ROMP compositions and ROMP materials, thermal insulation compositions and thermal insulation materials, and their uses

Abstract

The present invention relates to ROMP compositions, ROMP polymers, ROMP polymer composites, and thermal insulation materials and methods for insulating pipelines and related equipment, structures, and objects used in offshore drilling. The present invention relates to products comprising ROMP compositions, ROMP polymers, ROMP polymer composites, and thermal insulation materials.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 491,437, filed on 21 March 2023, the entirety of which is incorporated herein by reference.

[0002] The present invention relates to the field of thermally insulating pipelines and structures, particularly to the field of underwater pipelines and seafloor structures. More specifically, the present invention relates to ring-opening metathesis polymerization (ROMP) compositions, as well as ROMP polymers, ROMP polymer composites, and their insulating materials for thermally insulating offshore oil production facilities, particularly underwater pipelines and seafloor structures. The present invention also relates to methods for thermally insulating offshore oil production facilities and structures, as well as products comprising such ROMP compositions, ROMP polymers, ROMP polymer composites, and insulating materials, using such ROMP compositions, ROMP polymers, ROMP polymer composites, and insulating materials. [Background technology]

[0003] In offshore oil production, hydrocarbons need to be transported from underwater wellheads to shore facilities or other surface facilities for further distribution. As temperature decreases, resistance to the flow of liquids such as oil increases. Pipelines used to transport oil from underwater wellheads are generally insulated to prevent a significant drop in oil temperature. Furthermore, in the underwater environment, pipelines and other oil production facilities are exposed to compressive forces, saltwater corrosion, near-freezing water temperatures, the possibility of water absorption, seabed currents, and marine organisms. Most pipes and pipelines used in offshore oil production are made of metal, usually a certain grade of steel.

[0004] Installation conditions for underground and underwater pipelines and facilities are becoming increasingly stringent. Therefore, materials used to thermally insulate offshore production facilities and pipelines, including but not limited to underwater pipelines and facilities, as well as submarine pipelines and facilities, can be damaged during pipeline installation. For example, during installation, pipeline insulation is subjected to bending (bending stress) due to the sagging and winding / unwinding of the pipes, particularly in installation processes commonly known as S-lay, J-lay, and reel-lay methods.

[0005] Desirable features and / or properties of thermal insulation materials, particularly those for underwater use, include thermal stability above 150°C, resistance to hydrolysis above 150°C, flexibility with elongation at break greater than 5% at 25°C, fast curing time, low thermal conductivity, high impact strength, castability (high throughput with low capital expenditure), rigidity for robust pipe handling without external protection, ability to be processed in air, ability to adhere to thick sections without multilayering, ability to adhere to complex shapes, rapid and complete curing under production conditions, and ability to be processed in the presence of trace amounts of moisture (water). Furthermore, the industry requires thermal insulation materials possessing all of these desirable features and / or properties, particularly those for underwater use (e.g., insulation for pipes and pipelines, as well as other underwater equipment and seabed structures, e.g., coatings for field joints). As used herein, thermal stability means that the material maintains its structural integrity when exposed to high temperatures.

[0006] Polyurethane is used for insulation in underwater pipelines and equipment because it is relatively easy to process and generally has good mechanical properties. However, polyurethane insulation can undergo hydrolysis when exposed to high temperature and humidity environments. In offshore oil fields, especially in wellheads where oil temperatures are high, the polyurethane polymer network can hydrolyze, particularly at high temperatures where water can penetrate the polymer network, which negatively affects the insulation capacity of the polyurethane polymer.

[0007] Polypropylene is another polymer material used to insulate underwater pipelines and equipment. However, unlike polyurethane, lamination of polypropylene is a more difficult process, generally requiring the extrusion of multiple layers. Furthermore, polypropylenes such as isotactic polypropylene (iPP), used in polypropylene-based insulation products, have limited operating temperatures due to the upper limit of the melting point of thermoplastic polymers. Thermosetting polymers such as pDCPD-based thermosetting resins do not have such melting point limitations, potentially allowing for higher operating temperatures.

[0008] Polystyrene is another polymer material used to insulate underwater pipelines and equipment. However, because thermoplastic materials have a relatively low glass transition, they tend to flow once the glass transition is exceeded, thus limiting their operating temperature. Thermosetting materials such as pDCPD-based thermosetting resins may have a glass transition, but due to the crosslinking properties of thermosetting resins, the material does not flow, potentially allowing for higher operating temperatures.

[0009] Another material used for insulation in underwater pipelines and equipment is rigid epoxy syntactic foam, which combines hollow glass or ceramic spheres with epoxy resin. While this material has good thermal conductivity, it suffers from brittleness and rigidity, making it susceptible to damage when subjected to high stress forces and / or sudden impacts. Furthermore, these materials are difficult to remove and replace because they are attached to surfaces mechanically or using adhesives. Without the glass or ceramic microspheres, epoxy resin generally has low thermal conductivity, requires long curing cycles, and suffers from similar brittleness and rigidity issues, in addition to other limitations. Moreover, epoxy materials tend to absorb a considerable amount of water, which negatively impacts their thermal insulation properties when used underwater. Depending on the curing chemical reaction of the base epoxy, epoxy materials are prone to severe degradation due to hydrolysis, which can limit the material's service life.

[0010] Silicone and syntactic silicone, which combines silicone with hollow glass microspheres, are different polymer materials used to insulate underwater pipelines and equipment. However, both silicone and syntactic silicone can undergo hydrolysis when exposed to high-temperature and high-humidity environments. Furthermore, silicone generally requires a long curing cycle.

[0011] Phenolic compounds are another polymer material used to insulate underwater pipelines and equipment. However, phenolic compounds are generally difficult to adhere to such objects. This material also suffers from the problem of being brittle and hard, making it susceptible to damage when subjected to high stress forces and / or sudden impacts.

[0012] Another material for insulating underwater pipelines and equipment is elastomeramine-cured epoxy resin. While elastomeramine-cured epoxy resin may offer several advantages over polyurethane, these materials have some limitations, particularly in that preparing such elastomeramine-cured epoxy resin requires at least two steps and specialized equipment. Furthermore, these materials are highly viscous (e.g., 90,000 cP at 25°C), making them difficult to fill into complex molds.

[0013] Rubber materials, including silicone rubber, are examples of other materials used to insulate underwater pipelines and equipment. These materials lack attractive thermal and mechanical properties, generally require long curing cycles, and have other limitations.

[0014] Dicyclopentadiene polymers (pDCPD) prepared from Telene® 1650DCPD resin are another example of materials reported for use as field joint coatings, but this material (including similar materials such as Metton® DCPD resin and Pentamm® DCPD resin) has several limitations well known in the art. Both Telene® 1650DCPD resin (BF Goodrich / Telene SAS) and Metton® DCPD resin (Metton America / Hercules) are based on a two-component system containing a molybdenum or tungsten pre-catalyst (component B) dissolved in the DCPD monomer and an aluminum alkyl or aluminum alkyl halide co-catalyst (component A) dissolved in the DCPD monomer. These molybdenum and tungsten-catalyzed DCPD resins are extremely sensitive to chemical functional groups, as well as to air (oxygen) and moisture (water), even at trace levels. As a result of this sensitivity, DCPD resins catalyzed with molybdenum and tungsten are typically limited to processing using reaction injection molding (RIM) techniques, which require special and expensive processing and handling conditions and equipment, including special and expensive molds, injection equipment, and storage tanks. Furthermore, as a further consequence of this sensitivity, particularly to chemical functional groups, DCPD resins catalyzed with molybdenum and tungsten are generally unsuitable for use in preparing DCPD polymer composites.

[0015] Despite processing challenges, pDCPD possesses many beneficial properties for submarine insulation, including resistance to hydrolysis, creep resistance under hydrostatic pressure, fast curing time, low thermal conductivity, and high impact strength. However, pDCPD materials tend to be highly rigid and lack flexibility, which can lead to cracking during installation or operation.

[0016] In practice, commercially available DCPD monomer resins used in the molding of polymer articles typically contain 0 wt% to 30 wt% tricyclopentadiene and a smaller amount of higher oligomers of cyclopentadiene, such as tetramers and pentamers of cyclopentadiene (e.g., tetracyclopentadiene and pentacyclopentadiene).

[0017] Other ROMP polymer systems are also described as being used as submarine insulation. Copolymers of DCPD, TCPD, and monounsaturated cyclic olefin monomers are described in US10,711,090. These materials are more flexible than the DCPD and TCPD copolymers and are therefore more suitable for submarine installation and operating conditions. However, monounsaturated cyclic olefin monomers are more expensive to manufacture.

[0018] Therefore, despite the advances achieved in this field, improvements in materials used in thermally insulated pipelines and related equipment and structures used in offshore oil production, particularly polymer materials and / or polymer composite materials, remain necessary. [Overview of the Initiative]

[0019] The present invention addresses one or more of the aforementioned concerns and relates to ring-opening metathesis polymerization (ROMP) compositions and ROMP polymers, ROMP polymer composites, and their thermal insulation materials, and methods for coating, housing, and / or thermal insulating pipelines and related equipment, structures, and objects used in offshore drilling. The present invention also relates to products comprising the ROMP compositions, ROMP polymers, ROMP polymer composites, and thermal insulation materials of the present invention.

[0020] More specifically, the present invention relates to a ROMP composition, and this ROMP composition is a) A cyclic olefin composition comprising, essentially consisting of, or consisting of at least one polyunsaturated cyclic olefin, b) A catalyst composition comprising, essentially consisting of, or consisting of at least one metal carbene olefin metathesis catalyst, c) Optionally, at least one adhesion promoter, d) At least one plasticizer compound, e) at least one rubber-reinforced compound, It includes, essentially consists of, or is composed of The cyclic olefin composition does not contain, or substantially does not contain, monounsaturated cyclic olefins. At least one polyunsaturated cyclic olefin may or may not be substituted.

[0021] The present invention also relates to ROMP polymers or ROMP polymer composites comprising, essentially consisting of, or the reaction products of the ROMP composition of the present invention.

[0022] The present invention also relates to the use of ROMP polymers and / or ROMP polymer composites for thermal insulation of an object.

[0023] The present invention also relates to the use of ROMP polymers or ROMP polymer composites for thermally insulating an object from the surrounding environment.

[0024] The present invention also relates to the ROMP polymer or ROMP polymer composite of the present invention for use as a thermal insulation material.

[0025] The present invention also relates to a process for providing a ROMP polymer coating for marine applications, the process comprising: providing an object surface to be coated; providing a ROMP composition of the present invention; contacting the object surface with the ROMP composition or adhering the ROMP composition to the object surface; and exposing the ROMP composition to conditions effective for polymerization of the ROMP composition to form a ROMP polymer coating.

[0026] The present invention also relates to thermal insulation materials comprising, essentially consisting of, or comprising the ROMP composition, ROMP polymer, or ROMP polymer composite of the present invention.

[0027] The present invention also relates to an insulating material used for coating, housing, or insulating (1) an object, (2) at least a portion of an object, and / or (3) at least a portion of at least one surface of an object, wherein the insulating material comprises the ROMP composition, ROMP polymer, or ROMP polymer composite of the present invention.

[0028] The present invention also relates to the use of an insulating material for coating, housing, or insulating (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 insulating material comprises the ROMP composition, ROMP polymer, or ROMP polymer composite of the present invention.

[0029] The present invention also relates to a method for thermally insulating an object from a surrounding fluid, the method comprising interposing an insulating material between the object and the fluid, where the insulating material comprises the ROMP polymer or ROMP polymer composite of the present invention.

[0030] The present invention also relates to a method for coating, housing, or insulating (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 insulating material is a ROMP polymer or a ROMP polymer composite of the present invention.

[0031] The present invention also relates to a method for coating, housing, or insulating (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 insulating material, the method comprising: bringing the ROMP composition of the present invention into contact with (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; or adhering the ROMP composition of the present invention to (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; and exposing the ROMP composition to conditions effective in promoting the ROMP reaction of the ROMP composition to form the ROMP polymer or ROMP polymer composite of the present invention, wherein the insulating material is the ROMP polymer or ROMP polymer composite.

[0032] The present invention also relates to a process for adhering an insulating material composition to an object, the process comprising: setting up a mold around the object to define a cavity between the inner surface of the mold and the object; injecting an insulating material composition into the cavity, wherein the insulating material composition comprises the ROMP composition of the present invention; and exposing the insulating material composition to conditions effective in promoting the ROMP reaction of the ROMP composition to form the ROMP polymer or ROMP polymer composite of the present invention.

[0033] The present invention also relates to an object that is at least partially contained and / or coated by an insulating material, wherein the insulating material includes the ROMP polymer or ROMP polymer composite of the present invention.

[0034] The present invention also relates to a product including 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 of the present invention.

[0035] The present invention also relates to products manufactured by any of the methods described herein.

[0036] The embodiments described herein are not intended to be constrained. Various modifications in form and detail of the embodiments of the present invention, as well as other aspects and variations of the present invention, will become apparent to those skilled in the art from the following detailed description and examples. [Modes for carrying out the invention]

[0037] Terms and Definitions Unless otherwise specified, the present invention is not limited to, but may be modified as, specific reactants, substituents, catalysts, catalyst compositions, resin compositions, cyclic olefins, reaction conditions, or other such reactants. It should also be understood that the terms used herein are merely for the purpose of describing specific embodiments and should not be construed as limiting.

[0038] As used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly indicates otherwise. Therefore, for example, a reference to “substituent” includes not only a single substituent but also two or more substituents, etc.

[0039] Where used herein and in the appended claims, the terms “for example,” “as an example,” “e.g.,” or “including” are intended to introduce examples that further clarify the more general subject matter. Unless otherwise specified, these examples are provided solely to aid in understanding the invention and are not intended to limit it in any way.

[0040] In this specification and the subsequent claims, several terms will be used as defined below.

[0041] As used herein, the term “alkyl” refers to linear, branched, or cyclic saturated hydrocarbon groups containing 1 to about 24 carbon atoms, such as 1 to about 12 carbon atoms, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl, and others, although not necessarily. Generally, alkyl groups as used herein contain 1 to about 12 carbon atoms, although not necessarily. The term “lower alkyl” refers to alkyl groups with 1 to 6 carbon atoms, and the specific term “cycloalkyl” refers to cyclic alkyl groups typically having 4 to 8 carbon atoms, such as 5 to 7 carbon atoms. The term “substituted alkyl” refers to alkyl groups substituted with one or more substituents, and the terms “heteroatom-containing alkyl” and “heteroalkyl” refer to alkyl groups in which at least one carbon atom is replaced by a heteroatom. Unless otherwise indicated, the terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, substituted, and / or heteroatom-containing alkyls and lower alkyls, respectively.

[0042] As used herein, the term "alkylene" refers to a difunctional linear, branched, or cyclic alkyl group, where "alkyl" is as defined above.

[0043] As used herein, the term “alkenyl” refers to a linear, branched, or cyclic hydrocarbon group of 2 to about 24 carbon atoms (e.g., 2 to about 12 carbon atoms) containing at least one double bond, such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicocenyl, tetracocenyl, etc. The term “lower alkenyl” refers to an alkenyl group of 2 to 6 carbon atoms, and the specific term “cycloalkyl” refers to a cyclic alkenyl group of 5 to 8 carbon atoms, etc. The term “substituted alkenyl” refers to an alkenyl substituted with one or more substituents, and the terms “heteroatom-containing alkenyl” and “heteroalkenyl” refer to an alkenyl in which at least one carbon atom is replaced by a heteroatom. Unless otherwise indicated, the terms “alkenyl” and “lower alkenyl” include linear, branched, cyclic, unsubstituted, substituted, and / or heteroatom-containing alkenyls and lower alkenyls, respectively.

[0044] As used herein, the term “alkenylene” refers to a bifunctional linear, branched, or cyclic alkenyl group, where “alkenyl” is as defined above.

[0045] As used herein, the term “alkynyl” refers to a linear or branched hydrocarbon group of 2 to 24 carbon atoms (e.g., 2 to about 12 carbon atoms) containing at least one triple bond, such as ethynyl, n-propynyl, and similar groups. The term “lower alkynyl” means an alkynyl group of 2 to 6 carbon atoms. The term “substituted alkynyl” refers to an alkynyl substituted with one or more substituents, and the terms “heteroatom-containing alkynyl” and “heteroalkynyl” refer to an alkynyl in which at least one carbon atom is replaced by a heteroatom. Unless otherwise indicated, the terms “alkynyl” and “lower alkynyl” include linear, branched, unsubstituted, substituted, and / or heteroatom-containing alkynyls and lower alkynyls, respectively.

[0046] As used herein, the term “alkoxy” refers to an alkyl group linked via a single terminal ether bond. That is, an “alkoxy” group may be represented as an -O-alkyl group (where “alkyl” is as defined above). A “lower alkoxy” group refers to an alkoxy group containing 1 to 6 carbon atoms. Similarly, “alkenyloxy” and “lower alkenyloxy” refer to an alkenyl group and a lower alkenyl group linked via a single terminal ether bond, respectively, and “alkynyloxy” and “lower alkynyloxy” refer to an alkynyl group and a lower alkynyl group linked via a single terminal ether bond, respectively.

[0047] As used herein, the term “aryl” refers, unless otherwise specified, to an aromatic substituent comprising a single aromatic ring or multiple aromatic rings that are condensed, directly bonded, or indirectly bonded to one another (such as different aromatic rings bonded to a common group, such as a methylene or ethylene moiety). An aryl group may contain 5 to 24 carbon atoms (e.g., 5 to 14 carbon atoms). Exemplary aryl groups include one aromatic ring or two condensed or linked aromatic rings, such as phenyl, naphthyl, biphenyl, diphenyl ether, diphenylamine, and benzophenone. As will be further described below, “substituted aryl” refers to an aryl moiety substituted with one or more substituents, and the terms “heteroatom-containing aryl” and “heteroaryl” refer to an aryl substituent in which at least one carbon atom is replaced by a heteroatom.

[0048] As used herein, the term “aryloxy” refers to an aryl group linked via a single terminal ether bond (where “aryl” is as defined above). An “aryloxy” group can be represented as -O-aryl, where aryl is as defined 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, and 3,4,5-trimethoxy-phenoxy.

[0049] The term "alkalil" refers to an aryl group having an alkyl substituent, and the term "aralkyl" refers to an alkyl group having an aryl substituent, with "aryl" and "alkyl" being defined above. Alkalil and aralkyl groups may contain 6 to 24 carbon atoms (for example, 6 to 16 carbon atoms). Examples of alkalil groups include, but are not limited to, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, and 3-ethyl-cyclopenta-1,4-diene. 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-benzylcyclohexyl, 4-phenylcyclohexylmethyl, and 4-benzylcyclohexylmethyl. The terms "alkalyloxy" and "aralkyloxy" refer to substituents in the formula -OR, where R is alkalyl or aralkyl, respectively, as defined earlier.

[0050] The term "acyl" refers to substituents having the formulas -(CO)-alkyl, -(CO)-aryl, (CO)-aralkyl, -(CO)-alkalil, -(CO)-alkenyl, or -(CO)-alkynyl, while the term "acyloxy" refers to substituents having the formulas O(CO)-alkyl, O(CO)-aryl, -O(CO)-aralkyl, -O(CO)-alkalil, -O(CO)-alkenyl, or -O(CO)-alkynyl. Here, "alkyl," "aryl," "aralkyl," "alkalil," "alkenyl," and "alkynyl" are defined as described above.

[0051] The terms “cyclic” and “ring” refer to alicyclic or aromatic groups that may or may not involve substitution and / or heteroatom inclusion, and which may be monocyclic, bicyclic, or polycyclic. The term “alicyclic” is used in its traditional sense to refer to an aliphatic cyclic part as the opposite of an aromatic cyclic part, and which may be monocyclic, bicyclic, or polycyclic.

[0052] The terms "halo" and "halogen" are used in their traditional sense to refer to chloro substituents, bromo substituents, fluoro substituents, or iodine substituents.

[0053] "Hydrocarbyl" refers to a monovalent hydrocarbyl radical containing 1 to about 30 carbon atoms, such as 1 to about 24 carbon atoms, or 1 to about 12 carbon atoms, including linear, branched, and cyclic saturated and unsaturated species, such as alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and similar groups. The term "lower hydrocarbyl" refers to a hydrocarbyl group containing 1 to 6 carbon atoms, such as 1 to 4 carbon atoms, and the term "hydrocarbylen" refers to a divalent hydrocarbyl moiety containing 1 to about 30 carbon atoms, such as 1 to about 24 carbon atoms, or 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated, and unsaturated species. The term "lower hydrocarbylen" refers to a hydrocarbylen group containing 1 to 6 carbon atoms. The term "substituted hydrocarbyl" refers to hydrocarbyl substituted with one or more substituents, while the terms "heteroatom-containing hydrocarbyl" and "heterohydrocarbyl" refer to hydrocarbyl in which at least one carbon atom is replaced by a heteroatom. Similarly, "substituted hydrocarbylene" refers to hydrocarbylene substituted with one or more substituents, while the terms "heteroatom-containing hydrocarbylene" and "heterohydrocarbylene" refer to hydrocarbylene in which at least one carbon atom is replaced by a heteroatom. Unless otherwise indicated, the terms "hydrocarbyl" and "hydrocarbylene" should be interpreted as including substituted and / or heteroatom-containing hydrocarbyl and heteroatom-containing hydrocarbylene moieties, respectively.

[0054] In the term "heteroatom-containing hydrocarbyl group," the term "heteroatom-containing" refers to a hydrocarbon molecule or hydrocarbyl molecular fragment in which one or more carbon atoms are substituted with 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" substituents and "aromatic" substituents containing a heteroatom, respectively. Note that "heterocyclic" groups or compounds may or may not be aromatic, and furthermore, "heterocyclic" can be monocyclic, bicyclic, or polycyclic, as mentioned above with respect to the term "aryl." Examples of heteroalkyl groups include, but are not limited to, alkoxyaryls, alkylsulfanyl-substituted alkyls, and N-alkylated aminoalkyls. Examples of heteroaryl substituents include, but are not limited to, pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, and tetrazolyl. Examples of heteroatom-containing alicyclic groups include, but are not limited to, pyrrolidino, morpholino, piperazino, and piperidino.

[0055] The term "substituted," as in "substituted hydrocarbyl," "substituted alkyl," and "substituted aryl," means, as suggested in some of the definitions above, that in the hydrocarbyl, alkyl, aryl, or other moiety, 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 halo, hydroxyl, sulfhydryl, and C1-C. 24 Alkoxy, C2-C 24 Alkenyloxy, C2-C 24 Alkynyloxy, C5-C 24 Aryloxy, C6-C 24 Aralkyloxy, C6-C 24Alkali loxy, acyl (C2-C 24 Alkylcarbonyl (-CO-alkyl) and C6-C 24 Arylcarbonyl (-CO-aryl) included), acyloxy (-O-acyl, C2-C 24 Alkylcarbonyloxy (-O-CO-alkyl) and C6-C 24 Arylcarbonyloxy (-O-CO-aryl) included), C2-C 24 Alkoxycarbonyl (-(CO)-O-alkyl), C6-C 24 Aryloxycarbonyl (-(CO)-O-aryl), halocarbonyl (-(CO)-X (X is halo)), C2-C 24 Alkylcarbonato (-(CO)-O-alkyl), C6-C 24 Arylcarbonato (-(CO)-O-aryl), carboxy (-COOH), carboxylato (COO - ), carbamoyl (-(CO)-NH2), mono-(C1-C 24 Alkyl)-substituted carbamoyl ((CO)-NH(C1-C 24 Alkyl)), di-(C1-C 24 Alkyl)-substituted carbamoyl (-(CO)-N(C1-C 24 Alkyl)2), mono-(C1-C 24 Haloalkyl)-substituted carbamoyl (-(CO)-NH(C1-C 24 Haloalkyl)), di-(C1-C 24 Haloalkyl)-substituted carbamoyl (-(CO)-N(C1-C 24 Haloalkyl)2), mono-(C5-C 24 Aryl)-substituted carbamoyl ((CO)-NH-aryl), di-(C5-C 24 Aryl)-substituted carbamoyl (-(CO)-N(C5-C 24 Aryl)2), di-N-(C1-C 24 Alkyl), N-(C5-C 24 Aryl)-substituted carbamoyl (-(CO)-N(C1-C 24 Alkyl)(C5-C 24 Aryl), thiocarbamoyl (-(CS)-NH2), mono-(C1-C 24Alkyl)-substituted thiocarbamoyl (-(CS)-NH(C1-C 24 Alkyl)), di-(C1-C 24 Alkyl)-substituted thiocarbamoyl (-(CS)-N(C1-C 24 Alkyl)2), Mono-(C5-C) 24 (aryl)-substituted thiocarbamoyl (-(CS)-NH-aryl), di(C5-C 24 Aryl)-substituted thiocarbamoyl(-(CS)-N(C5-C 24 Ariel)2), di-N-(C1-C 24 Alkyl), N-(C5-C 24 Aryl)-substituted thiocarbamoyl(-(CS)-N(C1-C 24 Alkyl)(C5-C 24 Aryl), Carbamide (-NH-(CO)-NH2), Cyanide (-C≡N), Cyanate (-OC≡N), Thiocyanate (-SC≡N), Isocyanate (-N=C=O), Thiisocyanate (-N=C=S), Formyl (-(CO)-H), Thioformyl ((CS)-H), Amino (-NH2), Mono-(C1-C 24 Alkyl)-substituted amino(-NH(C1-C 24 Alkyl), di-(C1-C 24 Alkyl)-substituted amino(-N(C1-C 24 Alkyl)2), Mono-(C5-C) 24 aryl)-substituted amino(-NH(C5-C 24 Ariel), G-(C5-C 24 aryl)-substituted amino(-N(C5-C 24 Aryl)2), C2-C 24 Alkylamide (-NH-(CO)-alkyl), C6-C 24 Arylamide (-NH-(CO)-aryl), imino (-CR=NH(R contains but is not limited to a hydrogen atom), C1-C 24 Alkyl, C5-C 24 Aryl, C6C 24 Alkali, C6-C 24 Aralquil, etc.), C2-C 20 Alkylimino (CR=N(alkyl), R contains but is not limited to a hydrogen atom, C1C)24 Alkyl, C5-C 24 Ariel, C6-C 24 alkaryl, C6-C 24 Aralkyl (e.g.), arylimino (-CR=N(aryl), R contains but is not limited to a hydrogen atom, C1-C) 20 Alkyl, C5-C 24 Ariel, C6-C 24 alkaryl, C6-C 24 Aralkyl, etc.), nitro(-NO2), nitroso(NO), sulfo(-SO2-OH), sulfonate(-SO2-O) - ), C1-C 24 Alkylsulfanyl (-S-alkyl; also called "alkylthio"), C5-C 24 Aryl sulfanyl (-S-aryl; also called "arylthio"), C1-C 24 Alkylsulfinyl (-(SO)-alkyl), C5-C 24 Arylsulfinyl (-(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 Arylsulfonyl (-SO2-aryl), boryl (-BH2), borono (-B(OH)2), boronate (-B(OR)2, where R includes but is not limited to alkyl or other hydrocarbons), phosphono (-P(O)(OH)2), phosphonate (-P(O)(O - )2) phosphina(P(O)(O - )), phospho(-PO2), and phosphino(-PH2); and hydrocarbyl group C1-C 24 Alkyl (for example, C1-C 12 Alkyl, C1-C6 alkyl), C2-C 24 Alkenyl (for example, C2-C 12 Alkenyls (C2-C6 alkenyls), C2-C 24 Alkinyl (for example, C2-C 12Alkinyl (C2-C6 alkynyl), C5-C 24 Aryl (for example, C5-C) 14 Ariel), C6-C 24 Alkali (for example, C6-C 16 Alkali(s), and C6-C 24 Aralquil (for example, C6-C) 16 This includes Aralquil, etc.

[0056] The term "functionalization," as in "functionalized hydrocarbyl," "functionalized alkyl," "functionalized olefin," and "functionalized cyclic olefin," means that at least one hydrogen atom bonded to a carbon (or other) atom in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other part is replaced by one or more functional groups as described above. The term "functional group" means that it includes any functional species suitable for use as described herein. In particular, as used herein, the functional group will necessarily have the ability to react with or bond to the corresponding functional group on the substrate surface.

[0057] Furthermore, the aforementioned functional groups may be further substituted with one or more additional functional groups or one or more hydrocarbyl moieties, if the specific groups allow it. Similarly, the above hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties, as described above.

[0058] "At will" or "at will" means that the situation described below may or may not occur, and therefore the description includes both instances where the situation occurs and instances where it does not. For example, the phrase "at will" means that a non-hydrogen substituent may or may not be present on a given atom, and therefore the description includes both structures where the non-hydrogen substituent is present and structures where the non-hydrogen substituent is absent.

[0059] As used herein, the term “substrate material” is intended to mean any material having a substrate material that the ROMP composition of the present invention contacts, is adhered to, or is incorporated into the ROMP composition. Such materials include, but are not limited to, filaments, fibers, rovings, mats, fabrics, cloths, knits, cloths or other known structures, glass fibers and glass cloths, carbon fibers and carbon cloths, aramid fibers and aramid cloths, and reinforcing materials such as polyolefins or other polymer fibers or polymer cloths. Other suitable substrate materials include metal density modulators, particulate density modulators such as microspheres, glass microspheres, ceramic microspheres, microballoons, cenospheres, and macroparticulate density modulators such as glass or ceramic beads. The ROMP polymer composite may consist of one substrate material or a mixture of different substrate materials.

[0060] The term "polymer backbone" is intended to mean the chain of atoms in the polymer, including the main chain and any crosslinks, if the polymer is a crosslinked polymer.

[0061] As used herein, the term “field joint” is intended to generally mean the connection between adjacent members or parts made at the time of installation (i.e., in the field). The term “field joint” is a technical term often used to describe the welded ends of individual length pipes. For example, pipelines used for transporting oil and / or gas are in most cases formed from many individual pipes, such as steel pipes. During the manufacture of individual pipe sections, a rust-preventive coating is applied to the outer surface of the pipe, often in a manner that leaves the outer surface of the pipe ends uncoated. Furthermore, the pipes may then be coated with insulation, but the outer surface of the pipe ends remains uncoated. Pipelines are formed by connecting individual pipe sections by welding the uncoated pipe ends to each other. At least part of this welding process can be done at an onshore facility before loading the pipes onto a labor barge or reel vessel, with the remaining connections made offshore, after which the pipeline is deployed for offshore use. Alternatively, during the manufacture of individual pipe sections, a rust-preventive coating may be applied to the outer surface of the pipe, in a manner that also coats the outer surface of the pipe ends. In this case, the anti-corrosion coating must be removed from the pipe end before welding.

[0062] As is well known in the art, weight percentage (wt%) can be expressed in terms of gas chromatography (GC) area percentage (area %). Therefore, GC area % obtained from GC was reported as wt%. Weight percentage (wt%) and percentage by weight are used synonymously in this specification. Mole percentage (mol%) was calculated from weight percentage (wt%) as is well known in the art.

[0063] Cyclic olefin composition The cyclic olefin compositions used in the ROMP compositions of the present invention disclosed herein contain, essentially consist of, or comprise at least one polyunsaturated cyclic olefin, and the cyclic olefin composition does not contain or substantially contains a monounsaturated cyclic olefin (for example, based on the total weight of the cyclic olefin, 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, 0.01 wt% or less), and the monounsaturated cyclic olefin is selected from 5-octyl-2-norbornene (ONB). For example, the cyclic olefin composition may contain, essentially consist of, or comprise at least one polyunsaturated cyclic olefin, the cyclic olefin composition does not contain a monounsaturated cyclic olefin, and the monounsaturated cyclic olefin is selected from ONB. For example, a cyclic olefin composition may contain, essentially consist of, or be composed of at least one polyunsaturated cyclic olefin, and the cyclic olefin composition may substantially contain no monounsaturated cyclic olefins (for example, based on the total weight of the cyclic olefins, 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, 0.01 wt% or less), and the monounsaturated cyclic olefins may be selected from ONB.

[0064] The cyclic olefin compositions used in the ROMP compositions of the present invention disclosed herein may also comprise, essentially consist of, or be composed of at least one polyunsaturated cyclic olefin, and the cyclic olefin compositions may not contain, or substantially contain, a monounsaturated cyclic olefin (for example, based on the total weight of the cyclic olefin, 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, 0.01 wt% or less), and the monounsaturated cyclic olefin is selected from at least one substituted norbornene, comprising, but not limited to, a monounsaturated substituted norbornene surrounded by a cyclic olefin structure (D), (E), or (F) (as defined below). For example, a cyclic olefin composition may contain, essentially consist of, or consist of at least one polyunsaturated cyclic olefin, and the monounsaturated cyclic olefin is selected from at least one substituted norbornene, which contains, but is not limited to, a monounsaturated substituted norbornene surrounded by a cyclic olefin structure (D), (E), or (F) (as defined below). For example, a cyclic olefin composition may contain, essentially consist of, or consist of at least one polyunsaturated cyclic olefin; a cyclic olefin composition may substantially contain no monounsaturated cyclic olefins (e.g., based on the total weight of the cyclic olefins, 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, 0.01 wt% or less); and the monounsaturated cyclic olefin is selected from at least one substituted norbornene, including, but not limited to, monounsaturated substituted norbornene surrounded by cyclic olefin structures (D), (E), or (F) (as defined below).

[0065] The cyclic olefin composition used in the ROMP composition of the present invention disclosed in this specification may also contain at least one polyunsaturated cyclic olefin, may consist essentially of them, or may consist of them. The cyclic olefin composition does not contain or substantially does not contain (for example, based on the total weight of the cyclic olefin, 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, 0.01 wt% or less) monounsaturated cyclic olefins. For example, the cyclic olefin composition may contain at least one polyunsaturated cyclic olefin, may consist essentially of them, or may consist of them, and the cyclic olefin composition does not contain monounsaturated cyclic olefins. For example, the cyclic olefin composition may contain at least one polyunsaturated cyclic olefin, may consist essentially of them, or may consist of them, and the cyclic olefin composition substantially does not contain (for example, based on the total weight of the cyclic olefin, 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, 0.01 wt% or less) monounsaturated cyclic olefins.

[0066] When present, at least one polyunsaturated cyclic olefin and at least one monounsaturated cyclic olefin may be independently of each other, unsubstituted or substituted.

[0067] When present, at least one polyunsaturated cyclic olefin and at least one monounsaturated cyclic olefin may be independently of each other hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z * ) n -Fn substituted, where n is 0 or 1 and Fn is a functional group, Z *These are alkylenes, substituted alkylenes, heteroalkylenes, substituted heteroalkenes, arylenes, substituted arylenes, heteroarylenes, or hydrocarbylene linking groups such as substituted heteroarylene bonds, and functional groups (Fn).

[0068] A cyclic olefin composition may contain, based on the total weight of the cyclic olefin composition, at least one polyunsaturated cyclic olefin in an amount ranging from 90 to 100 wt% (e.g., 91 to 99.9 wt%, 92 to 99 wt%, 93 to 98 wt%, 94 to 97 wt%, 95 to 96 wt%) and at least one monounsaturated cyclic olefin in an amount ranging from 10 wt% or less (e.g., 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, 0.01 wt% or less, 0 wt%).

[0069] The ROMP compositions of the present invention disclosed herein may also be free of or substantially free of monounsaturated cyclic olefins (for example, based on the total weight of the ROMP composition, 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, 0.01 wt% or less). The monounsaturated cyclic olefin may be selected from ONB. Alternatively, the monounsaturated cyclic olefin may be selected from at least one substituted norbornene, including but not limited to monounsaturated substituted norbornene surrounded by cyclic olefin structures (D), (E), or (F) (as defined below). Alternatively, the monounsaturated cyclic olefin may be selected from any monounsaturated cyclic olefin. For example, the ROMP composition of the present invention may not contain a monounsaturated cyclic olefin, the monounsaturated cyclic olefin may be selected from ONB, or the monounsaturated cyclic olefin may be selected from at least one substituted norbornene, including but not limited to a monounsaturated substituted norbornene surrounded by a cyclic olefin structure (D), (E), or (F) (as defined below), or the monounsaturated cyclic olefin may be selected from any monounsaturated cyclic olefin. For example, the ROMP composition of the present invention may substantially contain no monounsaturated cyclic olefins (e.g., based on the total weight of the ROMP composition, 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, 0.01 wt% or less), the monounsaturated cyclic olefin may be selected from ONB, or the monounsaturated cyclic olefin may be selected from at least one substituted norbornene, including but not limited to a monounsaturated substituted norbornene surrounded by a cyclic olefin structure (D), (E), or (F) (as defined below), or the monounsaturated cyclic olefin may be selected from any monounsaturated cyclic olefin.

[0070] In other embodiments, the cyclic olefin composition used in the ROMP composition of the present invention disclosed herein comprises at least one polyunsaturated cyclic olefin in an amount of 70-90 wt% (e.g., 72-88 wt%, 74-86 wt%, 76-84 wt%, 78-82 wt%) and a monounsaturated cyclic olefin in an amount of 25 wt% or less (e.g., 20 wt% or less, 15 wt% or less, 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1 wt% or less, 0.5 wt%). The monounsaturated cyclic olefin is selected from ONB, or the monounsaturated cyclic olefin is selected from at least four substituted norbornenes, including but not limited to monounsaturated substituted norbornenes surrounded by cyclic olefin structures (D), (E), or (F) (as defined below), or the monounsaturated cyclic olefin is selected from any monounsaturated cyclic olefin.For example, a cyclic olefin composition may contain, based on the total weight of the cyclic olefin composition, 70-80 wt% (e.g., 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%) of dicyclopentadiene, 0.1-10 wt% (e.g., 0.1 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%) of tricyclopentadiene, and 25 wt% or less (e.g., 20 wt% or less, 15 wt% or less, 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, 5 wt% or less) The monounsaturated cyclic olefin may contain, essentially consist of, or consist of, a monounsaturated cyclic olefin of 4 wt% or less, 3 wt% or less, 2 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, 0.01 wt% or less, or 0 wt%, and the monounsaturated cyclic olefin is selected from ONB, or the monounsaturated cyclic olefin is selected from at least three substituted norbornenes, including but not limited to monounsaturated substituted norbornenes surrounded by cyclic olefin structures (D), (E), or (F) (as defined below), or the monounsaturated cyclic olefin is selected from any monounsaturated cyclic olefin.

[0071] In general, any cyclic olefin suitable for the metathesis reaction disclosed herein can be used in the cyclic olefin composition. Such cyclic olefins may be optionally substituted, optionally containing heteroatoms, monounsaturated, diunsaturated, or polyunsaturated C5-C5 24It is a hydrocarbon and can be monocyclic, bicyclic, or polycyclic. A cyclic olefin can generally be any cyclic olefin regardless of the presence or absence of strain, provided that the cyclic olefin can participate in a ring-opening metathesis polymerization (ROMP) reaction either alone or as part of a ROMP composition. Certain unstrained cyclic olefins, such as cyclohexene, are generally understood not to undergo a ROMP reaction by themselves, but under appropriate circumstances, such unstrained cyclic olefins can still have ROMP activity. For example, when present as a comonomer in a ROMP composition, an unstrained cyclic olefin can be ROMP-active. Thus, as used herein and as understood by those skilled in the art, the term "unstrained cyclic olefin" is intended to refer to an unstrained cyclic olefin that can undergo a ROMP reaction under any conditions or in any ROMP composition as long as the unstrained cyclic olefin is ROMP-active.

[0072] Generally, a cyclic olefin can be represented by the structure of formula (A).

Chemical formula

[0073] The monounsaturated cyclic olefin enclosed by structure (A) may also be represented by structure (B). [ka] In the formula, b is generally an integer, but it is not necessarily in the range of 1 to 10; typically it is between 1 and 5. R A1 and R A2 The structure (A) is as defined above, and R B1 , R B2 , R B3 , R B4 , R B5 , and R B6 These are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and -(Z * ) n -Fn(where n, Z * Selected from the group consisting of (and Fn are as defined above), R B1 ~R B6 If any of the parts is a substituted hydrocarbyl or a substituted heteroatom-containing hydrocarbyl, the substituents are one or more -(Z * ) n - May contain an Fn group. Therefore, R B1 , R B2 , R B3 , R B4 , R B5 , and R B6 For example, hydrogen, hydroxyl, C1-C 20 Alkyl, C5~C 20 Aryl, C1~C 20 Alkoxy, C5~C 20 Aryloxy, C2~C 20 Alkoxycarbonyl, C5~C 20 These can be aryloxycarbonyl, amino, amide, nitro, etc.

[0074] Furthermore, R B1 , R B2 , R B3 , R B4 , R B5 , and R B6 Any part of it is a different R B1 , R B2 , R B3 , R B4 , R B5 , and R B6By bonding to any of the moieties, a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms, or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms, or a combination thereof, can be provided. The bonding may include heteroatoms or functional groups, for example, ethers, esters, thioethers, aminos, alkylaminos, iminos, or anhydride moieties, but is not limited to these. The alicyclic group may be monocyclic, bicyclic, or polycyclic. If unsaturated, the cyclic group may be monounsaturated or polyunsaturated. If substituted, the ring may be monosubstituted or multiple substituted, and the substituents may independently be hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z * ) n -Fn(wherein n is 0 or 1, Z * And Fn are as defined above, and the functional group (Fn) is selected from those provided above.

[0075] Examples of monounsaturated, monocyclic olefins included in structure (B) include, but are not limited to, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, tricyclodecene, tetracyclodecene, octacyclodecene, and cycloeicosene, as well as their substituted versions, such as 1-methylcyclopentene, 1-ethylcyclopentene, 1-isopropylcyclohexene, 1-chloropentene, 1-fluorocyclopentene, 4-methylcyclopentene, 4-methoxycyclopentene, 4-ethoxycyclopentene, cyclopenta-3-enethiol, cyclopenta-3-ene, 4-methylsulfanylcyclopentene, 3-methylcyclohexene, 1-methylcyclooctene, and 1,5-dimethylcyclooctene.

[0076] A monocyclic diene reactant enclosed by structure (A) may also be represented by structure (C). [ka] In the formula, c and d are independently integers in the range of 1 to about 8, typically 2 to 4, for example 2 (therefore the reactant is cyclooctadiene), and R A1 and R A2 The structure (A) is as defined above, and R C1 , R C2 , R C3 , R C4 , R C5 , and R C6 R B1 ~R B6 It is defined similarly to R. C3 and R C4 The substituent may be non-hydrogenated, in which case the second olefin moiety is tetrasubstituted. Examples of monocyclic diene reactants include, but are not limited to, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, cyclohexadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, and their substituted analogs. The triene reactants are similar to the diene structure (C) and generally contain at least one methylene bond between any two olefin segments.

[0077] Bicyclic and polycyclic olefins enclosed by structure (A) may generally be represented by structure (D). [ka] In the formula, R A1 and R A2 The structure (A) is as defined above, and R D1 , R D2 , R D3 , and R D4 R B1 ~R B6As defined, e is an integer in the range of 1 to 8 (usually 2 to 4), and f is generally 1 or 2. T is a lower alkylene or alkenylene (generally substituted or unsubstituted methyl or ethyl), CHR G1 , C(R G1 )2, O, S, NR G1 PR G1 O=PR G1 , Si(R G1 )2, BR G1 , or As-R G1 And in the formula, R G1 These are alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkalyl, aralkyl, or alkoxy. Furthermore, R D1 , R D2 , R D3 , and R D4 Any part of it is a different R D1 , R D2 , R D3 , and R D4 The bonds can be attached to any of the moieties to provide a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms, or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms, or a combination thereof. The bonds may include heteroatoms or functional groups, and for example, the bonds may include, but are not limited to, ether, ester, thioether, amino, alkylamino, imino, or anhydride moieties.

[0078] A cyclic group can be monocyclic, bicyclic, or polycyclic. If unsaturated, the cyclic group can be monounsaturated or polyunsaturated. If substituted, the ring can be monosubstituted or multiple substituted, and the substituents can independently be hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z * ) n -Fn(wherein n is 0 or 1, Z * And Fn are as defined above, and the functional group (Fn) is selected from those provided above.

[0079] The cyclic olefin enclosed by structure (D) belongs to the norbornene group. As used herein, norbornene means any compound containing at least one norbornene or substituted norbornene moiety, including but not limited to norbornene, substituted norbornene(plural), norbornadiene, substituted norbornadiene(plural), polycyclic norbornene, and substituted polycyclic norbornene(plural). Norbornene within this group can generally be represented by the following structure (E). [ka] In the formula, R A1 and R A2 T is defined above for structure (A), and R is defined above for structure (D). E1 , R E2 , R E3 , R E4 , R E5 , R E6 , R E7 , and R E8 R B1 ~R B6 As defined above, "a" represents a single or double bond, "f" is generally 1 or 2, and "g" is an integer from 0 to 5. If "a" is a double bond, R E5 , R E6 One of the two, and R E7 , R E8 One of them does not exist.

[0080] Furthermore, R E5 , R E6 , R E7 , and R E8 Any part of it is a different R E5 , R E6 , R E7 , and R E8The ring can be bonded to any of the parts to provide a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms, or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms, or a combination thereof. The bond may contain heteroatoms or functional groups, for example, ether, ester, thioether, amino, alkylamino, imino, or anhydride moieties, but is not limited to these. The cyclic group may be monocyclic, bicyclic, or polycyclic. If unsaturated, the cyclic group may be monounsaturated or polyunsaturated. If substituted, the ring may be monosubstituted or multiple substituted, and the substituents may independently be hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z * ) n -Fn(wherein n is 0 or 1, Z * And Fn are as defined above, and the functional group (Fn) is selected from those provided above.

[0081] A cyclic olefin having at least one norbornene moiety has structure (F). [ka] In the formula, R F1 , R F2 , R F3 , and R F4 R B1 ~R B6 As defined above, "a" represents a single or double bond, and "g" is an integer from 0 to 5. If "a" is a double bond, then R F1 , R F2 One of the two, and R F3 , R F4 One of them does not exist.

[0082] Furthermore, R F1 , R F2 , R F3 , and R F4 Any part of it is a different R F1 , R F2 , RF3 , and R F4 By bonding to any of the moieties, a substituted or unsubstituted alicyclic group containing 4 to 30 ring carbon atoms, or a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms, or a combination thereof, can be provided. The bonding may include heteroatoms or functional groups, for example, ethers, esters, thioethers, aminos, alkylaminos, iminos, or anhydride moieties, but is not limited to these. The alicyclic group may be monocyclic, bicyclic, or polycyclic. If unsaturated, the cyclic group may be monounsaturated or polyunsaturated. If substituted, the ring may be monosubstituted or multiple substituted, and the substituents may independently be hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z * ) n -Fn(wherein n is 0 or 1, Z * And Fn are as defined above, and the functional group (Fn) is selected from those provided above.

[0083] One route for preparing hydrocarbyl-substituted and functionally substituted norbornene involves the Diels-Alder cycloaddition reaction, in which a cyclopentadiene or substituted cyclopentadiene is reacted at high temperature with a suitable dienophile to form a substituted norbornene adduct, as generally shown in Reaction Scheme 1 below. [ka] In the formula, R F1 ~R F4 The structure (F) is as previously defined.

[0084] Other norbornene adducts can be prepared by the thermal decomposition of dicyclopentadiene in the presence of a suitable dienophile. The reaction proceeds by the initial thermal decomposition of dicyclopentadiene to cyclopentadiene, followed by the Diels-Alder cycloaddition of cyclopentadiene and dienophile to obtain the adduct shown in Scheme 2 below. [ka] In the formula, "g" is an integer from 0 to 5, and R F1 From R F4 The structure (F) is as previously defined.

[0085] Norbornadiene and its higher Diels-Alder adduct can also be prepared by the thermal reaction of cyclopentadiene and dicyclopentadiene in the presence of an acetylene reactant, as shown in Scheme 3 below. [ka] In the formula, "g" is an integer from 0 to 5, and R F1 and R F4 The structure (F) is as previously defined.

[0086] Therefore, examples of bicyclic and polycyclic olefins include, but are not limited to, dicyclopentadiene (DCPD); trimers and other higher-order oligomers of cyclopentadiene, including tricyclopentadiene (cyclopentadiene trimer), cyclopentadiene tetramer, and cyclopentadiene pentamer; ethylidene norbornene; dicyclohexadiene; norbornene; 5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5-phenylnorbornene; 5-benzylnorbornene; 5-acetylnorbornene; 5-methoxycarbonylnorbornene; 5-ethyoxycarbonyl-1-norbornene; 5-methyl-5-methoxycarbonylnorbornene; 5-cyanonorbornene; 5,5,6-trimeth Examples include, but are not limited to, C2-2-norbornene; cyclohexenylnorbornene; endo,exo-5,6-dimethoxynorbornene; endo,endo-5,6-dimethoxynorbornene; endo,exo-5,6-dimethoxycarbonylnorbornene; endo,endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene; norbornadiene; tricycloundecene; tetracyclododecene; 8-methyltetracyclododecene; 8-ethyltetracyclododecene; 8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclododecene; 8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene; and similar compounds, as well as their structural isomers, stereoisomers, and mixtures thereof. Further examples of bicyclic and polycyclic olefins include C2-C 12Hydrocarbyl-substituted norbornene include, but are not limited to, 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. The bicyclic and polycyclic olefins disclosed herein may consist of various structural isomers and / or stereoisomers, all of which will be well understood by those skilled in the art to be suitable for use in the present invention. Such bicyclic and polycyclic olefins referred to herein include mixtures of any such structural isomers and / or stereoisomers unless otherwise specified.

[0087] Cyclic olefins include C5~C 24 Unsaturated hydrocarbons, as well as C5-C5 containing one or more (typically 2-12) heteroatoms such as O, N, S, or P. 24 This may include cyclic hydrocarbons. For example, crown ether cyclic olefins may contain numerous oxygen heteroatoms throughout the ring, and these are within the scope of the present invention. Furthermore, cyclic olefins may contain one or more (typically two or three) olefins C5-C 24 They can be hydrocarbons. For example, cyclic olefins can be monounsaturated, diunsaturated, or triunsaturated. Examples of cyclic olefins include, but are not limited to, cyclooctene, cyclododecene, and (c,t,t)-1,5,9-cyclododecatriene.

[0088] Cyclic olefins may also contain multiple (typically two or three) rings. For example, cyclic olefins can be monocyclic, bicyclic, or tricyclic. When a cyclic olefin contains two or more rings, the rings may be fused or unfused. Examples of cyclic olefins containing multiple rings include norbornene, dicyclopentadiene, tricyclopentadiene, and 5-ethylidene-2-norbornene.

[0089] Cyclic olefins are also, for example, C5~C 24 The cyclic hydrocarbons may be substituted, and one or more of the hydrogens (usually 2, 3, 4, or 5) are replaced by non-hydrogen substituents. Suitable non-hydrogen substituents can be selected from the substituents described above. For example, functionalized cyclic olefins, i.e., C5-C5 cyclic hydrocarbons in which one or more of the hydrogens (usually 2, 3, 4, or 5) are replaced by functional groups. 24 Cyclic hydrocarbons are within the scope of the present invention. Suitable functional groups can be selected from the functional groups described above. For example, a telechelic polymer containing a pendant alcohol group can be prepared using a cyclic olefin functionalized with an alcohol group. If a functional group on the cyclic olefin inhibits the metathesis catalyst, the functional group can be protected, and any protecting group commonly used in the art can be used. Acceptable protecting groups can be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 5th Ed. (New York: Wiley, 2014). Examples of functionalized cyclic olefins include, but are not limited to, 2-hydroxymethyl-5-norbornene, 2-[(2-hydroxyethyl)carboxylate]-5-norbornene, sidecanol, 5-n-hexyl-2-norbornene, and 5-n-butyl-2-norbornene.

[0090] Cyclic olefins incorporating any combination of the above features (i.e., heteroatoms, substituents, multiple olefins, multiple rings) are suitable for the methods disclosed herein. Furthermore, cyclic olefins incorporating any combination of the above features (i.e., heteroatoms, substituents, multiple olefins, multiple rings) are suitable for the inventions disclosed herein.

[0091] The cyclic olefins useful in the methods disclosed herein may be strained or unstrained. It will be understood that the degree of ring strain varies from cyclic olefin compound to cyclic olefin compound and depends on a number of factors, including ring size, the presence and identity of substituents, and the presence of multiple rings. Ring strain is one factor that determines the reactivity of a molecule to ring-opening olefin metathesis reactions. Highly strained cyclic olefins, such as certain bicyclic compounds, readily undergo ring-opening reactions with olefin metathesis catalysts. Less strained cyclic olefins, such as certain unsubstituted hydrocarbon monocyclic olefins, are generally less reactive. In some cases, ring-opening reactions of relatively unstrained (and therefore relatively unreactive) cyclic olefins may be possible in the presence of the olefin compounds disclosed herein. Furthermore, the cyclic olefins useful in the inventions disclosed herein may be strained or unstrained.

[0092] The ROMP composition and / or cyclic olefin composition of the present invention may comprise a plurality of cyclic olefins. A plurality of cyclic olefins may be used to prepare a metathesis polymer from an olefin compound. For example, two cyclic olefins selected from the above cyclic olefins may be used to form a metathesis product incorporating both cyclic olefins. When two or more cyclic olefins are used, an example of a second cyclic olefin is a cyclic alkenol, i.e., a C5-C5 cyclic olefin in which at least one of the hydrogen substituents is replaced by an alcohol or a protecting alcohol moiety to produce a functionalized cyclic olefin. 24 Examples include cyclic hydrocarbons.

[0093] The use of multiple cyclic olefins, particularly when at least one of the cyclic olefins is functionalized, allows for further control over the positions of functional groups within the product. For example, the density of crosslinking sites can be controlled in polymers and macromonomers prepared using the methods disclosed herein. By controlling the amount and density of substituents and functional groups, the physical properties of the product (e.g., melting point, tensile strength, glass transition temperature, etc.) can also be controlled. While these and other property controls are possible for reactions using only a single cyclic olefin, it will be understood that the use of multiple cyclic olefins further broadens the range of possible metathesis products and polymers formed.

[0094] Non-limiting examples of cyclic olefins include dicyclopentadiene; tricyclopentadiene; tetracyclopentadiene; norbornene; 5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5-tolyl-2-norbornene; 5-phenyl-2-norbornene; 5-benzylnorbornene; 5-acetylnorbornene; 5-methoxycarbonylnorbornene; 5-ethoxycarbonyl-1-norbornene; 5-methyl-5-methoxycarbonylnorbornene; 5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene; cyclohexenylnorbornene; endo,exo-5,6-dimethoxynorbornene; end o,endo-5,6-dimethoxynorbornene; endo,exo-5-6-dimethoxycarbonylnorbornene; endo,endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene; norbornadiene; tricycloundecene; tetracyclododecene; 8-methyltetracyclododecene; 8-ethyl-tetracyclododecene; 8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclo-dodecene; 8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene; higher-order oligomers of cyclopentadiene, such as cyclopentadiene tetramer, cyclopentadiene pentamer, etc.; and C2-C2 oligomers such as 5-butyl-2-norbornene.12 This includes, but is not limited to, hydrocarbyl-substituted 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; 5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5-butyl-2-norbornene; and 5-butenyl-2-norbornene.

[0095] In one embodiment, examples of polyunsaturated cyclic olefins include dicyclopentadiene, tricyclopentadiene, and 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, and 5-butenyl-2-norbornene.

[0096] In another embodiment, the polyunsaturated cyclic olefins include dicyclopentadiene, tricyclopentadiene, and 5-ethylidene-2-norbornene.

[0097] An example of a polyunsaturated cyclic olefin is dicyclopentadiene.

[0098] An example of a polyunsaturated cyclic olefin is tricyclopentadiene.

[0099] An example of a polyunsaturated cyclic olefin is 5-ethylidene-2-norbornene.

[0100] The cyclic olefin composition may contain a polyunsaturated cyclic olefin selected from dicyclopentadiene, tricyclopentadiene, 5-ethylidene-2-norbornene, and mixtures thereof. Based on the total weight of the cyclic olefin composition, dicyclopentadiene may be present in an amount of 90 wt% or more (e.g., 91 wt% or more, 92 wt% or more, 93 wt% or more, 94 wt% or more, 95 wt% or more, 96 wt% or more, 97 wt% or more, 98 wt% or more, 99 wt% or more, 99.9 wt% or more), and tricyclopentadiene and / or 5-ethylidene-2-norbornene may be present in an amount of 0.1 wt% or more (e.g., 1 wt% or more, 2 wt% or more, 3 wt% or more, 4 wt% or more, 5 wt% or more, 6 wt% or more, 7 wt% or more, 8 wt% or more, 9 wt% or more). For example, a cyclic olefin composition may contain, based on the total weight of the cyclic olefin composition, 90 to 100 wt% of dicyclopentadiene (e.g., 91 to 99.9 wt% dicyclopentadiene, 92 to 99 wt%, 93 to 98 wt%, 94 to 97 wt%, 95 to 96 wt%) and 0 to 10 wt% (e.g., 0.1 to 9 wt%, 1 to 8 wt%, 2 to 7 wt%, 3 to 6 wt%, 4 to 5 wt%) of tricyclopentadiene and / or 5-ethylidene-2-norbornene.

[0101] If present, monounsaturated cyclic olefins contain C2~C 12 Hydrocarbyl-substituted norbornene (e.g., C4~C 12 Hydrocarbyl-substituted norbornene, C6~C 12 Hydrocarbyl-substituted norbornene, C6~C 10 This includes hydrocarbyl-substituted norbornene. Examples of monounsaturated cyclic olefins include 5-tolyl-2-norbornene, 5-phenyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, and 5-dodecyl-2-norbornene.

[0102] catalyst composition The catalyst compositions used in the ROMP compositions of the present invention disclosed herein include, essentially consist of, or comprise at least one metal carbene olefin metathesis catalyst.

[0103] The 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 of formula (I). [ka] During the ceremony, M is a transition metal in Group 8, L 1 , L 2 , and L 3 It is a neutral electron donor ligand, n is either 0 or 1, and therefore L 3 It may or may not exist. m is 0, 1, or 2. k is either 0 or 1. X 1 and X 2 It is an anionic ligand, R 1 and R 2 These are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups. X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 Any two or more of these can combine to form one or more cyclic groups, and furthermore, X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 One or more of these may be bound to the carrier.

[0104] Furthermore, in equation (I), R 1 and R 2 One or both of are -(W) n -U + V - The formula may have the following structure, where W is selected from hydrocarbilene, substituted hydrocarbilene, heteroatom-containing hydrocarbilene, or substituted heteroatom-containing hydrocarbilene; U is a positively charged Group 15 or 16 element substituted with hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; V is a negatively charged counterion; and n is 0 or 1. Furthermore, R 1 and R 2 These can integrate to form an indenylidene moiety.

[0105] The catalyst may contain Ru or Os as a transition metal of Group 8, with Ru being preferred.

[0106] Numerous embodiments of catalysts useful in the reactions disclosed herein are described in further detail below. For convenience, catalysts are described in groups, but it should be emphasized that these groups are not intended to be limiting. That is, any of the catalysts useful in the present invention may fit into several of the descriptions of the groups described herein.

[0107] Next, catalysts of the first group are generally called first-generation Grubbs catalysts and have the structure of formula (I). For catalysts of the first group, M is a transition metal of group 8, m is 0, 1, or 2, and n, X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 The following is stated:

[0108] In the first group of catalysts, n is 0, and L 1 and L 2The ligand is independently selected from phosphines, sulfonated phosphines, phosphites, phosphinates, phosphonites, arsines, stivins, ethers (including cyclic ethers), amines, amides, imines, sulfoxides, carboxyls, nitrosyls, pyridines, substituted pyridines, imidazoles, substituted imidazoles, pyrazines, substituted pyrazines, and thioethers. An exemplary ligand is a trisubstituted phosphine. A trisubstituted phosphine is given by formula PR H1 R H2 R H3 It can be expressed as, however R H1 , R H2 , and R H3 Each of these is independently a substituted or unsubstituted aryl or C1-C 10 Alkyl, especially primary alkyl, secondary alkyl, or cycloalkyl. 1 and L 2 This can be independently selected from the group consisting of trimethylphosphine (PMe3), triethylphosphine (PEt3), tri-n-butylphosphine (PBu3), tri(ortho-tolyl)phosphine (Po-tolyl3), tri-tert-butylphosphine (P-tert-Bu3), tricyclopentylphosphine (P-cyclopentyl3), 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 This may be independently selected from phosphabicycloalkanes (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.).

[0109] X 1 and X 2X is an anionic ligand, which may be the same or different, or bonded to each other to form a cyclic group, which is usually, but not necessarily, a 5- to 8-membered ring. 1 and X 2 Each of these is independently a hydrogen atom, a halide, or one of the following groups, namely C1-C 20 Alkyl, C5~C 24 Aryl, C1~C 20 Alkoxy, C5~C 24 Aryloxy, C2~C 20 Alkoxycarbonyl, C6~C 24 Aryloxycarbonyl, C2~C 24 Ashiru, C2~C 24 Acyloxy, C1~C 20 Alkyl sulfonate, C5C 24 Aryl sulfonates, C1-C 20 Alkyl sulfanyl, C5~C 24 Aryl sulfanil, C1-C 20 Alkyl sulfinyl, NO3, -N=C=O, -N=C=S, or C5~C 24 It may be one of the arylsulfinyls. Optionally, X 1 and X 2 C1~C 12 Alkyl, C1-C 12 Alkoxy, C5~C 24 They may be substituted with one or more moieties selected from aryls and halides, and, except for halides, they may be further substituted with one or more groups selected from halides, C1-C6 alkyls, C1-C6 alkoxys, and phenyls. 1 and X 2 This can be a halide, benzoate ester, C2-C6 acyl, C2-C6 alkoxycarbonyl, C1-C6 alkyl, phenoxy, C1-C6 alkoxy, C1-C6 alkylsulfanyl, aryl, or C1-C6 alkylsulfonyl. 1 and X 2These can each be a halide, CF3CO2, CH3CO2, CFH2CO2, (CH3)3CO, (CF3)2(CH3)CO, (CF3)(CH3)2CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethane sulfonate. 1 and X 2 Each of these may be a chloride.

[0110] R 1 and R 2 These are independently hydrogen, hydrocarbyl (e.g., C1-C) 20 Alkyl, C2~C 20 Alkenyl, C2~C 20 Alkinyl, C5~C 24 Aryl, C6~C 24 Alkali, C6~C 24 (e.g., aralkyl), substituted hydrocarbyl (e.g., substituted C1-C) 20 Alkyl, C2~C 20 Alkenyl, C2~C 20 Alkinyl, C5~C 24 Aryl, C6~C 24 Alkali, C6~C 24 (e.g., aralkyl), heteroatom-containing hydrocarbyl (e.g., heteroatom-containing C1-C) 20 Alkyl, C2~C 20 Alkenyl, C2~C 20 Alkinyl, C5~C 24 Aryl, C6~C 24 Alkali, C6~C 24 (e.g., aralkyl) and substituted heteroatom-containing hydrocarbyl (e.g., substituted heteroatom-containing C1C) 20 Alkyl, C2~C 20 Alkenyl, C2~C 20 Alkinyl, C5~C 24 Aryl, C6~C 24 Alkali, C6~C 24 Selected from functional groups (such as aralkyl groups). 1 and R 2They may also bond to form a cyclic group, which may be aliphatic or aromatic and may contain substituents and / or heteroatoms. Generally, such a cyclic group contains 4 to 12 ring atoms, for example, 5, 6, 7, or 8.

[0111] In a particular catalyst, R 1 is hydrogen, and R 2 C1~C 20 Alkyl, C2~C 20 Alkenyl, and C5~C 24 Aryls, for example, C1-C6 alkyls, C2-C6 alkenyls, and C5-C 14 Selected from arrows, etc. 2 R may be phenyl, vinyl, methyl, isopropyl, or t-butyl, and may be optionally substituted with one or more moieties selected from the C1-C6 alkyl, C1-C6 alkoxy, phenyl, and functional group Fn as previously defined herein. 2 R may be phenyl or vinyl substituted with one or more moieties selected from methyl, ethyl, chloro, bromo, iodo, fluoro, nitro, dimethylamino, methyl, methoxy, and phenyl. 2 This can be phenyl or -CH=C(CH3)2.

[0112] X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 Any two or more of these (typically two, three, or four) can be combined to form a cyclic group including a bidentate ligand or a polydentate ligand, as disclosed, for example, in U.S. Patent No. 5,312,940. The disclosures of this U.S. patent are incorporated herein by reference. 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2If any of these combine to form a cyclic group, these cyclic groups may contain 4 to 12 atoms, such as 4, 5, 6, 7, or 8, or may contain two or three such rings, which may be fused or bonded. The cyclic groups may be aliphatic or aromatic, and may contain and / or be substituted with heteroatoms. The cyclic groups may, in some cases, form bidentate or tridentate ligands. Examples of bidentate ligands include, but are not limited to, bisphosphines, dialkoxides, alkyl diketonates, and aryl diketonates.

[0113] The second group of catalysts, generally called second-generation Grubbs catalysts, have the structure of formula (I), where L 1 This is a carbene ligand having the structure of formula (II). [ka] Therefore, the composite may have the structure of formula (III). [ka] In the formula, M, m, n, X 1 , X 2 , L 2 , L 3 , R 1 , and R 2 The substituents are as defined for the catalysts of the first group, and the remaining substituents are as follows: X and Y are heteroatoms typically selected from N, O, S, and P. Since O and S are divalent, if X is O or S, p is necessarily 0; if Y is O or S, q is necessarily 0 and k is 0 or 1. However, if X is N or P, p is 1; and if Y is N or P, q is 1. Both X and Y may be N. Q 1 Q 2 Q 3 , and Q 4Q is a linker, for example, hydrocarbilene (substituted hydrocarbilene, heteroatom-containing hydrocarbilene, and substituted heteroatom-containing hydrocarbilene, for example, including substituted and / or heteroatom-containing alkylene), or -(CO)-, and w, x, y, and z are independently 0 or 1, meaning each linker is arbitrary. w, x, y, and z may all be 0. Furthermore, Q 1 Q 2 Q 3 , and Q 4 Two or more substituents on adjacent atoms within the molecule may bond to form an additional cyclic group. R 3 , R 3A , R 4 , and R 4A X is independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl. Furthermore, X and Y may independently be selected from carbon and one of the above heteroatoms, and only one of X or Y may be carbon. Also, L 2 and L 3 These may integrate to form a single bidentate electron-donating heterocyclic ligand. Furthermore, R 1 and R 2 These can integrate to form an indenylidene moiety. Furthermore, X 1 , X 2 , L 2 , L 3 X and Y may be further coordinated to boron or carboxylate.

[0114] Furthermore, 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 these can combine to form a cyclic group, X1 , 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 these may be attached to the carrier. 1 , X 2 , L 1 , L 2 , L 3 , R 1 , R 2 , R 3 , R 3A , R 4 , and RR 4A Any two or more of these can also be considered as -A-Fn, where "A" is a divalent hydrocarbon moiety selected from alkylenes and arylalkylenes, the alkyl moiety of the alkylene group and the arylalkylene group can be linear or branched, saturated or unsaturated, cyclic or acyclic, substituted or unsubstituted, the aryl moiety of the arylalkylene may be substituted or unsubstituted, the heteroatom and / or functional group may be present in either the aryl or alkyl moiety of the alkylene group and the arylalkylene group, Fn is a functional group, or 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 RR 4A One or more of these may be bound to the carrier.

[0115] A specific class of carbene ligand having the structure of formula (II) (wherein R 3A and R4A They bond to form a cyclic group, and at least one of X or Y is nitrogen or Q 3 Or Q 4 A ligand (in which at least one is a heteroatom-containing hydrocarbilene or a substituted heteroatom-containing hydrocarbilene, and at least one heteroatom is nitrogen) is generally called an N-heterocyclic carbene (NHC) ligand.

[0116] R 3A and R 4A The carbene ligands can be linked together to form a cyclic group having the structure of formula (IV). [ka] In the formula, R 3 and R 4 This is as defined for the second group of catalysts described above, and R 3 and R 4 At least one of, for example, R 3 and R 4 Both are alicyclic or aromatic with 1 to about 5 rings and optionally contain one or more heteroatoms and / or substituents. Q is a linker, typically a hydrocarbylene linker including substituted hydrocarbylenes, heteroatom-containing hydrocarbylenes, and substituted heteroatom-containing hydrocarbylene linkers, where two or more substituents on adjacent atoms in Q may link to form additional cyclic structures, which may similarly be substituted to provide condensed polycyclic structures of 2 to about 5 cyclic groups. Q is often, though not necessarily, a diatomic or triatomic bond.

[0117] Therefore, L 1 Suitable examples of N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands include, but are not limited to, the following, in which DIPP or DiPP is diisopropylphenyl and Mes is 2,4,6-trimethylphenyl. [ka]

[0118] Therefore, L 1 Suitable N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands include, but are not limited to, the following. [ka] In the formula, R W1 , R W2 , R W3 , R W4 R is independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, or heteroatom-containing hydrocarbyl. W3 and R W4 One or both of these groups can be independently selected from halogen groups, nitro groups, amide groups, carboxyl groups, alkoxy groups, aryloxy groups, sulfonyl groups, carbonyl groups, thio groups, or nitroso groups.

[0119] L 1 Additional examples of suitable N-heterocyclic carbene (NHC) ligands are further described in U.S. Patents 7,378,528, 7,652,145, 7,294,717, 6,787,620, 6,635,768, and 6,552,139. ​​The disclosures of each of these U.S. patents are incorporated herein by reference.

[0120] Furthermore, U.S. Patent Application No. 6,838,489 (whose disclosure is incorporated herein by reference), which is incorporated herein by reference, may also be used in conjunction with the present invention.

[0121] When M is ruthenium, the complex may have the structure of formula (V). [ka] In the formula, n, X 1 , X 2 , L 2 , L 3, R 1 , and R 2 The following definitions apply to the catalysts of the first group, where k and R are defined as follows: 3 , R 4 Q and , are defined as for the catalysts of the second group.

[0122] More preferably, Q is -CR 11 R 12 -CR 13 R 14 - or -CR 11 =CR 13 -, for example -CR 11 R 12 -CR 13 R 14 - This is a diatomic bond with a structure such as R 11 , R 12 , R 13 , and R 14 These are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups. Examples of functional groups here include C1~C 12 Alkyl, C1-C 12 Alkoxy, C5~C 14 Carboxyl, C1-C13 20 Alkoxy, C5~C 24 Aryloxy, C2~C 20 Alkoxycarbonyl, C5~C 24 Alkoxycarbonyl, C2~C 24 Acyloxy, C1~C 20 Alkylthio, C5~C 24 Arylthio, C1C 20 Alkyl sulfonyl, and C1-C 20 Examples include alkylsulfinyls, but are not limited to these. 11 , R 12 , R 13 , and R 14 These are, independently, hydrogen, C1~C 12 Alkyl, substituted C1-C 12 Alkyl, C1-C 12Heteroalkyl, substituted C1-C 12 It can be selected from heteroalkyl, phenyl, and substituted phenyl. Alternatively, R 11 , R 12 , R 13 , and R 14 Any two of these are bonded to each other to form a substituted or unsubstituted, saturated or unsaturated ring structure, for example, C4~C 12 A alicyclic group or a C5 or C6 aryl group, which itself may be substituted with, for example, a linked or fused alicyclic group or aromatic group, or other substituents. In one further embodiment, R 11 , R 12 , R 13 , and R 14 One or more of these include one or more linkers. Furthermore, R 3 and R 4 This refers to unsubstituted phenyl, or C1-C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5~C 24 Aryl substitution C5~C 24 Aryl, C5~C 24 Heteroaryl, C6~C 24 Aralkil, C6~C 24 It may be a phenyl substituted with one or more substituents selected from alkaryl or halide. Furthermore, X 1 and X 2 It may be a halogen.

[0123] R 3 and R 4 If they are aromatic, they are usually, but not necessarily, composed of one or two aromatic rings, which may or may not be substituted, for example, R 3 and R 4 This can be phenyl, substituted phenyl, biphenyl, substituted biphenyl, etc. 3 and R 4 These may be the same, and each may be an unsubstituted phenyl or C1-C 20Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5~C 24 Aryl substitution C5~C 24 Aryl, C5~C 24 Heteroaryl, C6~C 24 Aralkil, C6~C 24 Phenyl substituted with up to three substituents selected from alkaryl or halide. Any substituents present are hydrogen, C1-C1 12 Alkyl, C1-C 12 Alkoxy, C5~C 14 Aryl substitution C5~C 14 It can be an aryl or halide. For example, R 3 and R 4 is mesityl (i.e., Mes as defined herein).

[0124] In a third group of catalysts having the structure of formula (I), M, m, n, X 1 , X 2 , R 1 , and R 2 This is as defined for the catalysts of the first group, L 1 L is a strongly coordinating neutral electron donor ligand, such as one of those described for the first and second groups of catalysts. 2 and L 3 is a weakly coordinating neutral electron donor ligand in the form of a optionally substituted heterocyclic group. In this case as well, n is 0 or 1, and therefore L 3 It may or may not be present. Generally, in catalysts of the third group, L 2 and L 3This refers to an optionally substituted five- or six-membered monocyclic group containing one to four (e.g., one to three, one to two) heteroatoms, or an optionally substituted bicyclic or polycyclic structure composed of two to five such five- or six-membered monocyclic groups. When a heterocyclic group is substituted, the substitution must not occur on a coordinating heteroatom. Furthermore, no single cyclic portion within a heterocyclic group is generally substituted with more than three substituents.

[0125] Regarding the third group of catalysts, L 2 and L 3 Examples, though not limited to them, include heterocycles containing nitrogen, sulfur, oxygen, or mixtures thereof.

[0126] L 2 and L 3 Suitable examples 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-imidazole, 1,2,3-triazole, 1,2,4-triazole, indole, 3H-indole, 1H-isoindole, cyclopenta(b)pyridine, indazole, quinoline, bisquinoline, isoquinoline, bisiisoquinoline, cinnoline, quinazoline, naphthyridine, piperidine, piperazine, pyrrolidine, pyrazolidine, quinuclididine, imidazolidine, picolimin, purine, benzimidazole, bismidazole, phenazine, acridine, and carbazole. Furthermore, the nitrogen-containing heterocycle may be optionally substituted with non-hydrogen substituents on the non-coordinating heteroatom.

[0127] L 2 and L 3 Suitable examples of sulfur-containing heterocycles include thiophene, 1,2-dithiol, 1,3-dithiol, thiepine, benzo(b)thiophene, benzo(c)thiophene, thionaphthene, dibenzothiophene, 2H-thiopyran, 4H-thiopyran, and thioanthrene.

[0128] L 2 and L 3 Suitable examples of oxygen-containing heterocycles include 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,2-dioxin, 1,3-dioxin, oxepin, furan, 2H1-benzopyran, coumarin, coumaron, chromene, chroman-4-one, isochromene-1-one, isochromene-3-one, xanthene, tetrahydrofuran, 1,4-dioxane, and dibenzofuran.

[0129] L 2 and L 3 Suitable examples of mixed heterocycles include isoxazole, oxazole, thiazole, isothiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxatriazole, 1,2,3,5-oxatriazole, 3H-1,2,3-dioxazole, 3H-1,2-oxathiol, 1,3-oxathiol, 4H-1,2-oxazine, 2H1,3-oxazine, 1,4-oxazine, 1,2,5-oxathidine, o-isoxazine, phenoxazine, phenothiazine, pyrano[3,4-b]pyrrole, indoxazine, benzoxazole, anthranil, and morpholine.

[0130] L 2 and L 3 The ligand can be an aromatic nitrogen-containing or oxygen-containing heterocyclic ligand, such as a monocyclic N-heteroaryl ligand optionally substituted with 1 to 3 substituents (e.g., 1 or 2). 2 and L 3Specific examples of ligands include 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, and 3,5-dibromo-4-dibromopyridine. This includes 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, and 3,5-dichloro-4-phenylpyridine.

[0131] Generally, L 2 and / or L 3 Any substituent present is a halo, C1~C 20 Alkyl, substituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, substituted C1-C 20 Heteroalkyl, C5~C 24 Aryl substitution C5~C 24 Aryl, C5~C 24 Heteroaryl, substituted C5~C 24 Heteroaryl, C6~C 24 Alkalyl, substitution C6~C 24 Alkali, C6~C 24 Heteroalkalinous, substituted C6~C 24 Heteroalkalinous, C6~C 24 Aralkyl, substitution C6~C 24 Aralkil, C6~C 24 Heteroaralkyl, substitution C6~C 24 A selection is made from heteroaralkyl and functional groups, and suitable functional groups include C1-C 20 Alkoxy, C5~C 24 Aryloxy, C2~C 20 Alkylcarbonyl, C6~C 24 Arylcarbonyl, C2~C20 Alkylcarbonyloxy, C6~C 24 Arylcarbonyloxy, C2~C 20 Alkoxycarbonyl, C6~C 24 Aryloxycarbonyl, Halocarbonyl, C2~C 20 Alkylcarbonate, C6~C 24 Arylcarbonate, Carboxylate, Carbamoyl, Mono-(C1~C) 20 Alkyl)-substituted carbamoyl, di-(C1~C 20 Alkyl)-substituted carbamoyl, di-N-(C1~C 20 Alkyl), N-(C5~C 24 Arial-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(C1C 20 Alkyl)-substituted thiocarbamoyl, di-N-(C1~C 20 Alkyl)-N-(C6~C 24 Arial-substituted thiocarbamoyl, mono-(C6~C) 24 aryl)-substituted thiocarbamoyl, di-(C6~C 24 Aryl)-substituted thiocarbamoyl, carbamide, formyl, thioformyl, amino, mono-(C1~C 20 Alkyl)-substituted amino, di-(C1~C 20 Alkyl)-substituted amino, mono-(C5~C) 24 Aryl)-substituted amino, di-(C5~C 24 Aryl)-substituted amino, di-N-(C1~C 20 Alkyl), N-(C5~C 24 Aryl)-substituted amino, C2~C 20 Alkylamide, C6C 24 Arylamide, imino, C1-C 20 Alkylimino, C5~C 24Examples include, but are not limited to, aryliminos, nitros, and nitroso substituents. Furthermore, two adjacent substituents may merge to form a ring, which is generally a 5-membered or 6-membered alicyclic ring or aryl ring, optionally containing 1 to 3 heteroatoms and 1 to 3 substituents as described above.

[0132] L 2 and L 3 The substituents include halo, C1-C 12 Alkyl, substituted C1-C 12 Alkyl, C1-C 12 Heteroalkyl, substituted C1-C 12 Heteroalkyl, C5~C 14 Aryl substitution C5~C 14 Aryl, C5~C 14 Heteroaryl, substituted C5~C 14 Heteroaryl, C6~C 16 Alkalyl, substitution C6~C 16 Alkali, C6~C 16 Heteroalkalinous, substituted C6~C 16 Heteroalkalinous, C6~C 16 Aralkyl, substitution C6~C 16 Aralkil, C6~C 16 Heteroaralkyl, substitution C6~C 16 Heteroaralkyl, C1~C 12 Alkoxy, C5~C 14 Aryloxy, C2~C 12 Alkylcarbonyl, C6~C 14 Arylcarbonyl, C2~C 12 Alkylcarbonyloxy, C6~C 14 Arylcarbonyloxy, C2~C 12 Alkoxycarbonyl, C6~C 14 Aryloxycarbonyl, Halocarbonyl, Formyl, Amino, Mono-(C1~C 12 Alkyl)-substituted amino, di-(C1~C 12 Alkyl)-substituted amino, mono-(C5~C) 14 Aryl)-substituted amino, di-(C5~C 14 Examples include, but are not limited to, aryl-substituted aminos and nitros.

[0133] In another embodiment, the substituents are halo, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, phenyl, substituted phenyl, formyl, N,N-di(C1-C6 alkyl)amino, nitro, and nitrogen heterocycles as described above (e.g., pyrrolidine, piperidine, piperazine, pyrazine, pyrimidine, pyridine, pyridazine, etc.).

[0134] L 2 and L 3 These can be combined to form a bidentate or polydentate ligand containing two or more coordinating heteroatoms, such as N, O, S, or P, including a Brookhardt-type diimine ligand. One representative bidentate ligand has the structure of formula (VI). [ka] In the formula, R 15 , R 16 , R 17 , and R 18 Hydrocarbyl (for example, C1-C) 20 Alkyl, C2~C 20 Alkenyl, C2~C 20 Alkinyl, C5~C 24 Aryl, C6~C 24 Alkali, or C6~C 24 Aralkyl), substituted hydrocarbyl (e.g., substituted C1-C) 20 Alkyl, C2~C 20 Alkenyl, C2~C 20 Alkinyl, C5~C 24 Aryl, C6~C 24 Alkali, or C6~C 24 Aralkyl), heteroatom-containing hydrocarbyl (e.g., C1~C 20 Heteroalkyl, C5~C 24 Heteroaryl, heteroatom-containing C6~C 24 Aralkyl or heteroatom-containing C6-C 24 Alkalyl, or hydrocarbyl containing substituted heteroatoms (e.g., substituted C1-C1)20 Heteroalkyl, C5~C 24 Heteroaryl, heteroatom-containing C6~C 24 Aralkyl or heteroatom-containing C6-C 24 Alkali() 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 Both may combine to form a ring, i.e., an N-heterocyclic ring. In such cases, the cyclic group can be a five-membered ring or a six-membered ring, and is typically an aromatic ring.

[0135] In catalysts of the fourth group having the structure of formula (I), two of the substituents integrate to form a bidentate or tridentate ligand. Examples of bidentate ligands include, but are not limited to, bisphosphines, dialkoxides, alkyl diketonates, and aryl diketonates. Specific examples include P(Ph)2CH2CH2P(Ph)2-, As(Ph)2CH2CH2As(Ph2)-, -P(Ph)2CH2CH2C(CF3)2O-, binaphtholate dianions, pinacolate dianions, -P(CH3)2(CH2)2P(CH3)2-, and -OC(CH3)2(CH3)2CO-. Examples of bidentate ligands include P(Ph)2CH2CH2P(Ph)2- and P(CH3)2(CH2)2P(CH3)2-. Examples of tridentate ligands include (CH3)2NCH2CH2P(Ph)CH2CH2N(CH3)2, but are not limited to these. Other tridentate ligands include X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 (For example, X 1 , L 1 , and L 2) Any three of these combine to form cyclopentadienyl, indenyl, or fluorenyl, each with C2~C 20 Alkenyl, C2C 20 Alkinyl, C1~C 20 Alkyl, C5~C 20 Aryl, C1~C 20 Alkoxy, C2~C 20 Alkenyloxy, C2~C 20 Alkynyloxy, C5C 20 Aryloxy, C2~C 20 Alkoxycarbonyl, C1~C 20 Alkylthio, C1~C 20 Alkyl sulfonyl, or C1-C 20 These compounds may be optionally substituted with alkylsulfinyl groups, each of which may be further substituted with a phenyl group optionally substituted with a C1-C6 alkyl, halide, C1-C6 alkoxy, or halide, C1-C6 alkyl, or C1-C6 alkoxy. In this type of compound, X, L 1 , and L 2 These may be combined to form cyclopentadienyl or indenyl, each being vinyl, C1-C 10 Alkyl, C5~C 20 Aryl, C1~C 10 Carboxylate, C2~C 10 Alkoxycarbonyl, C1~C 10 Alkoxy, or C5-C 20 They are optionally substituted with aryloxy groups, each of which is optionally substituted with a C1-C6 alkyl, halide, or C1-C6 alkoxy group, or with a phenyl group optionally substituted with a halide, C1-C6 alkyl, or C1C6 alkoxy. X, L 1 , and L 2 These can be combined to form cyclopentadienyl, which can optionally be substituted with vinyl, hydrogen, methyl, or phenyl. Examples of tetradentate ligands include, but are not limited to, O2C(CH2)2P(Ph)(CH2)2P(Ph)(CH2)2CO2, phthalocyanines, and porphyrins.

[0136] Complexes in which Y is coordinated to a metal are examples of catalysts in the fifth group and are generally called "Grubbs-Hobeida" catalysts. The Grubbs-Hobeida metathesis-activated metal carbene complex can be described by formula (VII). [ka] During the ceremony, M is a transition metal of Group 8, specifically Ru or Os, or more specifically Ru. X 1 , X 2 , and L 1 The first and second groups of catalysts are defined herein as previously defined, Y is a heteroatom selected from N, O, S, and P, for example, Y is either 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, and Y, Z, R 5 , R 6 , R 7 , and R 8 Any combination of these can combine to form one or more cyclic groups. n is 0, 1, or 2, and therefore, for divalent heteroatoms O or S, n is 1, and for trivalent heteroatoms N or P, n is 2. Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, and functionalized aryl, and the functional group(s) may be independently one or more, namely, alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl, and trimethylsilyl, and X 1 , X 2 , L 1 Y, Z, R 5 , R 6 , R 7 , and R 8 Any combination(s) of these can be attached to the carrier. Additional, R 5 , R 6 , R 7 , R 8 , and Z can independently be thioisocyanates, cyanates, or thiocyanates.

[0137] Examples of complexes containing a suitable Grubbs-Hoveida ligand in the present invention include the following: [ka] In the formula, L 1 , X 1 , X 2, and M are as described for any of the other groups of catalysts. Suitable chelate carbenes and carbene precursors are further described by Pederson et al. (U.S. Patent Nos. 7,026,495 and 6,620,955, both disclosures incorporated herein by reference) and Hoveyda et al. (U.S. Patent Nos. 6,921,735 and WO0214376, both disclosures incorporated herein by reference).

[0138] Other useful complexes include L by formula (I), (III), or (V). 2 and R 2 Examples include styrene compounds that have linked structures, such as those that also include functional groups for binding to a support. Examples of functional groups that are trialkoxysilyl functionalized moieties include, but are not limited to, the following. [ka]

[0139] Further examples of complexes with binding ligands include neutral NHC ligands and anionic ligands, neutral NHC ligands and alkylidine ligands, and neutral NHC ligands and L 2 Ligand, neutral NHC ligand and L 3 Examples include ligands, anionic ligands and alkylidine ligands, and bonds between any combination thereof. There are too many possible structures to list here, but some preferred structures based on formula (III) are as follows: [ka]

[0140] In addition to catalysts having the structure of formula (I) above, other transition metal carbene complexes include, but are not limited to, the following. A neutral ruthenium or osmium metal carbene complex formally in an oxidation state of +2, possessing 16 electrons, 5 coordination, and containing a metal center represented by general formula (IX); A neutral ruthenium or osmium metal carbene complex formally in an oxidation state of +2, possessing 18 electrons, 6 coordination, and containing a metal center represented by general formula (X); A cationic ruthenium or osmium metal carbene complex that is formally in an oxidation state of +2, has 14 electrons, is 4-coordinate, and contains a metal center represented by general formula (XI); A cationic ruthenium or osmium metal carbene complex that is formally in an oxidation state of +2, has 14 or 16 electrons, is 4-coordinate or 5-coordinate, and contains a metal center represented by general formula (XII). [ka] [ka] [ka] [ka] During the ceremony, M, X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 This is as defined for one of the four catalyst groups defined earlier, r and s are independently either 0 or 1. t is an integer in the range of 0 to 5. k is an integer in the range of 0 to 1. Y is any non-coordinating anion (e.g., halide ions, BF4). - etc. Z 1 and Z 2 These are independently -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)-, -OC(=O)O-, -S(=O)-, -S(=O)2-, -, and C1~C which are optionally substituted and / or optionally contain heteroatoms. 20 Selected from the hydrocarbylene bond, Z 3 is -P(R 2 )3 + or -N(R 2 )3 + These are any cationic moieties, X 1 , X 2 , L 1 , L 2 , L 3 , Z 1 , Z 2 , Z 3 , R 1 , and R 2 Two or more of these may combine to form a cyclic group (for example, a polydentate ligand), X 1 , X 2 , L 1 , L 2 , L 3 , Z 1 , Z 2 , Z 3 , R 1 , and R 2 One or more of these may be bound to the carrier.

[0141] Furthermore, 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 of formula (XIII). [ka] During the ceremony, M is a transition metal of Group 8, specifically ruthenium or osmium, or more specifically ruthenium. X 1 , X 2 , L 1 , and L 2The first and second groups of catalysts defined above are as previously defined, R G1 , R G2 , R G3 , R G4 , R G5 , and R G6 These are, independently, hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, thioisocyanate, cyanato, thiocyanato, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide, halogen A is selected from the group consisting of substituted amides, trifluoroamides, sulfides, disulfides, sulfonates, carbamates, silanes, siloxanes, phosphines, phosphates, borates, or -A-Fn, where "A" is a divalent hydrocarbon group selected from alkylenes and arylalkylenes, the alkyl moiety of the alkylene group and arylalkylene group can be linear or branched, saturated or unsaturated, cyclic or acyclic, substituted or unsubstituted, the aryl moiety of the arylalkylene may be substituted or unsubstituted, heteroatoms and / or functional groups may be present in either the aryl moiety or alkyl moiety of the alkylene group and arylalkylene group, Fn is a functional group, or R G1 , R G2 , R G3 , R G4 , R G5 , and R G6 Either one or more of these are bonded together to form a cyclic group, or R G1 , R G2 , R G3 , R G4 , R G5 , and R G6Any one or more of them may be bound to a carrier.

[0142] Additionally, one Group 8 transition metal complex of Formula XIII is a Group 8 transition metal complex of Formula (XIV).

Chemical formula

Chem.

[0144] Furthermore, another group of olefin metathesis catalysts 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 having the structure of Formula (XVI).

Chem.

[0145] Additionally, one Group 8 transition metal complex of formula (XVI) is a Group 8 transition metal complex containing a Schiff base ligand having the structure of formula (XVII).

Chemical formula

[0146] Additionally, another Group 8 transition metal complex of formula (XVI) is a Group 8 transition metal complex containing a Schiff base ligand having the structure of formula (XVIII). [ka] M, X 1 , L 1 , Z, R J7 , R J8 , R J9 , R J10 , and R J11 This is as defined above for the group 8 transition metal complex of formula XVI.

[0147] Furthermore, another group of olefin metathesis catalysts that can be used in the catalyst compositions of the present invention disclosed herein are group 8 transition metal complexes comprising a Schiff base ligand having the structure of formula (XIX). [ka] During the ceremony, M is a transition metal of Group 8, specifically ruthenium or osmium, or more specifically ruthenium. X 1 , L 1 , R 1 , and R 2 The first and second groups of catalysts defined above are as previously defined, Z is oxygen, sulfur, selenium, NR K5 PR K5 AsR K5 , and SbR K5 Selected from the group consisting of, m is 0, 1, or 2. R K1 , R K2 , R K3 , R K4 , and R K5 These are, independently, hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, thioisocyanate, cyanato, thiocyanato, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide, halogen A is selected from the group consisting of substituted amides, trifluoroamides, sulfides, disulfides, sulfonates, carbamates, silanes, siloxanes, phosphines, phosphates, borates, or -A-Fn, where "A" is a divalent hydrocarbon group selected from alkylenes and arylalkylenes, the alkyl moiety of the alkylene group and arylalkylene group can be linear or branched, saturated or unsaturated, cyclic or acyclic, substituted or unsubstituted, the aryl moiety of the arylalkylene may be substituted or unsubstituted, heteroatoms and / or functional groups may be present in either the aryl moiety or alkyl moiety of the alkylene group and arylalkylene group, Fn is a functional group, or R K1 , R K2 , R K3 , R K4 , and R K5 Either one or more of these are bonded together to form a cyclic group, or R K1 , R K2 , R K3 , R K4 , and R K5 One or more of these can be bound to the carrier.

[0148] Furthermore, catalysts of formulas (XVI) to (XIX) can be optionally brought into contact with an activating compound, in which case at least partial cleavage of the bond between the group 8 transition metal and at least one Schiff base ligand occurs, and the activating compound is copper(I) halide, Zn(R) Y1 )2 zinc compound (R Y1 (These are halogens, C1-C7 alkyls, or aryls), formula SnR Y2 R Y3 R Y4 R Y5 A tin compound represented by (R Y2 , R Y3 , R Y4 and R Y5 Each of these is halogen, C1~C 20 Alkyl, C3~C 10 (Independently selected from the group consisting of cycloalkyl, aryl, benzyl and C2-C7 alkenyl, and formula SiR Y6 R Y7 R Y8 R Y9 Silicon compounds represented by (R Y6 , R Y7 , R Y8 , R Y9 These are, independently, hydrogen, halogen, and C1-C. 20The catalyst is either a metal or silicon compound selected from the group consisting of alkyl, halo, C1-C7 alkyl, aryl, heteroaryl, and vinyl. Furthermore, the catalysts of formulas (XVI) to (XIX) may be contacted with an activating compound as needed, in which case at least partial cleavage of the bond between the group 8 transition metal and at least one Schiff base ligand occurs, and 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 be contacted with an activating compound as needed, in which case at least partial cleavage of the bond between the group 8 transition metal and at least one Schiff base ligand occurs, and the activating compound includes, but is not limited to, methanesulfonic acid, aminobenzenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, sulfanilic acid, trifluoromethanesulfonic acid; acetoacetic acid, barbituric acid, bromoacetic acid, bromobenzoic acid, chloroacetic acid, chlorobenzoic acid, chlorophenoxyacetic acid, chloropropionic acid, cis-cinnamic acid, cyanoacetic acid, cyanobutyric acid, cyanophenoxyvinegar Organic acids include, but are not limited to, monocarboxylic acids such as acids, cyanopropionic acid, dichloroacetic acid, dichloroacetylacetic acid, dihydroxybenzoic acid, dihydroxymalic acid, dihydroxytartaric acid, dinicotinic acid, diphenylacetic acid, fluorobenzoic acid, formic acid, furoic acid, furic acid, glycolic acid, hippuric acid, iodoacetic acid, iodobenzoic acid, lactic acid, lutidic acid, mandelic acid, α-naphthic acid, nitrobenzoic acid, nitrophenylacetic acid, o-phenylbenzoic acid, thioacetic acid, thiophenecarboxylic acid, trichloroacetic acid, and trihydroxybenzoic acid; as well as other acidic substances such as picric acid and uric acid.

[0149] Furthermore, other examples of catalysts that can be used in the catalyst compositions of the present invention are described in the following disclosures, U.S. Patents 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 Applications Nos. 12 / 303,615, 10 / 590,380, 11 / 465,651 (Publication No. US2007 / 0043188), and 11 / 465,651 (Publication No. US2008 / 0293905 amended publication), and European Patents Nos. EP1757613B1 and EP1577282B1, each of which is incorporated herein by reference.

[0150] Non-limiting examples of catalysts that may be used to prepare supported complexes and in the reactions disclosed herein include, but are not limited to, the following, some of which are identified throughout this disclosure by reference to their molecular weight for convenience. [ka] [ka] [ka] [ka] [ka]

[0151] In the molecular structure and formula described above, 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 via the N atom), Mes represents mesityl (i.e., 2,4,6-trimethylphenyl), DiPP and DIPP represent 2,6-di-isopropylphenyl, and MiPP represents 2-isopropylphenyl.

[0152] Further examples of catalysts useful for the preparation of supported complexes and in the reactions disclosed herein include: ruthenium(II) dichloro(3-methyl-2-butenylidene)bis(tricyclopentylphosphine)(C716); ruthenium(II) dichloro(3-methyl-2-butenylidene)bis(tricyclohexylphosphine)(C801); ruthenium(II) dichloro(phenylmethylene)bis(tricyclohexylphosphine)(C823); ruthenium(II)(1,3-bis-(2,4,6-trimethylphenyl Ruthenium(II)-2-imidazolidinylidene)dichloro(phenylmethylene)(triphenylphosphine)(C830); Ruthenium(II)dichloro(phenylvinylidene)bis(tricyclohexylphosphine)(C835); Ruthenium(II)dichloro(tricyclohexylphosphine)(o-isopropoxyphenylmethylene)(C601); Ruthenium(II)(1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)bis(3-bromopyridine)(C884);[1,3- [Bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(o-isopropoxyphenylmethylene)ruthenium(II)(C627);[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylidene)(triphenylphosphine)ruthenium(II)(C831);[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylidene)(methyldiphenylphosphine)ruthenium(II)(C769);[1,3-Bi [2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylidene)(tricyclohexylphosphine)ruthenium(II)(C848); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylidene)(diethylphenylphosphine)ruthenium(II)(C735); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylidene)(tri-n-butylphosphine)ruthenium(II)(C771);[1,3-Bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(triphenylphosphine)ruthenium(II)(C809); [1,3-Bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(methyldiphenylphosphine)ruthenium(II)(C747); [1,3-Bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro (3-methyl-2-butenylidene)(tricyclohexylphosphine)ruthenium(II)(C827); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(diethylphenylphosphine)ruthenium(II)(C713); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(tri-n-butylphosphine)ruthenium(II) )(C749);[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylindenylidene)(triphenylphosphine)ruthenium(II)(C931);[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylindenylidene)(methylphenylphosphine)ruthenium(II)(C869);[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro Ro(phenylindenylidene)(tricyclohexylphosphine)ruthenium(II)(C949); [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylindenylidene)(diethylphenylphosphine)ruthenium(II)(C835); and [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylindenylidene)(tri-n-butylphosphine)ruthenium(II)(C871).

[0153] Further catalysts useful in ROMP reactions and / or other metathesis reactions such as ring-closed metathesis, cross-metathesis, ring-opening cross-metathesis, autometathesis, ethenol decomposition, alkenolisis, acyclic diene metathesis polymerization, and combinations thereof include the following structures: [ka] [ka]

[0154] Generally, the transition metal complexes used as catalysts herein can be prepared by several different methods, including those described in Schwab et al. (1996) J. Am. Chem. Soc. 118:100-110, Scholl et al. (1999) Org. Lett. 6:953-956, Sanford et al. (2001) J. Am. Chem. Soc. 123:749-750, U.S. Patent No. 5,312,940, and U.S. Patent No. 5,342,909, the disclosures of each of these patents are incorporated herein by reference. See also U.S. Patent Publication No. 2003 / 0055262, WO02 / 079208, and U.S. Patent No. 6,613,910 by Grubbs et al., the disclosures of each of these patents are incorporated herein by reference. The synthesis method is described in WO03 / 11455A1 by Grubbs et al., and its disclosure is incorporated herein by reference.

[0155] Metal carbene olefin metathesis catalysts can be group 8 transition metal complexes having the structure of formula (I), commonly known as a "first-generation Grubbs" catalyst, formula (III), commonly known as a "second-generation Grubbs" catalyst, or formula (VII), commonly known as a "Grubbs-Hovbaida" catalyst.

[0156] The metal carbene olefin metathesis catalyst may have the structure of formula (I). [ka] During the ceremony, M is a transition metal in Group 8, L 1 , L 2 , and L 3 It is a neutral electron donor ligand, n is either 0 or 1. m is 0, 1, or 2. k is either 0 or 1. X 1 and X 2 is an anion ligand, R 1 and R 2 These are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups. X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 Any two or more of these can combine to form one or more cyclic groups, and furthermore, X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 One or more of these may be bound to the carrier. The metal carbene olefin metathesis catalyst may have the structure of formula (VII). [ka] During the ceremony, M is a transition metal in Group 8, L 1 It is a neutral electron donor ligand, X 1 and X 2 is an anion ligand, Y is a heteroatom selected from O or N, R 5 , R 6 , R 7 , and R 8 These are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups. n is 0, 1, or 2. Z is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups. Y, Z, R 5 , R 6 , R 7 , and R 8 Any combination of can be linked to form one or more cyclic groups, and furthermore, X 1 , X 2 , L 1 Y, Z, R 5 , R 6 , R 7 , and R 8 Any combination of these may be bonded to the carrier.

[0157] The metal carbene olefin metathesis catalyst may have the structure of formula (I). [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2is 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 L is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene. 2 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 This is an N-heterocyclic carbene independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene. X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 is phenyl or -CH=C(CH3)2 or thienyl; or R 1 and R 2These combine to form 3-phenyl-1H-indene. The metal carbene olefin metathesis catalyst may have the structure of formula (VII). [ka] During the ceremony, M is ruthenium, L 1 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 This is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene. X 1 and X 2 It is a chloride, Y is oxygen, R 5 , R 6 , R 7 , and R 8 Each of them is hydrogen, n is 1, Z is isopropyl.

[0158] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2 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 L is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene. 2 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 This is an N-heterocyclic carbene independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene. X 1 and X 2 It is a chloride, R 1is hydrogen, and R 2 is phenyl or -CH=C(CH3)2 or thienyl; or R 1 and R 2 These integrate to form an indenylidene moiety.

[0159] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2 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 L is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene. 2is 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 This is an N-heterocyclic carbene independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene. X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 is phenyl or -CH=C(CH3)2 or thienyl; or R 1 and R 2 It is integrated into an indenylidene moiety, and the indenylidene moiety is phenylindenylidene.

[0160] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2is 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 L is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene. 2 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 This is an N-heterocyclic carbene independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene. X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 is phenyl or -CH=C(CH3)2; or R 1 and R 2These integrate to form an indenylidene moiety.

[0161] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2 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 L is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene. 2 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 2This is an N-heterocyclic carbene independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene. X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 is phenyl or -CH=C(CH3)2; or R 1 and R 2 It is integrated into an indenylidene moiety, and the indenylidene moiety is phenylindenylidene.

[0162] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2 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 L is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene. 2is 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 This is an N-heterocyclic carbene independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene. X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 is phenyl or -CH=C(CH3)2; or R 1 and R 2 These integrate to form an indenylidene moiety.

[0163] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2is 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 L is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene. 2 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 This is an N-heterocyclic carbene independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene. X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 is phenyl or -CH=C(CH3)2; or R 1 and R 2 It is integrated into an indenylidene moiety, and the indenylidene moiety is phenylindenylidene.

[0164] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2 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 L is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 2 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 selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 is phenyl or -CH=C(CH3)2; or R 1 and R 2 These integrate to form an indenylidene moiety.

[0165] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2 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 L is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 2 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 selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 is phenyl or -CH=C(CH3)2; or R 1 and R 2 It is integrated into an indenylidene moiety, and the indenylidene moiety is phenylindenylidene.

[0166] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2 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 L is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 2 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 selected from 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 is phenyl or -CH=C(CH3)2 or thienyl; or R 1and R 2 These integrate to form an indenylidene moiety.

[0167] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2 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 L is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 2 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 selected from 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2is phenyl or -CH=C(CH3)2 or thienyl; or R 1 and R 2 It is integrated into an indenylidene moiety, and the indenylidene moiety is phenylindenylidene.

[0168] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2 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 L is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 2 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 selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, X 1and X 2 It is a chloride, R 1 is hydrogen, and R 2 is phenyl or -CH=C(CH3)2 or thienyl; or R 1 and R 2 These integrate to form an indenylidene moiety.

[0169] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2 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 L is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 2 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 2It is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 is phenyl or -CH=C(CH3)2 or thienyl; or R 1 and R 2 It is integrated into an indenylidene moiety, and the indenylidene moiety is phenylindenylidene.

[0170] Examples of metal carbene olefin metathesis catalysts having the structure of formula (VII) [ka] During the ceremony, M is ruthenium, L 1 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 This is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene. X 1 and X 2 It is a chloride, Y is oxygen, R 5 , R 6 , R 7 , and R8 Each of them is hydrogen, n is 1, Z is isopropyl.

[0171] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2 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 L is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene. 2 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 2This is an N-heterocyclic carbene independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene. X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 It is phenyl, -CH=C(CH3)2, or thienyl.

[0172] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2 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 L is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene. 2is 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 This is an N-heterocyclic carbene independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene. X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 It is phenyl, -CH=C(CH3)2, or thienyl.

[0173] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2 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 1L is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 2 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 selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 It is phenyl, -CH=C(CH3)2, or thienyl.

[0174] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2 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 1L is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 2 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 selected from 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 It is phenyl, -CH=C(CH3)2, or thienyl.

[0175] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2 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 1L is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene. 2 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 This is an N-heterocyclic carbene independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene. X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 It is phenyl or -CH=C(CH3)2.

[0176] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1and L 2 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 L is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene. 2 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 This is an N-heterocyclic carbene independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene. X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 It is phenyl or -CH=C(CH3)2.

[0177] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2 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 L is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 2 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 selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 It is phenyl or -CH=C(CH3)2.

[0178] Examples of metal carbene olefin metathesis catalysts having the structure of formula (I) [ka] During the ceremony, M is ruthenium, n is 0, m is 0, k is 1, L 1 and L 2 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 L is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 2 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 selected from 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 It is phenyl or -CH=C(CH3)2.

[0179] Examples of metal carbene olefin metathesis catalysts having the structure of formula (XV) [ka] During the ceremony, M is ruthenium, X1 and X 2 It is a chloride, L 1 and L 2 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 L is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene. 2 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 This is an N-heterocyclic carbene independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidene.

[0180] Examples of metal carbene olefin metathesis catalysts having the structure of formula (XV) [ka] During the ceremony, M is ruthenium, X 1 and X 2 It is a chloride, L 1 and L 2 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 L is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene. 2 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 This is an N-heterocyclic carbene independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene and 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene.

[0181] Examples of metal carbene olefin metathesis catalysts having the structure of formula (XV) [ka] During the ceremony, M is ruthenium, X 1 and X 2 It is a chloride, L 1 and L 2 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 L is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 2 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 selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene.

[0182] Examples of metal carbene olefin metathesis catalysts having the structure of formula (XV) [ka] During the ceremony, M is ruthenium, X 1 and X 2 It is a chloride, L 1 and L 2is 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 L is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, 2 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 selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene.

[0183] Suitable supports for any of the catalysts described herein may be synthetic, semi-synthetic, or naturally occurring materials, which may be organic or inorganic, such as polymers, ceramics, or metals. Bonding to the support is generally, but not necessarily, covalent, and the covalent bond may be direct or indirect. Indirect covalent bonds are typically, but not necessarily, mediated by functional groups on the support surface. Ionic bonds, including a combination of one or more anionic groups on a metal complex bonded to a cationic group-containing support, or a combination of one or more cationic groups on a metal complex bonded to a cationic group-containing support, are also preferred.

[0184] When used, suitable carriers may be selected from silica, silicates, alumina, aluminum oxide, silica-alumina, aluminosilicate, zeolite, titania, titanium dioxide, magnetite, magnesium oxide, boron oxide, clay, zirconia, zirconium dioxide, carbon, polymers, cellulose, cellulose polymers, amylose, amylose polymers, or combinations thereof. The carrier may include silica, silicates, or combinations thereof.

[0185] It is also possible to use a carrier that has been treated to include functional groups, inert moieties, and / or excess ligands. Any functional groups described herein are suitable for incorporation onto a carrier and can generally be achieved by techniques known in the art. In addition, inert moieties may be incorporated onto the carrier to control the arrangement or amount of composites linked to the carrier, for example, in order to generally reduce the number of available binding sites on the carrier.

[0186] A catalyst composition comprising at least one metal carbene olefin metathesis catalyst can be used in olefin metathesis reactions according to techniques known in the art. The catalyst compositions of the present invention are typically added to a ROMP composition as a solid, solution, or suspension. When the catalyst composition of the present invention is added to a ROMP composition as a suspension, at least one metal carbene olefin metathesis catalyst is suspended in a dispersion carrier such as mineral oil, paraffin oil, soybean oil, tri-isopropylbenzene, or any hydrophobic liquid having a viscosity high enough to effectively disperse the catalyst(s), being sufficiently inert, and having a boiling point high enough not to act as a low-boiling-point impurity in the olefin metathesis reaction. It will be understood that the amount of catalyst used in the reaction (i.e., "catalyst packing") depends on various factors such as the identity of the reactants and the reaction conditions used. Therefore, it will be understood that the catalyst packing can be optimally and independently selected for each reaction. On the other hand, generally, the catalyst is present in amounts ranging from a minimum of about 0.1 ppm, 1 ppm, or 5 ppm relative to the amount of the olefin substrate, to a maximum of about 10 ppm, 15 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, or 1000 ppm.

[0187] Generally, the catalyst will be present in the cyclic olefin composition in amounts ranging from a minimum of approximately 0.00001 mol%, 0.0001 mol%, or 0.0005 mol%, to a maximum of approximately 0.001 mol%, 0.0015 mol%, 0.0025 mol%, 0.005 mol%, 0.01 mol%, 0.02 mol%, 0.05 mol%, or 0.1 mol%, relative to the cyclic olefin(s) present.

[0188] When catalyst packing is expressed as the molar ratio of monomer to catalyst, the packing ("monomer-to-catalyst ratio") generally falls within a range of quantities from the lowest values ​​of approximately 10,000,000:1, 1,000,000:1, or 200,000:1 to the highest values ​​of approximately 100,000:1, 66,667:1, 40,000:1, 20,000:1, 10,000:1, 5,000:1, or 1,000:1.

[0189] The metathesis reactions disclosed herein may be carried out under a dry, inert atmosphere. Such an atmosphere may be created using any inert gas, including gases such as nitrogen and argon. The use of an inert atmosphere is optimal in that it promotes catalytic activity, and reactions carried out under an inert atmosphere are usually carried out with relatively low catalyst packing. The reactions disclosed herein may also be carried out in an oxygen-containing atmosphere and / or a water-containing atmosphere, and the reactions may be carried out under ambient conditions. However, the presence of oxygen or water in the reaction may require the use of higher catalyst packing compared to reactions carried out under an inert atmosphere. The reactions disclosed herein may also be carried out under reduced pressure, provided that the vapor pressure of the reactants is permissible.

[0190] The reactions disclosed herein can be carried out in a solvent, and any solvent inert to cross-metathesis can be used. Generally, solvents that can be used in 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, methylene chloride, 1,2-dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, methanol, ethanol, water, or mixtures thereof. The reactions disclosed herein can be carried out undiluted, i.e., without the use of a solvent.

[0191] The temperature at which the metathesis reaction is carried out by 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 the temperature may be within a range having any of these values ​​as an upper or lower limit. The reaction may be carried out at a temperature of at least about 35°C, or the reaction may be carried out at a temperature of at least about 50°C.

[0192] Adhesion promoter The optional adhesion promoter used in the ROMP composition of the present invention disclosed herein may be an acid-functionalized polyolefin.

[0193] Acid-functionalized polyolefins that can be used as adhesion promoters include those disclosed in US 7,465,773, the disclosure of which is incorporated herein by reference. For example, adhesion promoters that can be used in the present invention may be acid-functionalized polyolefins, such as polyolefins containing maleic anhydride. The polyolefins may be unsaturated and contain an alkene moiety such as polybutadiene. The polyolefins may have a vinyl content of 40, 35, or 30 wt% or less. The polyolefins may have an average anhydride equivalent weight in the range of 200 to 5000 g / mol per anhydride group (e.g., 4000, 3000, 2000, 1000, or 500 g / mol or less per anhydride group). Polyolefins containing maleic anhydride are liquids and typically have a viscosity of at least 2000, 3000, 4000, or 5000 mPas at 20°C or 25°C (DIN ENISO 3219). The viscosity at 20°C or 25°C may be 75,000 mPas or less (e.g., 30,000, 25,000, 20,000, or 15,000, or 10,000 mPas or less, less than 1,000 or 500 mPas). Polyolefins may have a viscosity of at least 50,000, 75,000, 100,000, 125,000, or less than 150,000 mPas at 45, 50, or 55°C. Viscosity indicates molecular weight. Polyolefins may have a molecular weight (Mn) of 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,500, 4,000, 3,500, or less than 3,000 g / mol. Polyolefins may have a molecular weight (Mn) of at least 1,000, 1,100, 1,200, 1,300, 1,400, 1,500, 1,600, 1,700, 1,800, 1,900, or 2,000 g / mol.Acid-functionalized polyolefins that can be used as adhesion promoters include polybutadienes containing maleic anhydride (e.g., Ricobond 1731, Polyvest EP MA 100, Ricon 130MA8, Ricon 130MA20, Ricon 131MA5, Ricon 131MA10, Ricon 131MA20, Ricon 184MA6, Ricobond 1731, Ricobond 1756 from Cray Valley, Polyvest EP MA 100, MA 75, EP MV MA 60 from Evonik, and Lithene Ultra PM4-7.5MA, N4-B-10MA, N4-5000-10 MA, AL-15MA from Synthomer (polybutadiene modified with maleic anhydride)).

[0194] Other adhesion promoters that may be used in the present invention may be any compound having at least two isocyanate groups. Compounds containing at least two isocyanate groups may be selected from the group consisting of at least one diisocyanate, at least one triisocyanate, or at least one polyisocyanate (i.e., containing four or more isocyanate groups), and mixtures thereof. In a more specific embodiment of the present invention, the adhesion promoter includes, or is not limited to, a diisocyanate compound or a mixture of diisocyanate compounds.

[0195] Compounds of isocyanate compounds containing at least two isocyanate groups can be selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functionalized hydrocarbyl compounds. As described above, suitable hydrocarbyl adhesion promoter compounds generally include alkyl, cycloalkyl, alkylene, alkenyl, alkynyl, aryl, cycloalkyl, alkaryl, and aralkyl compounds. Substituted heteroatom-containing and functionalized hydrocarbyl adhesion promoter compounds include the aforementioned hydrocarbyl compounds, as well as their variant forms.

[0196] Adhesion promoters that can be used in the present invention may be alkyl diisocyanates. Alkyl diisocyanates usually refer to linear, branched, or cyclic saturated or unsaturated hydrocarbon groups, such as diisocyanates containing 1 to about 24 carbon atoms, for example, 2 to about 12 carbon atoms (e.g., hexamethylene diisocyanate (HDI), octamethylene diisocyanate, decamethylene diisocyanate, etc., with 6 to 12 carbon atoms). Cycloalkyl diisocyanates typically contain a cyclic alkyl group having 4 to 16 carbon atoms. Cycloalkyl diisocyanates containing 6 to about 12 carbon atoms include cyclohexyl, cyclooctyl, and cyclodecyl. Cycloalkyl diisocyanates are produced as condensation products of acetone, called 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane, and are generally known as isophorone diisocyanate (IPDI) and isocyanato-[(isocyanatocyclohexyl)methyl]cyclohexane (H 12 It is known as an isomer of MDI. 12 MDI is derived from the hydrogenation form of aryl diisocyanate methylenediphenyl diisocyanate (MDI).

[0197] Adhesion promoters that may be used in the present invention may be aryl diisocyanates. An aryl diisocyanate refers to an aromatic diisocyanate containing a single aromatic ring, or multiple aromatic rings that are fused, directly bonded, or indirectly bonded (different aromatic rings bonded to a common group such as a methylene or ethylene moiety). An aryl diisocyanate may contain 5 to 24 carbon atoms (e.g., 5 to 14 carbon atoms). Exemplary aryl diisocyanates include one aromatic ring, or two fused or bonded aromatic rings, such as phenyl, tolyl, xylyl, naphthyl, biphenyl, diphenyl ether, and benzophenone. Examples of aromatic diisocyanates include toluene diisocyanate, tetramethylxylene diisocyanate (TMXDI), and methylenediphenyl diisocyanate (MDI), which may include any mixture of their three isomers, 2,2'-MDI, 2,4'-MDI, and 4,4'-MDI.

[0198] Adhesion promoters that can be used in the present invention may be polymer-containing isocyanates such as diisocyanates. A polymer-containing isocyanate refers to a polymer containing two or more terminal and / or pendant alkyl or aryl isocyanate groups. Polymer-containing isocyanates generally have minimal solubility in ROMP compositions and therefore provide improved mechanical properties. Examples of polymer-containing isocyanates include, but are not limited to, PM200 (poly MDI), Lupranate® (poly MDI manufactured by BASF), Krasol® isocyanate-terminated polybutadiem prepolymers such as Krasol®, LBD2000 (TDI-based), Krasol®, LBD3000 (TDI-based), Krasol®, NN-22 (MDI-based), Krasol®, NN-23 (MDI-based), and Krasol®, NN-25 (MDI-based). Krasol® isocyanate-terminated polybutadiene prepolymers are available from Cray Valley.

[0199] The adhesion promoters that can be used in the present invention may be trimers of alkyl diisocyanates and aryl diisocyanates. In the simplest form, any combination of polyisocyanate compounds can be trimerized to form an isocyanurate ring containing an isocyanate functional group. The trimers of alkyl diisocyanates and aryl diisocyanates may also be called alkyl diisocyanates or aryl diisocyanate isocyanurates. Examples of alkyl diisocyanate and aryl diisocyanate trimers include, but are not limited to, hexamethylene diisocyanate trimer (HDIt), isophorone diisocyanate trimer, toluene diisocyanate trimer, tetramethylxylene diisocyanate trimer, and methylenediphenyl diisocyanate trimer. Adhesion promoters include toluene diisocyanate, tetramethylxylene diisocyanate (TMXDI), and methylenediphenyl diisocyanate (MDI) (including any mixture of its three isomers 2,2'-MDI, 2,4'-MDI, and 4,4'-MDI), liquid MDI, solid MDI, hexamethylene diisocyanate trimer (HDIt), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and 4,4'-methyl This includes, but is not limited to, Lenbis (cyclohexyl isocyanate) (H12MDI), polymeric MDI (PM200), MDI prepolymer (Lupranate® 5080), liquid carbodiimide-modified 4,4'-MDI (Lupranate® MM103), liquid MDI (Lupranate® MI), liquid MDI (Mondur® ML), and liquid MDI (Mondur® MLQ).Adhesion promoters include, but are not limited to, methylenediphenyl diisocyanate (MDI) (including any mixture of its three isomers 2,2'-MDI, 2,4'-MDI, and 4,4'-MDI), liquid MDI, solid MDI, hexamethylene diisocyanate trimer (HDIt), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4'-methylenebis(cyclohexyl isocyanate) (H12MDI), polymeric MDI (PM200), MDI prepolymer (Lupranate® 5080), liquid carbodiimide-modified 4,4'-MDI (Lupranate® MM103), liquid MDI (Lupranate® MI), liquid MDI (Mondur® ML), and liquid MDI (Mondur® MLQ).

[0200] Additional adhesion promoters that can be used in the present invention include compositions comprising at least one compound containing at least two isocyanate groups (e.g., methylenediphenyl diisocyanate, hexamethylene diisocyanate) and at least one compound containing a heteroatom-containing functional group having a metathesis-active olefin (e.g., 2-hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate (HENB), 2-hydroxyethyl acrylate (HEA), oleyl alcohol, 9-decen-1-ol). Herein, the compounds can be combined in various ratios to form a preliminary reaction mixture. For example, pre-reaction mixtures include pre-reaction mixtures of liquid MDI (Mondur(T)MLQ) and 2-hydroxyethyl bicyclo[2.2.1]hept-2-enecarboxylate (HENB), pre-reaction mixtures of liquid MDI (Mondur(T)MLQ) and 2-hydroxyethyl acrylate (HEA), pre-reaction mixtures of liquid MDI (Mondur(T)MLQ) and oleyl alcohol, and pre-reaction mixtures of liquid MDI (Mondur(T)MLQ) and 9-decen-1-ol. The pre-reacted mixtures can be used as adhesion promoters of the present invention. Further examples of such adhesion promoters are described in US9,527,982, the disclosure of which is incorporated herein by reference. A mixture of HENB-MDI and an excess of unreacted MDI can also be used as an adhesion promoter of the present invention.

[0201] In some embodiments, for example, when a polyolefin containing maleic anhydride is used as an adhesion promoter, the adhesion promoter may not contain any isocyanate moieties at all. Furthermore, in some embodiments, the adhesion promoter does not contain any compound containing at least two isocyanate groups. In other embodiments, the ROMP composition does not contain any compound containing at least two isocyanate groups at all.

[0202] An additional adhesion promoter suitable for use in the present invention is of formula Fn-(A) nThe formula comprises a functionalized silane of -Si(Y*)3, where Y* is selected from halides (e.g., chlorides) or ORs, Fn is a functional group selected from acrylates, methacrylates, allyls, vinyls, alkenes, cycloalkenes, or norbornene, A is a divalent linking group selected from hydrocarbylenes, substituted hydrocarbylenes, heteroatom-containing hydrocarbylenes, or substituted heteroatom-containing hydrocarbylenes, n is 0 or 1, and R is selected from hydrocarbyls, substituted hydrocarbyls, heteroatom-containing hydrocarbyls, or substituted heteroatom-containing hydrocarbyls, e.g., lower alkyls (e.g., methyl, ethyl, or isopropyl), and also includes peroxides selected from dialkyl peroxides and diaryl peroxides.

[0203] Further adhesion promoters used in the present invention include those disclosed in International Patent Applications PCT / US2012 / 042850 and PCT / US2016 / 017449, which are incorporated herein by reference.

[0204] Additional adhesion promoters that may be used in the present invention are at least one polyoctenomer such as Vestenamer® (e.g., Vestenamer 8012, Vestenamer CS10). The polyoctenomer may be present in the ROMP composition in an amount ranging from 0.1 to 3 phr (e.g., 0.5 to 2 phr, 0.75 to 1.5 phr), for example, in an amount of 1 phr.

[0205] The ROMP composition of the present invention may use one or more of the aforementioned adhesion promoters in any combination. For example, at least one acid-functionalized polyolefin may be used in combination with at least one polyoctenomer.

[0206] Any concentration of adhesion promoter, if present, is sufficient for the present invention. For example, at least one adhesion promoter may be present in the ROMP composition in an amount ranging from 0.05 to 15 wt% (e.g., 0.1 to 13 wt%, 0.5 to 10 wt%, 1 to 8 wt%, 2 to 6 wt%, 3 to 5 wt%) based on the total weight of the ROMP composition. For example, the adhesion promoter may include at least one acid-functionalized polyolefin in an amount ranging from 0.1 to 10 wt% (e.g., 0.5 to 9 wt%, 1 to 8 wt%, 2 to 7 wt%, 3 to 6 wt%, 4 to 5 wt%) based on the total weight of the ROMP composition, and at least one polyoctenomer in an amount ranging from 0.05 to 5 wt% (e.g., 0.1 to 4 wt%, 0.5 to 3 wt%, 1 to 2 wt%) based on the total weight of the ROMP composition.

[0207] Plasticizer compounds The plasticizer compounds used in the ROMP compositions of the present invention disclosed herein include, essentially consist of, or comprise any compound or substance that improves the flexibility, processability, or extensibility of a plastic or elastomer.

[0208] For example, the plasticizer compound may be selected from the group consisting of polybutene oil (PB), polyalphaolefin oil, hydrocarbon resins, and mixtures thereof. The plasticizer compound may be PB oil.

[0209] PB oil is an oligomer or polymer made from butene monomers such as 1-butene and isobutene, or a mixture of butene monomers. PB oil is (C4H8) n It has a common repeating unit structure. PB oil made from isobutene monomers is sometimes called polyisobutene or polyisobutylene. PB oil made from 1-butene is sometimes called poly(1-butene). Commercial sources of polybutene oil that can be used in this invention include, for example, Indopol® H-15, H-25, H-50, H-100, H-300, H-1200, H-1500, H-1900, and H-2100. Higher molecular weight polybutene oils may be semi-solid at room temperature.

[0210] Polyalphaolefin oil may contain oligomers of C5-C18 olefins (e.g., C6-C14, C8-C12, C10), have a kinematic viscosity of 3-30 cSt or more at 100°C (e.g., 20 cSt or less, 4 cSt or more at 100°C), and a pour point of -10°C or lower (e.g., -20°C or lower, -30°C or lower). For example, polyalphaolefin oil may be a group IV hydrocarbon oil base stock, polyisobutene, wax isomerate lubricating oil base stock, ethylene / butene copolymer, or a mixture thereof. For example, polyalphaolefin oil may be a group IV hydrocarbon base stock, such as one derived from linear alphaolefins. For example, polyalphaolefin oil may be obtained from the oligomerization of linear alphaolefins, such as but not limited to C8, C10, C12, C14, C16, and C18. The number average molecular weight (M) that defines polyalphaolefin oil n Typical molecular weights, as defined by ), range from 250 g / mol to 10,000 g / mol (e.g., 300 g / mol, 500 g / mol, 1,000 g / mol, 2,000 g / mol, 4,000 g / mol, 6,000 g / mol, 7,000 g / mol, 9,000 g / mol, 9,500 g / mol). Commercially available polyalphaolefin oils include SpectraSyn100, SpectraSyn40, SpectraSyn10, SpectraSyn8, SpectraSyn6, SpectraSyn5, SpectraSyn4, SpectraSyn2, and SpectraSyn Elite300.

[0211] At least one plasticizer compound may be present in the ROMP composition in amounts ranging from 1 to 40 wt% (e.g., 5 to 45 wt%, 0.5 to 10 wt%, 10 to 40 wt%, 25 to 35 wt%) based on the total weight of the ROMP composition.

[0212] Rubber-reinforced compounds Rubber reinforcing compounds (also referred to herein as impact modifiers or elastomers) used in the ROMP compositions of the present invention as disclosed herein include, but are not limited to, butyl rubber, polyisobutylene, ethylene-propylene copolymer, styrene-ethylene / butylene-styrene copolymer, styrene-ethylene / propylene-styrene copolymer, ethylene-propylene-diene copolymer, ethylene-vinyl acetate, and nitrile rubber. Possible impact modifiers or elastomers include polybutadiene Diene 55AC10 (Firestone), polybutadiene Diene 55AM5 (Firestone), EPDM Royalene 301T, EPDM Buna T9650 (Bayer), styrene-ethylene / butylene-styrene copolymer Kraton G1651H, Polysar Butyl 301 (Bayer), polybutadiene Taktene 710 (Bayer), styrene-ethylene / butylene-styrene Kraton G1726M, styrene-ethylene / butylene-styrene Kraton G1650, ethylene-octene Engage 8150 (DuPont-Dow), styrene-butadiene Kraton D1184, EPDM Nordel 1070 (DuPont-Dow), and polyisobutylene Vistanex MML-140 (Exxon). Various polar impact modifiers or elastomers can also be used.

[0213] At least one rubber-reinforced compound may be selected from the group consisting of poly(styrene-ethylene-butylene-styrene), ethylene-propylene copolymer, ethylene-propylene dienterpolymer, and mixtures thereof. The rubber-reinforced compound may be ethylene-propylene copolymer (e.g., Vistalon 501, Vistalon 3702). The rubber-reinforced compound may be poly(styrene-ethylene-butylene-styrene) (e.g., Kraton 1650, Kraton 1651, Taipol 6151).

[0214] At least one rubber reinforcing compound may be present in the ROMP composition in amounts ranging from 0.01 to 30 wt% (e.g., 0.1 to 25 wt%, 1 to 20 wt%, 5 to 15 wt%, 7 to 12 wt%) based on the total weight of the ROMP composition.

[0215] ROMP composition As disclosed herein, the ROMP composition of the present invention is a) Cyclic olefin compositions disclosed herein, b) Catalyst compositions disclosed herein, c) Optionally, at least one adhesion promoter as disclosed herein, d) At least one plasticizer compound disclosed herein, e) at least one rubber-reinforced compound disclosed herein, It includes, essentially consists of, or is composed of The cyclic olefin composition does not contain, or substantially does not contain, monounsaturated cyclic olefins. At least one polyunsaturated cyclic olefin may or may not be substituted. The monounsaturated cyclic olefin is selected from ONB, or the monounsaturated cyclic olefin is selected from at least one substituted norbornene, including but not limited to monounsaturated substituted norbornene surrounded by cyclic olefin structures (D), (E), or (F) (as defined above), or the monounsaturated cyclic olefin is selected from any monounsaturated cyclic olefin.

[0216] The ROMP composition of the present invention may also comprise at least one substrate material. Furthermore, the ROMP composition may be deposited on at least one substrate material. The substrate material may be a functionalized substrate material, such as an amino-functionalized substrate or a heteroatom-functionalized substrate. Furthermore, the 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.

[0217] The ROMP composition of the present invention may further comprise an exogenous inhibitor. An exogenous inhibitor, or "gel modifier," for use in the present invention is disclosed in U.S. Patent No. 5,939,504, the disclosure of which is incorporated herein by reference. The ROMP composition of the present invention may further comprise a hydroperoxide gel modifier. A hydroperoxide gel modifier for use in the present invention (e.g., cumene hydroperoxide) is disclosed in International Patent Application No. PCT / US2012 / 042850.

[0218] The ROMP composition of the present invention may be formulated with additives as desired. Suitable additives include, but are not limited to, gel modifiers, hardness modifiers, antioxidants, ozone degradation inhibitors, stabilizers, crosslinking agents, fillers, binders, coupling agents, thixotropes, wetting agents, biocides, additional plasticizers, pigments, flame retardants, and dyes. Furthermore, the amount of additives present in the ROMP composition may vary depending on the specific type of additive used. The concentration of additives in the ROMP composition is typically in the range of 0.001 to 85 wt% (e.g., 0.01 to 75 wt%, 0.1 to 65 wt%, 1 to 55 wt%, 5 to 45 wt%, 10 to 35 wt%, 15 to 25 wt%) based on the total weight of the ROMP composition.

[0219] The ROMP composition of the present invention can be optionally formulated with or without a crosslinking agent selected from, for example, dialkyl peroxides, diacyl peroxides, and peroxy acids.

[0220] Antioxidants and anti-ozone agents include all antioxidants or anti-ozone agents used in the rubber or plastics industry. "Index of Commercial Antioxidants and Antiozonants, Fourth Edition" is available from Goodyear Chemicals, The Goodyear Tire and Rubber Company, Akron, Ohio 44316. Suitable stabilizers (i.e., antioxidants or ozone degradation inhibitors) include 2,6-di-tert-butyl-4-methylphenol (BHT); styrene phenols, e.g., Wingstay® S (Goodyear); 2- and 3-tert-butyl-4-methoxyphenol; alkylated hindered phenols, e.g., 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); and other bisphenols, e.g., Cyanox® 53 (Cytec Industries Inc.) and Permanax WSO; 2,2′-ethylidenebis(4,6-di-tert-butylphenol); 2,2′-methylenebis(4-methyl-6-(1-methylcyclohexyl)phenol); 4,4′-butylidenebis(6-tert-butyl-3-methylphenol); polybutylated bisphenol A; 4,4′-thiobis(6-tert-butyl-3-methylphenol); 4,4′-methylenebis(2,6-dimethylphenol); 1,1′-thiobis(2-naphthol); methylene-crosslinked polyalkylphenols, e.g., ethyl antioxidant 738; 2,2′-thiobis(4-methyl-6-tert-butylphenol); 2,2′-isobutylidenebis(4,6-dimethylphenol); 2,2′-methylenebis(4-methyl-6-cyclohexylphenol); butylation reaction products of para-cresol and dicyclopentadiene (e.g., Wingstay L);Tetrakis(methylene-3,5-di-tert-butyl-4-hydroxyhydrocinnamate)methane, i.e., Irganox® 1010 (BASF); 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, e.g., Ethanox® 330 (Albemarle Corporation); 4,4′-methylenebis(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, distearyl pentaerythritol diphosphite, phosphitephenols and bisphenols, e.g., Naugard® 492 (Chemtura Corporation), phosphite / phenol antioxidant blends, e.g., Irganox B215; di-n-octadecyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, 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 Examples include, but are not limited to, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylylenediphosphonite, diphenylamine, and 4,4′-dimethoxydiphenylamine. Such materials are typically used in ROMP compositions at levels of about 0.10 phr to 10 phr, for example, about 0.1 phr to 5 phr.

[0221] Suitable fillers include, for example, metal density modulators, particulate density modulators such as microspheres, and macroparticle density modulators such as glass or ceramic beads. Metal density modulators include, but are not limited to, powders, sintered, cut, flaked, filled, particle-formed, or granular metals, metal oxides, metal nitrides, and / or metal carbides. Metal density modulators include, among others, tungsten, tungsten carbide, aluminum, titanium, iron, lead, silicon oxide, aluminum oxide, boron carbide, and silicon carbide. Particulate density modulators include, but are not limited to, glass, metal, thermoplastic (either expandable or pre-expanded) or thermoset, and / or ceramic / silicate microspheres. Macroparticle density modulators include, but are not limited to, glass, plastic, or ceramic beads, metal rods, lumps, fragments, or shots, hollow glass, ceramic, plastic, or metal spheres, balls, or tubes.

[0222] The ROMP composition of the present invention can be prepared by combining a cyclic olefin composition, a catalyst composition, an optional adhesion promoter, a plasticizer compound, and a rubber reinforcing compound using any method known in the art.

[0223] The ROMP compositions of the present invention are generally less susceptible to air and / or moisture than resins used to prepare polyurethane and epoxy-based polymers, as well as DCPD polymers prepared from molybdenum and tungsten-catalyzed DCPD resins (e.g., Telene® DCPD resin, Metton® DCPD resin, Pentaam® DCPD resin). Therefore, the ROMP compositions of the present invention are generally more robust to a wider range of environmental conditions (e.g., temperature, humidity, etc.). Resin systems that are less affected by air and / or moisture are advantageous over air and / or moisture-sensitive resin systems, especially when coating (insulating) objects in marine environment settings such as ships, offshore oil drilling rigs, and offshore oil platforms.

[0224] Furthermore, the ROMP composition of the present invention offers improved ease of application compared to prior art ROMP compositions, particularly polypropylene-based ones. Unlike polypropylene-based compositions, which are mainly limited to extrusion, the ROMP composition of the present invention can be applied to objects and / or surfaces by various means such as injection, casting, leaching, injection, molding, spraying, rotational molding, centrifugal casting, pultrusion, and extrusion, but is not limited to these methods. Moreover, the ROMP composition of the present invention also offers improved ease of application compared to prior art ROMP compositions based on epoxy resins (e.g., elastomeramine-cured epoxy materials). Unlike epoxy-based resin systems (e.g., elastomeramine-cured epoxy materials) which are synthesized in at least two steps, the ROMP composition of the present invention requires only a single mixing step (e.g., mixing the ROMP composition of the present invention with the catalyst composition of the present invention) before application to the surface of an object or addition to a mold. DCPD resin systems, including two-component catalyst systems of molybdenum or tungsten (e.g., Telene® DCPD resin, Metton® DCPD resin, Pentaam® DCPD resin), require special and expensive processing and handling conditions and equipment such as special and expensive molds, injection equipment, and storage tanks. However, the ROMP compositions of the present invention can be applied to objects and / or surfaces of objects by various means, including but not limited to simple casting.

[0225] A particularly important advantage of the ROMP compositions of the present invention is that they are easy to handle and the resulting ROMP polymers and ROMP polymer composites, as described below, can be easily formulated to meet the needs / requirements of an application or service. For example, the ROMP compositions of the present invention used to prepare the ROMP polymers or ROMP polymer composites of the present invention can be easily formulated so that the resulting ROMP polymers or ROMP polymer composites exhibit physical, mechanical, and / or thermal properties ranging from elastomeric behavior and / or properties to rigid thermosetting behavior and / or properties, depending on the needs / requirements of the application.

[0226] ROMP polymers and ROMP polymer composites The present invention also relates to ROMP polymers or ROMP polymer composites comprising, essentially consisting of, or reaction products of the ROMP composition of the present invention, wherein the ROMP composition is subjected to conditions effective for polymerization of the ROMP composition.

[0227] The present invention also relates to the ROMP polymer or ROMP polymer composite of the present invention for use as a thermal insulation material.

[0228] The present invention also relates to the use of ROMP polymers or ROMP polymer composites for thermal insulation of an object. For example, any object can be thermally insulated from the surrounding environment or surrounding material using the ROMP polymers and / or ROMP polymer composites of the present invention, which may be gases (such as air), fluids (such as seawater or freshwater), solids (such as ice or underground solids in the case of buried pipelines), or mixtures thereof.

[0229] In particular, the ROMP polymer and ROMP polymer composites of the present invention are suitable for insulating objects such as oil pipelines in cold water (e.g., cold seawater, cold freshwater) and for insulating wellhead equipment. The ROMP polymer and ROMP polymer composites of the present invention can also be used for insulating other objects, including but not limited to pipes, underwater pipes, pipelines, oil pipelines, underwater oil pipelines, underwater pipelines, pipe fittings, hoses, hose fittings, tanks, containers, drums, manifolds, risers, field joints, configurations designated as Christmas trees (oilfield Christmas trees, subsea Christmas trees), jumpers, spool pieces, configurations designated as pipeline end terminations (PLETs), configurations designated as pipeline end manifolds (PLEMs), and other subsea structures and equipment. The ROMP polymer and ROMP polymer composites of the present invention may also be used to coat other objects such as robotic parts, devices, and vehicles used in subsea applications. Furthermore, the ROMP polymer and ROMP polymer composites of the present invention can be used to construct insulating structures such as configurations designated as underwater doghouses.

[0230] The present invention also relates to a process for ROMP polymer coating for marine applications, the process comprising: preparing an object surface to be at least partially coated, contained, or insulated; bringing the object surface into contact with a ROMP composition or depositing a ROMP composition onto the object surface; and exposing the ROMP composition to conditions effective for polymerization of the ROMP composition.

[0231] The ROMP polymers and ROMP polymer composites of the present invention are very suitable for coating, housing, or insulating objects immersed in water (e.g., freshwater, saltwater, seawater, etc.), but the ROMP polymers and ROMP polymer composites may also be used to coat, housing, or thermally insulating objects that are not exposed to an aqueous environment.

[0232] The ROMP polymer and ROMP polymer composites of the present invention can be used to coat, contain, or insulate objects (e.g., pipes and / or other underwater structures) where the temperature of the substance (e.g., hydrocarbons, oil, gas, etc.) transported by the object (e.g., pipes and / or other structures) is 160°C or higher. Therefore, by default, the ROMP polymer and / or ROMP polymer composites of the present invention can also be used to coat, contain, or insulate objects (e.g., pipes and / or other underwater structures) where the temperature of the substance (e.g., hydrocarbons, oil, gas, etc.) transported by the object (e.g., pipes and / or other underwater structures) is below 160°C.

[0233] The ROMP composition of the present invention can be applied to the surface of an object to be coated at least partially by methods known in the art, such as casting, centrifugal casting, pultrusion, molding, rotational molding, open molding, reaction injection molding (RIM), resin transfer molding (RTM), injection molding, vacuum impregnation, surface coating, filament winding, cell casting, dip casting, continuous casting, embedding, potting, encapsulation, film casting or solvent casting, gate casting, mold casting, slash casting, etc. Examples of manufacturing processes include, but are not limited to, casting, extrusion, mechanical foaming, chemical foaming, physical foaming, compression molding or matched die molding, spray-up, spray, vacuum-assisted resin transfer molding (VAR™), Seaman composite resin injection molding process (SCRIMP), blow molding, in-mold coating, in-mold painting or injection molding, vacuum molding, reinforced reaction injection molding (RRIM), structural reaction injection molding (SRIM), thermal expansion transfer molding (TERM), resin injection recirculation molding (RICM), controlled atmospheric pressure resin injection (CAPRI), and hand lay-up. For manufacturing techniques requiring the use of a RIM or impingement-style mix head, including but not limited to RIM, SRIM, and RRIM, the product may be molded using a single mix head or multiple mix heads and multiple material injection streams (e.g., two resin streams and one catalyst stream).

[0234] The ROMP polymer and / or ROMP polymer composites of the present invention do not necessarily need to be molded around the object to be insulated. Alternatively, ROMP polymer articles and ROMP polymer composite articles may be prepared independently by various methods known in the art and then attached to or placed around an object to thermally insulate the object from the surrounding environment. Furthermore, means for attaching ROMP polymer articles and ROMP polymer composite articles to an object may be any known means, including adhesive means and / or mechanical means such as fasteners, bolts, and screws. For example, the ROMP polymer and ROMP polymer composites may be prefabricated into sections molded to complement the object to be insulated. The prefabricated sections may then be fixed or attached to the object using any known means.

[0235] Furthermore, the object to be insulated may be pre-treated with any known tie coat or primer, which is 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, the tie coat or primer may be applied to the object to be insulated first, then the ROMP composition of the present invention may be applied to the object, and subsequently exposed to conditions effective for polymerization of the ROMP composition. Furthermore, the tie coat or primer may be applied to the object to be insulated, and then a ready-made ROMP polymer or ready-made ROMP polymer composite of the present invention may be attached to the object.

[0236] The ROMP polymer, ROMP polymer composites, and thermal insulation materials (described herein) of the present invention may have a thermal conductivity value of less than 0.180 W / m*K at an average temperature of 25°C, as determined by ASTM C518, when tested independently with a heat flow meter (FOX-50, LaserComp). The ROMP polymer, ROMP polymer composites, and thermal insulation materials of the present invention may be further reduced by the addition of glass microspheres.

[0237] The ROMP polymer, ROMP polymer composite, and thermal insulation material of the present invention may independently have peel adhesion strength to fused epoxy (FBE) of more than 2 MPa (e.g., more than 4 MPa, more than 5 MPa), as measured by the following method described in the General Procedures section. The FBE may be, for example, PipeClad HOT 150.

[0238] Insulation The present invention also covers thermal insulation materials comprising, essentially consisting of, or comprising the ROMP composition, ROMP polymer, or ROMP polymer composite of the present invention.

[0239] The ROMP polymer and ROMP polymer composites of the present invention exhibit improved thermal stability and / or improved hydrolysis stability compared to prior art thermal insulation materials. Thermal insulation materials made from the ROMP polymer of the present invention offer superior advantages over prior art thermal insulation materials made from polypropylene, and such ROMP polymers have improved thermal stability.

[0240] The present invention also relates to an insulating material used for coating, housing, or insulating (1) an object, (2) at least a portion of an object, and / or (3) at least a portion of at least one surface of an object, wherein the insulating material comprises the ROMP composition, ROMP polymer, or ROMP polymer composite of the present invention.

[0241] The present invention also relates to the use of an insulating material for coating, housing, or insulating (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 insulating material comprises the ROMP composition, ROMP polymer, or ROMP polymer composite of the present invention.

[0242] The present invention also relates to a method for thermally insulating an object from a surrounding fluid, the method comprising interposing an insulating material between the object and the fluid, where the insulating material comprises the ROMP composition, ROMP polymer, or ROMP polymer composite of the present invention.

[0243] The present invention also relates to a method for coating, housing, or insulating (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 insulating material includes the ROMP composition, ROMP polymer, or ROMP polymer composite of the present invention.

[0244] The present invention also relates to a method for coating, housing, or insulating (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 insulating material, the method comprising: bringing the ROMP composition of the present invention into contact with (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; or adhering the ROMP composition of the present invention to (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; and exposing the ROMP composition to conditions effective in promoting the ROMP reaction of the ROMP composition to form the ROMP polymer or ROMP polymer composite of the present invention, wherein the insulating material is the ROMP polymer or ROMP polymer composite.

[0245] The present invention also relates to a process for adhering an insulating material to an object, the process comprising: setting up a mold around the object to define a cavity between the inner surface of the mold and the object; injecting an insulating material into the cavity, wherein the insulating material composition comprises the ROMP composition of the present invention; and exposing the insulating material composition to conditions effective in promoting the ROMP reaction of the ROMP composition to form the ROMP polymer or ROMP polymer composite of the present invention.

[0246] The present invention relates to an object that is at least partially coated, housed, or insulated with the thermal insulation material of the present invention.

[0247] The objects to be housed, coated, and / or insulated can have any configuration, weight, size, thickness, or geometric shape. For example, pipes coated with the ROMP polymer and / or ROMP polymer composites of the present invention may have any outer diameter, inner diameter, and length.

[0248] Furthermore, the object to be contained, coated, and / or insulated may be constructed from any material, including but not limited to metals, metal alloys, plastics, rubber, polymers, wood, ceramics, glass, carbon, cement, and concrete.

[0249] Objects to be housed, coated, and / or insulated may be housed, coated, and / or insulated partially or entirely.

[0250] The insulation material can have any composition, weight, size, thickness, or geometric shape. Furthermore, the insulation material is not limited to a single polymer layer, but may include multiple polymer layers, each polymer layer may have the same or different composition.

[0251] The present invention also relates to a thermal insulation material comprising the ROMP polymer of the present invention, wherein the elongation at break of the ROMP polymer is in the range of 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%.

[0252] The present invention also relates to a thermal insulation material containing the ROMP polymer of the present 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%, and 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%~200%, 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% The range is ~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%.

[0253] The thermal insulation materials made from the ROMP polymer of the present invention have advantages over conventional thermal insulation materials made from polyurethanes and epoxy-based materials, including elastic amine-cured epoxy materials, in that the cyclic olefin (cyclic olefin monomer) used in the production of such ROMP polymers can be selected so that the resulting ROMP polymer does not contain carbon-heteroatom bonds in its polymer backbone. Therefore, the ROMP polymer of the present invention is generally more stable to hydrolysis than polyurethanes and / or epoxy-based polymers that have carbon-heteroatom bonds in their polymer backbone. Preferably, the ROMP polymer of the present invention has a polymer backbone containing only carbon-carbon single bonds and carbon-carbon double bonds, and the carbon atoms may be substituted or unsubstituted. The ROMP polymer of the present invention may optionally be hydrogenated by known methods, thereby obtaining hydrogenated ROMP polymers for use as thermal insulation materials.

[0254] Unexpectedly, the ROMP polymer, ROMP polymer composites, and thermal insulation materials of the present invention possessed some or all of the desired properties and / or characteristics specified above for thermal insulation materials, particularly for use in offshore drilling (e.g., underwater applications). Therefore, the ROMP polymer, ROMP polymer composites, and thermal insulation materials of the present invention satisfy this need in the industry.

[0255] While the present invention has been described in conjunction with its specific embodiments, it should be understood that the above description and subsequent embodiments are intended to illustrate, and not limit, the scope of the invention. Other aspects, advantages, and modifications within the scope of the invention will be apparent to those skilled in the art.

[0256] product The present invention also relates to products manufactured from the ROMP composition, ROMP polymer, ROMP polymer composite, or thermal insulation material of the present invention.

[0257] The present invention also relates to a product comprising an object in which at least a portion of at least one surface of the object is coated, contained, or insulated with the ROMP composition, ROMP polymer, ROMP polymer composite, or insulating material of the present invention.

[0258] The present invention also relates to articles manufactured from the ROMP composition of the present invention, wherein the ROMP composition is applied to at least one base material.

[0259] The present invention also relates to articles manufactured from the ROMP composition of the present invention and at least one base material, which are thermal insulation materials. Furthermore, the present invention also relates to articles manufactured from the ROMP composition of the present invention, wherein the ROMP composition is applied to at least one base material (e.g., a functionalized base material, e.g., a heteroatom functionalized base material, e.g., an amino functionalized base material, etc.), which are thermal insulation materials.

[0260] The present invention also relates to products manufactured by any of the methods described herein.

[0261] Exemplary embodiments of the present invention E1.a) A cyclic olefin composition comprising, essentially consisting of, or consisting of at least one polyunsaturated cyclic olefin, b) A catalyst composition comprising, essentially consisting of, or consisting of at least one metal carbene olefin metathesis catalyst, c) Optionally, at least one adhesion promoter, d) At least one plasticizer compound, e) at least one rubber-reinforced compound, It includes, essentially consists of, or is composed of The cyclic olefin composition does not contain, or substantially does not contain, monounsaturated cyclic olefins. The at least one polyunsaturated cyclic olefin may be substituted or unsubstituted. The monounsaturated cyclic olefin is selected from 5-octyl-2-norbornene (ONB) in the ROMP composition.

[0262] E2. The ROMP composition according to E1, wherein the monounsaturated cyclic olefin is selected from at least one monounsaturated substituted norbornene.

[0263] E3. The ROMP composition according to E1 or E2, wherein the monounsaturated cyclic olefin is selected from any monounsaturated cyclic olefin.

[0264] E4. The ROMP composition according to any one of E1 to E3, wherein the cyclic olefin composition comprises, based on the total weight of the cyclic olefin composition, 90 to 100 wt% (e.g., 91 to 99.9 wt%, 92 to 99 wt%, 93 to 98 wt%, 94 to 97 wt%, 95 to 96 wt%) of the at least one polyunsaturated cyclic olefin, or consists of essentially the same, and comprises 10 wt% or less (e.g., 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, 0.01 wt% or less, 0 wt%) of, or consists of essentially the same, or consists of the same.

[0265] E5. The ROMP composition according to any one of E1 to E4, which does not contain or substantially contains the monounsaturated cyclic olefin (for example, 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, 0.01 wt% or less, based on the total weight of the ROMP composition).

[0266] E6. The cyclic olefin composition is the ROMP composition according to any one of E1 to E5, wherein the cyclic olefin composition does not contain the monounsaturated cyclic olefin.

[0267] E7. The ROMP composition according to any one of E1 to E6, wherein the ROMP composition does not contain the monounsaturated cyclic olefin.

[0268] E8. The ROMP composition according to any one of E1 to E7, wherein the at least one polyunsaturated cyclic olefin is selected from the group consisting of dicyclopentadiene, tricyclopentadiene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, 5-butenyl-2-norbornene, and mixtures thereof.

[0269] E9. The ROMP composition according to any one of E1 to E8, wherein the at least one polyunsaturated cyclic olefin is selected from the group consisting of dicyclopentadiene, tricyclopentadiene, 5-ethylidene-2-norbornene, and mixtures thereof.

[0270] E10. The ROMP composition according to any one of E1 to E9, wherein the at least one polyunsaturated cyclic olefin is selected from the group consisting of dicyclopentadiene, tricyclopentadiene, and mixtures thereof.

[0271] E11. The ROMP composition according to any one of E1 to E10, wherein the cyclic olefin composition comprises, essentially consists of, or consists of 90 to 100 wt% (e.g., 91 to 99.9 wt%, 92 to 99 wt%, 93 to 98 wt%, 94 to 97 wt%, 95 to 96 wt%) of dicyclopentadiene and 0 to 10 wt% (e.g., 0.1 to 9 wt%, 1 to 8 wt%, 2 to 7 wt%, 3 to 6 wt%, 4 to 5 wt%) of tricyclopentadiene and / or 5-ethylidene-2-norbornene, based on the total weight of the cyclic olefin composition.

[0272] E12. The at least one metal carbene olefin meth-decomposition catalyst is a group 8 transition metal complex having the structure of formula (I), [ka] During the ceremony, M is a group 8 transition metal, L 1 , L 2 , and L 3 It is a neutral electron donor ligand, n is either 0 or 1, and therefore L 3 It may or may not exist. m is 0, 1, or 2. k is either 0 or 1. X 1 and X 2 It is an anionic ligand, R 1 and R 2 These are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-containing hydrocarbyl. X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 Any two or more of these can combine to form one or more cyclic groups, and furthermore, X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 A ROMP composition according to any one of items E1 to E11, wherein one or more of the above may be bound to a carrier.

[0273] E13. The at least one metal carbene olefin meth-decomposition catalyst is a group 8 transition metal complex having the structure of formula (I), M is ruthenium, n is O, m is O, k is 1, L 1 and L 2This 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 L is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)-2-imidazole-2-ylidene, and 1,3-bis(2,6-di-isopropylphenyl)-2-imidazole-2-ylidene. 2 This 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 This is an N-heterocyclic carbene independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)-2-imidazole-2-ylidene, and 1,3-bis(2,6-di-isopropylphenyl)-2-imidazole-2-ylidene. X 1 and X 2 It is a chloride, R 1 is hydrogen, and R 2 is phenyl or -CH=C(CH3)2, or R 1 and R2 The ROMP composition according to E12, wherein the ROMP composition integrates to form an indenylidene moiety.

[0274] E14. The at least one metal carbene olefin meth-decomposition catalyst is a group 8 transition metal complex having the structure of formula (VII), [ka] During the ceremony, M is a group 8 transition metal, X 1 and X 2 is an anion 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 8These are, independently, hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, s A is selected from the group consisting of phosphates, carbamates, silanes, siloxanes, phosphines, phosphates, borates, or -A-Fn, where A is a divalent hydrocarbon group selected from alkylenes and arylalkylenes, the alkyl portion of the alkylene and arylalkylene can be linear or branched, saturated or unsaturated, cyclic or acyclic, substituted or unsubstituted, the aryl portion of the arylalkylene may be substituted or unsubstituted, heteroatoms and / or functional groups may be present in either the aryl portion or the alkyl portion of the alkylene and arylalkylene, Fn is a functional group, and R 5 , R 6 , R 7 , and R 8 Any combination of these can combine to form one or more cyclic groups. n is 1 or 2, and therefore n is 1 for the divalent heteroatom O or S, and n is 2 for the trivalent heteroatom N or P. Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, and functionalized aryl, and the functional group may be independently one or more or less than or equal to: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl, and trimethylsilyl. X 1 , X 2 , L 1 V, Z, R 5 , R 6 , R 7 , and R 8 A ROMP composition according to any one of items E1 to E11, wherein any combination (singular or plural) of the following can be bound to a carrier.

[0275] E15. The ROMP composition according to any one of E1 to E14, wherein there exists at least one adhesion promoter composition, which is selected from the group consisting of an acid-functionalized polyolefin, a compound comprising at least two isocyanate groups, a composition comprising at least one compound comprising at least two isocyanate groups and at least one compound comprising a heteroatom-containing functional group having a metathesis-active olefin, at least one polyoctenomer, and mixtures thereof.

[0276] E16. The ROMP composition according to E15, wherein the acid-functionalized polyolefin is a polyolefin containing maleic anhydride.

[0277] E17. The ROMP composition according to E16, wherein the polyolefin comprises polybutadiene.

[0278] E18. The ROMP composition according to any one of E1 to E17, wherein the ROMP composition does not contain a compound comprising at least two isocyanate groups.

[0279] E19. The ROMP composition according to any one of E1 to E17, wherein the at least one compound comprising at least two isocyanate groups is a diisocyanate, a triisocyanate, or a polyisocyanate.

[0280] E20. The ROMP composition according to E19, wherein the at least one compound comprising at least two isocyanate groups is selected from the group consisting of toluene diisocyanate; tetramethylxylene diisocyanate (TMXDI); methylenediphenyl diisocyanate (MDI); a mixture of three MDI isomers 2,2′-MDI, 2,4′-MDI, and 4,4′-MDI; liquid MDI; solid MDI; hexamethylene diisocyanate trimer (HDIt); hexamethylene diisocyanate (HDI); isophorone diisocyanate (IPDI); 4,4′-methylenebis(cyclohexyl isocyanate) (H12MDI); polymer MDI (PM200); MDI prepolymer; liquid carbodiimide-modified 4,4′-MDI; and mixtures thereof.

[0281] E21. The ROMP composition according to E20, wherein the at least one compound comprising at least two isocyanate groups is 4,4′-methylenediphenyl diisocyanate (MDI).

[0282] E22. The ROMP composition according to E15, comprising at least one compound containing at least two isocyanate groups and at least one compound containing a heteroatom-containing functional group having a metathesis-active olefin, wherein the composition is selected from the group consisting of liquid MDI and 2-hydroxyethyl bicyclo[2.2.1]hept-2-ene carboxylate (HENB), liquid MDI and 2-hydroxyethyl acrylate (HEA), liquid MDI and oleyl alcohol, and liquid MDI and 9-decen-1-ol.

[0283] E23. The ROMP composition according to E22, comprising at least one compound containing at least two isocyanate groups and at least one compound containing a heteroatom-containing functional group having a metathesis-active olefin, selected from liquid MDI and HENB.

[0284] E24. A ROMP composition according to E22 or E23, wherein at least one compound comprising at least two isocyanate groups is pre-reacted with at least one compound comprising a heteroatom-containing functional group having a metathesis-active olefin.

[0285] E25. The ROMP composition according to E24, wherein the liquid MDI and the HENB are pre-reacted to form a HENB-MDI mixture.

[0286] E26. The ROMP composition according to E25, wherein the pre-reacted mixture of HENB-MDI further comprises an excess of unreacted MDI.

[0287] E27. The ROMP composition according to any one of the E1 to E26, wherein the at least one adhesion promoter composition is present in an amount ranging from 0.05 to 15 wt% (e.g., 0.1 to 13 wt%, 0.5 to 10 wt%, 1 to 8 wt%, 2 to 6 wt%, 3 to 5 wt%) based on the total weight of the ROMP composition.

[0288] E28. The at least one adhesion promoter composition comprises, essentially consists of, or consists of, the composition comprising at least one compound comprising at least two isocyanate groups, at least one compound comprising a heteroatom-containing functional group having a metathesis-active olefin, and the at least one acid-functionalized polyolefin. The at least one acid-functionalized polyolefin is present in an amount ranging from 0.025 to 10 wt% (e.g., 0.5 to 9 wt%, 1 to 8 wt%, 2 to 7 wt%, 3 to 6 wt%, 4 to 5 wt%) based on the total weight of the ROMP composition. The ROMP composition according to E13, comprising at least one compound containing at least two isocyanate groups and at least one compound containing a heteroatom-containing functional group having a metathesis-active olefin, present in an amount ranging from 0.025 to 5 wt% (e.g., 0.1 to 4 wt%, 0.5 to 3 wt%, 1 to 2 wt%) based on the total weight of the ROMP composition.

[0289] E29. The composition comprising at least one compound containing at least two isocyanate groups and at least one compound containing a heteroatom-containing functional group having a metathesis-active olefin is a preliminary reaction mixture of liquid MDI and 2-hydroxyethyl bicyclo[2.2.1]hept-2-ene carboxylate (HENB), The ROMP composition according to E26, wherein the at least one acid-functionalized polyolefin is a polybutadiene containing maleic anhydride.

[0290] E30. The ROMP composition according to E29, wherein the preliminary reaction mixture of liquid MDI and HENB further comprises an excess of unreacted MDI.

[0291] E31. The at least one adhesion promoter composition comprises, essentially consists of, or consists of at least one acid-functionalized polyolefin and at least one polyoctenomer. The at least one acid-functionalized polyolefin is present in an amount ranging from 0.025 to 10 wt% (e.g., 0.5 to 9 wt%, 1 to 8 wt%, 2 to 7 wt%, 3 to 6 wt%, 4 to 5 wt%) based on the total weight of the ROMP composition. The ROMP composition according to any one of claims E1 to E14, wherein the at least one polyoctenomer is present in an amount ranging from 0.025 to 5 wt% (e.g., 0.1 to 4 wt%, 0.5 to 3 wt%, 1 to 2 wt%) based on the total weight of the ROMP composition.

[0292] E32. The ROMP composition according to any one of E1 to E31, wherein the at least one plasticizer compound is selected from the group consisting of polybutene oil, polyalphaolefin oil, hydrocarbon resin, and mixtures thereof.

[0293] E33. The ROMP composition according to E32, wherein the at least one plasticizer compound is polybutene oil.

[0294] E34. The ROMP composition according to E32 or E33, wherein the at least one plasticizer compound is present in an amount ranging from 1 to 40 wt% (e.g., 5 to 35 wt%, 10 to 30 wt%, 25 to 30 wt%) based on the total weight of the ROMP composition.

[0295] E35. The ROMP composition according to any one of E1 to E34, wherein the at least one rubber reinforcing compound is selected from the group consisting of poly(styrene-ethylene-butylene-styrene), ethylene-propylene copolymer, ethylene-propylene dienterpolymer, and mixtures thereof.

[0296] E36. The ROMP composition according to E35, wherein the at least one rubber reinforcing compound is poly(styrene-ethylene-butylene-styrene).

[0297] E37. The ROMP composition according to E35 or E36, wherein the at least one rubber reinforcing compound is present in an amount ranging from 0.01 to 30 wt% (e.g., 0.1 to 25 wt%, 1 to 20 wt%, 5 to 15 wt%, 7 to 12 wt%) based on the total weight of the ROMP composition.

[0298] E38. A ROMP composition according to any one of the E1 to E37, further comprising, essentially consisting of, or comprising at least one additive.

[0299] E39. The ROMP composition according to E38, wherein the at least one additive is selected from the group consisting of gel modifiers, hardness modifiers, antioxidants, ozone degradation inhibitors, stabilizers, crosslinking agents, fillers, binders, coupling agents, thixotropes, wetting agents, biocides, additional plasticizers, chain stoppers, pigments, flame retardants, dyes, fibers, and reinforcing materials.

[0300] E40. The ROMP composition according to E38 or E39, wherein the at least one additive is present in the ROMP composition in an amount ranging from 0.001 to 85 wt% (e.g., 0.01 to 75 wt%, 0.1 to 65 wt%, 1 to 55 wt%, 5 to 45 wt%, 10 to 35 wt%, 15 to 25 wt%) based on the total weight of the ROMP composition.

[0301] E41. A ROMP polymer comprising the reaction product of a ROMP composition described in any one of E1 to E40, wherein the ROMP composition is exposed to conditions effective for polymerization of the ROMP composition.

[0302] A ROMP polymer composite comprising the reaction product of a ROMP composition according to any one of E42.E1 to E40, wherein the ROMP composition is exposed to conditions effective for polymerization of the ROMP composition.

[0303] An insulating material comprising any one of E43.E1 to E40, the ROMP polymer described in E41, or the ROMP polymer composite described in E42.

[0304] E44. The ROMP polymer, the polymer composite, and the thermal insulation material according to E41, E42, or E43, wherein the ROMP polymer, the polymer composite, and the thermal insulation material independently have a thermal conductivity of less than 0.180 W / m·K at an average temperature of 25°C (e.g., less than 0.170, less than 0.165, less than 0.160).

[0305] E45. The ROMP polymer, the polymer composite, and the thermal insulation material are independent of each other and have a peel adhesion strength to fusion epoxy (FBE) of more than 2 MPa (e.g., more than 3, more than 4, more than 5), as described in E41, the ROMP polymer composite, or the thermal insulation material described in E43.

[0306] E46. The ROMP polymer, ROMP polymer composite, or thermal insulation material according to E45, wherein the FBE is PipeClad HOT 150.

[0307] E47. A method for coating, containing, or insulating at least a portion of at least one surface of an object with the ROMP polymer described in E41 or the ROMP polymer composite described in E42, The ROMP composition is formed by combining the cyclic olefin composition, the catalyst composition, the at least one adhesion promoter, the at least one plasticizer compound, and the rubber reinforcing compound. The ROMP composition is brought into contact with at least a portion of at least one surface of the object, The ROMP composition is subjected to conditions effective for polymerizing the ROMP composition to form a ROMP polymer or a ROMP polymer composite. The method, including the method described above.

[0308] E48. A method of coating, housing, or insulating at least a portion of at least one surface of an object with the insulating material described in E43, The ROMP composition is formed by combining the cyclic olefin composition, the catalyst composition, the at least one adhesion promoter, the at least one plasticizer compound, and the rubber reinforcing compound. The ROMP composition is brought into contact with at least a portion of at least one surface of the object, The ROMP composition is subjected to conditions effective for polymerizing the ROMP composition to form a ROMP polymer or a ROMP polymer composite. Includes, The method wherein the ROMP polymer or the ROMP polymer composite is the thermal insulation material.

[0309] E49. The method according to E47 or E48, wherein the object is selected from the group consisting of pipes, pipelines, pipe fittings, hoses, hose fittings, tanks, containers, drums, manifolds, risers, field fittings, underwater Christmas trees, jumpers, spool pieces, pipeline ends, pipeline end manifolds, robot parts, robot devices, robot vehicles, wellhead equipment, underwater doghouses, and combinations thereof.

[0310] E50. A product comprising an object, wherein at least a portion of at least one surface of the object is coated or insulated with the ROMP polymer described in E41, the ROMP polymer composite described in E42, or the insulating material described in E43.

[0311] E51. The product described in E50, wherein the object is selected from the group consisting of pipes, pipelines, pipe fittings, hoses, hose fittings, tanks, containers, drums, manifolds, risers, field fittings, underwater Christmas trees, jumpers, spool pieces, pipeline ends, pipeline end manifolds, robot parts, robot devices, robot vehicles, wellhead equipment, underwater doghouses, and combinations thereof.

[0312] experiment In the following examples, efforts have been made to ensure accuracy for the values ​​used (e.g., quantity, temperature, etc.), but some experimental error and deviation should be considered. Unless otherwise specified, temperature is in degrees Celsius (°C), pressure is atmospheric pressure or near atmospheric pressure, and viscosity is in centipoise (cP). Additives added to the ROMP composition are reported as ppm, defined as the gram weight of the additive per 1 million grams of the cyclic olefin composition, or as phr, defined as the gram weight of the additive per 100 grams of the cyclic olefin composition.

[0313] The following examples are provided not to limit the present invention as described herein, but as representative examples of the compositions of the present invention, methods of use thereof, and articles produced from such compositions and methods. [Examples]

[0314] Materials and methods Unless otherwise specified, all glassware was dried in an oven, and all reactions were carried out under ambient conditions. Unless otherwise specified, all solvents and reagents were purchased from commercial suppliers and used as received.

[0315] The cyclic olefin composition "DCPD" was obtained from Cymetech Corporation (ULTRENE® 99) and is typically >99% dicyclopentadiene (DCPD). The cyclic olefin composition "DCPD-6T" was obtained from Cymetech Corporation (ULTRENE® 99-6) and is typically over 91% DCPD and 5-9% tricyclopentadiene (TCPD). Cyclic olefin compositions with a high TCPD content were manufactured as outlined in U.S. Patent No. 4,899,005. The cyclic olefin composition "DCPD-6ENB" was prepared by blending ULTRENE® 99 and 5-ethylidene-2-norbornene (ENB) until a final concentration of 6 wt% ENB was obtained. ENB was obtained from Nippon Chemical Texas Inc. Indopol H100 and Indopol H300 were obtained from Ineos. Vistalon 501, Vistalon 3702, and Spectrasyn 10 were obtained from ExxonMobil. Kraton 1650 was obtained from Kraton. Vestenamer 8012, Vestenamer CS10 (powder), Polyvest EP MA100, and Polyvest STE-60 were obtained from Evonik. Ricobond 1731 was obtained from Cray Valley. HENB-MDI adhesion promoter was prepared as schematically described in US9,527,982B2. Mondur MLQ was obtained from Covestro. Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was obtained from BASF (Irganox® 1076) or M Chemical (GUARD DOG® 1076). Vinyl norbornene was obtained from JX Nippon. Triphenylphosphine was used as received from PMC Organometallix. Black pigment (PC-80002) and burnt orange (PC-60109) were obtained from American Colors. Crystal Plus 500 FG mineral oil was obtained from STE Oil Company, Inc.CAB-O-SIL(registered trademark) TS610 fumed silica was obtained from Cabot Corporation.

[0316] The metal carbene olefin metathesis catalysts were purchased from Umicore and include [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(tricyclohexylphosphine)ruthenium(II) (Umicore Grubbs catalyst M207) and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-phenyl-1H-indene-1-ylidene)(triphenylphosphine)ruthenium(II) (Umicore Grubbs catalyst M200). Catalyst composition (A) was prepared by suspending Umicore Grubbs Catalyst M207 (0.7 wt%) in Crystal Plus 500FG containing 2 wt% CAB-O-SIL® TS610. Catalyst composition (B) was prepared by suspending Umicore Grubbs Catalyst M200 (0.75 wt%) in Crystal Plus 500FG containing 2 wt percent CAB-O-SIL® TS610.

[0317] Basic Procedure

[0318] The cyclic olefin composition was added to a mixing container of appropriate size, and then each additive was added individually and mixed into the cyclic olefin composition until the mixture was completely homogeneous. After obtaining the finished formulation, 100 to 1000 grams of resin was added to the container and heated to a temperature of 25 to 40°C. The catalyst composition was then added while stirring, and the mixture was cured in an oven or oil bath at the desired temperature of 40 to 50°C. If a prism was required to obtain a test sample for thermomechanical analysis, the catalyst mixture was added to a 2.5-inch x 2.5-inch x 12-inch aluminum rectangular prism mold that had been pre-equilibriumized at 50°C. The mold was then cured in an oven set to 50°C.

[0319] Thermal conductivity was determined by ASTM C518 at an average temperature of 25°C (the boundary between 30°C and 20°C) using Vespel or polycarbonate standards. Thermal conductivity values ​​were obtained from a single sample replica or the average of two sample replicas. Tensile tests were performed on 2 to 6 specimens according to ISO 527-2 Type 1B, and the reported values ​​were obtained from a single sample or the average of 2 to 5 repeated samples. Impact strength was measured on 3 to 5 specimens adjusted for at least 40 hours at 23±2°C and 50%±10% relative humidity according to ASTM D256, after which the specimens were transferred to a freezer kept at -18°C and held for at least 24 hours. Impact strength values ​​were obtained from a single sample replica or the average of 2 to 4 sample replicas.

[0320] Ingredients [Table 1]

[0321] Formulation (Phr value of cyclic olefin) [Table 2-1] [Table 2-2] [Table 2-3] [Table 2-4] [Table 2-5] [Table 2-6] [Table 2-7] [Table 2-8] [Table 2-9] [Table 2-10] [Table 2-11] [Table 2-12] [Table 2-13] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] [Table 8]

[0322] While the present invention has been described in conjunction with its specific embodiments, it should be understood that the above description and subsequent embodiments are intended to illustrate, and not limit, the scope of the invention. Other aspects, advantages, and modifications within the scope of the invention will be apparent to those skilled in the art.

Claims

1. a) A cyclic olefin composition comprising at least one polyunsaturated cyclic olefin, b) A catalyst composition comprising at least one metal carbene olefin metathesis catalyst, c) Optionally, at least one adhesion promoter and d) At least one plasticizer compound, e) at least one rubber-reinforced compound, Includes, The cyclic olefin composition does not contain, or substantially does not contain, monounsaturated cyclic olefins. The at least one polyunsaturated cyclic olefin may be substituted or unsubstituted. The monounsaturated cyclic olefin is selected from 5-octyl-2-norbornene (ONB) in the ROMp composition.

2. The ROM composition according to claim 1, wherein the monounsaturated cyclic olefin is selected from at least one monounsaturated substituted norbornene.

3. The ROM composition according to claim 1, wherein the monounsaturated cyclic olefin is selected from any monounsaturated cyclic olefin.

4. The ROMP composition according to any one of claims 1 to 3, wherein the cyclic olefin composition comprises 90 to 100 wt% of the at least one polyunsaturated cyclic olefin and 10 wt% or less of the monounsaturated cyclic olefin, based on the total weight of the cyclic olefin composition.

5. The ROM composition according to claim 4, wherein the ROM composition does not contain or substantially does not contain the monounsaturated cyclic olefin.

6. The ROMP composition according to claim 4, wherein the cyclic olefin composition does not contain the monounsaturated cyclic olefin.

7. The ROM composition according to claim 4, wherein the ROM composition does not contain the monounsaturated cyclic olefin.

8. The ROM composition according to claim 5, wherein the at least one polyunsaturated cyclic olefin is selected from the group consisting of dicyclopentadiene, tricyclopentadiene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, 5-butenyl-2-norbornene, and mixtures thereof.

9. The ROMP composition according to claim 8, wherein the at least one polyunsaturated cyclic olefin is selected from the group consisting of dicyclopentadiene, tricyclopentadiene, 5-ethylidene-2-norbornene, and mixtures thereof.

10. The ROMP composition according to claim 9, wherein the at least one polyunsaturated cyclic olefin is selected from the group consisting of dicyclopentadiene, tricyclopentadiene, and mixtures thereof.

11. The ROMP composition according to claim 10, wherein the cyclic olefin composition comprises 90 to 100 wt% of dicyclopentadiene and 0 to 10 wt% of tricyclopentadiene and / or 5-ethylidene-2-norbornene, based on the total weight of the cyclic olefin composition.

12. The at least one metal carbene olefin meth-decomposition catalyst is a group 8 transition metal complex having the structure of formula (I), 【Chemistry 1】 During the ceremony, M is a group 8 transition metal, L １ , L ２ , and L ３ It is a neutral electron donor ligand, n is either 0 or 1, and therefore L ３ It may or may not exist. m is 0, 1, or 2. k is either 0 or 1, X １ and X ２ It is an anionic ligand, R １ and R ２ These are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, and heteroatom-containing hydrocarbyl. X １ 、 X ２ 、 L １ 、 L ２ 、 L ３ 、 R １ 、 and R ２ Any two or more of them may combine to form one or more cyclic groups. Furthermore, any one or more of １ 、 X ２ 、 L １ 、 L ２ 、 L ３ 、 R １ 、 and R[[ID=Z7]] ２ may be bonded to a carrier. The ROMP composition according to claim 5.

13. The at least one metal carbene olefin meth-decomposition catalyst is a group 8 transition metal complex having the structure of formula (I), M is ruthenium, n is O, m is O, k is 1, L １ and L ２ is tri-n-butylphosphine (Pn-Bu ３ ), tricyclopentylphosphine (PCp ３ ), tricyclohexylphosphine (PCy ３ ), triisopropylphosphine (Pi-Pr ３ ), triphenylphosphine (PPh ３ ), methyldiphenylphosphine (PMePh ２ ), dimethylphenylphosphine (PMe ２ Ph), and diethylphenylphosphine (PET ２ A trisubstituted phosphine independently selected from the group consisting of Ph), or L １ L is an N-heterocyclic carbene selected from 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)-2-imidazole-2-ylidene, and 1,3-bis(2,6-di-isopropylphenyl)-2-imidazole-2-ylidene. ２ is tri-n-butylphosphine (Pn-Bu ３ ), tricyclopentylphosphine (PCp ３ ), tricyclohexylphosphine (PCy ３ ), triisopropylphosphine (P-i-Pr ３ ), triphenylphosphine (PPh ３ ), methyldiphenylphosphine (PMePh ２ ), dimethylphenylphosphine (PMe ２ Ph), and diethylphenylphosphine (PET ２ A trisubstituted phosphine selected from the group consisting of Ph), or L １ and L ２ This is an N-heterocyclic carbene independently selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)-2-imidazole-2-ylidene, and 1,3-bis(2,6-di-isopropylphenyl)-2-imidazole-2-ylidene. X １ and X ２ It is a chloride, R １ is hydrogen, and R ２ is phenyl or -CH=C(CH ３ ) ２ is, or R １ and R ２ The ROMP composition according to claim 12, wherein the molecules are integrated to form an indenylidene moiety.

14. The at least one metal carbene olefin meth-decomposition catalyst is a group 8 transition metal complex having the structure of formula (VII), 【Chemistry 2】 During the ceremony, M is a group 8 transition metal, X １ and X ２ is an anion 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 These are, independently, hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, s A is selected from the group consisting of phosphates, carbamates, silanes, siloxanes, phosphines, phosphates, borates, or -A-Fn, where A is a divalent hydrocarbon group selected from alkylenes and arylalkylenes, the alkyl portion of the alkylene and arylalkylene can be linear or branched, saturated or unsaturated, cyclic or acyclic, substituted or unsubstituted, the aryl portion of the arylalkylene may be substituted or unsubstituted, heteroatoms and / or functional groups may be present in either the aryl portion or the alkyl portion of the alkylene and arylalkylene, Fn is a functional group, and R ５ , R ６ , R ７ , and R ８ Any combination of these can combine to form one or more cyclic groups. n is 1 or 2, and therefore n is 1 for the divalent heteroatom O or S, and n is 2 for the trivalent heteroatom N or P. Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, and functionalized aryl, and the functional group may be independently one or more or less than the following: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl, and trimethylsilyl. X １ , X ２ , L １ V, Z, R ５ , R ６ , R ７ , and R ８ The ROMP composition according to claim 5, wherein any combination (singular or plural) of the above can be bound to a carrier.

15. The ROM composition according to claim 5, wherein there exists at least one adhesion promoter composition, which is selected from the group consisting of an acid-functionalized polyolefin, a compound comprising at least two isocyanate groups, a composition comprising at least one compound comprising at least two isocyanate groups and at least one compound comprising a heteroatom-containing functional group having a metathesis-active olefin, at least one polyoctenomer, and mixtures thereof.

16. The ROMP composition according to claim 15, wherein the acid-functionalized polyolefin is a polyolefin containing maleic anhydride.

17. The ROMP composition according to claim 16, wherein the polyolefin comprises polybutadiene.

18. The ROM composition according to claim 15, wherein the ROM composition does not contain a compound comprising at least two isocyanate groups.

19. The ROM composition according to claim 15, wherein the at least one compound comprising at least two isocyanate groups is a diisocyanate, a triisocyanate, or a polyisocyanate.

20. The ROM composition according to claim 19, wherein the at least one compound comprising at least two isocyanate groups is selected from the group consisting of toluene diisocyanate; tetramethylxylene diisocyanate (TMXDI); methylenediphenyl diisocyanate (MDI); a mixture of three MDI isomers 2,2'-MDI, 2,4'-MDI, and 4,4'-MDI; liquid MDI; solid MDI; hexamethylene diisocyanate trimer (HDIt); hexamethylene diisocyanate (HDI); isophorone diisocyanate (IPDI); 4,4'-methylenebis(cyclohexyl isocyanate) (H12MDI); polymer MDI (PM200); MDI prepolymer; liquid carbodiimide-modified 4,4'-MDI; and mixtures thereof.

21. The ROM composition according to claim 20, wherein the at least one compound comprising at least two isocyanate groups is 4,4'-methylenediphenyl diisocyanate (MDI).

22. The ROM composition according to claim 15, comprising at least one compound containing at least two isocyanate groups and at least one compound containing a heteroatom-containing functional group having a metathesis-active olefin, wherein the composition is selected from the group consisting of liquid MDI and 2-hydroxyethyl bicyclo[2.2.1]hept-2-ene carboxylate (HENB), liquid MDI and 2-hydroxyethyl acrylate (HEA), liquid MDI and oleyl alcohol, and liquid MDI and 9-decen-1-ol.

23. The ROM composition according to claim 22, comprising at least one compound containing at least two isocyanate groups and at least one compound containing a heteroatom-containing functional group having a metathesis-active olefin, the composition being selected from liquid MDI and HENB.

24. The ROM composition according to claim 22, wherein at least one compound containing at least two isocyanate groups and at least one compound containing a heteroatom-containing functional group having a metathesis-active olefin are subjected to a preliminary reaction.

25. The ROMP composition according to claim 24, wherein the liquid MDI and the HENB are pre-reacted to form a HENB-MDI mixture.

26. The ROMP composition according to claim 25, wherein the pre-reacted mixture of HENB-MDI further comprises an excess of unreacted MDI.

27. The ROM composition according to claim 5, wherein the at least one adhesion promoter composition is present in an amount ranging from 0.05 to 15 wt% based on the total weight of the ROM composition.

28. There exists the at least one adhesion promoter composition, and the at least one adhesion promoter composition comprises the composition comprising at least one compound comprising at least two isocyanate groups, at least one compound comprising a heteroatom-containing functional group having a metathesis-active olefin, and the at least one acid-functionalized polyolefin, The at least one acid-functionalized polyolefin is present in an amount ranging from 0.025 to 10 wt% based on the total weight of the ROM composition. The ROM composition according to claim 5, wherein the composition comprises at least one compound containing at least two isocyanate groups and at least one compound containing a heteroatom-containing functional group having a metathesis-active olefin, and is present in an amount ranging from 0.025 to 5 wt% based on the total weight of the ROM composition.

29. The composition comprising at least one compound containing at least two isocyanate groups and at least one compound containing a heteroatom-containing functional group having a metathesis-active olefin is a preliminary reaction mixture of liquid MDI and 2-hydroxyethyl bicyclo[2.2.1]hept-2-ene carboxylate (HENB), The ROMP composition according to claim 28, wherein the at least one acid-functionalized polyolefin is a polybutadiene containing maleic anhydride.

30. The ROMP composition according to claim 29, wherein the preliminary reaction mixture of liquid MDI and HENB further comprises an excess of unreacted MDI.

31. The present invention comprises the at least one adhesion promoter composition, the at least one acid-functionalized polyolefin, and the at least one polyoctenomer. The at least one acid-functionalized polyolefin is present in an amount ranging from 0.025 to 10 wt% based on the total weight of the ROM composition. The ROM composition according to claim 5, wherein the at least one polyoctenomer is present in an amount ranging from 0.025 to 5 wt% based on the total weight of the ROM composition.

32. The ROM composition according to claim 5, wherein the at least one plasticizer compound is selected from the group consisting of polybutene oil, polyalphaolefin oil, hydrocarbon resin, and mixtures thereof.

33. The ROM composition according to claim 32, wherein the at least one plasticizer compound is polybutene oil.

34. The ROM composition according to claim 32, wherein the at least one plasticizer compound is present in an amount ranging from 1 to 40 wt% based on the total weight of the ROM composition.

35. The ROM composition according to claim 5, wherein the at least one rubber reinforcing compound is selected from the group consisting of poly(styrene-ethylene-butylene-styrene), ethylene-propylene copolymer, ethylene-propylene dienterpolymer, and mixtures thereof.

36. The ROMP composition according to claim 35, wherein the at least one rubber reinforcing compound is poly(styrene-ethylene-butylene-styrene).

37. The ROM composition according to claim 35, wherein the at least one rubber reinforcing compound is present in an amount ranging from 0.01 to 30 wt% based on the total weight of the ROM composition.

38. The ROMP composition according to claim 5, further comprising at least one additive.

39. The ROM composition according to claim 38, wherein the at least one additive is selected from the group consisting of gel modifiers, hardness modifiers, antioxidants, ozone degradation inhibitors, stabilizers, crosslinking agents, fillers, binders, coupling agents, thixotropes, wetting agents, biocides, additional plasticizers, chain stoppers, pigments, flame retardants, dyes, fibers, and reinforcing materials.

40. The ROM composition according to claim 38, wherein the at least one additive is present in the ROM composition in an amount ranging from 0.001 to 85 wt% based on the total weight of the ROM composition.

41. A ROM polymer comprising the reaction product of the ROM composition according to claim 5, wherein the ROM composition is exposed to conditions effective for polymerizing the ROM composition.

42. A ROM polymer composite comprising the reaction product of the ROM composition according to claim 5, wherein the ROM composition is exposed to conditions effective for polymerizing the ROM composition.

43. A thermal insulation material comprising the ROM composition described in claim 5.

44. The ROMP polymer according to claim 41, wherein the ROMP polymer has a thermal conductivity of less than 0.180 W / m·K at an average temperature of 25°C.

45. The ROMMP polymer according to claim 41, wherein the ROMMP polymer has a peel adhesion strength to fused epoxy (FBE) of more than 2 MPa.

46. The ROMP polymer according to claim 45, wherein the FBE is PipeClad HOT 150.

47. A method for coating, housing, or insulating at least a portion of at least one surface of an object with the ROMP polymer described in claim 41, The ROM composition is formed by combining the cyclic olefin composition, the catalyst composition, the at least one adhesion promoter, the at least one plasticizer compound, and the rubber reinforcing compound. The ROM composition is brought into contact with at least a portion of at least one surface of the object, The ROM composition is subjected to conditions effective for polymerizing the ROM composition to form a ROM polymer or a ROM polymer composite. The method, including the method described above.

48. A method for coating, housing, or insulating at least a portion of at least one surface of an object with the insulating material described in claim 43, The ROM composition is formed by combining the cyclic olefin composition, the catalyst composition, the at least one adhesion promoter, the at least one plasticizer compound, and the rubber reinforcing compound. The ROM composition is brought into contact with at least a portion of at least one surface of the object, The ROM composition is subjected to conditions effective for polymerizing the ROM composition to form a ROM polymer or a ROM polymer composite. Includes, The method wherein the ROM polymer or the ROM polymer composite is the thermal insulation material.

49. The method according to claim 47, wherein the object is selected from the group consisting of pipes, pipelines, pipe fittings, hoses, hose fittings, tanks, containers, drums, manifolds, risers, field fittings, underwater Christmas trees, jumpers, spool pieces, pipeline ends, pipeline end manifolds, robot parts, robot devices, robot vehicles, wellhead equipment, underwater doghouses, and combinations thereof.

50. The method according to claim 48, wherein the object is selected from the group consisting of pipes, pipelines, pipe fittings, hoses, hose fittings, tanks, containers, drums, manifolds, risers, field fittings, underwater Christmas trees, jumpers, spool pieces, pipeline ends, pipeline end manifolds, robot parts, robot devices, robot vehicles, wellhead equipment, underwater doghouses, and combinations thereof.

51. A product comprising an object, wherein at least a portion of at least one surface of the object is coated or insulated with the ROM polymer described in claim 41.

52. The product according to claim 51, wherein the object is selected from the group consisting of pipes, pipelines, pipe fittings, hoses, hose fittings, tanks, containers, drums, manifolds, risers, field fittings, underwater Christmas trees, jumpers, spool pieces, pipeline ends, pipeline end manifolds, robot parts, robot devices, robot vehicles, wellhead equipment, underwater doghouses, and combinations thereof.

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