2-9 wt%, 3-8 wt%, 4-7 wt% or 5-6 wt%), based on the total weight of the olefin component; wherein the sum of the weight percentages of the cyclic olefins of formulas (I), (II) and (III) and the linear olefin of formula (IV) is 100 wt% of the olefin component.

[0070] Generally, any cyclic olefin suitable for the reactions disclosed herein can be used in this invention. The cyclic olefin may optionally be substituted, optionally contain heteroatoms, and be monounsaturated, diunsaturated, or polyunsaturated C5-C. 24 Hydrocarbons can be monocyclic, bicyclic, or polycyclic. When cycloalkenes contain more than one ring, these rings may be fused or unfused.

[0071] Cyclic olefins can generally be any strained or unstrained cyclic olefin, as long as the cyclic olefin can participate in the polymerization reaction alone or as part of a cyclic olefin composition.

[0072] The cycloolefins of formula (I) have the following structures:

[0073] Formula (I) in: R a H, or optionally substituted linear or branched C 1-24 Alkyl, optionally substituted straight or branched C 2-24 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g , -CN, -NO2, -CF3, -P(O)(OR h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, Optionally substituted spirocyclic heterocycles, -CH2- (optionally substituted heterocycles), Optionally substituted C 3-10 Cycloalkyl, -CH2- (optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 Aryl, -CH2- (optionally substituted C) 5-24 aryl), optionally substituted C 3-12 Cycloalkenyl, -CH2- (optionally substituted C) 3-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p -C(R) h (R) i )C(O)NR o OR nor ; Each R s It is an independent, optionally substituted straight or branched C 1-24 Alkyl, optionally substituted straight or branched C 2-24 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g , -CN, NO2, -CF3, -P(O)(OR h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, -CH2- (optionally substituted heterocycles), optionally substituted C 3-10 Cycloalkyl, -CH2- (optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 Aryl, -CH2- (optionally substituted C) 5-24 aryl), optionally substituted C 3-12 Cycloalkenyl, -CH2- (optionally substituted C) 3-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p or -C(R) h (R) i )C(O)NR o OR n ; t can be 0, 1, 2, 3, 4, 5, or 6; R f For OH, OR k NR g R h Optional substitution of straight or branched C 1-24 Alkyl, optionally substituted C 3-10cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl or optionally substituted C 3-12 Cycloalkenyl; R g H, or optionally substituted linear or branched C 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl, optionally substituted linear or branched C 2-24 alkenyl, -C(O)- (optionally substituted C) 5-24 aryl), -C(O)- (optionally substituted straight or branched C) 2-24 alkenyl) or optionally substituted C 3-12 Cycloalkenyl; R h R i R j R l R m R n R o and R p Each is independent of the other, consisting of H, optionally substituted linear or branched C. 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl or optionally substituted C 3-12 Cycloalkenyl; R k For optional substitution of linear or branched C 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl or optionally substituted C 3-12 Cycloalkenyl.

[0074] Cyclic alkenes can also be represented by formula (I), where: R a H, or optionally substituted linear or branched C 1-12 Alkyl, optionally substituted straight or branched C 2-12 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g , -CN, NO2, -CF3, -P(O)(OR h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R hOptionally substituted heterocycles, -CH2- (optionally substituted heterocycles), optionally substituted spirocyclic heterocycles, optionally substituted C 5-7 Cycloalkyl, -CH2- (optionally substituted C 5-7 cycloalkyl), optionally substituted C 6-10 Aryl, -CH2- (optionally substituted C) 6-10 aryl), optionally substituted C 5-12 Cycloalkenyl, -CH2- (optionally substituted C) 5-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p or -C(R) h (R) i )C(O)NR o OR n ; Each R s It is an independent, optionally substituted straight or branched C 1-12 Alkyl, optionally substituted straight or branched C 2-12 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g , -CN, NO2, -CF3, -P(O)(OR h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, -CH2- (optionally substituted heterocycles), optionally substituted C 5-7 Cycloalkyl, -CH2- (optionally substituted C 5-7 cycloalkyl), optionally substituted C 6-10 Aryl, -CH2- (optionally substituted C) 6-10 aryl), optionally substituted C 5-12 Cycloalkenyl, -CH2- (optionally substituted C)5-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p or -C(R) h (R) i )C(O)NR o OR n ; t can be 0, 1, 2, 3, or 4; R f For OH, OR k NR g R h Optional substitution of straight or branched C 1-12 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 Cycloalkenyl; R g H, or optionally substituted linear or branched C 1-12 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl, optionally substituted straight or branched C 2-12 alkenyl, -C(O)- (optionally substituted C) 6-10 aryl), -C(O)- (optionally substituted straight or branched C) 2-12 alkenyl) or optionally substituted C 5-12 Cycloalkenyl; R h R i R j R l R m R n R o and R p H, and optionally substituted linear or branched C, are independent of each other. 1-12 Alkyl, optionally substituted C 5-7cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 cycloalkenyl; and R k For optional substitution of straight or branched C 1-12 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 Cycloalkenyl.

[0075] Cyclic alkenes can also be represented by formula (I), where: R a H, or optionally substituted linear or branched C 1-6 Alkyl, optionally substituted straight or branched C 2-6 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g , -CN, NO2, -CF3, -P(O)(OR h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, Optionally substituted spirocyclic heterocycles, -CH2- (optionally substituted heterocycles), Optionally substituted C 5-7 Cycloalkyl, -CH2- (optionally substituted C 5-7 cycloalkyl), optionally substituted C 6-10 Aryl, -CH2- (optionally substituted C) 6-10 aryl), optionally substituted C 5-12 Cycloalkenyl or -CH2- (optionally substituted C) 5-12 (cycloalkenyl); t is 0; R f For OH, OR k NR g R h Optional substitution of straight or branched C 1-6 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 Cycloalkenyl; R g H, or optionally substituted linear or branched C 1-6 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10aryl, optionally substituted straight or branched C 2-6 alkenyl, -C(O)- (optionally substituted C) 6-10 aryl), -C(O)- (optionally substituted straight or branched C) 2-6 alkenyl) or optionally substituted C 5-12 Cycloalkenyl; R h H, or optionally substituted linear or branched C 1-6 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 cycloalkenyl; and R k For optional substitution of straight or branched C 1-6 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 Cycloalkenyl.

[0076] According to R s At the position of the tetracyclododeca-3-ene group, the cycloalkene of formula (I) can have the following structures: , Where: t is 1, R a and R s As defined in this article; R a and R s It can form optionally substituted polycyclic rings with the rest of the molecule.

[0077] Cyclic alkenes can also be represented by formula (I), where: R a for , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , or ; t=0.

[0078] A non-limiting example of the monomer of formula (I) can be expressed as: , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , or .

[0079] The cycloolefins of formula (II) have the following structures:

[0080] Equation (II) in: R b H, or optionally substituted linear or branched C 1-24 Alkyl, optionally substituted straight or branched C 2-24 Alkenyl, halogen, -C(O)R f-CH2-C(O)R f -OR g -CH2-OR g CN, NO2, -CF3, -P(O)(OR) h )2、-OP(O)(OR h )2、-Si(OR k 3、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, Optionally substituted spirocyclic heterocycles, -CH2- (optionally substituted heterocycles), Optionally substituted C 3-10 Cycloalkyl, -CH2- (optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 Aryl, -CH2- (optionally substituted C) 5-24 aryl), optionally substituted C 3-12 Cycloalkenyl, -CH2- (optionally substituted C) 3-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p or -C(R) h (R) i )C(O)NR o OR n ; Each R s It is an independently optional substitution of straight or branched C 1-24 Alkyl, optionally substituted straight or branched C 2-24 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g CN, NO2, -CF3, -P(O)(OR) h )2、-OP(O)(OR h )2、-S(O)2OR h-OS(O)2R h Optionally substituted heterocycles, -CH2- (optionally substituted heterocycles), optionally substituted C 3-10 Cycloalkyl, -CH2- (optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 Aryl, -CH2- (optionally substituted C) 5-24 aryl), optionally substituted C 3-12 Cycloalkenyl, -CH2- (optionally substituted C) 3-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p or -C(R) h (R) i )C(O)NR o OR n ; t can be 0, 1, 2, 3, 4, 5, or 6; R f For OH, OR k NR g R h Optional substitution of straight or branched C 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl or optionally substituted C 3-12 Cycloalkenyl; R g H, or optionally substituted linear or branched C 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl, optionally substituted straight or branched C 2-24 alkenyl, -C(O)- (optionally substituted C) 5-24 aryl), -C(O)- (optionally substituted straight or branched C) 2-24 alkenyl) or optionally substituted C 3-12Cycloalkenyl; R h R i R j R l R m R n R o and R p H, and optionally substituted linear or branched C, are independent of each other. 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl or optionally substituted C 3-12 cycloalkenyl; and R k For optional substitution of straight or branched C 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl or optionally substituted C 3-12 Cycloalkenyl.

[0081] Cycloolefins can also be represented by the structure shown in formula (II), wherein: R b H, or optionally substituted linear or branched C 1-12 Alkyl, optionally substituted straight or branched C 2-12 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g CN, NO2, -CF3, -P(O)(OR) h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, Optionally substituted spirocyclic heterocycles, -CH2- (optionally substituted heterocycles), Optionally substituted C 5-7 Cycloalkyl, -CH2- (optionally substituted C 5-7 cycloalkyl), optionally substituted C 6-10 Aryl, -CH2- (optionally substituted C) 6-10 aryl), optionally substituted C 5-12 Cycloalkenyl, -CH2- (optionally substituted C) 5-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h(R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p or -C(R) h (R) i )C(O)NR o OR n ; Each R s It is an independent, optionally substituted straight or branched C 1-12 Alkyl, optionally substituted straight or branched C 2-12 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g CN, NO2, -CF3, -P(O)(OR) h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, -CH2- (optionally substituted heterocycles), optionally substituted C 5-7 Cycloalkyl, -CH2- (optionally substituted C 5-7 cycloalkyl), optionally substituted C 6-10 Aryl, -CH2- (optionally substituted C) 6-10 aryl), optionally substituted C 5-12 Cycloalkenyl, -CH2- (optionally substituted C) 5-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o Rp or -C(R) h (R) i )C(O)NR o OR n ; t can be 0, 1, 2, 3, or 4; R f For OH, OR k NR g R h Optional substitution of straight or branched C 1-12 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 Cycloalkenyl; R g H, or optionally substituted linear or branched C 1-12 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl, optionally substituted straight or branched C 2-12 alkenyl, -C(O)- (optionally substituted C) 6-10 aryl), -C(O)- (optionally substituted straight or branched C) 2-12 alkenyl) or optionally substituted C 5-12 Cycloalkenyl; R h R i R j R l R m R n R o and R p H, and optionally substituted linear or branched C, are independent of each other. 1-12 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 cycloalkenyl; and R k For optional substitution of straight or branched C 1-12 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 Cycloalkenyl.

[0082] Cycloolefins can also be represented by formula (II), wherein: R b H, or optionally substituted linear or branched C 1-6 Alkyl, optionally substituted straight or branched C2-6 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g CN, NO2, -CF3, -P(O)(OR) h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, Optionally substituted spirocyclic heterocycles, -CH2- (optionally substituted heterocycles), Optionally substituted C 5-7 Cycloalkyl, -CH2- (optionally substituted C 5-7 cycloalkyl), optionally substituted C 6-10 Aryl, -CH2- (optionally substituted C) 6-10 aryl), optionally substituted C 5-12 Cycloalkenyl or -CH2- (optionally substituted C) 5-12 (cycloalkenyl); t is 0; R f For OH, OR k NR g R h Optional substitution of straight or branched C 1-6 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 Cycloalkenyl; R g H, or optionally substituted linear or branched C 1-6 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl, optionally substituted straight or branched C 2-6 alkenyl, -C(O)- (optionally substituted C) 6-10 aryl), -C(O)- (optionally substituted straight or branched C) 2-6 alkenyl) or optionally substituted C 5-12 Cycloalkenyl; R h H, or optionally substituted linear or branched C 1-6 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 cycloalkenyl; and R k For optional substitution of straight or branched C 1-6Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 Cycloalkenyl.

[0083] According to R s At the position of the 2-norbornene group, the cycloalkene of structural formula (II) can be represented as:

[0084] Where: t=1, R s and R b As defined in this article; R s and R b It can combine with the rest of the molecule to form optional substituted polycyclic structures.

[0085] Cycloolefins can also be represented by formula (II), wherein: R b for , , , , , , , , , , , , , , , , , , , , , , , , , , , , , or ; t=0.

[0086] A non-limiting example of the monomer of formula (II) can be expressed as: , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , or .

[0087] The cycloolefins of formula (III) have the following structures:

[0088] Equation (III) Where z is 0, 1, 2 or 3.

[0089] Cycloolefins can also be represented by the structure shown in formula (III), where z is 1 or 2.

[0090] Cycloolefins can also be represented by the structure shown in formula (III), where z is 2.

[0091] A non-limiting example of the monomer of formula (III) can be expressed as: , , , or .

[0092] Therefore, examples of cycloolefins of formulas (I), (II), and (III) include, but are not limited to: 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-5,6-dimethoxy-2-norbornene, endo-5,6-dimethoxy-2-norbornene, endo-5,6-dimethoxycarbonyl-2-norbornene, endo-5,6-dimethoxycarbonyl-2-norbornene, norbornene, tricycloundecene, tetracyclododecene, 8-methoxycarbonyl-tetracyclododecene, 8-cyano-tetracyclododecene; C1-C 12 Hydrocarbon-substituted norbornene, 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, etc.; C2-C 12 Hydrocarbon-substituted tetracyclododecenes, such as 8-methyl-tetracyclododecene, 8-ethyl-tetracyclododecene, 8-butyl-tetracyclododecene, 8-hexyl-tetracyclododecene, 8-octyl-2-tetracyclododecene, 8-decyl-2-tetracyclododecene, 8-dodecyl-2-tetracyclododecene, 8-dodecyl-2-tetracyclododecene, 8-vinyl-tetracyclododecene, 8-ethylene-2-tetracyclododecene, 8-isopropenyl-tetracyclododecene, 5-propenyl-tetracyclododecene, and 5-butenyl-tetracyclododecene.

[0093] Those skilled in the art will understand that the bicyclic and polycyclic olefins disclosed herein can consist of a variety of structural isomers and / or stereoisomers, any and all of which are applicable to the present invention. Unless otherwise stated, any reference herein to such bicyclic and polycyclic olefins includes any and all mixtures of structural isomers and / or stereoisomers.

[0094] The linear olefins used in this invention may be optionally substituted, optionally contain heteroatoms, or be monounsaturated or polyunsaturated.

[0095] The linear olefin of formula (IV) has the following structure, wherein R c and R d It can be either cis or trans configuration:

[0096] Formula (IV) in: R c and R d H, and optionally substituted linear or branched C, are independent of each other. 1-24 Alkyl, optionally substituted straight or branched C 2-24 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g CN, NO2, -CF3, -P(O)(OR) h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, -CH2- (optionally substituted heterocycles), Optionally substituted C 3-10 Cycloalkyl, -CH2- (optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 Aryl, -CH2- (optionally substituted C) 5-24 aryl), optionally substituted C 3-12 Cycloalkenyl, -CH2- (optionally substituted C) 3-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CRl (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p or -C(R) h (R) i )C(O)NR o OR n ; R f For OH, OR k NR g R h Optional substitution of straight or branched C 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl or optionally substituted C 3-12 Cycloalkenyl; R g H, or optionally substituted linear or branched C 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl, optionally substituted straight or branched C 2-24 alkenyl, -C(O)- (optionally substituted C) 5-24 aryl), -C(O)- (optionally substituted straight or branched C) 2-24 alkenyl) or optionally substituted C 3-12 Cycloalkenyl; R h R i R j R l R m R n R o and R p H, and optionally substituted linear or branched C, are independent of each other. 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl or optionally substituted C 3-12 cycloalkenyl; and R k For optional substitution of straight or branched C 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl or optionally substituted C 3-12 Cycloalkenyl.

[0097] Linear alkenes can also be represented by the structure shown in formula (IV), wherein: R c and R d H, and optionally substituted linear or branched C, are independent of each other. 1-12 Alkyl, optionally substituted straight or branched C 2-12 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g CN, NO2, -CF3, -P(O)(OR) h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, -CH2- (optionally substituted heterocycles), optionally substituted C 5-7 Cycloalkyl, -CH2- (optionally substituted C 5-7 cycloalkyl), optionally substituted C 6-10 Aryl, -CH2- (optionally substituted C) 6-10 aryl), optionally substituted C 5-12 Cycloalkenyl, -CH2- (optionally substituted C) 5-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p or -C(R) h (R) i )C(O)NR o OR n ; R f For OH, OR k NR g R h Optional substitution of straight or branched C 1-12 Alkyl, optionally substituted C 5-7cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 Cycloalkenyl; R g H, or optionally substituted linear or branched C 1-12 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl, optionally substituted straight or branched C 2-12 alkenyl, -C(O)- (optionally substituted C) 6-10 aryl), -C(O)- (optionally substituted straight or branched C) 2-12 alkenyl) or optionally substituted C 5-12 Cycloalkenyl; R h R i R j R l R m R n R o and R p H, and optionally substituted linear or branched C, are independent of each other. 1-12 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 cycloalkenyl; and R k For optional substitution of straight or branched C 1-12 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 Cycloalkenyl.

[0098] Linear alkenes can also be represented by formula (IV), where: R c and R d H, and optionally substituted linear or branched C, are independent of each other. 1-6 Alkyl, optionally substituted straight or branched C 2-6 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g CN, NO2, -CF3, -P(O)(OR) h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R hOptionally substituted heterocycles, -CH2- (optionally substituted heterocycles), Optionally substituted C 5-7 Cycloalkyl, -CH2- (optionally substituted C 5-7 cycloalkyl), optionally substituted C 6-10 Aryl, -CH2- (optionally substituted C) 6-10 aryl), optionally substituted C 5-12 Cycloalkenyl or -CH2- (optionally substituted C) 5-12 (cycloalkenyl); R f For OH, OR k NR g R h Optional substitution of straight or branched C 1-6 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 Cycloalkenyl; R g H, or optionally substituted linear or branched C 1-6 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl, optionally substituted straight or branched C 2-6 alkenyl, -C(O)- (optionally substituted C) 6-10 aryl), -C(O)- (optionally substituted straight or branched C) 2-6 alkenyl) or optionally substituted C 5-7 Cycloalkenyl; R h H, or optionally substituted linear or branched C 1-6 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 cycloalkenyl; and R k For optional substitution of straight or branched C 1-6 Alkyl, optionally substituted C 5-7 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 5-12 Cycloalkenyl.

[0099] Linear alkenes can also be represented by formula (IV), where:

[0100] .

[0101] An unrestricted instance of equation (IV) can be represented as:

[0102] .

[0103] The olefin component of the coating composition of the present invention may include, substantially consist of, or consist of at least one cyclic olefin selected from the group consisting of formulas (I) and (II), at least one cyclic olefin selected from the group consisting of formulas (I) and (III), or at least one cyclic olefin selected from the group consisting of formulas (II) and (III). The coating composition of the present invention may contain only cyclic olefins of formulas (I), (II), and (III) or mixtures thereof, or as described above, may contain at least one specific cyclic olefin selected from one of formulas (I), (II), and (III), but not linear olefins of formula (IV). The coating composition of the present invention may contain at least one cyclic olefin selected from the group consisting of formula (III) (e.g., dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), and mixtures thereof). The coating composition of the present invention may contain dicyclopentadiene (DCPD) and tricyclopentadiene (TCPD). The ratio of DCPD to TCPD is 3:7 to 2:3 (DCPD wt% : TCPD wt%).

[0104] In the coating composition of the present invention, the olefin component may comprise, consist essentially of, or consist of the following: At least one cyclic olefin of formula (I) in the range of 0-100% (0.1-99.9%, 0.5-99.8%, 1-99.7%, 5-99%, 10-95%, 15-90%, 20-85%, 25-80%, 30-75%, 35-70%, 40-65%, 45-60%, 50-55%). At least one cyclic olefin of formula (II) in the range of 0-100% (0.1-99.9%, 0.5-99.8%, 1-99.7%, 5-99%, 10-95%, 15-90%, 20-85%, 25-80%, 30-75%, 35-70%, 40-65%, 45-60%, 50-55%). At least one cyclic olefin of formula (III) in the range of 0-100% (0.1-99.9%, 0.5-99.8%, 1-99.7%, 5-99%, 10-95%, 15-90%, 20-85%, 25-80%, 30-75%, 35-70%, 40-65%, 45-60%, 50-55%); and At least one linear olefin of formula (IV) in the range of 0-20% (0.1-15%, 0.5-10%, 1-9%, 2-8%, 3-7%, 4-6%); The sum of the contents of cyclic olefins of formula (I), formula (II) and formula (III) and linear olefins of formula (IV) is 100%.

[0105] The olefin component may be present in the coating composition of the present invention in an amount of about 35-99.9 wt% (e.g. 40-99 wt%, 45-98 wt%, 50-95 wt%, 55-90 wt%, 60-85 wt%, 65-80 wt%, 70-75 wt%), based on the total weight of the coating composition.

[0106] Metal carbene olefin metathesis catalyst The metal carbene olefin metathesis catalyst that can be used in the olefin resin compositions disclosed herein is a group 8 transition metal complex having the structure of formula (I).

[0107] (I) in: M is a group 8 transition metal; L 1 L 2 and L 3 It is a neutral electron donor ligand; n is 0 or 1, thus making L 3 It may exist or it may not exist; m is 0, 1, or 2; k is 0 or 1; X 1 and X 2 It is an anionic ligand; and R 1 and R 2 Each is independently selected from hydrogen, hydrocarbon group, substituted hydrocarbon group, heteroatom-containing hydrocarbon group, substituted heteroatom-containing hydrocarbon group and functional group; Among them, X 1 X 2 L 1 L 2 L 3 R 1 and R 2 Any two or more of them can together form one or more cyclic groups, and further, X 1 X 2 L 1 L 2 L 3 R 1 and R 2Any one or more of them can be connected to the carrier.

[0108] Furthermore, in equation (I), R 1 and R 2 One or both of them can have a structure -(W) n -U + V - Wherein, W is selected from alkylene groups, substituted alkylene groups, heteroatom-containing alkylene groups, or substituted heteroatom-containing alkylene groups; U is a positively charged element of Group 15 or Group 16 substituted with hydrogen, a hydrocarbon group, a substituted hydrocarbon group, a heteroatom-containing hydrocarbon group, or a substituted heteroatom-containing hydrocarbon group; V is a negatively charged counterion; n is 0 or 1. Furthermore, R... 1 and R 2 They can together form an indenylidene group.

[0109] The catalyst may contain a Group 8 transition metal, Ru or Os, preferably Ru.

[0110] Various embodiments of catalysts that can be used in the reactions disclosed herein are described in more detail below. For convenience, the catalysts are described in groups, but it should be emphasized that these groups are in no way limiting. That is, any catalyst that can be used in the present invention may conform to the description of more than one group described herein.

[0111] The first group of catalysts, commonly referred to as first-generation Grubbs-type catalysts, has the structure shown in formula (I). For the first group of catalysts, M is a Group 8 transition metal, m is 0, 1, or 2, and n, X 1 X 2 L 1 L 2 L 3 R 1 and R 2 As described below.

[0112] For the first group of catalysts, n is 0, L 1 and L 2 Independently selected from phosphine, sulfonated phosphite, phosphinite, phosphonite oxide, arsine, antimony, ether (including cyclic ethers), amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine, imidazole, substituted imidazole, pyrazine, substituted pyrazine, and thioether. An exemplary ligand is a trisubstituted phosphine. A trisubstituted phosphine can be represented by the general formula PR. H1 R H2 R H3 , where R H1 R H2 and RH3 Each is independently a substituted or unsubstituted aryl group or a C1-C group. 10 Alkyl groups, especially primary alkyl, secondary alkyl, or cycloalkyl groups. 1 and L 2 It can be independently selected from the group consisting of trimethylphosphine (PMe3), triethylphosphine (PEt3), tri-n-butylphosphine (PBu3), tri(o-tolyl)phosphine (Po-tolyl3), tri-tert-butylphosphine (P-tert-Bu3), tricyclopentylphosphine (PCyclopentyl3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), trioctylphosphine (POct3), triisobutylphosphine (Pi-Bu3), triphenylphosphine (PPh3), tri(pentafluorophenyl)phosphine (P(C6F5)3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph). Alternatively, L 1 and L 2 It can 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, etc.)).

[0113] X 1 and X 2 These are anionic ligands, which can be the same or different, or linked together to form cyclic groups, typically but not limited to five- to eight-membered rings. X 1 and X 2 Each can be independently hydrogen, halogen, or one of the following groups: C1-C 20 Alkyl, C5-C 24 Aryl, C1-C 20 Alkoxy, C5-C 24 Aryloxy group, C2-C 20 Alkoxycarbonyl, C6-C 24 aryloxycarbonyl, C2-C 24 Acyl group, C2-C 24 Acyloxy group, C1-C 20 Alkyl sulfonates, C5-C 24 Aryl sulfonates, C1-C 20 Alkyl thio, C5-C 24 Arylthio, C1-C 20 Alkyl sulfinyl, NO3, -N=C=O, -N=C=S or C5-C 24 Arylsulfinyl. Optionally, X1 and X 2 It can be substituted by one or more groups, said groups being selected from C1-C1. 12 Alkyl, C1-C 12 Alkoxy, C5-C 24 Aryl and halogen groups; wherein, in addition to halogens, these groups may be further substituted by one or more groups selected from halogens, C1-C6 alkyl groups, C1-C6 alkoxy groups, and phenyl groups. X 1 and X 2 It can be a halide, benzoate, C2-C6 acyl, C2-C6 alkoxycarbonyl, C1-C6 alkyl, phenoxy, C1-C6 alkoxy, C1-C6 alkylthio, aryl, or C1-C6 alkylsulfonyl. X 1 and X 2 Each can be a halide, CF3CO2, CH3CO2, CFH2CO2, (CH3)3CO, (CF3)2(CH3)CO, (CF3)(CH3)2CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethane-sulfonate. X 1 and X 2 Each can be a chloride.

[0114] R 1 and R 2 Independently selected from hydrogen, hydrocarbon groups (e.g., C1-C) 20 Alkyl, C2-C 20 alkenyl, C2-C 20 alkynyl group, C5-C 24 Aryl, C6-C 24 Alkyl, C6-C 24 Araneyl groups, etc.), substituted hydrocarbon groups (e.g., substituted C1-C... 20 Alkyl, C2-C 20 alkenyl, C2-C 20 alkynyl group, C5-C 24 Aryl, C6-C 24 Alkyl, C6-C 24 Aryl groups, etc.), heteroatom-containing hydrocarbon groups (e.g., C1-C heteroatom-containing groups). 20 Alkyl, C2-C 20 alkenyl, C2-C 20 alkynyl group, C5-C 24 Aryl, C6-C 24 Alkyl, C6-C 24 Aryl groups, etc.) and substituted heteroatom-containing hydrocarbon groups (e.g., substituted heteroatom-containing C1-C...). 20 Alkyl, C2-C20 alkenyl, C2-C 20 alkynyl group, C5-C 24 Aryl, C6-C 24 Alkyl, C6-C 24 Aryl groups, etc., and functional groups. R 1 and R 2 They can also be linked together to form cyclic groups, which can be aliphatic or aromatic and may contain substituents and / or heteroatoms. Typically, such cyclic groups contain 4 to 12 (e.g., 5, 6, 7 or 8) ring atoms.

[0115] In some catalysts, R 1 For hydrogen, R 2 Selected from C1-C 20 Alkyl, C2-C 20 alkenyl and C5-C 24 Aryl groups, such as C1-C6 alkyl, C2-C6 alkenyl and C5-C 14 Aryl. R 2 It can be phenyl, vinyl, methyl, isopropyl, or tert-butyl, optionally substituted with one or more groups selected from C1-C6 alkyl, C1-C6 alkoxy, phenyl, and the functional group Fn as defined above. 2 It can be a phenyl or vinyl group substituted with one or more groups selected from methyl, ethyl, chlorine, bromine, iodine, fluorine, nitro, dimethylamino, methyl, methoxy, and phenyl. R 2 It can be phenyl or -CH=C(CH3)2.

[0116] X 1 X 2 L 1 L 2 L 3 R 1 and R 2 Any two or more (typically two, three, or four) of the ligands may together form a cyclic group, including bidentate or polydentate ligands, such as those disclosed in U.S. Patent Application No. 5,312,940, the disclosure of which is incorporated herein by reference. When X 1 X 2 L 1 L 2 L 3 R 1 and R 2When any one of the elements is linked to form a cyclic group, these cyclic groups may contain 4 to 12 atoms (e.g., 4, 5, 6, 7, or 8), or may contain 2 or 3 such rings, which may be fused or linked. The cyclic groups may be aliphatic or aromatic, and may contain heteroatoms and / or be substituted. In some cases, the cyclic groups may form bidentate or tripentate ligands. Examples of bidentate ligands include, but are not limited to, bisphosphine, dialkoxide, alkyldiketonate, and aryldiketonate.

[0117] The second group of catalysts, commonly referred to as second-generation Grubbs-type catalysts, has the structure shown in formula (I), where L 1 For carbene ligands with the structure of formula (II), , (II) Therefore, the complex can have the structure shown in formula (III). , (III) Where M, m, n, X 1 X 2 L 2 L 3 R 1 and R 2 As defined in the first group of catalysts, the remaining substituents are defined as follows: X and Y are heteroatoms, typically selected from N, O, S, and P. Since O and S are divalent atoms, when X is O or S, p must be 0; when Y is O or S, q must be 0, and k is 0 or 1. However, when X is N or P, p is 1; when Y is N or P, q is 1. Both X and Y can be N. Q 1 Q 2 Q 3 and Q 4 For connecting bonds, such as alkylene groups (including substituted alkylene groups, heteroatom-containing alkylene groups, and substituted heteroatom-containing alkylene groups, such as substituted and / or heteroatom-containing alkylene groups) or -(CO)-, w, x, y, and z are independently 0 or 1, indicating that each connecting bond is optional. w, x, y, and z can all be 0. Furthermore, Q 1 Q 2 Q 3 and Q 4 Two or more substituents on adjacent atoms can link together to form additional cyclic groups; and R 3 R 3A R4 and R 4A Independently selected from hydrogen, hydrocarbon groups, substituted hydrocarbon groups, heteroatom-containing hydrocarbon groups, and substituted heteroatom-containing hydrocarbon groups. Furthermore, X and Y can be independently selected from carbon and one of the aforementioned heteroatoms, but no more than one of X and Y can be a carbon atom. Further, L 2 and L 3 They can collectively form a bidentate electron donor heterocyclic ligand. Furthermore, R 1 and R 2 They can co-form indenyl groups. Furthermore, X 1 X 2 L 2 L 3 X and Y can further coordinate with boron or carboxylate.

[0118] In addition, X 1 X 2 L 1 L 2 L 3 R 1 R 2 R 3 R 3A R 4 R 4A Q 1 Q 2 Q 3 and Q 4 Any two or more of them can together form a cyclic group, X 1 X 2 L 2 L 3 Q 1 Q 2 Q 3 Q 4 R 1 R 2 R 3 R 3A R 4 and R 4A Any one or more of them can be attached to the carrier. X 1 X 2 L 1 L 2 L 3 R 1 R 2 R 3 R 3A R 4 and R 4AAny two or more of them can also be represented as -A-Fn, where "A" is a divalent hydrocarbon group selected from alkylene and arylalkylene, wherein the alkyl portion of the alkylene and arylalkylene can be straight-chain or branched, saturated or unsaturated, cyclic or acyclic, substituted or unsubstituted, wherein the aryl portion of the arylalkylene can be substituted or unsubstituted, wherein heteroatoms and / or functional groups can be present in the aryl or alkyl portion of the alkylene and arylalkylene, Fn is a functional group, or together they form a cyclic group, and X 1 X 2 L 2 L 3 Q 1 Q 2 Q 3 Q 4 R 1 R 2 R 3 R 3A R 4 and R 4A Any one or more of them can be connected to the carrier.

[0119] A specific class of carbene ligands with the structure of formula (II) are commonly referred to as N-heterocyclic carbene (NHC) ligands, where R 3A and R 4A They are linked to form a cyclic group, where at least one of X or Y is nitrogen, or Q... 3 Or Q 4 At least one of them is a heteroatom-containing hydrocarbon group or a substituted heteroatom-containing hydrocarbon group, wherein at least one heteroatom is nitrogen.

[0120] R 3A and R 4A They can be linked to form cyclic groups, giving the carbene ligand the structure shown in formula (IV).

[0121] (IV) Among them, R 3 and R 4 As defined in the second group of catalysts above, R 3 and R 4 At least one of them (e.g., R) 3 and R 4Q is an alicyclic or aromatic compound having 1 to 5 rings, and optionally contains one or more heteroatoms and / or substituents. Q is a linking bond, typically an alkylene group linking bond, including substituted alkylene groups, heteroatom-containing alkylene groups, and substituted heteroatom-containing alkylene groups; wherein two or more substituents on adjacent atoms in Q can also be linked to form additional cyclic structures, which can be similarly substituted to form fused polycyclic structures having 2 to 5 rings. Q is typically (but not necessarily) a two-atom or three-atom linking bond.

[0122] Therefore, it is suitable as L 1 Examples of N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands include, but are not limited to, the following compounds, where DIPP or DiPP represents diisopropylphenyl and Mes represents 2,4,6-trimethylphenyl:

[0123]

[0124]

[0125]

[0126] .

[0127] Therefore, it is suitable as L 1 Other examples of N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands include, but are not limited to, the following: , Where R W1 R W2 R W3 and R W4 Independently, it is hydrogen, an unsubstituted hydrocarbon group, a substituted hydrocarbon group, or a hydrocarbon group containing a heteroatom; wherein, R W3 and R W4 One or both of them can be independently selected from halogen, nitro, amide, carboxyl, alkoxy, aryloxy, sulfonyl, carbonyl, thio, or nitroso.

[0128] Furthermore, U.S. patent applications 7,378,528, 7,652,145, 7,294,717, 6,787,620, 6,635,768, and 6,552,139 further describe what is suitable as L 1 Examples of N-heterocyclic carbene (NHC) ligands, the contents of which are incorporated herein by reference.

[0129] In addition, the thermally activated N-heterocyclic carbene precursor disclosed in U.S. Patent Application No. 6,838,489 can also be used in this invention, the disclosure of which is incorporated herein by reference.

[0130] When M is ruthenium, the composition can have the structure shown in formula (V).

[0131] (V) Where, n, X 1 X 2 L 2 L 3 R 1 and R 2 As defined in the first group of catalysts, k, R 3 R 4 And Q is as defined in the second group of catalysts.

[0132] More preferably, Q is a structure with -CR 11 R 12 -CR 13 R 14 -or-CR 11 =CR 13 - Diatomic bonding, such as -CR 11 R 12 -CR 13 R 14 -, where R 11 R 12 R 13 and R 14 Independently selected from hydrogen, hydrocarbon groups, substituted hydrocarbon groups, heteroatom-containing hydrocarbon groups, substituted heteroatom-containing hydrocarbon groups, and functional groups. Examples of functional groups include, but are not limited to, carboxyl groups, C1-C... 20 Alkoxy, C5-C 24 Aryloxy group, C2-C 20 Alkoxycarbonyl, C5-C 24 aryloxycarbonyl, C2-C 24 Acyloxy group, C1-C 20 Alkyl thio, C5-C 24 Arylthio, C1-C 20 alkylsulfonyl and C1-C 20 Alkyl sulfinyl group; optionally substituted with one or more groups selected from C1-C1. 12 Alkyl, C1-C 12 Alkoxy, C5-C 14 Aryl, hydroxyl, mercapto, formyl, and halides. R 11 R 12 R 13 and R 14It can be independently selected from hydrogen, C1-C 12 Alkyl, substituted C1-C 12 Alkyl, C1-C 12 Heteroalkyl, substituted C1-C 12 Heteroalkyl, phenyl, and substituted phenyl. Alternatively, R 11 R 12 R 13 and R 14 Any two elements can be linked to form substituted or unsubstituted, saturated or unsaturated ring structures (e.g., C4-C). 12 (Alicyclic group or C5 or C6 aromatic group), the ring structure itself can be substituted, for example, by linking or fused alicyclic or aromatic groups, or other substituents. On the other hand, R 11 R 12 R 13 and R 14 Any one or more of them contain one or more connection keys. Furthermore, R 3 and R 4 It can be an unsubstituted phenyl or a phenyl substituted with one or more substituents, wherein the substituents are selected from C1-C1. 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 heteroaryl, C6-C 24 Araneyl, C6-C 24 Alkyl or aryl groups or halides. Additionally, X 1 and X 2 It can be halogen.

[0133] When R 3 and R 4 When they are aromatic, they usually, but not necessarily, consist of one or two aromatic rings; they may or may not be substituted, for example, R... 3 and R 4 It can be phenyl, substituted phenyl, biphenyl, substituted biphenyl, etc. R 3 and R 4 They can be the same, and each can be an unsubstituted phenyl or a phenyl substituted with up to three substituents selected from C1-C1. 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24Aryl, C5-C 24 heteroaryl, C6-C 24 Araneyl, C6-C 24 Alkyl aryl or halides. Any substituents present can be hydrogen, C1-C. 12 Alkyl, C1-C 12 Alkoxy, C5-C 14 Aryl, substituted C5-C 14 Aryl or halides. For example, R 3 and R 4 It is mesityl (i.e., Mes as defined in this paper).

[0134] The third group of catalysts has the structure shown in formula (I), where M, m, n, and X are... 1 X 2 R 1 and R 2 As defined in the first group of catalysts; L 1 A strongly coordinated neutral electron-donating ligand, such as any of the ligands described in the first and second groups of catalysts; L 2 and L 3 It is a weakly coordinated neutral electron-donating ligand, in the form of an optionally substituted heterocyclic group. Similarly, n is 0 or 1, such that L... 3 It may or may not be present. Typically, in the third group of catalysts, L... 2 and L 3 This refers to a substituted five- or six-membered monocyclic group containing 1 to 4 (e.g., 1 to 3, 1 to 2) heteroatoms, or a substituted bicyclic or polycyclic structure consisting of 2 to 5 such five- or six-membered monocyclic groups. If the heterocyclic group is substituted, substitution must not be made on the coordinating heteroatom, and no single cyclic group within the heterocyclic group is typically substituted by more than 3 substituents.

[0135] For the third group of catalysts, L 2 and L 3 Examples include, but are not limited to, heterocycles containing nitrogen, sulfur, oxygen, or mixtures thereof.

[0136] Applicable to L 2 and L 3Examples of nitrogen-containing heterocycles include pyridine, bipyridine, pyridazine, pyrimidine, bipyridamine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, pyrrole, 2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazolium, 1,2,3-triazole, 1,2,4-triazole, indole, 3H-indole, 1H-isoindole, cyclopentyl(b)pyridine, indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, cyclopentylene, quinazoline, naphthidine, piperidine, piperazine, pyrrolidine, pyrazolidine, quinine ring, imidazoline, picolylimine, purine, benzimidazole, bisimidazole, phenazine, acridine, and carbazole. Furthermore, the nitrogen-containing heterocycle may optionally be substituted with non-hydrogen substituents on the noncoordinate heteroatom.

[0137] Applicable to L 2 and L 3 Examples of sulfur-containing heterocycles include thiophene, 1,2-dithiocyclopentadiene, 1,3-dithiocyclopentadiene, thiepin, benzo(b)thiophene, benzo(c)thiophene, benzothiophene, dibenzothiophene, 2H-thiaran, 4H-thiaran, and thioanthrene.

[0138] Applicable to L 2 and L 3 Examples of oxygen-containing heterocycles include 2H-pyran, 4H-pyran, 2-pyranone, 4-pyranone, 1,2-dioxin, 1,3-dioxin, oxaheptaene, furan, 2H-1-benzopyran, coumarin, coumarone, chromene, benzodihydropyran-4-one, isochromen-1-one, isochromen-3-one, xanthan, tetrahydrofuran, 1,4-dioxane, and dibenzofuran.

[0139] Applicable to L 2 and L 3 Examples of mixed heterocyclic compounds include isoxazole, oxazole, thiazole, isothiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxtriazole, 1,2,3,5-oxtriazole, 3H-1,2,3-dioxazole, 3H-1,2-oxathiole, 1,3-oxathiole, 4H-1,2-oxazine, 2H-1,3-oxazine, 1,4-oxazine, 1,2,5-oxathiazine, o-isooxazine, phenoxazine, phenthiazine, pyrano[3,4-b]pyrrole, indoxazine, benzoxazole, anthranil, and morpholine.

[0140] L 2 and L3 The ligand can be an aromatic nitrogen- or oxygen-containing heterocycle, such as a monocyclic N-heteroaryl ligand optionally substituted with 1 to 3 (e.g., 1 or 2) substituents. L 2 and L 3 Specific examples of ligands are pyridines and substituted pyridines, such as 3-bromopyridine, 4-bromopyridine, 3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6-dibromopyridine, 3-chloropyridine, 4-chloropyridine, 3,5-dichloropyridine, 2,4,6-trichloropyridine, 2,6-dichloropyridine, 4-iodopyridine, 3,5-diiodopyridine, 3,5-dibromo-4-methylpyridine, 3,5-dichloro-4-methylpyridine, 3,5-dimethyl-4-bromopyridine, 3,5-dimethylpyridine, 4-methylpyridine, 3,5-diisopropylpyridine, 2,4,6-trimethylpyridine, 2,4,6-triisopropylpyridine, 4-(tert-butyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine, 3,5-dichloro-4-phenylpyridine, etc.

[0141] Typically, in L 2 and / or L 3 Any substituents present on the surface are selected from: halogens, C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5-C 24 Aryl, substituted C5-C 24 Aryl, C5-C 24 heteroaryl, substituted C5-C 24 heteroaryl, C6-C 24 Alkyl, substituted C6-C 24 Alkyl, C6-C 24 Heteroalkylaryl, substituted C6-C 24 Heteroalkylaryl, C6-C 24 Aryl alkyl, substituted C6-C 24 Araneyl, C6-C 24 Heteroalkyl, substituted C6-C 24 Heteroaryl groups, and various functional groups; suitable functional groups include, but are not limited to: C1-C 20 Alkoxy, C5-C 24 Aryloxy group, C2-C 20 Alkyl carbonyl, C6-C 24 aryl carbonyl, C2-C 20 Alkyl carbonyl group, C6-C 24 aryl carbonyl group, C2-C 20 Alkoxycarbonyl, C6-C 24 Aromatic oxycarbonyl, halogenated carbonyl, C2-C 20Alkyl carbonate group, C6-C 24 Aryl carbonate group, carboxyl group, carboxyl group, carbamoyl group, mono(C1-C) 20 alkyl)-substituted carbamoyl, di(C1-C 20 alkyl)-substituted carbamoyl, di-N-(C1-C 20 Alkyl), N-(C5-C) 24 aryl)-substituted carbamoyl, mono(C5-C) 24 aryl)-substituted carbamoyl, di(C6-C) 24 aryl)-substituted carbamoyl, thiocarbamoyl, mono(C1-C) 20 alkyl)-substituted thiocarbamoyl, di(C1-C 20 alkyl)-substituted thiocarbamoyl, di-N-(C1-C) 20 alkyl)-N-(C6-C 24 aryl)-substituted thiocarbamoyl, mono-(C6-C) 24 aryl)-substituted thiocarbamoyl, di(C6-C) 24 Aryl)-substituted thiocarbamoyl, ureoyl, formyl, thiocarbamoyl, amino, mono(C1-C) 20 alkyl) substituted amino, di(C1-C 20 Alkyl) substituted amino, mono(C5-C) 24 aryl)-substituted amino groups, di(C5-C) 24 aryl-substituted amino groups, di-N-(C1-C) 20 Alkyl), N-(C5-C) 24 aryl-substituted amino groups, C2-C 20 Alkylamide group, C6-C 24 Aryl amide group, imine group, C1-C 20 Alkylimine group, C5-C 24 Arylimine, nitro, and nitroso groups. Furthermore, two adjacent substituents can together form a ring, typically a five- or six-membered aliphatic or aryl ring, optionally containing 1-3 heteroatoms and 1-3 substituents as described above.

[0142] L 2 and L 3 Substituents on the surface include, but are not limited to: halogens, C1-C 12 Alkyl, substituted C1-C 12 Alkyl, C1-C 12 Heteroalkyl, substituted C1-C 12 Heteroalkyl, C5-C 14 Aryl, substituted C5-C 14 Aryl, C5-C 14heteroaryl, substituted C5-C 14 heteroaryl, C6-C 16 Alkyl, substituted C6-C 16 Alkyl, C6-C 16 Heteroalkylaryl, substituted C6-C 16 Heteroalkylaryl, C6-C 16 Aryl alkyl, substituted C6-C 16 Araneyl, C6-C 16 Heteroalkyl, substituted C6-C 16 Heteroaryl, C1-C 12 Alkoxy, C5-C 14 Aryloxy group, C2-C 12 Alkyl carbonyl, C6-C 14 aryl carbonyl, C2-C 12 Alkyl carbonyl group, C6-C 14 aryl carbonyl group, C2-C 12 Alkoxycarbonyl, C6-C 14 Aromatic oxycarbonyl, halocarbonyl, formyl, amino, mono-(C1-C) 12 alkyl)-substituted amino, bis-(C1-C) 12 Alkyl) substituted amino, mono-(C5-C) 14 aryl)-substituted amino groups, bis-(C5-C) 14 Aryl-substituted amino groups and nitro groups.

[0143] In another embodiment, the substituent is a halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, phenyl, substituted phenyl, formyl, N,N-bis(C1-C6 alkyl)amino, nitro, and nitrogen-containing heterocycles as described above (including, for example, pyrrolidine, piperidine, piperazine, pyrazine, pyrimidine, pyridine, pyridazine, etc.).

[0144] L 2 and L 3 They can also co-form bidentate or polydentate ligands containing two or more (usually two) coordinating heteroatoms (such as N, O, S, or P), for example, Brookhart-type diimine ligands. A representative bidentate ligand has the structure shown in formula (VI).

[0145] (VI) Where R 15 R 16 R 17 and R 18 It can be a hydrocarbon group (e.g., C1-C). 20 Alkyl, C2-C 20 alkenyl, C2-C 20alkynyl group, C5-C 24 Aryl, C6-C 24 Alkyl or C6-C 24 Araneyl groups), substituted hydrocarbon groups (e.g., substituted C1-C...) 20 Alkyl, C2-C 20 alkenyl, C2-C 20 alkynyl group, C5-C 24 Aryl, C6-C 24 Alkyl or C6-C 24 Aryl groups), heteroatom-containing hydrocarbon groups (e.g., C1-C) 20 Heteroalkyl, C5-C 24 heteroaryl, C6-C containing heteroatoms 24 Aryl groups or C6-C groups containing heteroatoms 24 Alkyl groups), substituted heteroatom-containing hydrocarbon groups (e.g., substituted C1-C...). 20 Heteroalkyl, C5-C 24 heteroaryl, C6-C containing heteroatoms 24 Aryl groups or C6-C groups containing heteroatoms 24 alkylaryl), or (1)R 15 and R 16 (2)R 17 and R 18 (3)R 16 and R 17 , or (4)R 15 and R 16 and R 17 and R 18 They can co-form rings, i.e., N-heterocyclic rings. In this case, the cyclic groups formed can be five-membered or six-membered rings, usually aromatic rings.

[0146] In the fourth group of catalysts having the structure shown in formula (I), the two substituents can together form a bidentate or a tripentate ligand. Examples of bidentate ligands include, but are not limited to, bisphosphine, dialkoxylates, alkyl diketoates, and aryl diketoates. Specific examples include P(Ph)2CH2CH2P(Ph)2-, As(Ph)2CH2CH2As(Ph2)-, -P(Ph)2CH2CH2C(CF3)2O-, binaphtholate dianions, pinacolated ianions, -P(CH3)2(CH2)2P(CH3)2-, and -OC(CH3)2(CH3)2CO-. Among them, the bidentate ligands can 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 X. 1 X 2 L 1 L 2 L 3 R 1 and R 2 Any three of them (e.g., X) 1 L 1 and L 2 The cyclopentadienyl, indenyl, or fluorenyl groups formed together, and each cyclopentadienyl, indenyl, or fluorenyl group may optionally be substituted by: C2-C 20 alkenyl, C 2- C 20 Alkyne group, C1-C 20 Alkyl, C5-C 20 Aryl, C1-C 20 Alkoxy, C2-C 20 Alkenyl groups, C2-C 20 Acryloxy group, C5-C 20 Aryloxy group, C2-C 20 Alkoxycarbonyl, C1-C 20 Alkylthio, C1-C 20 alkylsulfonyl or C1-C 20 Alkyl sulfinyl groups, each of which may be further substituted with a C1-C6 alkyl, a halide, a C1-C6 alkoxy, or a phenyl group (optionally substituted with a halide, a C1-C6 alkyl, or a C1-C6 alkoxy). In such compounds, X, L 1 and L 2 They can co-form cyclopentadienyl or indenyl groups, each optionally bonded by a vinyl group or a C1-C group. 10 Alkyl, C5-C 20 Aryl, C1-C10 Carboxylic esters, C2-C 10 Alkoxycarbonyl, C1-C 10 Alkoxy or C5-C 20 Aryloxy substitution, wherein each of the above substituents is optionally substituted with a C1-C6 alkyl, halogen, C1-C6 alkoxy, or phenyl (optionally substituted with a halogen, C1-C6 alkyl, or C1-C6 alkoxy). X, L 1 and L 2 They can co-form a cyclopentadienyl group, optionally substituted with vinyl, hydrogen, methyl, or phenyl groups. Tetradentate ligands include, but are not limited to, O2C(CH2)2P(Ph)(CH2)2P(Ph)(CH2)2CO2, phthalocyanine, and porphyrin.

[0147] Among them, the complex obtained by coordination of Y with a metal is an example of the fifth group of catalysts, usually referred to as the "Grubbs-Hoveyda" catalyst. The Grubbs-Hoveyda metathesis active metal carbene complex can be represented by formula (VII).

[0148] (VII) in: M is a group 8 transition metal, especially Ru or Os, or more particularly Ru; X 1 X 2 and L 1 As defined above 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; R 5 R 6 R 7 and R 8 Each is 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 (where "A" and "Fn" are as defined above); Y, Z, R 5 R 6 R 7 and R 8 Any combination of these can be linked together to form one or more cyclic groups; n is 0, 1, or 2, such that n is 1 when the heteroatom is divalent O or S; n is 2 when the heteroatom is trivalent N or P; and n is 2 when the heteroatom is divalent N or P. Z is selected from the group consisting of hydrogen, alkyl, aryl, functionalized alkyl, and functionalized aryl, wherein the functionalized group may independently be one or more of the following groups: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, urethane, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec-butyl, tert-butyl, neopentyl, benzyl, phenyl, and trimethylsilyl; and X 1 X 2 L 1 Y, Z, R 5 R 6 R 7 and R 8 Any one or more combinations of these can be attached to the carrier. Furthermore, R... 5 R 6 R 7 R 8 Z can be independently a thioisocyanate, cyanate, or thiocyanate.

[0149] Examples of complexes containing the Grubbs-Hoveyda ligand suitable for use in this invention include:

[0150] Where L 1 X 1 X 2 And M as described for any other group of catalysts. Suitable chelated carbenes and carbene precursors are further described in detail in Pederson et al. (U.S. Patent Nos. 7,026,495 and 6,620,955, the disclosures of which are incorporated herein by reference) and Hoveyda et al. (U.S. Patent Nos. 6,921,735 and WO0214376, the disclosures of which are incorporated herein by reference).

[0151] Other available complexes include L according to formula (I), formula (III) or formula (V). 2 and R 2 Structures formed by interconnection, such as styrene compounds (including functional groups for attachment to a support). Examples of said functional groups being trialkoxysilyl functionalized groups include, but are not limited to, the following:

[0152] Further examples of complexes containing linker ligands include: neutral NHC ligands with anionic ligands, neutral NHC ligands with alkylene ligands, and neutral NHC ligands with L... 2 Ligands, neutral NHC ligands and L 3 Those ligands, anionic ligands, and alkylene ligands, and any combination thereof, that have bonds between them. Due to the large number of possible structures, they cannot all be listed here, but some suitable structures based on formula (III) include: .

[0153] In addition to the catalysts having the structure shown in formula (I) above, other transition metal carbene complexes include, but are not limited to: A neutral ruthenium or osmium metal carbene complex containing a metal center in the +2 oxidation state, with 16 electrons and a five-coordinate structure, has the general formula (IX). A neutral ruthenium or osmium metal carbene complex containing a metal center in the +2 oxidation state, with 18 electrons and a six-coordinate structure, has the general formula (X). A ruthenium or osmium metal carbene complex containing a metal center in the +2 oxidation state, having 14 electrons and a four-coordinate structure, has the general formula (XI); and A ruthenium or osmium metal carbene complex containing a metal center in the +2 oxidation state, with 14 or 16 electrons, having a tetracoordinate or pentacoordinate structure, respectively, and its general formula is (XII).

[0154] in: M, X 1 X 2 L 1 L 2 L 3 R 1 and R 2 As defined by any of the four groups of catalysts previously defined; r and s are each independently 0 or 1; t is an integer in the range of 0-5; k is an integer in the range of 0-1; Y is any noncoordinate anion (e.g., halide ions, BF4). - wait); Z 1 and Z 2 Each is independently selected from -O-, -S-, and -NR. 2 -、-PR 2 -、-P(=O)R 2 -、P(OR 2)-、P(=O)(OR 2 -, C(=O)-, -C(=O)O-, -OC(=O)O-, -OC(=O)O-, -S(=O)-, -S(=O)2-, and C1-C with optional substitution and / or optional heteroatom content. 20 Hydroxyl linkage; Z 3 It can be any cationic group, such as -P(R) 2 )3 + or -N(R) 2 )3 + ;and X 1 X 2 L 1 L 2 L 3 Z 1 Z 2 Z 3 R 1 and R 2 Any two or more of them can together form a cyclic group (e.g., a polydentate ligand), where X 1 X 2 L 1 L 2 L 3 Z 1 Z 2 Z 3 R 1 and R 2 Any one or more of them can be connected to the carrier.

[0155] In addition, another group of metal carbene olefin metathesis catalysts that can be used in the catalyst compositions of the present invention disclosed herein are group 8 transition metal complexes having the structure shown in formula (XIII):

[0156] (XIII) in: M is a group 8 transition metal, particularly ruthenium or osmium, or more particularly ruthenium; X 1 X 2 L 1 and L 2 As defined in the first and second groups of catalysts above; R G1 R G2 R G3 R G4 R G5 and R G6Each is independently selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, alkenyl containing heteroatoms, 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, cyanate, thiocyanate, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide, halogen-substituted amide, trifluoro The group consisting of amides, sulfides, disulfides, sulfonates, carbamates, silanes, siloxanes, phosphines, phosphates, borates, or -A-Fn (where "A" is a divalent hydrocarbon group selected from alkylene and arylalkylene groups, wherein the alkyl portion of the alkylene and arylalkylene groups can be straight-chain or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted; wherein the aryl portion of the arylalkylene group can be substituted or unsubstituted, and heteroatoms and / or functional groups can be present in the aryl or alkyl portion of the alkylene and arylalkylene groups; Fn is a functional group), or R G1 R G2 R G3 R G4 R G5 and R G6 Any one or more of them can be interconnected to form a cyclic group, or R G1 R G2 R G3 R G4 R G5 and R G6 Any one or more of them can be connected to the carrier.

[0157] Furthermore, one of the group 8 transition metal complexes shown in formula (XIII) is the same as the group 8 transition metal complex shown in formula (XIV):

[0158] (XIV) in: M, X 1 X 2 L 1 L 2 As defined above for Group 8 transition metal complexes of formula (XIII); R G7 R G8 R G9 R G10 R G11 R G12 R G13 R G14 R G15 and RG16 As mentioned above, the R of the group 8 transition metal complex of formula (XIII) G1 R G2 R G3 R G4 R G5 and G6 Defined, or R G7 R G8 R G9 R G10 R G11 R G12 R G13 R G14 R G15 and R G16 Any one or more of them can be interconnected to form a ring structure, or R G7 R G8 R G9 R G10 R G11 R G12 R G13 R G14 R G15 and R G16 Any one or more of them can be connected to the carrier.

[0159] In addition, another group 8 transition metal complex represented by formula (XIII) is the group 8 transition metal complex represented by formula (XV):

[0160] (XV) Among them, M and X 1 X 2 L 1 and L 2 As defined above for Group 8 transition metal complexes of formula (XIII); In addition, another type of olefin metathesis catalyst that can be used in the catalyst compositions of the present invention disclosed herein is a group 8 transition metal complex containing a Schiff base ligand and having the structure shown in formula (XVI):

[0161] (XVI) in: M is a group 8 transition metal, particularly ruthenium or osmium, or more particularly ruthenium; X 1 and L 1 As defined above for the first and second groups of catalysts; Z is selected from oxygen, sulfur, selenium, and NR. J11 PR J11AsR J11 and SbR J11 Groups; and R J1 R J2 R J3 R J4 R J5 R J6 R J7 R J8 R J9 R J10 and R J11 Each is independently selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, alkenyl containing heteroatoms, 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, cyanate, thiocyanate, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide, halogen-substituted amide, trihaloalkyl, alkylamino, alkylthiosulfonyl, alkylamino ... The group consisting of fluoroamides, sulfides, disulfides, sulfonates, carbamates, silanes, siloxanes, phosphines, phosphates, borates, or -A-Fn (where "A" is a divalent hydrocarbon group selected from alkylene and arylalkylene groups, wherein the alkyl portion of the alkylene and arylalkylene groups can be straight-chain or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted; wherein the aryl portion of the arylalkylene group can be substituted or unsubstituted, and heteroatoms and / or functional groups can be present in the aryl or alkyl portion of the alkylene and arylalkylene groups; Fn is a functional group), or R J1 R J2 R J3 R J4 R J5 R J6 R J7 R J8 R J9 R J10 and R J11 Any one or more of them can be interconnected to form a cyclic group, or R J1 R J2 R J3 R J4 R J5 R J6 R J7 R J8 R J9 R J10 and R J11 Any one or more of them can be connected to the carrier.

[0162] Furthermore, one group 8 transition metal complex shown in formula (XVI) is a group 8 transition metal complex containing a Schiff base ligand and having the structure shown in formula (XVII):

[0163] (XVII) in: M, X 1 L 1 Z, R J7 R J8 R J9 R J10 and R J11 As defined above for Group 8 transition metal complexes of formula (XVI); and R J12 R J13 R J14 R J15 R J16 R J17 R J18 R J19 R J20 and R J21 As mentioned above, for the R of the group 8 transition metal complex of formula (XVI) J1 R J2 R J3 R J4 R J5 and J6 Defined, or R J7 R J8 R J9 R J10 R J11 R J12 R J13 R J14 R J15 R J16 R J17 R J18 R J19 R J20 and R J21 Any one or more of them can be interconnected to form a ring structure, or R J7 R J8 R J9 R J10 R J11 R J12 R J13 R J14 R J15 R J16 R J17 R J18 R J19 RJ20 and R J21 Any one or more of them can be connected to the carrier.

[0164] In addition, another group 8 transition metal complex shown in formula (XVI) is a group 8 transition metal complex containing a Schiff base ligand and having the structure shown in formula (XVIII):

[0165] Formula (XVIII) Among them, M and X 1 L 1 Z, R J7 R J8 R J9 R J10 and R J11 As defined above for Group 8 transition metal complexes of formula (XVI).

[0166] In addition, another type of olefin metathesis catalyst that can be used in the catalyst compositions of the present invention disclosed herein is a group 8 transition metal complex containing a Schiff base ligand and having the structure shown in formula (XIX):

[0167] (XIX) in: M is a group 8 transition metal, particularly ruthenium or osmium, or more particularly ruthenium; X 1 L 1 R 1 and R 2 As defined above for the first and second groups of catalysts; Z is selected from oxygen, sulfur, selenium, and NR. K5 PR K5 AsR K5 and SbR K5 The group formed; m is 0, 1, or 2; and R K1 R K2 R K3 R K4 and R K5Each is independently selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, alkenyl containing heteroatoms, 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, cyanate, thiocyanate, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide, halogen-substituted amide, trifluoro The group consisting of amides, sulfides, disulfides, sulfonates, carbamates, silanes, siloxanes, phosphines, phosphates, borates, or -A-Fn (where "A" is a divalent hydrocarbon group selected from alkylene and arylalkylene groups, wherein the alkyl portion of the alkylene and arylalkylene groups can be straight-chain or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted; wherein the aryl portion of the arylalkylene group can be substituted or unsubstituted, and heteroatoms and / or functional groups can be present in the aryl or alkyl portion of the alkylene and arylalkylene groups; Fn is a functional group), or R K1 R K2 R K3 R K4 R K4 and R K5 Any one or more of them can be interconnected to form a cyclic group, or R K1 R K2 R K3 R K4 R K4 and R K5 Any one or more of them can be connected to the carrier. Furthermore, the catalysts of formulas (XVI) to (XIX) may optionally be contacted with an activating compound to at least partially break the bond between the group 8 transition metal and at least one Schiff base ligand; wherein the activating compound is a metal or silicon compound, selected from: copper (I) halides; with the general formula Zn(R Y1 Zinc compounds of 2, wherein R Y1 Halogen, C1-C7 are alkyl or aryl; derived from the formula SnR Y2 R Y3 R Y4 R Y5 The tin compound represented by R Y2 R Y3 R Y4 and RY 5 Each independently selects free halogens, C1-C 20 Alkyl, C3-C 10 The group consisting of cycloalkyl, aryl, benzyl, and C2-C7 alkenyl groups; and the group consisting of SiR Y6 R Y7R Y8 R Y9 The silicon compound represented, where R Y6 R Y7 R Y8 and R Y9 Each is independently selected from hydrogen, halogen, and C1-C. 20 The group consists of alkyl, halogroup, C1-C7 alkyl, aryl, heteroaryl, and vinyl groups. Furthermore, the catalysts of formulas (XVI) to (XIX) may optionally be contacted with an activating compound to at least partially break the bond between the group 8 transition metal and at least one Schiff base ligand; 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. Furthermore, the catalysts of formulas (XVI) to (XIX) may optionally be contacted with an activating compound to at least partially break the bond between the Group 8 transition metal and at least one Schiff base ligand; wherein the activating compound is an organic acid, such as: sulfonic acids, including but not limited to methanesulfonic acid, aminobenzenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, p-aminobenzenesulfonic 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, cyanoethyl... Acids, cyanobutyric acid, cyanophenoxyacetic acid, cyanopropionic acid, dichloroacetic acid, dichloroacetoacetic acid, dihydroxybenzoic acid, dihydroxymalic acid, dihydroxytartaric acid, dinicotinic acid, diphenylacetic acid, fluorobenzoic acid, formic acid, furan carboxylic acid, furoic acid, glycolic acid, hippuric acid, iodoacetic acid, iodobenzoic acid, lactic acid, rutinic acid, mandelic acid, α-naphthoic 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.

[0168] In addition, other examples of catalysts that can be used in the catalyst compositions of the present invention can be found in the following publications, the contents of which are incorporated herein by reference: U.S. Patent Nos. 7,687,635, 7,671,224, 6,284,852, 6,486,279 and 5,977,393; International Publication No. WO2010 / 037550; U.S. Patent Nos. 12 / 303,615, 10 / 590,380, 11 / 465,651 (Publication No. US2007 / 0043188) and 11 / 465,651 (Publication No. US 2008 / 0293905, amended); and European Patent Nos. EP1757613B1 and EP1577282B1.

[0169] Non-limiting examples of catalysts that can be used to prepare supported complexes and for use in the reactions disclosed herein include the following, some of which are identified herein by reference to their molecular weight for convenience:

[0170]

[0171]

[0172]

[0173]

[0174]

[0175] .

[0176] In the above molecular structural formula and chemical formula, 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 mesitylyl (i.e., 2,4,6-trimethylphenyl), DiPP and DIPP represent 2,6-diisopropylphenyl, and MiPP represents 2-isopropylphenyl.

[0177] Further examples of catalysts used in the preparation of supported complexes and in the reactions disclosed herein include the following: dichloro(3-methyl-2-butenyl)bis(tricyclopentylphosphine)ruthenium(II) (C716); dichloro(3-methyl-2-butenyl)bis(tricyclohexylphosphine)ruthenium(II) (C801); dichloro(phenylmethylene)bis(tricyclohexylphosphine)ruthenium(II) (C823); (1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl)dichloro(phenylmethylene)(triphenylphosphine)ruthenium(II) (C830); dichloro(phenylvinylene)bis(tricyclohexylphosphine)ruthenium(II) (C835); dichloro(tricyclohexylphosphine)(o-isopropoxyphenylmethylene) (Methyl)ruthenium(II) (C601); (1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl)dichloro(phenylmethylene)bis(3-bromopyridine)ruthenium(II) (C884); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]dichloro(o-isopropoxyphenylmethylene)ruthenium(II) (C627); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]dichloro(benzylidene)(triphenylphosphine)ruthenium(II) (C831); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]dichloro(benzylidene)(methyldiphenylphosphine)ruthenium(II) (C769); [1 [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]dichloro(benzylene)(tricyclohexylphosphine)ruthenium(II) (C848); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]dichloro(benzylene)(diethylphenylphosphine)ruthenium(II) (C735); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]dichloro(benzylene)(tri-n-butylphosphine)ruthenium(II) (C771); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]dichloro(3-methyl-2-butenyl)(triphenylphosphine)ruthenium(II) (C809); [1,3-bis-(2,4,6-... [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolium]dichloro(3-methyl-2-butenyl)(methyldiphenylphosphine)ruthenium(II) (C747); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolium]dichloro(3-methyl-2-butenyl)(tricyclohexylphosphine)ruthenium(II) (C827); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolium]dichloro(3-methyl-2-butenyl)(diethylphenylphosphine)ruthenium(II) (C713); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolium]dichloro(3-methyl-2-butenyl)(tri-n-butylphosphine)ruthenium(II) (C749);[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]dichloro(phenylindenylidene)(triphenylphosphine)ruthenium(II) (C931); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]dichloro(phenylindenylidene)(methylphenylphosphine)ruthenium(II) (C869); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]dichloro(phenylindenylidene)(methylphenylphosphine)ruthenium(II) (C869); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]dichloro(phenylindenylidene)(methylphenylphosphine)ruthenium(II) (C931); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolium]dichloro(phenylindene)(diethylphenylphosphine)ruthenium(II) (C949); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolium]dichloro(phenylindene)(diethylphenylphosphine)ruthenium(II) (C835); and [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolium]dichloro(phenylindene)(tri-n-butylphosphine)ruthenium(II) (C871).

[0178] Other catalysts that can be used in ROMP reactions and / or other metathesis reactions (e.g., closed-ring metathesis, cross-metathesis, open-ring cross-metathesis, autometathesis, ethylene alcoholysis, enolization, acyclic diene metathesis polymerization and combinations thereof) include the following structures:

[0179] .

[0180] Typically, the transition metal complexes used as catalysts in this paper can be prepared by several different methods, such as 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 U.S. Patent Nos. 749-750, 5,312,940, and 5,342,909, the disclosures of which are incorporated herein by reference. See also U.S. Patent Publication No. 2003 / 0055262, WO 02 / 079208, and 6,613,910, the disclosures of which are incorporated herein by reference. A synthetic method is described in WO 03 / 11455A1, the disclosure of which is incorporated herein by reference.

[0181] Metal carbene olefin metathesis catalysts can be group 8 transition metal complexes with the structure of formula (I) (commonly referred to as "first-generation Grubbs" catalysts), group 8 transition metal complexes with the structure of formula (III) (commonly referred to as "second-generation Grubbs" catalysts), or group 8 transition metal complexes with the structure of formula (VII) (commonly referred to as "Grubbs-Hoveyda" catalysts).

[0182] Metal carbene olefin metathesis catalysts can have the structure shown in formula (I).

[0183] (I) in: M is a group 8 transition metal; L 1 L 2 and L 3 It is a neutral electron donor ligand; n is 0 or 1; m is 0, 1, or 2; k is 0 or 1; X 1 and X 2 It is an anionic ligand; R 1 and R 2 Each is independently selected from hydrogen, hydrocarbon group, substituted hydrocarbon group, heteroatom-containing hydrocarbon group, substituted heteroatom-containing hydrocarbon group and functional group; Among them, X 1 X 2 L 1 L 2 L 3 R 1 and R 2 Any two or more of them can together form one or more cyclic groups, and further, X 1 X 2 L 1 L 2 L 3 R 1 and R 2 One or more of them can be connected to the carrier; The structure shown in equation (VII)

[0184] (VII) in: M is a group 8 transition metal; L 1 It is a neutral electron donor ligand; X1 and X 2 It is an anionic ligand; Y is a heteroatom, selected from O or N; R 5 R 6 R 7 and R 8 Each is independently selected from hydrogen, hydrocarbon group, substituted hydrocarbon group, heteroatom-containing hydrocarbon group, substituted heteroatom-containing hydrocarbon group and functional group; n is 0, 1, or 2; and Z is selected from hydrogen, hydrocarbon group, substituted hydrocarbon group, heteroatom-containing hydrocarbon group, substituted heteroatom-containing hydrocarbon group and functional group; Among them, Y, Z, R 5 R 6 R 7 and R 8 Any combination of these can connect to form one or more cyclic groups; furthermore, X 1 X 2 L 1 Y, Z, R 5 R 6 R 7 and R 8 Any combination of these can be attached to the carrier.

[0185] Metal carbene olefin metathesis catalysts can have the structure shown in formula (I).

[0186] (I) in: M is ruthenium; n is 0; m is 0; k is 1; L 1 and L 2 For trisubstituted phosphine, each is independently selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or, L 1 For N-heterocyclic carbene, selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethylcarbene, 1,3-bis(2,4,6-trimethylphenyl)imidazolidinedimethylcarbene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethylcarbene, and 1,3-bis(2,6-diisopropylphenyl)imidazolidinedimethylcarbene, L 2It is a trisubstituted phosphine, selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L 1 and L 2 For N-heterocyclic carbenes, each is independently selected. , 3-double(2) , 4 , 6-Trimethylphenyl)-2-imidazolidinedimethyl, 1 , 3-double(2) , 4 , 6-Trimethylphenyl)imidazol-2-ylene, 1 , 3-double(2) , 6-Diisopropylphenyl)-2-imidazolidinedimethyl and 1 , 3-double(2) , The group consisting of 6-diisopropylphenyl)imidazol-2-subunits; X 1 and X 2 It is a chloride; and R 1 For hydrogen, R 2 It is phenyl or -CH=C(CH3)2 or thiophene; or R 1 and R 2 Together they form 3-phenyl-1H-indene; The structure shown in equation (VII)

[0187] (VII) in: M is ruthenium; L 1 It is a trisubstituted phosphine, selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L 1 It is an N-heterocyclic carbene, selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethylcarbene, 1,3-bis(2,4,6-trimethylphenyl)imidazolidinedimethylcarbene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethylcarbene, and 1,3-bis(2,6-diisopropylphenyl)imidazolidinedimethylcarbene; X 1 and X 2 It is a chloride; Y represents oxygen; R 5 R 6 R 7 Both R8 and R8 are hydrogen; n is 1; and z stands for isopropyl.

[0188] An example of a metal carbene olefin metathesis catalyst has the structure shown in formula (I).

[0189] (I) in: M is ruthenium; n is 0; m is 0; k is 1; L 1 and L 2 Each of the three substituted phosphines is independently selected from tri-n-butylphosphine (Pn-Bu 3 ), tricyclopentylphosphine (PCp) 3 ), tricyclohexylphosphine (PCy) 3 ), triisopropylphosphine (Pi-Pr) 3 ), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh) 2 ), dimethylphenylphosphine (PMe) 2 Ph) and diethylphenylphosphine (PEt) 2 Ph); or L 1 For N-heterocyclic carbene, selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethylcarbene, 1,3-bis(2,4,6-trimethylphenyl)imidazolidinedimethylcarbene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethylcarbene, and 1,3-bis(2,6-diisopropylphenyl)imidazolidinedimethylcarbene, L 2 It is a trisubstituted phosphine, selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L 1 and L 2 It is an N-heterocyclic carbene, each independently selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethylcarbene, 1,3-bis(2,4,6-trimethylphenyl)imidazolidinedimethylcarbene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethylcarbene, and 1,3-bis(2,6-diisopropylphenyl)imidazolidinedimethylcarbene; X1 and X 2 It is a chloride; and R 1 For hydrogen, R 2 It is phenyl or -CH=C(CH3)2 or thiophene; or R 1 and R 2 Together they form the indene subunit.

[0190] An example of a metal carbene olefin metathesis catalyst has the structure shown in formula (VII).

[0191] (VII) in: M is ruthenium; L 1 It is a trisubstituted phosphine, selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L 1 It is an N-heterocyclic carbene, selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethylcarbene, 1,3-bis(2,4,6-trimethylphenyl)imidazolidinedimethylcarbene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethylcarbene, and 1,3-bis(2,6-diisopropylphenyl)imidazolidinedimethylcarbene; X 1 and X 2 It is a chloride; Y represents oxygen; R 5 R 6 R 7 and R 8 Each is hydrogen; n is 1; and z stands for isopropyl.

[0192] An example of a metal carbene olefin metathesis catalyst has the structure shown in formula (XV).

[0193] (XV) in: M is ruthenium; X 1 and X 2 It is a chloride; and L 1 and L 2The phosphine is trisubstituted and is independently selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L 1 For N-heterocyclic carbene, selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethylcarbene, 1,3-bis(2,4,6-trimethylphenyl)imidazolidinedimethylcarbene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethylcarbene, and 1,3-bis(2,6-diisopropylphenyl)imidazolidinedimethylcarbene, L 2 It is a trisubstituted phosphine, selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L 1 and L 2 It is an N-heterocyclic carbene, each independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethylcarbene, 1,3-bis(2,4,6-trimethylphenyl)imidazolidinedimethylcarbene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethylcarbene, and 1,3-bis(2,6-diisopropylphenyl)imidazolidinedimethylcarbene.

[0194] Metal carbene olefin metathesis catalysts include, for example, Umicore ruthenium metathesis Grubbs catalysts. ® First generation: M101 (dichloro(3-phenyl-1H-indenylidene)bis(tricyclohexylphosphine)ruthenium(II)), M102 (dichloro(benzylidene)bis(tricyclohexylphosphine)ruthenium(II)), M103 (dichloro(3-methyl-2-butenyl)bis(tricyclohexylphosphine)ruthenium(II)), M104 (dichloro(2-thienomethyl)bis(tricyclohexylphosphine)ruthenium(II)) and M110 (dichlorobis(isobutylphosphine)(3-phenyl-1H-indenylidene)ruthenium(II)); Umicore ruthenium metathesis Grubbs catalyst ®Second generation: M200 ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]dichloro(3-phenyl-1H-indene-1-yl)(triphenylphosphine)ruthenium(II)), M201 ([1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]dichloro(3-phenyl-1H-indene-1-yl)(triphenylphosphine)ruthenium(II)), M202 ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]dichloro(3-phenyl-1H-indene-1-yl)(triphenylphosphine)ruthenium(II)) [1,3-bis(2,4,6-trimethylphenyl)imidazolium-2-yl]dichloro(3-phenyl-1H-indene-1-yl)(tricyclohexylphosphine)ruthenium(II)), M203([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolium-2-yl]dichloro(3-phenyl-1H-indene-1-yl)(tricyclohexylphosphine)ruthenium(II)), M204([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolium-2-yl]dichloro(benzylidene)(tricyclohexylphosphine)ruthenium(II)), M206([1 [1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethyl]dichloro(benzylidene)(tricyclohexylphosphine)ruthenium(II)], M207([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]dichloro(3-methyl-2-buteneyl)(tricyclohexylphosphine)ruthenium(II)], M208([4,5-dimethyl-1,3-bis(2,4,6-trimethylphenyl)imidazol-2-yl]dichloro(2-thiophenemethyl) The following catalysts were used: ruthenium(II)-tricyclohexylphosphine, M209-[1,3-bis(2,4,6-trimethylphenyl)imidazolium-2-ylidene]dichloro(2-thienomethyl)(tricyclohexylphosphine)ruthenium(II) and M220-cis-[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolium-2-ylidene]dichloro(3-phenyl-1H-inden-1-ylidene)(triisopropylphosphite)ruthenium(II); and Umicore ruthenium metathesis Grubbs catalyst. ® Second generation (N-ligand): M310 ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]dichloro(3-phenyl-1H-indene-1-yl)(pyridyl)ruthenium(II)) and M350 ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]-[2-[[(2-methylphenyl)imino]methyl]-phenolic]-[3-phenyl-1H-indene-1-yl](chloro)ruthenium(II)); Umicore ruthenium metathesis Hoveyda-Grubbs catalyst ®First / Second Generation: M700 (Dichloro(2-isopropoxybenzyl)(tricyclohexylphosphine)ruthenium(II)), M710 ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolium]dichloro[(2-isopropoxy)(5-trifluoroacetamido)benzyl]ruthenium(II)), M711 ([1,3-bis(2,4,6-diisopropylphenyl)-2-imidazolium]dichloro[(2-isopropoxy)(5-trifluoroacetamido)benzyl]ruthenium(II)), M720 ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolium]dichloro(2-isopropoxybenzyl)ruthenium(II)), M721 ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolium]dichloro(2-isopropoxybenzyl)ruthenium(II)), [1,3-bis(2,6-diisopropylphenyl)-2-imidazolium]dichloro(2-isopropoxybenzyl)ruthenium(II)], M722 ([1,3-bis(2,6-diisopropylphenyl)-2-imidazolium]dichloro(2-isopropoxybenzyl)ruthenium(II)), M730 ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolium]dichloro[5-(isobutoxycarbonylamino)-2-isopropoxybenzyl]ruthenium(II)) and M731 ([1,3-bis(2,6-diisopropylphenyl)-2-imidazolium]dichloro[5-(isobutoxycarbonylamino)-2-isopropoxybenzyl]ruthenium(II)); Umicore bisNHC ruthenium metathesis Grubbs catalyst ® Second generation: M800 (bis[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethyl]dichloro(3-phenyl-1H-inden-1-yl)ruthenium(II)); and Umicore Z-selective ruthenium metathesis Hoveyda-Grubbs catalyst. ® Second generation: M2001 (1-[Rel-(2R,5R,7R)-adamantane-2,1-diyl][3-(2,4,6-trimethylphenyl)]-2-imidazolidinediyl](nitryl-O,O')(o-isopropoxybenzyl)ruthenium(II)).

[0195] Metal carbene olefin metathesis catalysts that can also be used in this invention include, for example, those disclosed in PCT / US2021 / 045673, the disclosure of which is incorporated herein by reference.

[0196] Suitable supports for any catalyst described herein may be synthetic, semi-synthetic, or naturally occurring materials, which may be organic or inorganic, such as polymers, ceramics, or metals. The connection between the catalyst and the support is typically (but not necessarily) covalent, and this covalent connection may be direct or indirect. Indirect covalent connections are typically (but not necessarily) achieved through functional groups on the support surface. Ionic connections also apply, including combinations of one or more anionic groups on a metal complex coupled to a support containing cationic groups, or combinations of one or more cationic groups on a metal complex coupled to a support containing anionic groups.

[0197] When used, a suitable carrier may be selected from silica, silicates, alumina, aluminum oxides, silica-alumina, aluminosilicates, zeolites, titanium oxides, titanium oxides, magnetite, magnesium oxide, boron oxide, clay, zirconium oxide, zirconium dioxide, carbon, polymers, cellulose, cellulose polymers, amylosic polymers, or combinations thereof. The carrier may include silica, silicates, or combinations thereof.

[0198] Supports that have been treated to include functional groups, inert groups, and / or excess ligands may also be used. Any functional group described herein is suitable for binding to a support and can generally be achieved using techniques known in the art. Inert groups may also be introduced onto the support, typically to reduce the number of available attachment sites on the support, for example, to control the location or number of complexes attached to the support.

[0199] According to techniques known in the art, metal carbene olefin metathesis catalysts can be used in olefin metathesis reactions. Metal carbene olefin metathesis catalysts are typically added to coating compositions in solid, solution, or suspension form. When a metal carbene olefin metathesis catalyst is added to a coating composition in suspension form, the catalyst is suspended in a carrier oil, such as mineral oil, paraffin oil, soybean oil, triisopropylbenzene, or any hydrophobic liquid, which has a sufficiently high viscosity to allow for effective dispersion of the catalyst and has sufficient inertness and a sufficiently high boiling point to prevent it from acting as a low-boiling-point impurity in the olefin metathesis reaction. It should be understood that the amount of catalyst used in the reaction (i.e., the "catalyst loading") depends on various factors, such as the type of reactants and the reaction conditions employed. Therefore, for each reaction, the catalyst loading can be preferably and independently selected. However, generally speaking, the catalyst content is in the range of about 0.1 ppm, 1 ppm or 5 ppm to about 10 ppm, 15 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm or 1000 ppm relative to the amount of olefin substrate.

[0200] The catalyst content is typically as low as about 0.00001 mol%, 0.0001 mol%, or 0.0005 mol% relative to the cyclic olefins present in the cyclic olefin composition, and as high as 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%.

[0201] When expressed as a molar ratio of monomer to catalyst, the catalyst loading (“monomer to catalyst ratio”) is typically in the range of approximately 10,000,000:1, 1,000,000:1, or 200,000:1, and approximately 100,000:1, 66,667:1, 40,000:1, 20,000:1, 10,000:1, 5,000:1, or 1,000:1. The metathesis reactions disclosed herein can be carried out under a dry, inert atmosphere. This atmosphere can be formed using any inert gas, including gases such as nitrogen and argon. An inert atmosphere is preferred for promoting catalyst activity, and a relatively low catalyst loading is typically used when the reaction is carried out under an inert atmosphere. The reactions disclosed herein can also be carried out in an oxygen- and / or water-containing atmosphere, and the reactions can be carried out under ambient conditions. However, the presence of oxygen or moisture in the reaction may require a higher catalyst loading compared to reactions carried out under an inert atmosphere. The reactions disclosed herein can also be carried out under reduced pressure if the vapor pressure of the reactants allows.

[0202] The reactions disclosed herein can be carried out in solvents, and any solvent that is inert to cross-metathesis can be used. Typically, solvents that can be used for metathesis reactions include organic solvents, protic solvents, or aqueous solvents, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof. Exemplary solvents include benzene, toluene, p-xylene, dichloromethane, 1,2-dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, methanol, ethanol, water, or mixtures thereof. The reactions disclosed herein can be carried out under pure conditions (i.e., without the use of solvents).

[0203] It should be understood that the temperature for the metathesis reaction carried out according to the method disclosed herein can be adjusted as needed, and may be at least about 78°C, 40°C, -10°C, 0°C, 10°C, 20°C, 25°C, 35°C, 50°C, 70°C, 100°C, or 150°C, or any of these values ​​may be used as the upper or lower limit of the temperature range. The reaction can be carried out at a temperature of at least about 35°C, or at a temperature of at least about 50°C.

[0204] When expressed as a percentage by weight (wt%) of the catalyst, the content of at least one metal carbene olefin metathesis catalyst in the olefin resin composition may be about 0.01-40 wt% (e.g., 0.1-35 wt%, 1-35 wt%, 5-25 wt%, 10-20 wt%) based on the total weight of the olefin resin composition.

[0205] thermoplastic hydrocarbon resins The coating composition of the present invention may contain at least one thermoplastic hydrocarbon resin. The thermoplastic hydrocarbon resins that can be used in the coating compositions of the present invention can be any thermoplastic hydrocarbon resin known in the art. For example, thermoplastic hydrocarbon resins include, but are not limited to, PMR, DCPD, C5, C9, C5 / C9, terpenes and IC thermoplastic resins, and hydrogenated, partially hydrogenated and unhydrogenated forms of these resins, as well as mixtures thereof.

[0206] As used herein, the term "C5 thermoplastic resin" refers to an aliphatic C5 hydrocarbon thermoplastic resin prepared by monomer polymerization, wherein the monomers include C5 and / or C6 olefins with boiling points in the range of about 20°C to about 200°C at atmospheric pressure. These monomers are typically produced in petroleum processing processes, such as cracking. The aliphatic C5 hydrocarbon thermoplastic resin of this invention can be produced by any method known in the art. The aliphatic C5 hydrocarbon thermoplastic resin can be prepared by cationic polymerization of cracked petroleum feedstocks containing C5 and C6 alkanes, olefins, and dienes (also referred to as "C5 monomers"). These monomer feedstocks contain cationic polymerizable monomers, such as 1,3-pentadiene, which, together with cyclopentene, pentene, 2-methyl-2-butene, 2-methyl-2-pentene, cyclopentadiene, and dicyclopentadiene, serve as the main reactant components. The polymerization reaction is catalyzed using Friedel-Crafts polymerization catalysts, such as Lewis acids (e.g., boron trifluoride (BF3), boron trifluoride complexes, aluminum trichloride (AlCl3), and alkyl aluminum chloride). In addition to the reactants, the non-polymerizable components in the feedstock include saturated hydrocarbons, which in some cases are co-distilled with unsaturated components (such as pentane, cyclopentane, or 2-methylpentane). Solid acid catalysts can also be used to produce aliphatic C5 hydrocarbon thermoplastic resins. Aliphatic C5 hydrocarbon thermoplastic resins include unhydrogenated, partially hydrogenated, or fully hydrogenated resins. Aliphatic C5 thermoplastic resins can be produced using Piccotac... ® C5 and Eastotac ® The C5H2 thermoplastic resin was obtained from Eastman Chemical Company (Kingsport, Tenn., USA). As used herein, the term "C5 / C9 thermoplastic resin" refers to an aliphatic / aromatic C5 / C9 thermoplastic resin prepared by monomer polymerization, wherein the monomer comprises: at least one unsaturated aromatic C8, C9, and / or C10 substance having a boiling point of about 100°C to about 300°C at atmospheric pressure; and at least one monomer comprising C5 and / or C6 olefin substances having a boiling point of about 20°C to about 200°C at atmospheric pressure. The C5 and / or C6 substances may include alkanes, alkenes, and dienes, and are also referred to as "C5 monomers". These monomer streams contain cationic polymerizable monomers, such as 1,3-pentadiene, which, together with cyclopentene, pentene, 2-methyl-2-butene, 2-methyl-2-pentene, cyclopentadiene, and dicyclopentadiene, serve as the main reactant components. Unsaturated aromatic C8, C9, and / or C10 monomers may be derived from petroleum distillates produced by naphtha cracking and are referred to as "C9 monomers". These monomer streams contain cationic monomers such as styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, indene, dicyclopentadiene, divinylbenzene, and other alkyl-substituted derivatives of these components. In some cases, Friedel-Crafts polymerization catalysts, such as Lewis acids (e.g., boron trifluoride (BF3), boron trifluoride complexes, aluminum trichloride (AlCl3), and alkylaluminum chloride), are used to catalyze the polymerization reaction. Solid acid catalysts can also be used to produce aliphatic / aromatic C5 / C9 hydrocarbon thermoplastic resins. In addition to the reactants, non-polymerizable components include aromatic hydrocarbons such as xylene, ethylbenzene, cumene, ethyltoluene, indene, methylindene, naphthalene, and other similar compounds. Non-polymerizable components in the feed stream can be incorporated into the thermoplastic resin through alkylation. Aliphatic / aromatic C5 / C9 hydrocarbon thermoplastic resins include unhydrogenated resins, partially hydrogenated resins, and fully hydrogenated resins. Aliphatic / aromatic C5 / C9 thermoplastic resins can be produced using Piccotac... ® The thermoplastic resin is available from Eastman Chemical Company. The C5 to C9 ratio is unrestricted. In other words, the C5 monomer content in a C5 / C9 thermoplastic resin can be any range between 0.1% and 100%, and conversely, the C9 monomer content in a C5 / C9 thermoplastic resin can be any range between 0.1% and 100%. As used herein, the term "C9 thermoplastic resin" refers to an aromatic C9 hydrocarbon thermoplastic resin, which is a thermoplastic resin prepared by polymerization of monomers comprising unsaturated aromatic C8, C9, and / or C10 substances with boiling points of about 100°C to about 300°C at atmospheric pressure. These monomers are typically produced in petroleum processing processes, such as cracking. The aromatic C9 hydrocarbon thermoplastic resin of this invention can be produced by any method known in the art. Aromatic C9 hydrocarbon thermoplastic resins can be prepared by cationic polymerization of aromatic C8, C9, and / or C10 unsaturated monomers derived from petroleum distillates from naphtha cracking, referred to as "C9 monomers". These monomer streams contain cationicly polymerizable monomers such as styrene, α-methylstyrene (AMS), β-methylstyrene, vinyltoluene, indene, dicyclopentadiene, divinylbenzene, and other alkyl-substituted derivatives of these components. In the polymerization of some C9 resins, aliphatic olefin monomers containing 4-6 carbon atoms are also present. In some cases, Friedel-Crafts polymerization catalysts, such as Lewis acids (e.g., boron trifluoride (BF3), boron trifluoride complexes, aluminum trichloride (AlCl3), and alkylaluminum chloride), are used to catalyze the polymerization reaction. In addition to the reactants, non-polymerizable components include, but are not limited to, aromatic hydrocarbons such as xylene, ethylbenzene, cumene, ethyltoluene, indene, methylindene, naphthalene, and other similar chemicals. Non-polymerizable components in the feed stream can be incorporated into the thermoplastic resin through alkylation. C9 hydrocarbon thermoplastic resins include unhydrogenated, partially hydrogenated, or fully hydrogenated resins. Aromatic C9 hydrocarbon thermoplastic resins can be produced using Picco ® C9 thermoplastic resins, as well as aliphatic hydrogenated and aliphatic / aromatic partially hydrogenated C9 H2 hydrocarbon thermoplastic resins, can be obtained as Regalite. ® The thermoplastic resin was obtained from Eastman Chemical Company. As used herein, the term "DCPD thermoplastic resin" refers to dicyclopentadiene (DCPD) thermoplastic resin, typically prepared by ring-opening metathesis polymerization (ROMP) or thermal polymerization of dicyclopentadiene in the presence of a strong acid catalyst (such as aqueous maleic acid or sulfuric acid). Dicyclopentadiene can also be prepared by the Diels-Alder reaction of two cyclopentadiene molecules, resulting in two stereoisomers: internal-DCPD and external-DCPD. Typically, over 90% of the DCPD molecules in commercially available DCPD are internal. DCPD thermoplastic resins include aromatic-modified DCPD resins as well as hydrogenated, partially hydrogenated, and non-hydrogenated resins; however, in most cases, only H2DCPD will be described here, as it is the most readily available form of DCPD on the market. Aromatic-modified DCPD is also considered a DCPD thermoplastic resin. Aromatic modification is carried out, for example, through C9 resin oils, styrene, or α-methylstyrene (AMS). Hydrogenated and partially hydrogenated DCPD, as well as aromatically modified DCPD resins that are hydrogenated and partially hydrogenated, can be produced using Escorez. ® 5000 series resin (ExxonMobil Chemicals, TX, US) was purchased.

[0207] As used herein, the term "IC thermoplastic resin" or "IC resin" refers to indene-coumarone (IC) thermoplastic resin, i.e., a synthetic thermoplastic terpene resin prepared using indene and coumarone feedstocks derived from heavy solvent naphtha obtained by distilling coal tar, a byproduct of coke production. The heavy solvent naphtha is rich in coumarone and indene, especially indene, and can be modified with phenol. These feedstocks can be formed by polymerization in BF3 or BF3 ether compounds. After polymerization, the catalyst can be removed by alkaline washing or lime treatment. Unreacted naphtha can be removed by steam distillation, thus separating the resin. IC thermoplastic resins can be used as plasticizers and can maintain stress-strain properties at high levels. Examples of such resins include Novales. ® C-indulamine and Novales ® CA phenol-modified indene-coumarone thermoplastic resins are available from Rutgers Germany GmbH in Duisburg, Germany. As used herein, the term "PMR" refers to a pure monomeric thermoplastic resin. Pure monomeric thermoplastic resins are prepared by polymerization of styrene-based monomers, such as styrene, α-methylstyrene, vinyltoluene, and other alkyl-substituted styrene. Pure monomeric thermoplastic resins are prepared by any method known in the art. In some cases, the pure monomeric raw materials used to prepare pure monomeric thermoplastic resins are synthetically produced or highly purified monomeric substances. For example, styrene can be obtained from ethylbenzene, or α-methylstyrene from cumene. Pure monomeric hydrocarbon thermoplastic resins can be prepared by cationic polymerization of styrene-based monomers (such as styrene, α-methylstyrene, vinyltoluene, and other alkyl-substituted styrene) using Friedel-Crafts polymerization catalysts, such as Lewis acids (e.g., boron trifluoride (BF3), boron trifluoride complexes, aluminum trichloride (AlCl3), and alkylaluminum chloride). Solid acid catalysts can also be used to prepare pure monomeric thermoplastic resins. The pure monomeric thermoplastic resins disclosed herein are unhydrogenated, partially hydrogenated, or fully hydrogenated resins. As used herein, the term "hydrogenated" can also be alternatively represented by the abbreviation "H2," where H2 appears before or after the resin type name to indicate that the resin type is hydrogenated or partially hydrogenated, such as "PMR H2" and "C5 H2." When "H2" is used herein, "H2" indicates both fully hydrogenated and partially hydrogenated resin samples. Therefore, "H2" refers to a resin in a fully hydrogenated or at least partially hydrogenated state. In some cases, pure monomeric thermoplastic resins are used as Piccolastic... ® Styrene-based thermoplastic resins, Kristalex ® Styrene / alkylstyrene hydrocarbon thermoplastic resins, Piccotex ® Alkyl styrene thermoplastic resins and Regalrez ® Hydrogenated or partially hydrogenated pure monomer thermoplastic resins are available from Eastman Chemical Company (Kingsport, Tenn., USA). As used herein, the term "terpene thermoplastic resin" or "polyterpene resin" refers to a thermoplastic resin prepared from at least one terpene monomer. For example, α-pinene, β-pinene, d-limonene, and dipentene can be polymerized in the presence of aluminum chloride to obtain a polyterpene thermoplastic resin. Other examples of polyterpene thermoplastic resins include Sylvares. ® TR 1100 and Sylvatraxx ® 4125 terpene thermoplastic resin (AZ Chem Holdings, LP, Jacksonville, Fla, US) and Piccolyte ®A125 terpene thermoplastic resin (Pinova, Inc., Brunswick, Ga., US). Terpene thermoplastic resins can also be modified with aromatic compounds. Sylvares ® ZT 105LT and Sylvares ® ZT 115 LT terpene thermoplastic resin is an aromatic modified resin (Az Chem Holdings, LP, Jacksonville, Fla., US). Preferably, the thermoplastic hydrocarbon resin is selected from PB-100 and Nevchem. ® 100, LX ® -2181, Nevchem ® The group consisting of 140 and its mixtures.

[0208] It should be understood that the thermoplastic hydrocarbon resins covered by the definitions of certain types of thermoplastic hydrocarbon resins (e.g., DCPD, PMR, C5, C9, C5 / C9, IC, terpenes, etc., including hydrogenated, partially hydrogenated, and unhydrogenated forms of these resins) also include resins of the same type produced by mixing or blending different raw materials to produce raw materials for the production of thermoplastic hydrocarbon resins. Furthermore, it should be understood that, at least for the PMR and terpene thermoplastic hydrocarbon resins discussed herein, these thermoplastic hydrocarbon resins include various known derivatives of such thermoplastic hydrocarbon resins, such as phenol-modified and rosin-modified forms of the resins.

[0209] At least one thermoplastic hydrocarbon resin that can be used in this invention includes, for example, those thermoplastic hydrocarbon resins disclosed in PCT / US2021 / 045673, the disclosure of which is incorporated herein by reference.

[0210] The number average molecular weight of thermoplastic hydrocarbon resins can be 200-3000 g / mol.

[0211] The glass transition temperature of thermoplastic hydrocarbon resins can be 30-150℃ (e.g., 40-140℃, 50-130℃, 60-120℃, 70-110℃, 80-100℃, 90-95℃). The content of thermoplastic hydrocarbon resin in the coating composition can be 0 to about 25 wt% (e.g. 0-21 wt%, 0.01-20 wt%, 0.1-15 wt%, 0.5-10 wt%, 1-9 wt%, 2-8 wt%, 3-7 wt%, 4-6 wt%), based on the total weight of the coating composition.

[0212] Inorganic packing The coating compositions of the present invention can optionally be prepared together with inorganic fillers. Inorganic fillers that can be used in the coating compositions of the present invention include, but are not limited to, aluminum powder or alloys thereof, aluminum flakes (e.g., aluminum flake slurry) or alloys thereof, zinc-aluminum flakes (e.g., zinc-aluminum flake slurry) or alloys thereof, mica iron oxide, mica, glass flakes, calcium silicate, wollastonite, talc, calcium carbonate, barium sulfate, silica, dolomite, silicates, kaolin, feldspar, carbon nanotubes, and graphene. Preferred inorganic fillers include mica, mica iron oxide, aluminum flakes (slurry), zinc aluminum flakes (slurry), talc, glass flakes, and mixtures thereof. Metal flakes, such as zinc, aluminum, magnesium, and nickel, can be added to coatings as inorganic fillers to provide cathodic protection as sacrificial anodes. As taught in U.S. Patent No. 7,794,626 (the disclosure of which is incorporated herein by reference), they can also be used in combination with conductive fillers to provide electrochemical corrosion protection for the substrate.

[0213] The inorganic filler content in the coating composition of the present invention can be about 0-70 wt% (e.g., 0.1-65 wt%, 0.5-60 wt%, 1-55 wt%, 5-50 wt%, 10-45 wt%, 15-40 wt%, 20-35 wt%, 25-30 wt%), based on the total weight of the coating composition. In some preferred embodiments, the inorganic filler content in the coating composition can be 0-about 20 wt% (e.g., 0.05-15 wt%, 0.1-10 wt%, 0.5-5 wt%, 1-4 wt%, 2-3 wt%) or about 14-64 wt% (e.g., 27-58 wt%), based on the total weight of the coating composition.

[0214] Adhesion promoter The adhesion promoter used in the coating composition of the present invention can be selected from functionalized polyolefins.

[0215] For example, the polyolefin may be acid-functionalized. Acid-functionalized polyolefins that can be used as adhesion promoters include those disclosed in U.S. Patent No. 7,465,773, the disclosure of which is incorporated herein by reference. For example, adhesion promoters that can be used in this invention may be acid-functionalized polyolefins, such as polyolefins containing maleic anhydride. The polyolefin may be unsaturated and contain olefin groups, such as polybutadiene. The vinyl content of the polyolefin may be no more than 40 wt%, 35 wt%, or 30 wt%. The average anhydride equivalent of the polyolefin may be 200-5000 g / mol per anhydride group (e.g., no more than 4000, 3000, 2000, 1000, or 500 g / mol per anhydride group). Polyolefins containing maleic anhydride are liquids, typically with a viscosity of at least 2000 mPas, 3000 mPas, 4000 mPas, or 5000 mPas at 20°C or 25°C (DIN EN ISO 3219). The viscosity at 20°C or 25°C may not exceed 75,000 mPas (e.g., not exceeding 30,000, 25,000, 20,000, 15,000, or 10,000 mPas; less than 1000 or 500 mPas). Polyolefins have a viscosity of at least 50,000 mPas, 75,000 mPas, 100,000 mPas, 125,000 mPas, or 150,000 mPas at 45°C, 50°C, or 55°C. Viscosity may reflect molecular weight. The molecular weight (Mn) of polyolefins can be no greater than 10,000 g / mol, 9,000 g / mol, 8,000 g / mol, 7,000 g / mol, 6,000 g / mol, 5,000 g / mol, 4,500 g / mol, 4,000 g / mol, 3,500 g / mol, or 3,000 g / mol. The molecular weight (Mn) of polyolefins can be at least 1,000 g / mol, 1,100 g / mol, 1,200 g / mol, 1,300 g / mol, 1,400 g / mol, 1,500 g / mol, 1,600 g / mol, 1,700 g / mol, 1,800 g / mol, 1,900, or 2,000 g / mol. Acid-functionalized polyolefins that can be used as adhesion promoters include maleic anhydride-modified polybutadiene (e.g., CrayValley's Ricon). ® 130MA8, Ricon ® 130MA13, Ricon ® 130MA20, Ricon131MA5, Ricon ® 131MA10, Ricon ® 131MA20, Ricon ®184MA6, Ricobond ® 1731HS, Ricobond ® 1756HS and Ricobond ® 2031; Polyvest of Evonik ® EPMA100, Polyvest ® MA75, Polyvest ® EPMVMA60, and Lithene of Synthomer ® UltraPM4 - 7.5MA, Lithene ® UltraN4 - B - 10MA, Lithene ® UltraN4 - 5000 - 10MA, Lithene ® UltraN4 - 5000 - 15MA, Lithene ® UltraAL - 15MA). Other adhesion promoters that can be used in this invention include silane-functionalized polyolefins, such as silane-containing polyolefins (also referred to herein as silane-grafted polyolefins). The polyolefin may be unsaturated and contain olefin groups, such as polybutadiene. The average silane functionality of each polymer chain may be 0.1-2. The silane-containing polyolefin is a liquid, typically with a viscosity of at least 2000 mPas, 3000 mPas, 4000 mPas, 5000 mPas, 7500 mPas, 15000 mPas, or 30000 mPas at 20°C or 25°C (DIN EN ISO 3219). The viscosity at 20°C or 25°C may not exceed 75,000 mPas (e.g., not exceeding 30,000, 25,000, 20,000, or 15,000 or 10,000 mPas; less than 1000 or 500 mPas). The viscosity of polyolefins at 45°C, 50°C, or 55°C is at least 50,000 mPas, 75,000 mPas, 100,000 mPas, 125,000 mPas, or 150,000 mPas, respectively. Viscosity reflects molecular weight. The molecular weight (Mn) of polyolefins may not exceed 10,000 g / mol, 9,000 g / mol, 8,000 g / mol, 7,000 g / mol, 6,000 g / mol, 5,000 g / mol, 4,500 g / mol, 4,000 g / mol, 3,500 g / mol, or 3,000 g / mol. The molecular weight (Mn) of the polyolefin can be at least 800 g / mol, 900 g / mol, 1,000 g / mol, 1,100 g / mol, 1,200 g / mol, 1,300 g / mol, 1,400 g / mol, 1,500 g / mol, 1,600 g / mol, 1,700 g / mol, 1,800 g / mol, 1,900 g / mol, or 2,000 g / mol. Silane-functionalized polyolefins that can be used with adhesion promoters are silane-functionalized polybutadiene (also referred to herein as silane-grafted polybutadiene). Silane-functionalized polybutadiene includes, but is not limited to, Ricon from Cray Valley. ® 603. Evonik's Polyvest ® ST-E 60 and Polyvest ® ST-E 100, and Shin Etsu's X-12-1267B and X-12-1267B-ES.

[0216] Epoxidized polybutadiene can also be used, including but not limited to Nagase's DENALEX. ® R-15EPT and DENALEX® R-45EPT, and Poly bd in Cray Valley ® 605E and Poly bd ® 700S.

[0217] Silane and maleic anhydride modified polyolefins can also be used, including but not limited to Shin Etsu's X-12-1287A.

[0218] Silane and epoxy resin modified adhesion promoters can also be used, including but not limited to Shin Etsu's KR-516, which is an oligomeric coupling agent containing reactive functional groups in addition to alkoxysilyl groups.

[0219] Isocyanate-terminated polybutadiene prepolymers, including but not limited to Krasol from Cray Valley, can also be used. ® LBD2000 (TDI base), Krasol ® LBD3000 (TDI base), Krasol ® NN-22 (MDI-based), Krasol ® NN-23 (MDI-based) and Krasol ® NN-25 (MDI base).

[0220] Preferred adhesion promoters are functionalized polybutadiene, such as maleic anhydride-functionalized polybutadiene, silane-functionalized polybutadiene, epoxidized polybutadiene, silane and maleic anhydride-modified polybutadiene, and mixtures thereof. At least one adhesion promoter may be a liquid.

[0221] The acid content of at least one adhesion promoter can be 0.1-100 mgKOH / g (e.g., 1-75 mgKOH / g, 5-50 mgKOH / g, 10-25 mgKOH / g, 15-20 mgKOH / g).

[0222] The adhesion promoter may be present in the coating composition at a content of about 0.01-10 wt% (e.g., 0.05-9 wt%, 0.05-6 wt%, 0.1-8 wt%, 0.5-7 wt%, 1-6 wt%, 2-5 wt%, 3-4 wt%), based on the total weight of the coating composition.

[0223] Paint additives The coating compositions of the present invention can optionally be prepared together with coating additives. Suitable coating additives include, but are not limited to, gel modifiers, hardness modifiers, impact modifiers, antioxidants, anti-ozone agents, binders, thixotropic adhesives, rheology modifiers, corrosion inhibitors, dispersants, wetting agents, plasticizers, pigments, flame retardants, dyes, fibers, reinforcing materials, coupling agents, ultraviolet absorbers, ultraviolet stabilizers, film-forming agents, and lubricants. Preferably, the coating additive is selected from the group consisting of at least one rheology modifier, at least one corrosion inhibitor, at least one pigment, and mixtures thereof.

[0224] Suitable rheology modifiers include both inorganic and organic rheology modifiers. Inorganic rheology modifiers include clays and organoclays (hectorite, bentonite, attapulgite, kaolin, pyrophyllite, and talc), minerals (such as fumed silica, precipitated silica, precipitated calcium carbonate, and montmorillonite), and organometallic cementitious agents (such as zirconates and aluminates). Organic rheology modifiers include castor oil derivatives, modified polyurea, polyamides, calcium sulfonate, cellulose, and hydrophobic ethoxylated polyurethane resins. Examples of suitable rheology modifiers include: fumed silica (e.g., Cab-O-Sil TS610 and TS720 from Cabot Corp, and AEROSIL 972 and AEROSIL 974 from Evonik), organoclays (e.g., BENTOLITE L-10, BENTOLITE-WH, CLAYTONE 40, CLAYTONE AF, MINERALCOLLOID BP, and Garamite 7303 from BYK Chemie, bentonite 149, bentonite 329, bentonite 331, and bentonite 344 from Brentag Specialities, and Attagel from BASF), polyaminoamide phosphates, high molecular weight carboxylates of polyaminoamides, and alkyleneamine salts of unsaturated fatty acids (all available from BYK Chemie USA via ANTI TERRA™), and polyamide-modified castor oil derivatives (e.g., Luvotix ZH5 and Luvitix from Lehmann & Voss). ZH50), micronized amide waxes (e.g., Crayvallac SUPER from Arkema). Preferred rheology modifiers are selected from fumed silica (e.g., Cab-O-Sil TS720), organoclays (e.g., Garamite 7303), and mixtures thereof.

[0225] The rheology modifier may be present in the coating composition at a content of about 0.01-10 wt% (e.g., 0.05-9 wt%, 0.1-8 wt%, 0.5-7 wt%, 1-6 wt%, 2-5 wt%, 3-4 wt%), based on the total weight of the coating composition.

[0226] Suitable corrosion inhibitors include, but are not limited to, zinc phosphate-based corrosion inhibitors, calcium borosilicate-based corrosion inhibitors, and zinc-based and aluminum-based corrosion inhibitors. Preferably, the corrosion inhibitor is selected from Halox SZP391, Halox CW-2230, Halox 700, and mixtures thereof. The corrosion inhibitor may be present in the coating composition at a content of about 0.01-15 wt% (e.g., 0.05-10 wt%, 0.1-9 wt%, 0.5-8 wt%, 1-7 wt%, 2-6 wt%, 3-5 wt%), based on the total weight of the coating composition. Suitable pigments include, but are not limited to, carbon black, TiO2, orange pigment dispersions, Pigment Yellow 184 in mineral oil, TiO2 in mineral oil, and Sudan Blue II. Preferably, the pigments are selected from carbon black, TiO2, and mixtures thereof.

[0227] The pigment content in the coating composition may be about 0.001-5 wt% (e.g. 0.005-4 wt%, 0.01-3 wt%, 0.05-2 wt%, 0.1-1 wt%, 0.2-0.5 wt%), based on the total weight of the coating composition. The coating compositions of the present invention may be formulated with or without a crosslinking agent, for example, a crosslinking agent selected from dialkyl peroxides, diacyl peroxides and peroxy acids.

[0228] Antioxidants and antiozone agents include any antioxidants or antiozone agents used in the rubber or plastics industry. The "Index of Commercial Antioxidants and Antiozone Agents, Fourth Edition" is available from Goodyear Chemicals, The Goodyear Tire and Rubber Company, Akron, Ohio 44316. Suitable stabilizers (i.e., antioxidants or antiozone agents) include, but are not limited to: 2,6-di-tert-butyl-4-methylphenol (BHT), styreneated phenol (such as Wingstay), etc. ®S(Goodyear)), 2- and 3-tert-butyl-4-methoxyphenol, alkylation 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), various bisphenols (such as Cyanox) ® 53 (Cytec Industries Inc.) and Permanax ® WSO), 2,2′-ethylidene bis(4,6-di-tert-butylphenol), 2,2′-methylene bis(4-methyl-6-(1-methylcyclohexyl)phenol), 4,4′-butylidene bis(6-tert-butyl-3-methylphenol), polybutylbisphenol A, 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-methylene bis(2,6-dimethylphenol), 1,1′-thiobis(2-naphthol), methylene-bridged polyalkylphenols (e.g., ethyl antioxidant 738), 2,2′-thiobis(4-methyl-6-tert-butylphenol), 2,2′-isobutylidene bis(4,6-dimethylphenol), 2,2′-methylene bis(4-methyl-6-cyclohexylphenol), butylated products of p-cresol and dicyclopentadiene (e.g., Wingstay). L), tetra(methylene-3,5-di-tert-butyl-4-hydroxycinnamate)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)), 4,4 1,3,5-methylene bis(2,6-di-tert-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 (Emerald Performance Materials), 2,5-di-tert-amylhydroquinone, tert-butylhydroquinone, tris(nonylphenyl phosphite), bis(2,4-di-tert-butyl)pentaerythritol diphosphite, distearate pentaerythritol diphosphite, phosphite-esterified phenols and bisphenols (e.g., Naugard ®492 (Chemtura), phosphite / phenolic antioxidant blends (e.g., Irganox B215), di-n-octadecyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonates (e.g., Irganox 1093), 1,6-hexamethylenebis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionate) (e.g., Irganox 259), and octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate (i.e., Irganox 1076), tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite, diphenylamine, and 4,4′-dimethoxydiphenylamine. These materials are typically added to coating compositions at amounts of approximately 0.10 phr to 10 phr, for example, approximately 0.1 phr to 5 phr.

[0229] Suitable fillers include, for example, metal density modifiers, particulate density modifiers (e.g., microspheres), and macroparticle density modifiers (e.g., glass beads or ceramic beads). Metal density modifiers include, but are not limited to, powdered, sintered, flaked, sheet-like, scraped, granular, or particulate metals, metal oxides, metal nitrides, and / or metal carbides. Particulate density modifiers particularly include tungsten, tungsten carbide, aluminum, titanium, iron, lead, silicon oxide, alumina, boron carbide, and silicon carbide. Particulate density modifiers include, but are not limited to, glass, metals, thermoplastics (expandable or pre-expandable), or thermosetting plastics and / or ceramic / silicate microspheres. Macroparticle density modifiers include, but are not limited to, glass, plastic, or ceramic beads; metal rods, blocks, sheets, or pellets; hollow glass, ceramic, plastic, or metal spheres, balls, or tubes.

[0230] The content of coating additives in the coating composition can be 0 to about 25 wt% (e.g., 0.01-20 wt%, 0.05-15 wt%, 0.1-14 wt%, 0.5-13 wt%, 1-12 wt%, 2-11 wt%, 3-10 wt%, 4-9 wt%, 5-8 wt%, 6-7 wt%), based on the total weight of the coating composition.

[0231] Coating composition The coating composition of the present invention may further comprise at least one substrate material. Furthermore, the coating composition may be applied to at least one substrate material. The substrate material may be a functionalized substrate material, such as a heteroatom-functionalized substrate, such as an amino-functionalized substrate. Additionally, at least one substrate material may be, for example, a glass substrate material or a carbon substrate material. Advantageously, the substrate material may comprise an aminosilane-treated substrate.

[0232] The coating compositions of the present invention may further comprise exogenous inhibitors. Exogenous inhibitors or “gel-modifying additives” used in the present invention are disclosed in U.S. Patent No. 5,939,504, the disclosure of which is incorporated herein by reference. The coating compositions of the present invention may further comprise hydroperoxide gel modifiers. Hydroperoxide gel modifiers used in the present invention (e.g., cumene hydroperoxide) are disclosed in PCT / US2012 / 042850, the disclosure of which is incorporated herein by reference.

[0233] The coating compositions of the present invention can be prepared by combining an olefin component, a metal carbene olefin metathesis catalyst, an optional thermoplastic hydrocarbon resin, an inorganic filler, an adhesion promoter, and optional coating additives using any method known in the art. Resins used to prepare polyurethanes and epoxy polymers, as well as DCPD resins catalyzed by molybdenum and tungsten (e.g., Telene) ® DCPD resin, Metton ® DCPD resin, Pentam ® Compared to DCPD polymers prepared from DCPD resins, the coating compositions of the present invention are generally less sensitive to air and / or moisture. Therefore, the coating compositions of the present invention are generally more resistant to a wider range of environmental conditions (e.g., temperature, humidity, etc.). Resin systems with lower sensitivity to air and / or moisture have advantages over more sensitive resin systems, especially in situations requiring coating (for corrosion protection) of objects in on-site marine environments (e.g., ships, offshore oil drilling platforms, etc.).

[0234] Furthermore, the coating compositions of the present invention offer improved ease of application compared to prior art coating compositions, particularly polypropylene systems. Unlike polypropylene systems primarily limited to extrusion processes, the coating compositions of the present invention can be applied to objects and / or object surfaces in a variety of ways, including but not limited to casting, pouring, injection, molding, spraying, rotational molding, centrifugal casting, pultrusion, and extrusion. Moreover, the coating compositions of the present invention offer improved ease of application compared to prior art epoxy resin-based coating compositions (e.g., elastomeric amine-cured epoxy materials). Unlike epoxy resin systems requiring at least two synthesis steps (e.g., elastomeric amine-cured epoxy materials), the coating compositions of the present invention require only one mixing step (e.g., mixing the coating composition of the present invention with the catalyst composition of the present invention) before application to the object surface or addition to a mold. Unlike DCPD resin systems containing molybdenum or tungsten bicomponent catalyst systems (e.g., Telene), the present invention provides a more convenient application experience. ® DCPD resin, Metton ® DCPD resin, Pentam ®DCPD resins, such systems require specialized and expensive processing and handling conditions and equipment, including specialized and expensive molds, injection molding equipment and storage tanks, while the coating compositions of the present invention can be applied to objects and / or object surfaces in a variety of ways, including but not limited to simple casting.

[0235] A particular advantage of the coating compositions of the present invention is their ease of handling and formulation, enabling the ROMP polymers and ROMP polymer composites discussed below to meet the needs / requirements of the application or service. For example, the coating compositions of the present invention used to prepare the ROMP polymers or ROMP polymer composites of the present invention can be readily formulated, allowing the prepared ROMP polymers or ROMP polymer composites to exhibit a range of physical, mechanical, and / or thermal properties, ranging from elastomeric behavior and / or characteristics to rigid thermosetting behavior and / or characteristics, depending on the needs / requirements of the application.

[0236] ROMP polymer and ROMP polymer composites The present invention also relates to ROMP polymers or ROMP polymer composites comprising, being mainly composed of, or being composed of, the reaction products of the coating compositions of the present invention, wherein the coating compositions have undergone condition treatment for effectively polymerizing coating compositions. The present invention also relates to using the ROMP polymer and / or ROMP polymer composite material of the present invention as a corrosion-resistant material.

[0237] The present invention also relates to the use of ROMP polymers or ROMP polymer composites for preventing corrosion of objects. For example, the ROMP polymers and / or ROMP polymer composites of the present invention can be used to prevent any object from being corroded by its surrounding environment or surrounding materials, wherein the surrounding environment or surrounding materials can be gases (such as air), fluids (liquids) (such as seawater, fresh water), or solids (such as ice or underground solids, as in the case of buried pipelines) or mixtures thereof. In particular, the ROMP polymer and ROMP polymer composite material of the present invention are suitable for corrosion protection of objects, such as oil pipelines in cold water (e.g., cold seawater, cold freshwater). The ROMP polymer and ROMP polymer composite material of the present invention can also be used to prevent corrosion of other objects, including but not limited to pipes, subsea pipelines, pipelines, oil pipelines, subsea oil pipelines, subsea pipelines, pipe fittings, hoses, hose fittings, tanks, containers, drums, manifolds, risers, field joints, configurations known as treehouses (oilfield treehouses, subsea treehouses), jumpers, connecting pipe sections, configurations known as pipeline endtermination (PLET), configurations known as pipeline end manifolds (PLEM), and other subsea structures and equipment. The ROMP polymer and ROMP polymer composite material of the present invention can also be used to coat other objects, such as robotic components, devices, and vehicles for subsea applications. Furthermore, the ROMP polymer and ROMP polymer composite material of the present invention can be used to construct corrosion-resistant structures, such as configurations known as subsea doghouses.

[0238] The present invention also relates to a method for using ROMP polymer coatings in marine applications, the method comprising: providing at least partially coated surfaces of an object with a coating composition to be coated, or contacting the object surface with the coating composition, or applying the coating composition to the object surface; and subjecting the coating composition to conditions that enable effective polymerization of the coating composition.

[0239] While the ROMP polymers and ROMP polymer composites of the present invention are well suited for coating or covering objects that are immersed in water (such as fresh water, salt water, seawater, etc.), these ROMP polymers and ROMP polymer composites can also be used for coating or covering objects that are not exposed to aquatic environments.

[0240] The ROMP polymer and ROMP polymer composite material of the present invention can be used to coat or cover objects (e.g., pipelines and / or other subsea structures) where the temperature of the substance (e.g., hydrocarbons, oil, natural gas, etc.) transported by the object (e.g., pipelines and / or other subsea structures) is greater than or equal to 160°C. Therefore, by default, the ROMP polymer and / or ROMP polymer composite material of the present invention can also be used to coat or cover objects (e.g., pipelines and / or other subsea structures) where the temperature of the substance (e.g., hydrocarbons, oil, natural gas, etc.) transported by the object (e.g., pipelines and / or other subsea structures) is less than 160°C.

[0241] The coating composition of the present invention is applied to the surface of an object to be at least partially coated using methods known in the art. Examples of such methods include, but are not limited to, casting, centrifugal casting, pultrusion, molding, rotational molding, open molding, reaction injection molding (RIM), resin transfer molding (RTM), casting, vacuum impregnation, surface coating, fiber winding, unit casting, dip casting, continuous casting, embedding, potting, encapsulation, thin film casting or solvent casting, gate casting, mold casting, coating casting, extrusion, mechanical foaming, chemical foaming, physical foaming, compression molding or die molding, spray molding, spraying, vacuum-assisted resin transfer molding (VARTM), Seeman composite resin injection molding process (SCRIMP), blow molding, in-mold coating, in-mold spraying or injection, vacuum forming, reinforced reaction injection molding (RRIM), structural reaction injection molding (SRIM), thermal expansion transfer molding (TERM), resin injection recycling molding (RICM), controlled atmospheric pressure resin infusion (CAPRI), and hand lay-up molding. For manufacturing techniques that require the use of RIM or impact mixing heads, including but not limited to RIM, SRIM and RRIM, articles can be molded using a single mixing head or multiple mixing heads and multiple material injection streams (e.g., two resin streams and one catalyst stream).

[0242] The ROMP polymer and / or ROMP polymer composite of the present invention do not necessarily require molding around an object to prevent corrosion. Alternatively, ROMP polymer articles and ROMP polymer composite articles can be prepared independently by various methods known in the art, and then attached or placed around an object to prevent corrosion by the surrounding environment. Furthermore, the method of attaching ROMP polymer articles and ROMP polymer composite articles to an object can use any known method, including adhesive methods and / or mechanical methods (e.g., fasteners, bolts, screws, etc.). For example, ROMP polymers and ROMP polymer composites can be prefabricated into components complementary to the shape of the object to be protected from corrosion. The prefabricated components can then be fixed or attached to the object using any known method.

[0243] Furthermore, the object to be protected against corrosion can be pretreated with any known adhesive coating or primer suitable for improving and / or enhancing the adhesion of the ROMP polymer and ROMP polymer composite of the present invention to the object. For example, an adhesive coating or primer can be applied to the object to be protected against corrosion first, and then the coating composition of the present invention can be applied to the object, followed by placing the coating composition under conditions that allow for effective polymerization. Alternatively, an adhesive coating or primer can be applied to the object to be protected against corrosion, followed by the attachment of the pre-formed ROMP polymer or pre-formed ROMP polymer composite of the present invention to the object.

[0244] Corrosion-resistant materials The present invention also relates to an anti-corrosion material comprising the coating composition of the present invention, ROMP polymer or ROMP polymer composite material, mainly composed of the coating composition of the present invention, ROMP polymer or ROMP polymer composite material, or composed of the coating composition of the present invention, ROMP polymer or ROMP polymer composite material. The ROMP polymer and ROMP polymer composites of the present invention provide improved thermal stability and / or improved hydrolytic stability compared to prior art corrosion-resistant materials. Corrosion-resistant materials made from the ROMP polymer of the present invention have advantages over prior art corrosion-resistant materials made from polypropylene because the ROMP polymer of the present invention has improved thermal stability.

[0245] The present invention also relates to anti-corrosion materials for coating or covering: (1) an object; (2) at least a portion of the object; and / or (3) at least a portion of at least one surface of the object; wherein the anti-corrosion material comprises the coating composition of the present invention, a ROMP polymer, or a ROMP polymer composite material.

[0246] The present invention also relates to the use of anti-corrosion materials for coating or covering the following: (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 anti-corrosion material comprises the coating composition of the present invention, a ROMP polymer, or a ROMP polymer composite material.

[0247] The present invention also relates to a method for preventing an object from being corroded by a surrounding fluid, the method comprising: placing an anti-corrosion material between the object and the fluid, wherein the anti-corrosion material comprises the coating composition of the present invention, a ROMP polymer, or a ROMP polymer composite material.

[0248] The present invention also relates to a method of coating or covering the following with an anti-corrosion material: (1) an object; (2) at least a portion of the object; and / or (3) at least a portion of at least one surface of the object; wherein the anti-corrosion material comprises the coating composition of the present invention, a ROMP polymer, or a ROMP polymer composite material.

[0249] The present invention also relates to a method of coating or covering: (1) an object; (2) at least a portion of the object; and / or (3) at least a portion of at least one surface of the object with an anti-corrosion material; said method comprising: contacting or applying the coating composition of the present 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 placing the coating composition under conditions that effectively promote the ROMP reaction of the coating composition to form the ROMP polymer or ROMP polymer composite of the present invention; wherein the anti-corrosion material is a ROMP polymer or a ROMP polymer composite.

[0250] The present invention also relates to a method of applying an anti-corrosion material to an object, comprising: placing a mold around the object to form a cavity between the inner surface of the mold and the object; injecting the anti-corrosion material into the cavity, wherein the anti-corrosion material composition comprises the coating composition of the present invention; and subjecting the anti-corrosion material composition to conditions that effectively promote the ROMP reaction of the coating composition to form the ROMP polymer or ROMP polymer composite of the present invention.

[0251] This invention relates to objects that are at least partially coated or covered with the anti-corrosion material of this invention.

[0252] The object to be coated and / or coated can have any configuration, weight, size, thickness, or geometry. For example, a pipe coated with the ROMP polymer and / or ROMP polymer composite of the present invention can have any outer diameter, inner diameter, and length.

[0253] Furthermore, the object to be covered and / or coated can be made of any material, including but not limited to metals, metal alloys, plastics, rubber, polymers, wood, ceramics, glass, carbon, cement, concrete, etc.

[0254] The object to be covered and / or coated may be partially or completely covered and / or coated.

[0255] Corrosion-resistant materials can have any configuration, weight, size, thickness, or geometry. Furthermore, corrosion-resistant materials are not limited to a single polymer layer but can also comprise multiple polymer layers, each of which can contain the same or different components.

[0256] The present invention also relates to an anti-corrosion material comprising the ROMP polymer of the present invention, wherein the elongation at break of the ROMP polymer is at least 20%, at least 50%, at least 75%, at least 100%, at least 125%, at least 150%, at least 175%, at least 200%, at least 225%, at least 250%, at least 275%, at least 300%, or at least 400%.

[0257] This invention also relates to an anti-corrosion material comprising the ROMP polymer of this invention, wherein the elongation at break of the ROMP polymer is 20%-400%, 20%-300%, 20%-275%, 20%-250%, 20%-225%, 20%-200%, 20%-175%, 20%-150%, 20%-125%, 20%-100%, 20%-75%, 20%-50%, 50%-300%, 50%-275%, 50%-250%, 50%-225%, 50%-200%. %, 50%-175%, 50%-150%, 50%-125%, 50%-100%, 50%-75%, 75%-400%, 75%-300%, 75%-275%, 75%-250%, 75%-225%, 75%-200%, 75%-175%, 75%-150%, 75%-125%, 75%-100%, 100%-400%, 100%-300%, 100%-275%, 100%-250%, 100%-225%, 100%-2 0.00%, 100%-175%, 100%-150%, 100%-125%, 125%-400%, 125%-300%, 125%-275%, 125%-250%, 125%-225%, 125%-200%, 125%-175%, 125%-150%, 150%-400%, 150%-300%, 150%-275%, 150%-250%, 150%-225%, 150%-200%, 150%-175%, 175%-400% %, 175%-300%, 175%-275%, 175%-250%, 175%-225%, 175%-200%, 200%-400%, 200%-300%, 200%-275%, 200%-250%, 200%-225%, 225%-400%, 225%-300%, 225%-275%, 225%-250%, 250%-400%, 250%-300%, 250%-275%, 275%-400%, or 275%-300%.

[0258] The corrosion-resistant materials made from the ROMP polymers of this invention have an advantage over existing corrosion-resistant materials made from polyurethane and epoxy materials (including elastomeric amine-cured epoxy materials): the cyclic olefins (cyclic olefin monomers) used to manufacture such ROMP polymers can be selected, resulting in ROMP polymers without carbon-heteroatom bonds in the polymer backbone. Therefore, the ROMP polymers of this invention generally exhibit higher hydrolytic stability than polyurethane and / or epoxy polymers, whose polymer backbones contain carbon-heteroatom bonds. Preferably, the polymer backbone of the ROMP polymers of this invention contains only carbon-carbon single and carbon-carbon double bonds, wherein carbon atoms may be substituted or unsubstituted. The ROMP polymers of this invention can optionally be hydrogenated by any known method, thereby providing hydrogenated ROMP polymers suitable for corrosion protection.

[0259] Surprisingly, the ROMP polymers, ROMP polymer composites, and anti-corrosion materials of the present invention possess some or all of the characteristics and / or properties desired by the aforementioned anti-corrosion materials, particularly for use in offshore drilling (e.g., subsea applications). Therefore, the ROMP polymers, ROMP polymer composites, and anti-corrosion materials of the present invention meet this industry need.

[0260] Products The present invention also relates to articles prepared from the coating composition of the present invention, ROMP polymer, ROMP polymer composite material or anti-corrosion material.

[0261] The present invention also relates to an article comprising an object, wherein at least a portion of at least one surface of the object is coated or covered with the coating composition of the present invention, a ROMP polymer, a ROMP polymer composite material, or an anti-corrosion material.

[0262] The present invention also relates to articles made from the coating composition of the present invention, wherein the coating composition is applied to at least one substrate material.

[0263] This invention also relates to articles prepared from the coating composition of this invention and at least one substrate material, wherein the articles are anti-corrosion materials. Furthermore, this invention relates to articles prepared from the coating composition of this invention, wherein the coating composition is applied to at least one substrate material, the substrate material being, for example, a functionalized substrate, such as a heteroatom-functionalized substrate (e.g., an amino-functionalized substrate); wherein the articles are anti-corrosion materials.

[0264] The present invention also relates to articles prepared by any of the methods described herein.

[0265] Exemplary embodiments of the present invention E1) A coating composition comprising, substantially comprising, or consisting of the following: a) At least one olefin resin composition, comprising, substantially comprising, or comprising the following: a.1) At least one olefin component, consisting of the following: a.1.1) Based on the total weight of the olefin components, 80-100 wt% of at least one cyclic olefin, said cyclic olefin being selected from the group consisting of formula (I), formula (II) and formula (III); and a.1.2) Based on the total weight of the olefin component, 0-20 wt% of at least one linear olefin of formula (IV); Wherein, the sum of the wt% of the cyclic olefins of formulas (I), (II) and (III) and the wt% of the linear olefin of formula (IV) is 100 wt% of the olefin component; a.2) At least one metal carbene olefin metathesis catalyst, wherein the molar ratio of olefin to catalyst is from 10,000,000:1 to 1,000:1; and a.3) Optionally, at least one thermoplastic hydrocarbon resin; b) Optionally, at least one inorganic filler; c) at least one adhesion promoter, said adhesion promoter being selected from functionalized polyolefins; and d) Optionally, at least one paint additive; Among them, the cyclic olefins of formula (I), formula (II) and formula (III) and the linear olefin of formula (IV) have the following structures:

[0266] in: R a H, or optionally substituted linear or branched C 1-24 Alkyl, optionally substituted straight or branched C 2-24 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g , -CN, -NO2, -CF3, -P(O)(OR h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, -CH2- (optionally substituted heterocycles), optionally substituted C 3-10 Cycloalkyl, -CH2- (optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24Aryl, -CH2- (optionally substituted C) 5-24 aryl), optionally substituted C 3-12 Cycloalkenyl, -CH2- (optionally substituted C) 3-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p -C(R) h (R) i )C(O)NR o OR n or ; R b H, or optionally substituted linear or branched C 1-24 Alkyl, optionally substituted straight or branched C 2-24 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g , -CN, -NO2, -CF3, -P(O)(OR h )2、-OP(O)(OR h )2、-Si(OR k 3、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, Optionally substituted spirocyclic heterocycles, -CH2- (optionally substituted heterocycles), Optionally substituted C 3-10 Cycloalkyl, -CH2- (optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 Aryl, -CH2- (optionally substituted C) 5-24 aryl), optionally substituted C 3-12 Cycloalkenyl, -CH2- (optionally substituted C) 3-12 cycloalkenyl), C(R) h (R) i COOR j-C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p or -C(R) h (R) i )C(O)NR o OR n ; R c and R d H, and optionally substituted linear or branched C, are independent of each other. 1-24 Alkyl, optionally substituted straight or branched C 2-24 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g CN, NO2, -CF3, -P(O)(OR) h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, -CH2- (optionally substituted heterocycles), optionally substituted C 3-10 Cycloalkyl, -CH2- (optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 Aryl, -CH2- (optionally substituted C) 5-24 aryl), optionally substituted C 3-12 Cycloalkenyl, -CH2- (optionally substituted C) 3-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m(OR) n ), -C(R h (R) i )C(O)NR o R p or -C(R) h (R) i )C(O)NR o OR n ; R d H, or optionally substituted linear or branched C 1-24 Alkyl, optionally substituted straight or branched C 2-24 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g CN, NO2, -CF3, -P(O)(OR) h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, -CH2- (optionally substituted heterocycles), Optionally substituted C 3-10 Cycloalkyl, -CH2- (optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 Aryl, -CH2- (optionally substituted C) 5-24 aryl), optionally substituted C 3-12 Cycloalkenyl, -CH2- (optionally substituted C) 3-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p or -C(R) h (R) i )C(O)NR o OR n ; Each Rs Independently, for the optional substitution of straight or branched C 1-24 Alkyl, optionally substituted straight or branched C 2-24 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g , -CN, -NO2, -CF3, -P(O)(OR h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, -CH2- (optionally substituted heterocycles), Optionally substituted C 3-10 Cycloalkyl, -CH2- (optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 Aryl, -CH2- (optionally substituted C) 5-24 aryl), optionally substituted C 3-12 Cycloalkenyl, -CH2- (optionally substituted C) 3-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p or -C(R) h (R) i )C(O)NR o OR n ; R f For OH, OR k NR g R h Optional substitution of straight or branched C 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl or optionally substituted C 3-12 Cycloalkenyl; Rg H, or optionally substituted linear or branched C 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl, optionally substituted straight or branched C 2-24 alkenyl, -C(O)- (optionally substituted C) 5-24 aryl), -C(O)- (optionally substituted straight or branched C) 2-24 alkenyl) or optionally substituted C 3-12 Cycloalkenyl; R h R i R j R l R m R n R o and R p H, and optionally substituted linear or branched C, are independent of each other. 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl or optionally substituted C 3-12 Cycloalkenyl; R k For optional substitution of straight or branched C 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl or optionally substituted C 3-12 Cycloalkenyl; t is 0, 1, 2, 3, 4, 5, or 6; and z can be 0, 1, 2, or 3.

[0267] E2) The coating composition described in E1, wherein: R a H, or optionally substituted linear or branched C 1-12 Alkyl, optionally substituted straight or branched C 2-6 Alkenyl, halogen, -C(O)R f -OR g , -CN, -NO2, -CF3, -P(O)(OR h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocyclic rings, Optionally substituted C 3-10 cycloalkyl, optionally substituted C 6-10 aryl, optionally substituted C 3-12 cycloalkenyl or ; R b R c and R d H, and optionally substituted linear or branched C, are independent of each other. 1-12 Alkyl, optionally substituted straight or branched C 2-6 Alkenyl, halogen, -C(O)R f -OR g , -CN, -NO2, -CF3, -P(O)(OR h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocyclic rings, Optionally substituted C 3-10 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-12 Cycloalkenyl; R f For OH, OR k NR g R h Optional substitution of C 1-12 Alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 3-12 Cycloalkenyl; R g R h R i R j R l R m R n R o and R p H and C, which are mutually independent of each other, are optionally substituted. 1-12 Alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 3-12 Cycloalkenyl; R k C is an optional replacement 1-12 Alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 3-12 Cycloalkenyl; t is 0; and z is 2.

[0268] E3) The coating composition described in E1 or E2, wherein: The cyclic olefin of formula (I) is 2-ethylidene-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene or a mixture thereof. The cyclic olefin of formula (II) is 2-hydroxyethyl bicyclo[2.2.1]hept-5-en-2-carboxylic acid ester, [3-(triethoxysilyl)propyl]-bicyclo[2.2.1]hept-5-en-2-methylene ester, octyl-norbornene, 5-norbornene-2-methanol, 5-norbornene-2-exo,3-exo-diethanol, 2-hydroxyethyl bicyclo[2.2.1]hept-5-en-2- Carboxylic acid esters, norbornene triethoxysilane, 5-(perfluorobutyl)bicyclo[2.2.1]hept-2-ene, 2,2,3,3,4,4,5,5,6,6,7,7-dodecylheptylbicyclo[2,2,1]hept-5-ene-2-carboxylic acid ester, bicyclo[2.2.1]hept-5-ene-2-carboxylic acid, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl ester, or mixtures thereof; and The cyclic olefins of formula (III) are dicyclopentadiene, tricyclopentadiene, or mixtures thereof.

[0269] E4) The coating composition of any one of E1-E3, wherein the coating composition comprises at least one cyclic olefin, the cyclic olefin being represented by the group consisting of formulas (I) and (II).

[0270] The coating composition according to any one of E5, E1-E3, wherein the coating composition comprises at least one cyclic olefin selected from the group consisting of formula (I) and formula (III).

[0271] The coating composition according to any one of E6)E1-E3, wherein the coating composition comprises at least one cyclic olefin selected from the group consisting of formula (II) and formula (III).

[0272] The coating composition of any one of E7, E1-E3, wherein the coating composition comprises at least one cyclic olefin selected from the group consisting of formula (I), formula (II) and formula (III).

[0273] The coating composition of any one of E8, E1-E3, wherein the coating composition comprises at least one cyclic olefin selected from the group consisting of formula (III).

[0274] E9) The coating composition of E8, wherein at least one cyclic olefin is selected from dicyclopentadiene (DCPD), tricyclopentadiene (TCPD) and mixtures thereof. The coating composition described in E10) and E9, wherein the ratio of DCPD to DCPD is 3:7 to 2:3 DCPD wt% : TCPD wt%.

[0275] E11) The coating composition according to any one of E1-E10, wherein the olefin component is present in the coating composition at a content of about 35-99.9 wt% (e.g. 40-99 wt%, 45-98 wt%, 50-95 wt%, 55-90 wt%, 60-85 wt%, 65-80 wt%, 70-75 wt%), based on the total weight of the coating composition.

[0276] E12) The coating composition according to any one of E1-E11, wherein the at least one metal carbene olefin metathesis catalyst is a group 8 transition metal complex having the structure of formula (I):

[0277] (I) in: M is a group 8 transition metal; L 1 L 2 and L 3 It is a neutral electron donor ligand; n is 0 or 1, therefore L 3 It may exist or it may not exist; m is 0, 1, or 2; k is 0 or 1; X 1 and X 2 It is an anionic ligand; and R 1 and R 2 Each is independently selected from hydrogen, hydrocarbon group, substituted hydrocarbon group, and hydrocarbon group containing heteroatoms; Among them, X 1 X 2 L 1 L 2 L 3 R 1 and R 2 Any two or more of them can together form one or more cyclic groups, and further, X 1 X 2 L 1 L 2 L 3 R 1 and R 2 Any one or more of them can be connected to the carrier.

[0278] E13) The coating composition of E12, wherein the at least one metal carbene olefin metathesis catalyst is a group 8 transition metal complex having the structure of formula (I), wherein: M is ruthenium; n is 0; m is 0; k is 1; L 1 and L 2 It is a trisubstituted phosphine, independently selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L 1 It is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethylcarbene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethylcarbene, 1,3-bis(2,4,6-trimethylphenyl)-2-imidazol-2-dimethylcarbene, and 1,3-bis(2,6-diisopropylphenyl)-2-imidazol-2-dimethylcarbene; L 2 It is a trisubstituted phosphine, selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L 1 and L 2 It is an N-heterocyclic carbene, independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinediene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinediene, 1,3-bis(2,4,6-trimethylphenyl)-2-imidazol-2-diene, and 1,3-bis(2,6-diisopropylphenyl)-2-imidazol-2-diene.

[0279] X 1 and X 2 For chlorine; and R 1 For hydrogen, R 2 It is phenyl or –CH=C(CH3)2; or R 1 and R 2 Together they form the indene subunit.

[0280] The coating composition described in any one of E14)E1-E13, wherein the at least one metal carbene olefin metathesis catalyst is a group 8 transition metal complex having the structure of formula (VII):

[0281] (VII) in: M is a group 8 transition metal; X 1 and X 2 It is an anionic ligand; L 1 It is a neutral electron donor ligand; Y is a heteroatom, selected from N, O, S, and P; R 5 R 6 R 7 and R 8 Each is independently selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, alkenyl containing heteroatoms, 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, amino, imino, amide, trifluoroamide, sulfide, disulfide, sulfonate. The group consisting of urethane esters, silanes, siloxanes, phosphine, phosphate esters, borate esters, or -A-Fn (where "A" is a divalent hydrocarbon group selected from alkylene and arylalkylene groups, wherein the alkyl portion of the alkylene and arylalkylene groups can be straight-chain or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the arylalkylene group can be substituted or unsubstituted, wherein heteroatoms and / or functional groups can be present in the aryl or alkyl portion of the alkylene and arylalkylene groups, and Fn is a functional group); or R 5 R 6 R 7 and R 8 Any combination of them can be interconnected to form one or more cyclic groups; n is either 1 or 2, therefore n is 1 when the heteroatom is divalent O or S; and n is 2 when the heteroatom is trivalent N or P; and... Z is selected from hydrogen, alkyl, aryl, functionalized alkyl, and functionalized aryl; wherein the functionalized group may independently be one or more of the following groups: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, urethane, silane, siloxane, phosphine, phosphate or borate; methyl, isopropyl, sec-butyl, tert-butyl, neopentyl, benzyl, phenyl and trimethylsilyl; and Among them, X 1 X 2 L1 V, Z, R 5 R 6 R 7 and R 8 Any combination or multiple combinations can be attached to the carrier.

[0282] The coating composition according to any one of E1-E14 (E15), wherein the thermoplastic hydrocarbon resin is present in the coating composition at a content of 0-about 25 wt% (e.g. 0.01-20 wt%, 0.1-15 wt%, 0.5-10 wt%, 1-9 wt%, 2-8 wt%, 3-7 wt%, 4-6 wt%) based on the total weight of the coating composition.

[0283] E16) The coating composition according to any one of E1-E15, wherein the olefin resin composition is present in the coating composition at a content of about 5-99.99 wt% (e.g., 10-99.98 wt%, 15-99.89 wt%, 20-99.88 wt%, 25-99 wt%, 30-95 wt%, 35-90 wt%, 40-85 wt%, 45-80 wt%, 50-75 wt%, 55-70 wt%, 60-65 wt%), based on the total weight of the coating composition.

[0284] The coating composition of any one of E1-E16 (E17) wherein the inorganic filler is selected from aluminum powder or its alloy, aluminum flakes or its alloy, zinc aluminum flakes or its alloy, mica iron oxide, mica, glass flakes, calcium silicate, wollastonite, talc, calcium carbonate, barium sulfate, silicon dioxide and mixtures thereof.

[0285] The coating composition of any one of E1-E17 (E18) wherein the inorganic filler is selected from aluminum powder, aluminum flakes (slurry), zinc aluminum flakes (slurry), mica iron oxide, mica, glass flakes, calcium silicate, wollastonite, talc and mixtures thereof.

[0286] The coating composition described in any one of E1-E18 (E19) wherein the inorganic filler is selected from aluminum flakes (slurry), zinc aluminum flakes (slurry), mica iron oxide, mica, glass flakes, talc and mixtures thereof.

[0287] The coating composition according to any one of E20) E1-E19, wherein the inorganic filler is present in the coating composition at a content of 0-about 70 wt% (e.g. 0.1-65 wt%, 0.5-60 wt%, 1-55 wt%, 5-50 wt%, 10-45 wt%, 15-40 wt%, 20-35 wt%, 25-30 wt%), preferably 0-about 20 wt% (e.g. 0.05-15 wt%, 0.1-10 wt%, 0.5-5 wt%, 1-4 wt%, 2-3 wt%) or about 14-64 wt% (e.g. 27-58 wt%), based on the total weight of the coating composition.

[0288] The coating composition according to any one of E21) E1-E17, wherein the adhesion promoter is selected from at least one functionalized polybutadiene.

[0289] The coating composition of E22) and E21) wherein the functionalized polybutadiene is selected from maleic anhydride-functionalized polybutadiene, silane-functionalized polybutadiene, epoxidized polybutadiene, silane and maleic anhydride-modified polybutadiene, and mixtures thereof. The coating composition of any one of E23) E1-E22, wherein the adhesion promoter is selected from maleic anhydride-functionalized polybutadiene, silane-functionalized polybutadiene, or a mixture thereof. E24) The coating composition described in E22 or E23, wherein the maleic anhydride-functionalized polybutadiene is selected from Ricobond 1731, Polyvest MA 100 and mixtures thereof.

[0290] The coating composition described in E25, E22, or E23, wherein the silane-functionalized polybutadiene is selected from Polyvest ST E60, Polyvest ST E100, SEX-12-1287A, SEX-12-1267B, and mixtures thereof.

[0291] The coating composition described in E26) and E22, wherein the silane and maleic anhydride-modified polybutadiene are selected from X-12-1287A.

[0292] E27) The coating composition described in E1-E17, wherein the adhesion promoter is an oligomeric coupling agent containing reactive functional groups and alkoxysilyl groups (e.g., KR-516).

[0293] The coating composition according to any one of E28) E1-E27, wherein the adhesion promoter is present in the coating composition at a content of about 0.01-10 wt% (e.g. 0.05-9 wt%, 0.1-8 wt%, 0.5-7 wt%, 1-6 wt%, 2-5 wt%, 3-4 wt%), based on the total weight of the coating composition.

[0294] E29) The coating composition of any one of E1-E28, wherein the coating composition comprises a coating additive selected from the group consisting of gel modifiers, hardness modifiers, impact modifiers, antioxidants, anti-ozone agents, binders, thixotropic adhesives, rheology modifiers, corrosion inhibitors, dispersants, wetting agents, plasticizers, pigments, flame retardants, dyes, fibers, reinforcing materials, coupling agents, ultraviolet absorbers, ultraviolet stabilizers, film-forming agents, lubricants, and mixtures thereof. The coating composition of E30) E29, wherein the coating additive is selected from the group consisting of at least one rheology modifier, at least one corrosion inhibitor, at least one pigment, and mixtures thereof.

[0295] The coating compositions described in E31, E29 and E30, wherein the corrosion inhibitor is selected from zinc phosphate-based corrosion inhibitors, calcium borosilicate-based corrosion inhibitors, zinc-based and aluminum-based corrosion inhibitors and mixtures thereof.

[0296] E32) The coating composition of E31, wherein the corrosion inhibitor is selected from Halox SZP391, Halox CW-2230, Halox 700 and mixtures thereof. The coating composition according to any one of E33, E29-E31, wherein the corrosion inhibitor is present in the coating composition at a content of about 0.01-15 wt% (e.g. 0.05-10 wt%, 0.1-9 wt%, 0.5-8 wt%, 1-7 wt%, 2-6 wt%, 3-5 wt%), based on the total weight of the coating composition. The coating composition according to any one of E34, E29-E33, wherein the pigment is selected from carbon black, TiO2, orange pigment dispersion, pigment yellow 184 in mineral oil, TiO2 in mineral oil, Sudan Blue II and mixtures thereof. The coating composition described in E35) and E34, wherein the pigment is selected from carbon black, TiO2 and mixtures thereof. The coating composition according to any one of E36, E29-E35, wherein the pigment is present in the coating composition at a content of about 0.001-5 wt% (e.g. 0.005-4 wt%, 0.01-3 wt%, 0.05-2 wt%, 0.1-1 wt%, 0.2-0.5 wt%), based on the total weight of the coating composition. The coating composition according to any one of E37, E29-E36, wherein the coating additive is selected from at least one rheology modifier.

[0297] The coating composition described in any one of E38, E29-E37, wherein the rheology modifier is selected from fumed silica, organoclay and mixtures thereof.

[0298] The coating composition according to any one of E29-E38 (E39) wherein the rheology modifier is present in the coating composition at a content of about 0.01-10 wt% (e.g. 0.05-9 wt%, 0.1-8 wt%, 0.5-7 wt%, 1-6 wt%, 2-5 wt%, 3-4 wt%), based on the total weight of the coating composition.

[0299] The coating composition according to any one of E40, E29-E39, wherein the coating additive is present in the coating composition at a content of 0-about 25 wt% (e.g. 0.01-20 wt%, 0.05-15 wt%, 0.1-14 wt%, 0.5-13 wt%, 1-12 wt%, 2-11 wt%, 3-10 wt%, 4-9 wt%, 5-8 wt%, 6-7 wt%), based on the total weight of the coating composition.

[0300] E41) The coating composition of E1, wherein: The olefin component is selected from dicyclopentadiene, tricyclopentadiene, or mixtures thereof; The inorganic filler is selected from mica, mica iron oxide, aluminum flakes (slurry), zinc aluminum flakes (slurry), talc, calcium silicate, glass flakes, aluminum powder, wollastonite and mixtures thereof; The adhesion promoter is selected from maleic anhydride-functionalized polybutadiene, silane-functionalized polybutadiene, epoxidized polybutadiene, silane and maleic anhydride-modified polybutadiene, silane and epoxy-modified polybutadiene, and mixtures thereof; and The coating additive is selected from at least one rheology modifier.

[0301] E42) The coating composition of E1, wherein: The olefin component is selected from dicyclopentadiene, tricyclopentadiene, or mixtures thereof; The inorganic filler is selected from mica, mica iron oxide, aluminum flakes (slurry), zinc aluminum flakes (slurry), talc, glass flakes and mixtures thereof; The adhesion promoter is selected from maleic anhydride-functionalized polybutadiene, silane-functionalized polybutadiene, and mixtures thereof; and The coating additive is selected from at least one rheology modifier.

[0302] The coating composition described in E43) E1 includes: The olefin component, based on the total weight of the coating composition, is present in an amount of about 5-99.99 wt% (e.g., 10-99.98 wt%, 15-99.89 wt%, 20-99.88 wt%, 25-99 wt%, 30-95 wt%, 35-90 wt%, 40-85 wt%, 45-80 wt%, 50-75 wt%, 55-70 wt%, 60-65 wt%); wherein the olefin component is selected from dicyclopentadiene, tricyclopentadiene, and mixtures thereof. Thermoplastic hydrocarbon resin, based on the total weight of the coating composition, the content of the thermoplastic hydrocarbon resin is 0-about 25 wt% (e.g. 0.01-20 wt%, 0.1-15 wt%, 0.5-10 wt%, 1-9 wt%, 2-8 wt%, 3-7 wt%, 4-6 wt%).

[0303] The inorganic filler, based on the total weight of the coating composition, has a content of 0-about 70 wt% (e.g., 0.1-65 wt%, 0.5-60 wt%, 1-55 wt%, 5-50 wt%, 10-45 wt%, 15-40 wt%, 20-35 wt%, 25-30 wt%), preferably 0-about 20 wt% (e.g., 0.05-15 wt%, 0.1-10 wt%, 0.5-5 wt%, 1-4 wt%, 2-3 wt%) or about 14-64 wt% (e.g., 27-58 wt%); wherein the inorganic filler is selected from mica, mica iron oxide, aluminum flakes (slurry), zinc aluminum flakes (slurry), talc, calcium silicate, glass flakes, aluminum powder, wollastonite, and mixtures thereof; An adhesion promoter, based on the total weight of the coating composition, is present in an amount of approximately 0.01-10 wt% (e.g., 0.05-9 wt%, 0.1-8 wt%, 0.5-7 wt%, 1-6 wt%, 2-5 wt%, 3-4 wt%); wherein the adhesion promoter is selected from maleic anhydride-functionalized polybutadiene, silane-functionalized polybutadiene, and mixtures thereof; and The coating additive, based on the total weight of the coating composition, has a content of 0-about 5 wt% (e.g., 0.05-4 wt%, 0.1-3 wt%, 0.5-2 wt%, 1-1.5 wt%); wherein the coating additive is selected from rheology modifiers.

[0304] The coating composition described in E44) E1 includes: The olefin component, based on the total weight of the coating composition, is present in an amount of about 41-72 wt%; wherein the olefin component is selected from dicyclopentadiene, tricyclopentadiene, and mixtures thereof; Thermoplastic hydrocarbon resin, based on the total weight of the coating composition, comprises a content of 0-about 21 wt% of the thermoplastic hydrocarbon resin. The inorganic filler, based on the total weight of the coating composition, contains approximately 27-58 wt% inorganic filler; wherein the inorganic filler is selected from mica, mica iron oxide, aluminum flakes (slurry), zinc aluminum flakes (slurry), talc, glass flakes, and mixtures thereof. An adhesion promoter, based on the total weight of the coating composition, wherein the content of the adhesion promoter is approximately 0.05-6 wt%; wherein the adhesion promoter is selected from maleic anhydride-functionalized polybutadiene, silane-functionalized polybutadiene, and mixtures thereof; and The coating additive, based on the total weight of the coating composition, has a content of 0-about 5 wt%; wherein the coating additive is selected from fumed silica, organoclay and mixtures thereof.

[0305] The coating composition of any one of E45, E41-E44, wherein the maleic anhydride-functionalized polybutadiene is selected from Ricobond 1731, Polyvest MA 100 and mixtures thereof.

[0306] The coating composition of any one of E46, E41-E45, wherein the silane-functionalized polybutadiene is selected from Polyvest ST E60, Polyvest ST E100, SEX-12-1287A, SEX-12-1267B and mixtures thereof.

[0307] The coating composition of any one of E47, E41-E43, wherein the rheology modifier is selected from fumed silica, organoclay and mixtures thereof.

[0308] The coating composition described in E48) and E47, wherein the fumed silica is Cab-O-Sil TS720 and the organoclay is Garamite 7303.

[0309] The coating composition described in any one of E49, E41-E48 further comprises at least one corrosion inhibitor selected from zinc phosphate-based corrosion inhibitors, calcium borosilicate-based corrosion inhibitors, zinc-based and aluminum-based corrosion inhibitors, and mixtures thereof.

[0310] The coating composition described in E50) E49, wherein the corrosion inhibitor is selected from Halox SZP391, Halox CW-2230, Halox 700 and mixtures thereof. The coating composition of E51, E49 or E50, wherein the corrosion inhibitor is present in the coating composition at a content of about 0.01-15 wt% (e.g. 0.05-10 wt%, 0.1-9 wt%, 0.5-8 wt%, 1-7 wt%, 2-6 wt%, 3-5 wt%), based on the total weight of the coating composition. The coating composition described in any one of E52, E41-E51 further comprises at least one pigment selected from carbon black, TiO2, orange pigment dispersion, pigment yellow 184 in mineral oil, TiO2 in mineral oil, Sudan Blue II, and mixtures thereof. The coating composition described in E53) E52, wherein the pigment is selected from carbon black, TiO2 and mixtures thereof. E54) The coating composition of E52 or E53, wherein the pigment is present in the coating composition at a content of about 0.001-5 wt% (e.g. 0.005-4 wt%, 0.01-3 wt%, 0.05-2 wt%, 0.1-1 wt%, 0.2-0.5 wt%), based on the total weight of the coating composition. E55) A method for coating a substrate material, comprising: Optionally, an adhesion promoter may be applied to the substrate surface; Apply the coating composition of any one of E1-E54 to the surface of a substrate; and The coating applied to the substrate surface cures at room temperature.

[0311] The method described in E56) and E55 further includes the step of bonding a second substrate: bonding the two substrates together by placing the second substrate on the coated substrate.

[0312] The method described in E57 and E55, wherein the coating applied to the surface of the substrate is cured at room temperature. E58) An article of manufacture prepared by any one of the methods described in E55-E57.

[0313] E59) An article comprising a substrate coated with a cured coating composition, wherein the coating composition is any one of E1-E54.

[0314] The article described in E60) E59, wherein the substrate is a metal surface.

[0315] The article described in E61) E59, wherein the substrate is a non-metallic surface.

[0316] test In the following examples, every effort has been made to ensure the accuracy of the data used (e.g., content, temperature, etc.), but some experimental errors and biases still need to be considered. Unless otherwise stated, temperature is in degrees Celsius (°C), pressure is at or near atmospheric pressure, and viscosity is in centipoise (cP). The additive content added to the coating composition is expressed in ppm (defined as: grams of additive per million grams of cyclic olefin composition) or phr (defined as: grams of additive per 100 grams of cyclic olefin composition).

[0317] The following examples are not intended to limit the invention described herein, but are provided as representative examples of the compositions of the invention, methods of using them, and articles made from these compositions and methods.

[0318] Example Materials and Methods Unless otherwise specified, all glassware was oven-dried, and reactions were carried out under ambient conditions. Unless otherwise specified, all solvents and reagents were purchased from commercial suppliers and used upon receipt. The cyclic olefin resins, fillers, rheology modifiers, color pigments and dispersions, corrosion inhibitors and adhesion promoters used in the examples are listed in Tables 1-6. “2-Hydroxyethylbicyclo[2.2.1]hepta-2-ene-5-carboxylic acid ester” is defined herein as HENB. “Methylene diphenyl diisocyanate” is defined herein as MDI.

[0319] Table 1. Cycloolefin resin (RSN) package

[0320] Table 2 Filler (FIL) Package

[0321] Table 3 Rheology Modifier (RM) Packages

[0322] Table 4 Color (COLR) Pigments and Dispersions Packages

[0323] Table 5 Corrosion Inhibitor (CORR-INH) Package

[0324] Table 6 Adhesion Promoter (AP) Package

[0325] General steps Add the olefin component to a mixing container of appropriate size. Add the inorganic filler, adhesion promoter, and coating additives (rheology modifier, color pigment and pigment dispersion, corrosion inhibitor) to the olefin component and mix them until the mixture is completely homogeneous. Laboratory Sample Preparation: To prepare the coated samples, a thin-film applicator was used to apply the catalytically formulated coating to a sandblasted 10 cm × 10 cm (4” × 4”) carbon steel plate with a 500 µm (20 mil) gap setting. Steel grit was used, following the SSPC-SP 10 surface treatment standard, to achieve a surface profile of 50–75 μm (2–3 mils). The catalytically formulated coating was prepared using a ruthenium catalyst suspension and resin formulation at a weight ratio of 1:50. The coated samples were cured under ambient conditions for 7 days in a well-ventilated fume hood before testing.

[0326] Pull-off adhesion test samples: Procedures similar to ASTM D4551 were followed. The coated surface was roughened with 100-grit sandpaper, and 14 mm aluminum dollies were sandblasted to promote adhesion between the epoxy adhesive and the coated surface. The epoxy adhesive was cured at room temperature for 24 hours before testing. Pull-off adhesion tests were performed using an automated portable pull-off adhesion tester. Adhesion failure modes and adhesion values ​​were reported. Various failure mode codes were reported, such as ACS (Adhesion failure between coating and substrate), CC (Cohesive failure between coating), and ACG (Adhesion failure between coating and adhesive).

[0327] Hot water (95°C) immersion test: A procedure similar to ASTM D870 was followed. After the specified curing time (7 days of ambient curing (RT–7 days)), the coated samples were completely immersed in a 95°C deionized water bath for 7 days. After 7 days, the samples were removed from the water bath for visual inspection. Pull-out adhesion testing was also performed after immersion. Salt Spray Corrosion Chamber Test (ASTM B117): This test covers the procedures for testing the corrosion resistance of coatings under continuous salt spray conditions. Prior to testing, a fully coated steel plate is crisscrossed according to ISO 12944-9, Section A.1. The crisscross is performed using a drill bit mounted on a drill press, with dimensions of 50 mm × 2 mm. The crisscrossed sample is placed in the salt spray chamber at an angle of 15°–30° to the vertical. The salt solution is prepared by dissolving 5 ± 1 parts by weight of sodium chloride (total impurities ≤0.3%) in 95 parts by weight of type IV water conforming to D1193. The temperature of the salt spray chamber is 35 ± 2°C. After 3 weeks of continuous salt spray testing, the sample is removed from the salt spray chamber, rinsed with clean running water to remove salt deposits, and then dried immediately. Using a hard, sharp knife, the delaminated coating around the crisscross is removed horizontally by inserting the blade under the loose coating until no further coating peeling is detected. After removing the non-adhesive coating, the corrosion width of the steel was measured at nine points (the midpoint of the scribe line and four other points 5 mm apart on either side of the midpoint). The corrosion creep at the scribe line was calculated using the following formula with an accuracy of 0.1 mm:

[0328] Where C is the average of the nine width measurements, and W is the measured and recorded line width.

[0329] Results and Discussion Table 7 shows that, compared to compositions with a high content of AP1 (6 phr) adhesion promoter and a control group without AP, in both resin formulations RSN 1 and RSN 2 / THR 1 (70 / 30), a low dose (1 phr) of polybutadiene maleic anhydride (PBD-MA) adhesion promoter (AP9) provided a favorable adhesion failure mode (ACG) and good pull-out adhesion values, demonstrating the high efficiency of the PBD-MA adhesion promoter.

[0330] Table 7. Performance of Resin After Adding Adhesion Promoter

[0331] Table 8 shows that in formulations containing inorganic filler (FIL 1), PBD-MA adhesion promoters (AP3 and AP9) can be used over a wide range of dosages to achieve good adhesion failure modes and pull-out values ​​after 7 days of curing at room temperature. After immersion in 95°C water for 1 week, AP9 adhesion promoter exhibited superior adhesion compared to AP3.

[0332] Table 8. Cycloolefin resin compositions containing 40 phr mica filler

[0333] Table 9 shows that in filler formulations based on resin RSN 1 and inorganic filler FIL 1, different types of PBD-MA adhesion promoters and polybutadiene silane (PBD-silane) adhesion promoters all achieved good adhesion performance. After immersion in water at 95°C, some PBD-MA and PBD-silane provided superior adhesion compared to the others.

[0334] Table 9. Cycloolefin resin compositions containing 40 phr mica filler and different adhesion promoters

[0335]

[0336] Table 10 shows that in filler formulations based on resin RSN 2 / THR 1 (70 / 30) and inorganic filler FIL 1, different types of polybutadiene maleic anhydride (PBD-MA) adhesion promoters and polybutadiene silane (PBD-silane) adhesion promoters all achieved good adhesion performance. After immersion in water at 95°C, some PBD-MA and PBD-silane adhesion promoters exhibited even better adhesion.

[0337] Table 10 Cycloolefin resin compositions containing 70 phr RSN 2, 30 phr THR 1, 40 phr FIL 1 and different adhesion promoters

[0338] Table 11 shows that PBD-MA adhesion promoter is effective and compatible with various inorganic fillers. Some inorganic fillers exhibit superior adhesion performance after immersion in water at 95°C.

[0339] Table 11 Cycloolefin resin compositions containing adhesion promoters, rheology modifiers, and different filler packs

[0340] Table 12 shows that, in high-content filler formulations, both PBD-MA and PBD-silane adhesion promoters are effective across a wide range of inorganic filler dosages (40 phr to 140 phr). Different fillers were used in combination.

[0341] Table 12 Cycloolefin resin compositions containing different adhesion promoters and different high-concentration filler packs.

[0342] PBD-MA and PBD-silane adhesion promoters are used in combination and are compatible with other coating additives (such as rheology modifiers RM 1 and RM 2) to obtain suitable rheological properties for the application.

[0343] Table 13 Cycloolefin resin compositions containing 100 phr RSN 1 and various adhesion promoters, rheology modifiers, and filler packets.

[0344] Table 14 shows that the PBD-MA adhesion promoter is compatible with the corrosion inhibitor. This combination exhibits excellent initial pull-out adhesion after curing at room temperature for 7 days, retains good adhesion after immersion in 95°C water for 1 week, and shows good anti-corrosion performance (low rust creep value) after 3 months of salt spray corrosion chamber testing, while retaining good adhesion.

[0345] Table 14 Cycloolefin resin compositions containing 100 phr RSN 1, 40 phr FIL 1, 1 phr AP9, 4 phr RM1, 5 phr COLR and different corrosion inhibitor packets

[0346] Table 15 shows that PBD-MA adhesion promoter is compatible with different color pigments and pigment dispersions, and exhibits good initial adhesion and good overall adhesion after immersion in water at 95°C.

[0347] Table 15 Cycloolefin resin compositions containing different color pigments and color dispersions

[0348] Table 17 shows that by appropriately selecting resins (RSN 1, RSN 2), thermoplastic hydrocarbon resins (THR 1), inorganic fillers (e.g., FIL 1, FIL 4, FIL 5), adhesion promoters (PBD-MA and PBD-silane), rheology modifiers (RM1, RM2), and corrosion inhibitors (CORR-INH 1, CORR-INH 2, CORR-INH 3), excellent corrosion resistance with low rust creep values ​​and good adhesion can be obtained. The examples in Table 16 demonstrate that PBD-MA and PBD-silane adhesion promoters exhibit superior performance compared to known norbornene-isocyanate and norbornene-silane adhesion promoters.

[0349] Table 16 ASTM B117 Salt Spray Corrosion Test Formulation

[0350] Table 17 Results of ASTM B117 Salt Spray Corrosion Test

[0351] It should be understood that although the invention has been described in conjunction with its specific embodiments, the foregoing description and examples are intended to illustrate rather than 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.

Claims

1. A coating composition comprising: a) At least one olefin resin composition, comprising: a.1) At least one olefin component, comprising: a.1.1) Based on the total weight of the olefin components, 80-100 wt% of at least one cyclic olefin, said cyclic olefin being selected from the group consisting of formula (I), formula (II) and formula (III); and a.1.2) Based on the total weight of the olefin component, 0-20 wt% of at least one linear olefin of formula (IV); Wherein, the sum of the wt% of the cyclic olefins of formulas (I), (II), and (III) and the wt% of the linear olefin of formula (IV) is 100 wt% of the olefin component; and a.2) At least one metal carbene olefin metathesis catalyst, wherein the molar ratio of olefin to catalyst is 10,000,000:1 to 1,000:1; and a.3) Optionally, at least one thermoplastic hydrocarbon resin; b) Optionally, at least one inorganic filler; c) At least one adhesion promoter, said adhesion promoter being selected from functionalized polyolefins; and d) Optionally, at least one paint additive; Among them, the cyclic olefins of formula (I), formula (II) and formula (III) and the linear olefin of formula (IV) have the following structures: in: R a H, or optionally substituted linear or branched C 1-24 Alkyl, optionally substituted straight or branched C 2-24 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g , -CN, -NO2, -CF3, -P(O)(OR h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, -CH2- (optionally substituted heterocycles), optionally substituted C 3-10 Cycloalkyl, -CH2- (optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 Aryl, -CH2- (optionally substituted C) 5-24 aryl), optionally substituted C 3-12 Cycloalkenyl, -CH2- (optionally substituted C) 3-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p -C(R) h (R) i )C(O)NR o OR n or ; R b H, or optionally substituted linear or branched C 1-24 Alkyl, optionally substituted straight or branched C 2-24 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g , -CN, -NO2, -CF3, -P(O)(OR h )2、-OP(O)(OR h )2、-Si(OR k 3、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, Optionally substituted spirocyclic heterocycles, -CH2- (optionally substituted heterocycles), Optionally substituted C 3-10 Cycloalkyl, -CH2- (optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 Aryl, -CH2- (optionally substituted C) 5-24 aryl), optionally substituted C 3-12 Cycloalkenyl, -CH2- (optionally substituted C) 3-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p or -C(R) h (R) i )C(O)NR o OR n ; R c and R d H, and optionally substituted linear or branched C, are independent of each other. 1-24 Alkyl, optionally substituted straight or branched C 2-24 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g CN, NO2, -CF3, -P(O)(OR) h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, -CH2- (optionally substituted heterocycles), optionally substituted C 3-10 Cycloalkyl, -CH2- (optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 Aryl, -CH2- (optionally substituted C) 5-24 aryl), optionally substituted C 3-12 Cycloalkenyl, -CH2- (optionally substituted C) 3-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p or -C(R) h (R) i )C(O)NR o OR n ; R d H, or optionally substituted linear or branched C 1-24 Alkyl, optionally substituted straight or branched C 2-24 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g CN, NO2, -CF3, -P(O)(OR) h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, -CH2- (optionally substituted heterocycles), optionally substituted C 3-10 Cycloalkyl, -CH2- (optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 Aryl, -CH2- (optionally substituted C) 5-24 aryl), optionally substituted C 3-12 Cycloalkenyl, -CH2- (optionally substituted C) 3-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p or -C(R) h (R) i )C(O)NR o OR n ; Each R s Independently, for the optional substitution of straight or branched C 1-24 Alkyl, optionally substituted straight or branched C 2-24 Alkenyl, halogen, -C(O)R f -CH2-C(O)R f -OR g -CH2-OR g , -CN, -NO2, -CF3, -P(O)(OR h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocycles, -CH2- (optionally substituted heterocycles), Optionally substituted C 3-10 Cycloalkyl, -CH2- (optionally substituted C 3-10 cycloalkyl), optionally substituted C 5-24 Aryl, -CH2- (optionally substituted C) 5-24 aryl), optionally substituted C 3-12 Cycloalkenyl, -CH2- (optionally substituted C) 3-12 cycloalkenyl), C(R) h (R) i COOR j -C(R) h (R) i )C(O)H、-C(R h (R) i )C(O)R k -C(R) h (R) i )CR l (OR m (OR) n ), -C(R h (R) i )C(O)NR o R p or -C(R) h (R) i )C(O)NR o OR n ; R f For OH, OR k NR g R h Optional substitution of straight or branched C 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl or optionally substituted C 3-12 Cycloalkenyl; R g H, or optionally substituted linear or branched C 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl, optionally substituted straight or branched C 2-24 alkenyl, -C(O)- (optionally substituted C) 5-24 aryl), -C(O)- (optionally substituted straight or branched C) 2-24 alkenyl) or optionally substituted C 3-12 Cycloalkenyl; R h R i R j R l R m R n R o and R p H, and optionally substituted linear or branched C, are independent of each other. 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl or optionally substituted C 3-12 Cycloalkenyl; R k For optional substitution of straight or branched C 1-24 Alkyl, optionally substituted C 3-10 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 5-24 aryl or optionally substituted C 3-12 Cycloalkenyl; t is 0, 1, 2, 3, 4, 5, or 6; and z can be 0, 1, 2, or 3.

2. The coating composition according to claim 1, wherein: R a H, or optionally substituted linear or branched C 1-12 Alkyl, optionally substituted straight or branched C 2-6 Alkenyl, halogen, -C(O)R f -OR g , -CN, -NO2, -CF3, -P(O)(OR h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocyclic rings, Optionally substituted C 3-10 cycloalkyl, optionally substituted C 6-10 aryl, optionally substituted C 3-12 cycloalkenyl or ; R b R c and R d H, and optionally substituted linear or branched C, are independent of each other. 1-12 Alkyl, optionally substituted straight or branched C 2-6 Alkenyl, halogen, -C(O)R f -OR g , -CN, -NO2, -CF3, -P(O)(OR h )2、-OP(O)(OR h )2、-S(O)2OR h -OS(O)2R h Optionally substituted heterocyclic rings, Optionally substituted C 3-10 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-12 Cycloalkenyl; R f For OH, OR k NR g R h Optional substitution of C 1-12 Alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 3-12 Cycloalkenyl; R g R h R i R j R l R m R n R o and R p H, and optionally substituted linear or branched C, are independent of each other. 1-12 Alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 3-12 Cycloalkenyl; R k C is an optional replacement 1-12 Alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocyclic, optionally substituted C 6-10 aryl or optionally substituted C 3-12 Cycloalkenyl; t is 0; and z is 2.

3. The coating composition according to claim 1 or 2, wherein: The cyclic olefin of formula (I) is 2-ethylidene-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene, 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylbridged naphthalene or a mixture thereof. The cyclic olefin of formula (II) is a 2-hydroxyethyl bicyclic [ 2.2.1] Hepta-5-en-2-carboxylic acid ester, [3-(triethoxysilyl)propyl]-bicyclo[2.2.1]hepta-5-en-2-methylene ester, octyl-norbornene, 5-norbornene-2-methanol, 5-norbornene-2-ex,3-ex-diethanol, 2-hydroxyethylbicyclo[2.2.1]hepta-5-en-2-carboxylic acid ester, norbornene triethoxysilane, 5-(perfluorobutyl)bicyclo[2.2.1]hepta-2-ene, 2,2,3,3,4,4,5,5,6,6,7,7-dodecylfluoroheptylbicyclo[2,2,1]hepta-5-en-2-carboxylic acid ester, bicyclo[2.2.1]hepta-5-en-2-carboxylic acid, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl ester or mixtures thereof; and The cyclic olefins of formula (III) are dicyclopentadiene, tricyclopentadiene, or mixtures thereof.

4. The coating composition according to claim 1, wherein, The coating composition contains at least one cyclic olefin, which is represented by the group consisting of formulas (I) and (II).

5. The coating composition according to claim 1, wherein, The coating composition contains at least one cyclic olefin, which is selected from the group consisting of formula (I) and formula (III).

6. The coating composition according to claim 1, wherein, The coating composition contains at least one cyclic olefin, which is selected from the group consisting of formula (II) and formula (III).

7. The coating composition according to claim 1, wherein, The coating composition contains at least one cyclic olefin, which is selected from the group consisting of formula (I), formula (II) and formula (III).

8. The coating composition according to claim 1, wherein, The coating composition contains at least one cyclic olefin, which is selected from the group consisting of formula (III).

9. The coating composition according to claim 8, wherein, At least one cyclic olefin is selected from dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), and mixtures thereof.

10. The coating composition according to claim 9, wherein, The ratio of DCPD to DCPD is 3:7 to 2:3 (DCPD wt%: TCPD wt%).

11. The coating composition according to claim 1, wherein, The olefin component is present in the coating composition at a content of about 35-99.9 wt%, based on the total weight of the coating composition.

12. The coating composition according to claim 1, wherein, The at least one metal carbene olefin metathesis catalyst is a group 8 transition metal complex having the structure of formula (I): （I） in: M is a group 8 transition metal; L 1 L 2 and L 3 It is a neutral electron donor ligand; n is 0 or 1, therefore L 3 It may exist or it may not exist; m is 0, 1, or 2; k is 0 or 1; X 1 and X 2 It is an anionic ligand; and R 1 and R 2 Each is independently selected from hydrogen, hydrocarbon group, substituted hydrocarbon group, and hydrocarbon group containing heteroatoms; Among them, X 1 X 2 L 1 L 2 L 3 R 1 and R 2 Any two or more of them can together form one or more cyclic groups, and further, X 1 X 2 L 1 L 2 L 3 R 1 and R 2 Any one or more of them can be connected to the carrier.

13. The coating composition according to claim 12, wherein, The at least one metal carbene olefin metathesis catalyst is a group 8 transition metal complex having the structure of formula (I), wherein: M is ruthenium; n is 0; m is 0; k is 1; L 1 and L 2 It is a trisubstituted phosphine, independently selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L 1 It is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethylcarbene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethylcarbene, 1,3-bis(2,4,6-trimethylphenyl)-2-imidazol-2-dimethylcarbene, and 1,3-bis(2,6-diisopropylphenyl)-2-imidazol-2-dimethylcarbene; L 2 It is a trisubstituted phosphine, selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L 1 and L 2 It is an N-heterocyclic carbene, independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinedimethylcarbene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinedimethylcarbene, 1,3-bis(2,4,6-trimethylphenyl)-2-imidazol-2-dimethylcarbene and 1,3-bis(2,6-diisopropylphenyl)-2-imidazol-2-dimethylcarbene; X 1 and X 2 For chlorine; and R 1 For hydrogen, R 2 It is phenyl or –CH=C(CH3)2; or R 1 and R 2 Together they form the indene subunit.

14. The coating composition according to claim 1, wherein, The at least one metal carbene olefin metathesis catalyst is a group 8 transition metal complex having the structure of formula (VII): (VII) in: M is a group 8 transition metal; X 1 and X 2 It is an anionic ligand; L 1 It is a neutral electron donor ligand; Y is a heteroatom, selected from N, O, S, and P; R 5 R 6 R 7 and R 8 Each is independently selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, alkenyl containing heteroatoms, 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, amino, imino, amide, trifluoroamide, sulfide, disulfide Sulfonate esters, carbamate esters, silanes, siloxanes, phosphine, phosphate esters, borate esters, or -A-Fn, wherein A is a divalent hydrocarbon group selected from alkylene and arylalkylene groups, wherein the alkyl portion of the alkylene and arylalkylene groups can be straight-chain or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the arylalkylene group can be substituted or unsubstituted, wherein heteroatoms and / or functional groups can be present in the aryl or alkyl portion of the alkylene and arylalkylene groups, and Fn is a functional group; R 5 R 6 R 7 and R 8 Any combination of them can be interconnected to form one or more cyclic groups; n is either 1 or 2, therefore n is 1 when the heteroatom is divalent O or S; and n is 2 when the heteroatom is trivalent N or P; and... Z is selected from the group consisting of hydrogen, alkyl, aryl, functionalized alkyl, and functionalized aryl, wherein the functionalized group may independently be one or more of the following groups: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, urethane, silane, siloxane, phosphine, phosphate or borate; methyl, isopropyl, sec-butyl, tert-butyl, neopentyl, benzyl, phenyl and trimethylsilyl; and Among them, X 1 X 2 L 1 V, Z, R 5 R 6 R 7 and R 8 Any combination or multiple combinations can be attached to the carrier.

15. The coating composition according to claim 1, wherein, The thermoplastic hydrocarbon resin is present in the coating composition at a content of 0-about 25 wt%, based on the total weight of the coating composition.

16. The coating composition according to claim 1, wherein, The olefin resin component is present in the coating composition at a content of about 5-99.9 wt%, based on the total weight of the coating composition.

17. The coating composition according to claim 1, wherein, The inorganic filler is selected from aluminum powder or its alloys, aluminum sheets or their alloys, zinc-aluminum sheets or their alloys, mica iron oxide, mica, glass sheets, calcium silicate, wollastonite, talc, calcium carbonate, barium sulfate, silicon dioxide and their mixtures.

18. The coating composition according to claim 1, wherein, The inorganic filler is selected from aluminum powder, aluminum flakes (slurry), zinc-aluminum flakes (slurry), mica iron oxide, mica, glass flakes, calcium silicate, wollastonite, talc and mixtures thereof.

19. The coating composition according to claim 1, wherein, The inorganic filler is selected from aluminum flakes (slurry), zinc-aluminum flakes (slurry), mica iron oxide, mica, glass flakes, talc and mixtures thereof.

20. The coating composition according to claim 1, wherein, The inorganic filler is present in the coating composition at a content of about 20-60 wt%, based on the total weight of the coating composition.

21. The coating composition according to claim 1, wherein, The adhesion promoter is selected from at least one functionalized polybutadiene.

22. The coating composition according to claim 21, wherein, The functionalized polybutadiene is selected from maleic anhydride-functionalized polybutadiene, silane-functionalized polybutadiene, epoxidized polybutadiene, silane and maleic anhydride-modified polybutadiene, and mixtures thereof.

23. The coating composition according to claim 1, wherein, The adhesion promoter is selected from maleic anhydride-functionalized polybutadiene, silane-functionalized polybutadiene, or mixtures thereof.

24. The coating composition according to claim 23, wherein, The maleic anhydride-functionalized polybutadiene is selected from Ricobond 1731, Polyvest MA 100, and mixtures thereof.

25. The coating composition according to claim 23, wherein, The silane-functionalized polybutadiene is selected from Polyvest ST E60, Polyvest ST E100, SEX-12-1287A, SEX-12-1267B and mixtures thereof.

26. The coating composition according to claim 22, wherein, The silane and maleic anhydride-modified polybutadiene is selected from X-12-1287A.

27. The coating composition according to claim 1, wherein, The adhesion promoter is an oligomeric coupling agent containing reactive functional groups and alkoxysilyl groups.

28. The coating composition according to claim 1, wherein, The adhesion promoter is present in the coating composition at a content of about 0.01-10 wt%, based on the total weight of the coating composition.

29. The coating composition according to claim 1, wherein, The coating composition comprises coating additives selected from the group consisting of gel modifiers, hardness modifiers, impact modifiers, antioxidants, anti-ozone agents, adhesives, thixotropic adhesives, rheology modifiers, corrosion inhibitors, dispersants, wetting agents, plasticizers, pigments, flame retardants, dyes, fibers, reinforcing materials, coupling agents, ultraviolet absorbers, ultraviolet stabilizers, film-forming agents, lubricants, and mixtures thereof.

30. The coating composition according to claim 29, wherein, The coating additive is selected from the group consisting of at least one rheology modifier, at least one corrosion inhibitor, at least one pigment, and mixtures thereof.

31. The coating composition according to claim 29, wherein, The corrosion inhibitor is selected from zinc phosphate-based corrosion inhibitors, calcium borosilicate-based corrosion inhibitors, zinc-based and aluminum-based corrosion inhibitors, and mixtures thereof.

32. The coating composition according to claim 31, wherein, The corrosion inhibitor is selected from Halox SZP391, Halox CW-2230, Halox 700 and mixtures thereof.

33. The coating composition according to claim 29, wherein, The corrosion inhibitor is present in the coating composition at a content of about 0.01-15 wt%, based on the total weight of the coating composition.

34. The coating composition according to claim 29, wherein, The pigments are selected from carbon black, TiO2, orange pigment dispersion, pigment yellow 184 in mineral oil, TiO2 in mineral oil, Sudan Blue II and mixtures thereof.

35. The coating composition according to claim 34, wherein, The pigment is selected from carbon black, TiO2 and mixtures thereof.

36. The coating composition according to claim 29, wherein, The pigment is present in the coating composition at a content of about 0.001-5 wt%, based on the total weight of the coating composition.

37. The coating composition according to claim 29, wherein, The coating additive is selected from at least one rheology modifier.

38. The coating composition according to claim 29, wherein, The rheology modifier is selected from fumed silica, organoclay and mixtures thereof.

39. The coating composition according to claim 29, wherein, The rheology modifier is present in the coating composition at a content of about 0.01-10 wt%, based on the total weight of the coating composition.

40. The coating composition according to claim 29, wherein, The content of the coating additive in the coating composition is about 0.01-25 wt%, based on the total weight of the coating composition.

41. The coating composition according to claim 1, wherein: The olefin component is selected from dicyclopentadiene, tricyclopentadiene, or mixtures thereof; The inorganic filler is selected from mica, mica iron oxide, aluminum flakes (slurry), zinc aluminum flakes (slurry), talc, calcium silicate, glass flakes, aluminum powder, wollastonite and mixtures thereof; The adhesion promoter is selected from maleic anhydride-functionalized polybutadiene, silane-functionalized polybutadiene, epoxidized polybutadiene, silane and maleic anhydride-modified polybutadiene, silane and epoxy-modified polybutadiene, and mixtures thereof; and The coating additive is selected from at least one rheology modifier.

42. The coating composition according to claim 1, wherein: The olefin component is selected from dicyclopentadiene, tricyclopentadiene, or mixtures thereof; The inorganic filler is selected from mica, mica iron oxide, aluminum flakes (slurry), zinc aluminum flakes (slurry), talc, glass flakes and mixtures thereof; The adhesion promoter is selected from maleic anhydride-functionalized polybutadiene, silane-functionalized polybutadiene, and mixtures thereof; and The coating additive is selected from at least one rheology modifier.

43. The coating composition according to claim 1, comprising: Based on the total weight of the coating composition, approximately 35-99.89% of the olefin component, wherein the olefin component is selected from dicyclopentadiene, tricyclopentadiene, and mixtures thereof; Based on the total weight of the coating composition, 0-about 25 wt% thermoplastic hydrocarbon resin; Based on the total weight of the coating composition, approximately 0.1-65 wt% of inorganic fillers, wherein the inorganic fillers are selected from mica, mica iron oxide, aluminum flakes (slurry), zinc aluminum flakes (slurry), talc, calcium silicate, glass flakes, aluminum powder, wollastonite and mixtures thereof; Based on the total weight of the coating composition, approximately 0.01-10 wt% of an adhesion promoter, wherein the adhesion promoter is selected from maleic anhydride-functionalized polybutadiene, silane-functionalized polybutadiene, and mixtures thereof; and Based on the total weight of the coating composition, 0-about 5 wt% of coating additives, wherein the coating additives are selected from rheology modifiers.

44. The coating composition according to claim 1, comprising: Based on the total weight of the coating composition, approximately 41-72 wt% of an olefin component, wherein the olefin component is selected from dicyclopentadiene, tricyclopentadiene, or mixtures thereof; Based on the total weight of the coating composition, 0-about 21 wt% thermoplastic hydrocarbon resins; Based on the total weight of the coating composition, approximately 27-58 wt% of inorganic fillers, wherein the inorganic fillers are selected from mica, mica iron oxide, aluminum flakes (slurry), zinc aluminum flakes (slurry), talc, glass flakes, and mixtures thereof; Based on the total weight of the coating composition, approximately 0.05-6 wt% of an adhesion promoter, wherein the adhesion promoter is selected from maleic anhydride-functionalized polybutadiene, silane-functionalized polybutadiene, and mixtures thereof; and Based on the total weight of the coating composition, 0-about 5 wt% of coating additives, wherein the coating additive is at least one rheology modifier selected from fumed silica, organoclay and mixtures thereof.

45. The coating composition according to any one of claims 41-44, wherein, The maleic anhydride-functionalized polybutadiene is selected from Ricobond 1731, Polyvest MA 100, and mixtures thereof.

46. ​​The coating composition according to any one of claims 41-44, wherein, The silane-functionalized polybutadiene is selected from Polyvest ST E60, Polyvest ST E100, SEX-12-1287A, SEX-12-1267B and mixtures thereof.

47. The coating composition according to any one of claims 41-43, wherein, The rheology modifier is selected from fumed silica, organoclay and mixtures thereof.

48. The coating composition according to claim 47, wherein, The fumed silica is Cab-O-Sil TS720, and the organic clay is Garamite 7303.

49. The coating composition according to any one of claims 41-44, wherein the coating composition further comprises at least one corrosion inhibitor selected from zinc phosphate-based corrosion inhibitors, calcium borosilicate-based corrosion inhibitors, zinc-based and aluminum-based corrosion inhibitors, and mixtures thereof.

50. The coating composition according to claim 49, wherein, The corrosion inhibitor is selected from Halox SZP391, Halox CW-2230, Halox 700 and mixtures thereof.

51. The coating composition according to claim 49, wherein, The corrosion inhibitor is present in the coating composition at a content of about 0.01-15 wt%, based on the total weight of the coating composition.

52. The coating composition according to any one of claims 41-44, wherein, The coating composition further comprises at least one pigment selected from carbon black, TiO2, orange pigment dispersion, pigment yellow 184 in mineral oil, TiO2 in mineral oil, Sudan Blue II, and mixtures thereof.

53. The coating composition according to claim 52, wherein, The pigment is selected from carbon black, TiO2 and mixtures thereof.

54. The coating composition according to claim 52, wherein, The pigment is present in the coating composition at a content of about 0.001-5 wt%, based on the total weight of the coating composition.

55. A method for coating a substrate material, comprising: Optionally, an adhesion promoter may be applied to the substrate surface; Apply the coating composition of claim 1 to the surface of a substrate; and The coating applied to the substrate surface cures at room temperature.

56. The method of claim 55, further comprising the step of bonding a second substrate: bonding the two substrates together by placing the second substrate on the coated substrate.

57. The method of claim 55, wherein, The coating applied to the substrate surface cures at room temperature.

58. An article of manufacture prepared by the method of claim 55.

59. An article comprising a substrate coated with a cured coating composition, wherein the coating composition is the coating composition of claim 1.

60. The article of claim 59, wherein, The substrate is a metal surface.

61. The article of claim 59, wherein, The substrate is a non-metallic surface.

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