Cycloolefin metathesis composition and polymerization method thereof

Abstract

The invention relates to a cycloolefin metathesis composition and a polymerization method thereof. The cycloolefin metathesis composition comprises at least one cyclic olefin; a cyclic olefin metathesis catalyst in a molar ratio to the cyclic olefin of less than 1 / 100,000; a peroxide inhibitor in a mass ratio of 0.1 to 10 phr with respect to the cyclic olefin; a peroxide modifier in a mass ratio of 5 to 1000 ppm with respect to the cyclic olefin; and an auxiliary catalyst [1, 3-bis (2, 4, 6-trimethylphenyl)-2-imidazolidine subunit] (phenyl methylene) bipyridine ruthenium dichloride, the content of which is 10%-20% of the cyclic olefin metathesis catalyst. The cyclic olefin metathesis catalyst and the peroxide inhibitor are combined and used according to a certain ratio, so that the loading capacity of the catalyst is reduced, the cost of the cyclic olefin metathesis composition is reduced, and the mechanical property of the cured cyclic olefin metathesis composition is improved, so that the cyclic olefin metathesis composition is better suitable for wide chemical application.

Description

Technical Field

[0001] The present invention relates to cycloolefin resins, and more particularly to a cycloolefin metathesis composition and a polymerization method thereof. Background Art

[0002] Dicyclopentadiene (C 10 H 12 , DCPD) is an important organic chemical raw material, mainly purified from the C5 fraction or C9 fraction in the process of petroleum cracking. DCPD is an unsaturated compound containing two double bonds and several ring structures. It can undergo polymerization under certain conditions. It is mainly used in industry for unsaturated polyesters, cycloolefin copolymers, polydicyclopentadiene, etc., and has important application prospects in the fields of chemical industry and materials.

[0003] Polydicyclopentadiene (PDCPD) is a high-performance thermosetting polymer derived from DCPD through ring-opening metathesis polymerization (ROMP). PDCPD has low density, extremely high impact strength, good toughness, acid and alkali resistance, and aging resistance, making it widely used in many industrial fields such as heavy equipment, automobiles, and construction.

[0004] PDCPD curing usually uses two types of catalytic systems: ruthenium or tungsten-molybdenum. Both types of catalysts complete curing through the olefin metathesis mechanism. Among them, the tungsten-molybdenum catalyst system is more sensitive to water and oxygen, and requires a higher curing temperature and a longer reaction time, which has more stringent requirements on the production process. Ruthenium catalysts, especially Grubbs catalysts, have good compatibility with water and oxygen and can complete curing under mild conditions. Compared with tungsten-molybdenum catalysts, PDCPD prepared by ruthenium catalysts has better mechanical properties and surface quality.

[0005] The high price of ruthenium-based catalysts limits the industrial application prospects of this type of formulation. In the existing DCPD curing process, there are problems such as high peroxide content, large catalyst dosage and high curing temperature. These problems lead to high energy consumption and high raw material costs in the curing process, and demanding reaction conditions, which are not conducive to widespread application in industrial production. In addition, high peroxide content may also trigger side reactions and affect the performance stability of the final product. Therefore, there is an urgent need for an improved solution that can reduce the impurity content, reduce the amount of catalyst or use a mild curing temperature to improve the process economy, environmental protection and product quality. At the same time, adjusting the operable time of DCPD curing through additives without affecting the performance of the cured product can provide DCPD with a variety of process options and application directions.

[0006] Cross-references to related literature: Chatterjee et al., J. Am. Chem. Soc. 2003, 11360-11370; Trnka et al., J. Am. Chem. Soc. 2003, 125, 2546-2558; Mukherjee et al., Macromolecules 2015, 48, 6791-6800; Chem. Eur. J. 2014, 20, 14120-14125; International patent application publication WO2007075427 A1; International patent application publication WO2002079126 A1; U.S. patent application publication US 8519069 A2; The above-mentioned related documents are incorporated herein by reference in their entirety. Summary of the invention

[0007] The technical problem to be solved by the present application is to provide a cycloolefin metathesis composition with low catalyst dosage, strong oxidation resistance and controllable curing time and a polymerization method thereof.

[0008] In order to solve the above technical problems, according to one aspect of the present application, a cyclic olefin metathesis composition is provided, comprising: at least one cyclic olefin; a cyclic olefin metathesis catalyst, the molar ratio of which relative to the cyclic olefin is less than 1 / 100000; and a peroxide inhibitor, the mass ratio of which relative to the cyclic olefin is 0.1-10 phr; a peroxide modifier, the mass ratio of which relative to the cyclic olefin is 5-1000 ppm; and an auxiliary catalyst [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl](phenylmethylene)bipyridinedichloride ruthenium, the content of which is 10%-20% of the cyclic olefin metathesis catalyst.

[0009] According to an embodiment of the present application, at least one cyclic olefin can be selected from cyclooctene, cyclooctadiene, cyclononadiene, dicyclopentadiene, tricyclopentadiene, 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-ethoxycarbonyl-1-norbornene, 5-methyl-5-methoxy-carbonylnorbornene, 5,5,6-trimethyl-2-norbornene, 2,3-dimethoxynorbornene, norbornene or a combination thereof. Preferably, at least one cyclic olefin can be selected from cyclooctene, cyclooctadiene, cyclononadiene, norbornene, dicyclopentadiene or a combination thereof. More preferably, the at least one cyclic olefin may be dicyclopentadiene. Still more preferably, the at least one cyclic olefin may be a combination of dicyclopentadiene and tricyclopentadiene.

[0010] According to an embodiment of the present application, the at least one cyclic olefin may be selected from cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, and cyclodecene.

[0011] According to an embodiment of the present application, the cyclic olefin metathesis catalyst may include a metal carbene olefin isotope catalyst, preferably, the cyclic olefin metathesis catalyst may include a metal ruthenium carbene olefin isotope catalyst. Preferably, the cyclic olefin metathesis catalyst may be selected from [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl] The group consisting of (o-isopropoxybenzylidene) dichloride, [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](phenylmethylene) bipyridine dichloride, [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-methyl-2-butenylidene)(tricyclohexylphosphine) dichloride, [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tri(n-butyl)phosphine) dichloride, [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](phenylmethylene)(tricyclohexylphosphine) dichloride and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](phenylindenylidene)(tri(n-butyl)phosphine) dichloride.

[0012] According to an embodiment of the present application, the peroxide inhibitor can be selected from thiodipropionic acid diester, bis(3,5-di-tert-butyl-4-hydroxyphenyl) sulfide, disulfide dipropionamide, hydrogenated hydroquinone, butylated hydroxyanisole, 3,5-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-p-cresol, 2,2-methylenebis(4-methyl-6-tert-butylphenol), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] or a combination thereof.

[0013] According to an embodiment of the present application, the peroxide modifier may be selected from di-tertiarybutyl peroxide (Luperox® DI), di-tert-butylperoxyisopropylbenzene (Perkadox BC-FF), dicumyl peroxide (Perkadox 14S-FL), or any combination thereof.

[0014] According to an embodiment of the present application, the cyclic olefin metathesis catalyst may be a complex having a structure shown in Formula G:

[0015] Among them, L 2 , L 3 are independently selected from neutral electron donor ligands, n is 0 or 1, X 1 , X 2 is halogen, R 1 and R 2 are independently selected from hydrogen, hydrocarbon groups, substituted hydrocarbon groups, hydrocarbon groups containing heteroatoms, substituted hydrocarbon groups containing heteroatoms, and functional groups, R 3 and R 4 is an aromatic group; Q is a group having the structure -CR 5 R 6 -CR 7 R 8 -or- CR 5 =CR 7 - diatomic connection, where R 5 , R 6 , R 7 and R 8 L is independently selected from hydrogen, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon group containing a heteroatom, a substituted hydrocarbon group containing a heteroatom, and a functional group; 2 , L 3 , X 1 , X 2 , R 1 , R 2 , R 3 and R 4 Any two or more of them together form one or more cyclic groups.

[0016] According to another aspect of the present application, a polymerization method of a cycloolefin metathesis composition is provided, wherein the cycloolefin metathesis composition is the cycloolefin metathesis composition as described above, and the polymerization method comprises the following steps: S1 prepares a cyclic olefin solution; S2: adding a peroxide inhibitor to the cyclic olefin solution, wherein the amount of the peroxide inhibitor added is 0.1 to 10 phr relative to the mass ratio of the cyclic olefin; S3 was stirred in an inert gas atmosphere for more than 24 hours; S4: dissolving a cyclic olefin metathesis catalyst in a molar ratio of less than 1 / 100000 relative to the cyclic olefin in a dispersant, and dissolving the dissolved cyclic olefin metathesis catalyst solution in the cyclic olefin solution; S5 is heat cured at 110°C-130°C for 3-5 hours; Before step S4, adding an oxide modifier in a mass ratio of 5-1000 ppm relative to the cyclic olefin to the cyclic olefin solution; and During step S4, a co-catalyst is added in an amount of 10%-20% of the cyclic olefin metathesis catalyst.

[0017] Compared with the prior art, the cycloolefin metathesis composition and polymerization method thereof according to the embodiments of the present application can achieve at least the following beneficial effects: In one embodiment, in a cyclic olefin metathesis reaction catalyzed by an olefin metathesis catalyst (e.g., a cyclic olefin metathesis catalyst), a peroxide inhibitor is added to reduce impurities in the resin that may cause the catalyst to fail so as to improve the catalyst utilization efficiency. In the actual production process, the amount of catalyst used can be effectively reduced, or milder curing conditions can be used, thereby achieving the purpose of reducing production costs and being environmentally friendly.

[0018] In another embodiment, in a cyclic olefin metathesis reaction catalyzed by an olefin metathesis catalyst (e.g., a cyclic olefin metathesis catalyst), the catalyst utilization efficiency is improved by adding a highly active second catalyst (also referred to as a cocatalyst or secondary catalyst, which has the same meaning in the claims and the specification).

[0019] In yet another embodiment, in a cyclic olefin metathesis reaction catalyzed by an olefin metathesis catalyst (eg, a cyclic olefin metathesis catalyst), the operation time is adjusted by adding a peroxide modifier, thereby effectively enhancing the flexibility and freedom in the operation time.

[0020] Generally, the amount of the peroxide inhibitor and the second catalyst added can improve the degree of cure and mechanical properties of the cured product formed by the ROMP reaction in the presence of the peroxide inhibitor or the second catalyst, compared to a ring-opening metathesis polymerization (ROMP) reaction catalyzed by the same cyclic olefin metathesis catalyst in the absence of the added peroxide inhibitor and the second catalyst, thereby greatly improving product performance.

[0021] By introducing a variety of peroxide inhibitors into dicyclopentadiene (DCPD), the peroxide content was significantly reduced, and the peroxide concentration in DCPD was greatly reduced. This improvement effectively reduced the demand for ruthenium catalysts during the curing process, greatly reduced the amount of catalyst used under the same conditions, and significantly improved the economy and sustainability of the reaction.

[0022] In addition, if the amount of catalyst remains unchanged, milder curing conditions can also be considered, further reducing energy consumption and equipment requirements, and broadening the application range of the curing process. These improvements improve the environmental friendliness of the process, enhance product performance and production economy. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings of the embodiments will be briefly introduced below. Obviously, the drawings in the following description only relate to some embodiments of the present application, rather than limiting the present application.

[0024] Figure 1 This is a dynamic mechanical analysis (DMA) spectrum of the cured product according to Example 4j of the present application.

[0025] Figure 2 It is the viscosity growth curve according to Examples 6a-6c of the present application. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical scheme and advantages of the present invention clearer, the technical scheme in the embodiment of the present invention will be clearly and completely described below in conjunction with the accompanying drawings of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work belong to the scope of protection of the present invention. Unless otherwise defined, the technical terms or scientific terms used herein should be the usual meanings understood by people with general skills in the field to which the present invention belongs. "Including" and similar words used in this article mean that the elements or objects appearing before the word include the elements or objects listed after the word and their equivalents, without excluding other elements or objects. Unless otherwise specified, the "connection" described in this article can be a direct connection or an indirect connection, that is, connected through an intermediate.

[0027] Unless otherwise indicated, the present invention is not limited to specific reactants, substituents, catalysts, reaction conditions, etc., as these may vary. Also, the terminology used herein is only used to describe specific embodiments and should not be construed as limiting.

[0028] As used in the specification and claims, the terms "for example," "for example," "such as," or "including" are used to help the understanding of the present invention through additional examples and are not intended to be limiting in any way.

[0029] In this specification and claims, some terms are mentioned and their specific definitions are as follows: The term "alkyl" as used herein refers to a straight chain, branched chain, or cyclic saturated hydrocarbon group generally containing 1 to about 24 carbon atoms, preferably 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, octyl, cyclopentyl, cyclohexyl, etc. The term "lower alkyl" refers to an alkyl group of 1 to 6 carbon atoms, and the term "cycloalkyl" refers to a cyclic alkyl group, generally having 4 to 8, preferably 5 to 7 carbon atoms. The term "substituted alkyl" refers to an alkyl group substituted with one or more substituent groups, and the term "heteroalkyl" refers to an alkyl group in which at least one carbon atom is substituted with a heteroatom. Unless otherwise specified, the terms "alkyl" and "lower alkyl" include straight chain, branched chain, cyclic, unsubstituted, substituted, and / or heteroatom-containing alkyl and lower alkyl groups, respectively. The term "alkylene" refers to a difunctional straight chain, branched chain, or cyclic alkyl group.

[0030] As used herein, the terms "cyclic" and "ring" refer to alicyclic or aromatic groups that may or may not be substituted and / or contain heteroatoms, and may be monocyclic, bicyclic or polycyclic. The term "alicyclic" is used in the conventional sense, relative to aromatic cyclic moieties, to refer to aliphatic cyclic moieties and may be monocyclic, bicyclic or polycyclic.

[0031] The term "alkenyl" as used herein refers to a straight chain, branched chain, or cyclic hydrocarbon group containing at least one double bond from 2 to about 24 carbon atoms, such as vinyl, n-propenyl, isopropenyl, octenyl, etc. Preferred alkenyl groups herein contain 2 to 10 carbon atoms. The term "lower alkenyl" refers to an alkenyl group of 2 to 6 carbon atoms, and the term "cycloalkenyl" refers to a cyclic alkenyl group, preferably having 5 to 8 carbon atoms. The term "substituted alkenyl" refers to an alkenyl group substituted with one or more substituents, and the term "heteroalkenyl" refers to an alkenyl group in which at least one carbon atom is substituted with a heteroatom. Unless otherwise specified, the terms "alkenyl" and "lower alkenyl" include straight chain, branched chain, cyclic, unsubstituted, substituted, and / or heteroatom-containing alkenyl and lower alkenyl groups, respectively. The term "alkenylene" refers to a difunctional straight chain, branched chain, or cyclic alkenyl group.

[0032] As used herein, the term "alkynyl" refers to a straight or branched hydrocarbon group having 2 to about 24 carbon atoms and containing at least one triple bond, such as ethynyl, n-propynyl, etc. Preferred alkynyl groups herein contain 2 to about 10 carbon atoms. The term "lower alkynyl" refers to an alkynyl group having 2 to 6 carbon atoms. The term "substituted alkynyl" refers to an alkynyl substituted with one or more substituents, and the term "heteroalkynyl" refers to an alkynyl in which at least one carbon atom is substituted with a heteroatom. Unless otherwise indicated, the terms "alkynyl" and "lower alkynyl" include straight chain, branched, unsubstituted, substituted, and / or heteroatom-containing alkynyl and lower alkynyl, respectively.

[0033] As used herein, the term "alkoxy" refers to an alkyl group bound through a single terminal ether linkage; for example, "alkoxy" can be represented as -O-alkyl. "Lower alkoxy" refers to an alkoxy group containing 1 to 6 carbon atoms. Similarly, "alkenyloxy" and "lower alkenyloxy" refer to alkenyl and lower alkenyl groups, respectively, bound through a single terminal ether linkage, while "alkynyloxy" and "lower alkynyloxy" refer to alkynyl and lower alkynyl groups, respectively, bound through a single terminal ether linkage.

[0034] As used herein, the term "aryl", unless otherwise indicated, refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings fused together, directly or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety). Preferred aryl groups contain 5 to 24 carbon atoms, and preferred aryl groups contain 5 to 14 carbon atoms. Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, for example, phenyl, naphthyl, biphenyl, diphenyl ether, diphenylamine, benzophenone, etc. "Substituted aryl" refers to an aryl moiety substituted with one or more substituents, while the term "heteroaryl" refers to an aryl substituent in which at least one carbon atom is substituted with a heteroatom, as further described below.

[0035] As used herein, the term "aryloxy" refers to an aryl group that is linked by a single terminal ether. An "aryloxy" group can be represented as -O-aryl. Preferred aryloxy groups contain 5 to 24 carbon atoms, and preferred aryloxy groups contain 5 to 14 carbon atoms. Exemplary aryloxy groups include phenoxy, o / m / p-halogenated phenoxy, o / m / p-methoxyphenoxy, 2,4-dimethoxyphenoxy, 3,4,5-trimethoxyphenoxy, and the like.

[0036] As used herein, the term "alkaryl" refers to an aryl group having an alkyl substituent, and the term "aralkyl" refers to an alkyl group having an aryl substituent. Preferred alkaryl and aralkyl groups contain 6 to 24 carbon atoms, and preferred alkaryl and aralkyl groups contain 6 to 16 carbon atoms. Exemplary alkaryl groups include p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 3-ethyl-cyclopenta-1,4-diene, etc. Exemplary aralkyl groups include benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenylbutyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, etc. The terms "alkaryloxy" and "aralkyloxy" refer to substituents of the formula -OR, wherein R refers to alkaryl or aralkyl.

[0037] As used herein, the term "acyl" refers to a substituent having the formula -(CO)-alkyl, -(CO)-aryl or -(CO)-aralkyl, and the term "acyloxy" refers to a substituent having the formula -O(CO)-alkyl, -O(CO)-aryl or -O(CO)-aralkyl. In addition, the term "acyl" also refers to a substituent having the formula -(CO)-aryl, -(CO)-alkenyl or -(CO)-alkynyl, and the term "acyloxy" also refers to a substituent having the formula -O(CO)-alkaryl, -O(CO)-alkenyl or -O(CO)-alkynyl.

[0038]

[0046] As used herein, the terms "halo" and "halogen" refer to fluoro, chloro, bromo, or iodo substituents.

[0039] As used herein, the term "hydrocarbyl" refers to a monovalent hydrocarbon group containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, and most preferably 1 to 12 carbon atoms, including straight chain, branched chain, cyclic, saturated and unsaturated types, such as alkyl, alkenyl, aryl, etc. The term "lower hydrocarbon group" refers to a hydrocarbon group containing 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and the term "alkylene group" refers to a divalent hydrocarbon group containing 1 to about 30 carbon atoms, preferably 1 to 24 carbon atoms, and most preferably 1 to 12 carbon atoms, including straight chain, branched chain, cyclic, saturated and unsaturated types. The term "lower alkylene group" refers to an alkylene group of 1 to 6 carbon atoms. The term "substituted hydrocarbon group" refers to a hydrocarbon group substituted with one or more substituent groups, and the term "heterohydrocarbyl group" refers to a hydrocarbon group in which at least one carbon atom is substituted with a heteroatom. The term "substituted hydrocarbylene" refers to a hydrocarbylene substituted with one or more substituents, and the term "heterohydrocarbylene" refers to a hydrocarbylene in which at least one carbon atom is substituted with a heteroatom. Unless otherwise indicated, the terms "hydrocarbylene" and "hydrocarbylene" will be interpreted as including substituted and / or heteroatom-containing hydrocarbylene and hydrocarbylene moieties, respectively.

[0040] As used herein, the term "heteroatom-containing" refers to a hydrocarbon molecule or hydrocarbon molecule group in which one or more carbon atoms are replaced with atoms other than carbon atoms, such as nitrogen, oxygen, sulfur, phosphorus or silicon. The term "heteroalkyl" refers to an alkyl substituent containing a heteroatom, the term "heterocycle" refers to a cyclic substituent containing a heteroatom, the terms "heteroaryl" and "heteroaromatic" refer to an aryl and aromatic substituent containing a heteroatom, etc. Exemplary heteroalkyls include alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated aminoalkyl, etc. Exemplary heteroaryl substituents include pyrrolyl, pyridyl, indolyl, pyrimidinyl, 1,2,4-triazolyl, etc. Examples of heteroatom-containing alicyclic groups include pyrrolidinyl, morpholinyl, piperazinyl, piperidinyl, etc.

[0041] The term "substituted" in "substituted hydrocarbon", "substituted alkyl", "substituted aryl" and the like means that at least one hydrogen atom in a hydrocarbon, alkyl, aryl or other group is replaced with a non-hydrogen substituent. Such substituents include, but are not limited to, functional groups referred to herein as "Fn", such as halide, hydroxyl, thiol, alkoxy, alkenyloxy, alkynyloxy, aryloxy, aralkyloxy, acyl, acyloxy, alkoxycarbonyl, acyloxycarbonyl, halocarbonyl, alkyl / arylcarbonyl, carboxyl, carboxylic acid, carbamoyl, monoalkyl-substituted carbamoyl, diaryl-substituted carbamoyl, di-N-alkyl, N-aryl-substituted carbamoyl, thiocarbamoyl, mono / dialkyl-substituted thiocarbamoyl, monoaryl-substituted thiocarbamoyl, The functional groups of "Fn" include, but are not limited to, isocyanate, thioisocyanate, alkylsulfonyl, alkylsulfonyl, alkylsulfonyl, alkylsulfinyl, alkylsulfonyl, mono / dialkylaminosulfonyl, arylsulfonyl, borane, dihydroxyborane, borate, phosphono, phosphonic acid, phosphinyl, phospho and phosphino. Other functional groups referred to as "Fn" herein include, but are not limited to, isocyanate and thioisocyanate.

[0042] The term "functionalized" in the terms "functionalized hydrocarbyl", "functionalized alkyl", "functionalized olefin", "functionalized cyclic olefin", etc., means that at least one hydrogen atom in the hydrocarbyl, alkyl, olefin, cyclic olefin or other moiety is replaced with the above functional group. The term "functional group" is meant to include any functional species suitable for the purposes described herein. Where the specific group permits, the functional group can be further substituted with another functional group or hydrocarbyl moiety.

[0043] "Optional," "optionally," or "optionally" means that the subsequently described event may or may not occur, such that the description includes instances where the event occurs and instances where the event does not occur. For example, the phrase "optionally substituted" means that a non-hydrogen substituent may or may not be present on a given atom, such that the description includes structures in which the non-hydrogen substituent is present or absent.

[0044] The addition of an olefin metathesis catalyst to a cycloolefin or a composition thereof can initiate a polymerization reaction under appropriate conditions, and the time during which the formed resin composition has a sufficiently low viscosity and is fluid and can be used in a production operation process is called the "operating time". As the polymerization reaction proceeds, the viscosity of the resin increases so that the resin is no longer able to flow freely, which is the so-called gel state. After the resin has reached the gel state, the polymerization reaction continues until no more monomers are consumed, which is the so-called solidified state. The term "operating time" used herein may also be understood as "gel time", which specifically refers to the time taken from the completion of mixing of all components of the composition to the viscosity reaching 2000 mPa·s, as measured by a viscometer or by other suitable techniques.

[0045] Below, embodiments of the present application are described in detail.

[0046] The inventors have found that pre-treating the cycloolefin resin with a peroxide inhibitor can effectively reduce the peroxide content in the resin and make it possible to reduce the catalyst content in the composition or make the curing conditions milder. This discovery will effectively reduce the production and use costs of the composition. When the composition of the peroxide inhibitor and the resin is configured, the content of the peroxide inhibitor is generally equivalent to a range of 0.2 wt% to 5 wt% of the resin. Suitable peroxide inhibitors include, but are not limited to: 2,6-di-tert-butyl-4-methylphenol (BHT), styrenated phenol, 2- and 3-tert-butyl-4-methoxyphenol; 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), 2,2'-ethylidenebis(4,6-di-tert-butylphenol ), 2,2'-methylenebis(4-methyl-6-(1-methylcyclohexyl)phenol), 4,4'-butylenebis(6-tert-butyl-3-methylphenol), polybutylated bisphenol A, 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-methylenebis(2,6-dimethylphenol), 1,1'-thiobis(2-naphthol), methylene-bridged polyalkylphenol, 2,2'-thiobis(4-methyl-6-tert-butylphenol), 2,2'-isobutylenebis(4,6-dimethylphenol), 2,2'-methylenebis(2,6-dimethylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 4,4'-methylenebis(2,6-di-tert-butylphenol), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2,5-di-tert-amylhydroquinone, tert-butylhydroquinone, tris(nonylphenylphosphite), di(2,4-di-tert-butyl)-1,3,5-tris(2,6-di-tert-butyl)-1,3,5-tris(3,5-di-tert-butyl)-1,3,5-tris(2,4 ... dibutyl)pentaerythritol) diphosphite, distearyl pentaerythritol diphosphite, phosphite phenols and bisphenols, phosphite / phenol peroxide inhibitor blends, di-n-octadecyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, 1,6-hexamethylene bis (3-(3,5-di-tert-butyl-4-hydroxyphenyl propionate), octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphite, diphenylamine and 4,4'-dimethoxy-diphenylamine.

[0047] Adding a peroxide modifier to the resin can effectively extend the operating time of the resin composition to adapt to more molding processes. Generally, alkyl, aryl, and acyl peroxides are used. Suitable peroxides include, but are not limited to, butyl-4,4-bis(tert-butylperoxy)valerate (Trigonox 17-40B-PD), 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane (Trigonox 29-40B-PD), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (Trigonox 101), tert-butylperoxy-2-ethylhexyl carbonate (Trigonox 117 Solar), tert-amylperoxy-2-ethylhexyl carbonate (Trigonox 131 Solar), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne (Trigonox 145-E85), 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane (Trigonox 147-E85), tert-butylperoxy-2-ethylhexyl carbonate ... 301), 3,3,5,7,7-pentamethyl-1,2,4-trioxepane (Trigonox 311), di-tert-butyl peroxide (Trigonox B), tert-butyl peroxide isopropylbenzene (Trigonox T), tert-butyl peroxyisopropyl carbonate (Trigonox BPIC-CP75), di(tert-butylperoxyisopropyl)benzene (Perkadox 14S-FL), diisopropylbenzene peroxide (Perkadox BC-FF), dibenzoyl peroxide (Perkadox L-40 RPS), di(2,4-dichlorobenzoyl) peroxide (Perkadox PD-50S-PS), di(4-methylbenzoyl) peroxide (Perkadox PM-5OS-PS), tert-butyl peroxyneodecanoate (LUPEROX® 10), 2,5-dimethyl-2,5-di-tert-butylperoxy-3-hexyne (LUPEROX ® 101), 2,5-dimethyl-2,5-di-tert-butylperoxy-3-hexyne (LUPEROX ® 2,5-2,5), di(2-ethylhexyl) peroxydicarbonate (LUPEROX ® 223S), di-sec-butyl peroxydicarbonate (LUPEROX ® 225), 2,5-dimethyl-2,5-di-tert-butylperoxy-3-hexyne (LUPEROX ® 256), tert-butyl peroxy-2-ethylhexanoate (LUPEROX ® 26) Tert-butyl peroxy-3,5,5-trimethylhexanoate (LUPEROX ® 270 HP), di-tert-butyl peroxide (LUPEROX ®DI), di-tert-amyl peroxide (LUPEROX ® DTA), tert-butyl peroxybenzoate (LUPEROX ® P). Peroxide can be added directly to the reaction mixture to maintain its modification activity over a long shelf life.

[0048] The main component of the resin composition disclosed herein is one or more cyclic olefins. Generally speaking, any cyclic olefin suitable for the olefin metathesis reaction disclosed herein can be used. This cyclic olefin can be optionally substituted, optionally containing heteroatoms, optionally functionalized, monounsaturated, diunsaturated or polyunsaturated, and can be a monocyclic, bicyclic or polycyclic hydrocarbon. The cyclic olefin can generally be any stressed or unstressed cyclic olefin, provided that the cyclic olefin can participate in the ROMP reaction alone or as a part of a ROMP cyclic olefin composition. Although some unstressed cyclic olefins themselves are generally unable to undergo ROMP reactions, they may be ROMP active in appropriate circumstances. For example, when present as a comonomer in a ROMP composition, unstressed cyclic olefins may be ROMP active. Therefore, as used herein and as will be understood by those skilled in the art, the term "unstressed cyclic olefin" refers to those unstressed cyclic olefins that can undergo ROMP reactions under any conditions or in any ROMP composition, provided that the unstressed cyclic olefin is ROMP active.

[0049] Generally speaking, the cyclic olefin can be represented by the structure of Formula A below:

[0050] Where J and R A as follows: R A Selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl; if substituted hydrocarbyl or substituted heterohydrocarbyl, wherein the substituent can be a functional group ("Fn") such as phosphino, phosphino, amino, amido, imino, nitro, hydroxy, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxyl, mercapto, formyl, aminomethyl, epoxy, styryl, silyl, siloxy, silyl or halogen.

[0051] J is a saturated or unsaturated alkylene, substituted alkylene, heteroatom-containing alkylene, or substituted heteroatom-containing alkylene linkage. Two or more substituents attached to ring atoms in J may be attached to form a bicyclic or polycyclic olefin. J will generally contain about 5 to 14 ring atoms, typically 5 to 8 ring atoms per ring.

[0052] The monounsaturated cyclic olefin reactant encompassed by structure A may be represented by structure B:

[0053] Where b is an integer, usually in the range of 1 to 5, R A Same definition as above, and R B1 , R B2 , R B3 , R B4 , R B5 and R B6 R is independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl. B1 , R B2 , R B3 , R B4 , R B5 and R B6 It can be hydrogen, hydroxyl, alkyl, aryl, alkoxy, aryloxy, amino, amide, nitro, etc. In addition, R B1 , R B2 , R B3 , R B4 , R B5 and R B6 Any one of them can be connected to the R B1 , R B2 , R B3 , R B4 , R B5 and R B6 Any other group in to form a bicyclic or polycyclic olefin, and the connection may include heteroatoms or functional groups, such as ethers, esters, thioethers, amino groups, alkylamino groups, imino groups or anhydrides. Examples of monounsaturated monocyclic olefins included in structural formula B include, but are not limited to, cyclohexene, cyclooctene, cyclononene and their substituted forms such as 1-methylcyclopentene, 1-isopropylcyclohexene, 4-methylcyclopentene, 4-methoxycyclopentene, cyclopent-3-ene-thiol, cyclopent-3-ene, 3-methylcyclohexene, 1,5-dimethylcyclooctene, etc.

[0054] The monocyclic diene reactant encompassed by structure A can be generally represented by structure C:

[0055] wherein c and d are independently integers ranging from 2 to 4, preferably 2, R A Same definition as above, and R C1 , R C2 , R C3 , R C4 , R C5 and R C6 Definition and R B1 To R B6Similar, among which R C3 and R C4 is a non-hydrogen substituent. Examples of monocyclic diene reactants include, but are not limited to, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,5-cyclooctadiene, and 1,3-cyclooctadiene.

[0056] Bicyclic and polycyclic olefin reactants encompassed by structure A can be generally represented by structure D:

[0057] Where R A Same definition as above, R D1 , R D2 , R D3 , R D4 , R D5 and R D6 Definition and R B1 To R B6 The same, T is a methylene, heteroatom or substituted heteroatom, preferably norbornene and oxa-norbornene compounds. Therefore, examples of bicyclic and polycyclic olefin reactants include, but are not limited to, dicyclopentadiene, tricyclopentadiene, dicyclohexadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-methoxycarbonyl norbornene, (endo, endo)-5,6-dimethoxynorbornene, (endo, exo)-5,6-dimethoxycarbonyl norbornene, 2,3-dimethoxynorbornene, etc. Other examples of bicyclic and polycyclic olefins include, but are not limited to, higher oligomers of cyclopentadiene such as cyclopentadiene tetramers, pentamers, etc.; hydrocarbyl-substituted norbornenes, 5-butyl-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, etc.

[0058] The cyclic olefin may also contain multiple rings. When the cyclic olefin contains more than one ring, the rings may be fused or non-fused. Preferred examples of cyclic olefins containing multiple rings include norbornene, dicyclopentadiene and 5-ethylidene-2-norbornene.

[0059] One route for preparing substituted norbornenes utilizes a Diels-Alder reaction, where cyclopentadiene or its substituents react with a dienophile at elevated temperature to form a norbornene adduct (Scheme 1).

[0060]

[0061] Among them, R E1 , R E2 , R E3 and R E4 Same definition as R B1, R B2 , R B3 , R B4 , R B5 and R B6 .

[0062] Olefin Metathesis Catalysts The olefin metathesis catalyst complex of the present invention is preferably a ruthenium complex having structural formula E.

[0063]

[0064] Among them, L 1 , L 2 , L 3 is a neutral ligand, n is 0 or 1, m is 0, 1 or 2, X 1 , X 2 is anionic ligand, R 1 , R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl and a functional group, wherein X 1 , X 2 , L 1 , L 2 , L 3 , R 1 and R 2 Any two or more of them can together form one or more cyclic groups.

[0065] The first group of catalysts, often referred to as first generation Grubbs catalysts, have a structure of Formula E. For the first group of catalysts, m is 0, 1 or 2, n is 0, L 1 and L 2 is independently selected from phosphines, phosphonates, phosphites, phosphites, ethers, amines, imines, carboxyls, pyridines, substituted pyridines, imidazoles, substituted imidazoles, and thioethers. An exemplary ligand is a trisubstituted phosphine. A preferred trisubstituted phosphine has the formula PR H1 R H2 R H3 , where R H1 , R H2 , R H3 are each independently aryl or alkyl. 1 and L 2 Independently selected from the group consisting of trimethylphosphine, triethylphosphine, tri-n-butylphosphine, tri(o-tolyl)phosphine, tri-tert-butylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, triisopropylphosphine, triisobutylphosphine, trioctylphosphine, triphenylphosphine, tri(pentafluorophenyl)phosphine. 1 and X 2 is an anionic ligand, which may be the same or different, or linked together to form a cyclic group, usually a five- to eight-membered ring. Preferably, X1 and X 2 Each is independently hydrogen, halogen or one of the following groups: alkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, acyl, acyloxy, alkylsulfonate, arylsulfonate, alkylsulfanyl, arylsulfanyl, alkylsulfinyl or arylsulfinyl. More preferably, X 1 and X 2 Each of X is halogen, trifluoroformyl, formate, trimethylcarbonyl, phenoxy, methoxy, ethoxy, tosylate, mesylate. Most preferably, X 1 and X 2 Each is chlorine. 1 and R 2 R is independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, and substituted heterohydrocarbyl. 1 and R 2 They may also be linked to form cyclic groups, which may be aliphatic or aromatic and may contain substituents and / or heteroatoms. Typically, such cyclic groups contain 4 to 12, preferably 5, 6, 7 or 8 ring atoms.

[0066] The second group of catalysts, generally referred to as second generation Grubbs catalysts, have the structure of Formula E, where L 1 It is a carbene ligand having a structure of formula F.

[0067]

[0068] Among them, R 3 and R 4 Independently selected from hydrogen, hydrocarbon, substituted hydrocarbon, heterohydrocarbon and substituted heterohydrocarbon. Q is a linker, typically an alkylene linker, including substituted alkylene, heteroatom-containing alkylene and substituted heteroatom-containing alkylene linkers, wherein two or more substituents on adjacent atoms in Q may also be connected to form additional cyclic structures, which may be similarly substituted to provide a fused ring structure of 2 to 4 cyclic groups.

[0069] The preferred complex has the structure of Formula G.

[0070]

[0071] Preferably, Q has the structure -CR 5 R 6 -CR 7 R 8 -or- CR 5 =CR 7 -, preferably -CR 5 R 6 -CR 7 R 8 - diatomic connection, where R5 , R 6 , R 7 and R 8 R is independently selected from hydrogen, hydrocarbon, substituted hydrocarbon, heterohydrocarbon, substituted heterohydrocarbon and functional groups. Examples of functional groups herein include carboxyl, alkoxy, aryloxy, alkoxycarbonyl and acyloxy, optionally substituted with one or more moieties selected from alkyl, alkoxy, aryl, hydroxyl, mercapto, formyl and halogen. 5 , R 6 , R 7 and R 8 is preferably independently selected from hydrogen, alkyl, substituted alkyl, heteroalkyl, substituted heteroalkyl, phenyl and substituted phenyl. 5 , R 6 , R 7 and R 8 Any two of R may be linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure. 3 and R 4 X may be phenyl or phenyl substituted with one or more substituents selected from the group consisting of alkyl, substituted alkyl, heteroalkyl, substituted heteroalkyl, aryl, substituted aryl, heteroaryl, aralkyl, alkaryl or halogen. 1 and X 2 It's a halogen.

[0072] The third group of catalysts is generally referred to as "Grubbs-Hoveyda" catalysts. Grubbs-Hoveyda catalysts can be described by formula H.

[0073]

[0074] Among them, X 1 , X 2 and L 1 The definition is the same as above, Y is a heteroatom, R 9 , R 10 , R 11 and R 12 Each is independently selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylsulfanyl, aminosulfonyl, mono / dialkylaminosulfonyl, alkylsulfonyl, nitro, alkylsulfinyl, trihaloalkyl, carboxyl, aldehyde, cyano or hydroxyl. Y, Z, R 9 , R 10 , R 11 and R 12can be connected to form a cyclic group. n is 0, 1 or 2; n is 1 for a divalent heteroatom O or S, and is 2 for a trivalent heteroatom N or P. Z is a group selected from hydrogen, an alkyl group, an aryl group, a substituted alkyl group, and a substituted aryl group.

[0075] Another group of olefin metathesis catalysts encompassed by Formula F can be represented by Formula I:

[0076] Among them, X 1 , X 2 , L 1 and L 2 The definition of R is the same as that of the first and second groups of catalysts. 13 , R 14 , R 15 , R 16 , R 17 and R 18 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, alkylsulfanyl, aminosulfonyl, mono / dialkylaminosulfonyl, alkylsulfonyl, nitro, alkylsulfinyl, trihaloalkyl, carboxyl, aldehyde, cyano or hydroxyl.

[0077] Examples of catalysts that can be used in the reactions disclosed herein include, but are not limited to, the following:

[0078] In the above structural formula, Ph represents a phenyl group, Cy represents a cyclohexyl group, i-Pr represents an isopropyl group, Mes represents trimesyl (2,4,6-trimethylphenyl), DIPP represents 2,6-diisopropylphenyl, and tBu represents a tert-butyl group.

[0079] Generally, the transition metal complexes used as catalysts herein can be prepared by several different methods, as described in Chatterjee et al., J. Am. Chem. Soc. 2003, 11360-11370; Trnka et al., J. Am. Chem. Soc. 2003, 125, 2546-2558; Mukherjee et al., Macromolecules 2015, 48, 6791-6800; Chem. Eur. J. 2014, 20, 14120-14125; International Patent Application Publication WO2007075427 A1; International Patent Application Publication WO2002079126 A1; U.S. Patent Application Publication US8519069 A2; the disclosure of each of which is incorporated herein by reference.

[0080] The metathesis catalyst described below can be used in olefin metathesis reaction according to technology known in the art. The catalyst is usually added to the reaction medium as a solid or as a suspension or solution in which the catalyst is suspended in a suitable liquid. The amount of catalyst used in the reaction depends on various factors, such as reactant characteristics, additive characteristics and the reaction conditions adopted. Therefore, it should be understood that the amount of catalyst can be optimized and selected independently for each reaction. Generally, the catalyst will be added in a ratio of about 1 / 1000000, 1 / 500000, 1 / 200000, 1 / 100000, 1 / 50000, 1 / 40000, 1 / 20000, 1 / 10000 relative to the amount (molar ratio) of the olefin substrate.

[0081] In addition, suitable impact modifiers or elastomers include, but are not limited to, natural rubber, butyl rubber (IIR), polyisoprene (PI), polybutadiene, polyisobutylene (PIB), ethylene-propylene copolymer (EPM), styrene-butadiene-styrene triblock rubber (SBS), random styrene-butadiene rubber (SBR), styrene-isoprene-styrene triblock rubber (SIS), styrene-ethylene / butylene-styrene copolymer (SEBS), styrene-ethylene / propylene-styrene copolymer (SEEPS), ethylene-propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA) and nitrile rubber, or any combination thereof.

[0082] In a preferred embodiment, the metathesis reaction disclosed herein can be carried out under a dry inert atmosphere. This atmosphere can use any inert gas, including gases such as nitrogen and argon, and can be produced. Preferably, the selection is implemented under an atmosphere of nitrogen and argon to make the use of low-load catalysts possible. The reaction disclosed herein can also be carried out under an oxygen-containing and / or water-containing atmosphere, and in one embodiment, the reaction is implemented under ambient conditions.

[0083] The reactions disclosed herein can all be carried out in a solvent, using a solvent that is inert to the olefin metathesis reaction. Generally, organic solvents such as hydrocarbons, halogenated hydrocarbons, ethers, alcohols, etc. are used in the metathesis reaction herein. Examples include, but are not limited to, benzene, toluene, dichloromethane, 1,2-dichloroethane, dichlorobenzene, tetrahydrofuran, ether, methanol, ethanol, or mixtures thereof. Preferably, the reaction is carried out in a small amount or without solvent.

[0084] The temperature of the metathesis reaction disclosed herein should be adjusted as needed and can be -78 °C, -40 °C, -10 °C, 0 °C, 20 °C, 25 °C, 35 °C, 70 °C, 100 °C or 170 °C.

[0085] Example Some examples are listed below, which further illustrate the present invention but should not limit the scope of the present invention in any way.

[0086] In the following examples, experimental errors and deviations should be considered. Unless otherwise specified, "DCPD" and "liquefied DCPD" (except "pure DCPD") refer to modified liquid raw materials containing 10% to 15% by mass of tricyclopentadiene and a small amount of higher cyclopentadiene homologues, "ppm" refers to the number of parts (mass) of the relevant substance corresponding to one million parts (mass) of DCPD, "phr" refers to the number of parts (mass) of the relevant substance corresponding to one hundred parts (mass) of DCPD, "n / n, relative to the monomer" refers to the ratio of the molar number of the relevant substance to the pure DCPD equivalent to the mass of liquefied DCPD, and the curing procedure "a °C × bh" refers to continuous curing for bh while maintaining a temperature of a °C.

[0087] Materials and test methods Unless otherwise noted, all glassware and curing vessels were oven dried and reactions were performed under ambient conditions. Unless otherwise noted, all solvents and reagents were purchased from commercial suppliers and used as received.

[0088] Liquefied dicyclopentadiene (liquefied DCPD) was obtained from Guangdong Xinhua Yue Petrochemical Group Co., Ltd. and contains 10% to 15% tricyclopentadiene and a small amount of higher cyclopentadiene homologues.

[0089] Bis(3,5-di-tert-butyl-4-hydroxyphenyl) sulfide was obtained from Guangzhou Yuanda New Materials Co., Ltd. (Peroxide Inhibitor 1035). N,N'-Dimethyl-3,3'-dithiodipropionamide was obtained from Beijing Solaibao Technology Co., Ltd. Tert-butyl-4-hydroxyanisole was obtained from Shanghai MacLean Biochemical Technology Co., Ltd. 2,2-Methylenebis(4-methyl-6-tert-butylphenol) was obtained from Shanghai MacLean Biochemical Technology Co., Ltd. (Peroxide Inhibitor 2246). Pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate was obtained from BASF (China) Co., Ltd. (IRGANOX ® 1010).

[0090] Metathesis catalysts were prepared by standard methods and included [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene] (o-isopropoxybenzylidene) ruthenium dichloride (G627), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene] (phenylmethylene) bipyridine ruthenium dichloride (G727), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene] (3-methyl-2-butenylidene)(tricyclohexylphosphine) ruthenium dichloride (G827), ...). [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl](benzylidene)(tri(n-butyl)phosphine)dichlororuthenium (G771), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl](phenylmethylene)(tricyclohexylphosphine)dichlororuthenium (G849) and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl](phenylindenyl)(tri(n-butyl)phosphine)dichlororuthenium (G871). Catalyst dispersant (3M TM Novec TM 72DE) was obtained from 3M China Co., Ltd. and used directly.

[0091] Di-tert-butyl peroxide was obtained from Sigma-Aldrich (Shanghai) Trading Co., Ltd. (Luperox ® DI) and used directly. Dicumyl peroxide was obtained from Nouryon Chemicals (Ningbo) Co., Ltd. (Perkadox BC-FF) and used directly. Di-tert-butyl cumyl hydroperoxide was obtained from Nouryon Chemicals (Ningbo) Co., Ltd. (Perkadox 14S-FL) and used directly.

[0092] The determination of peroxide content in DCPD raw materials is carried out in accordance with the standard: GB / T 12688.4-2011, Test methods for industrial styrene, Part 4: Determination of peroxide content by titration method.

[0093] Glass transition temperature (Tg) was measured using thermal dynamic mechanical analysis (DMA) on a TA DMA Q800 (standard: ASTM D5023). Scanning temperature: 40 – 200 °C, 5 °C / min. Test mode: three-point bending. The Tan δ value was taken as the Tg measurement result.

[0094] Tensile properties were determined using standard techniques (Standard: ISO 527-2:2012) and all results are the average of 6 samples.

[0095] The operating time was measured on a Brookfield DVNXLVMJC viscometer and the data were analyzed using RheocalcT software. The 100 g sample was measured at a set temperature of 25 °C using a No. 2 spindle set at 14 rpm. Data points were recorded at 2 s intervals.

[0096] Example 1 The peroxide content in liquefied DCPD is reduced by adding a peroxide inhibitor.

[0097] At room temperature, various peroxide inhibitors were added to 150 g of liquefied DCPD in a specified amount and stirred for 24 h in an inert gas atmosphere. The obtained solution was tested for peroxide content (Table 1). As can be seen from Table 1, the peroxide content was significantly reduced by adding peroxide inhibitors. Because the reduction of peroxides enhances the activity of the catalyst, the total amount of catalyst can be reduced.

[0098] Table 1: Peroxide content of raw materials after adding different amounts of various peroxide inhibitors

[0099] Example 2 Curing of DCPD with the addition of a peroxide inhibitor.

[0100] At room temperature, a specified amount of various peroxide inhibitors were added to 250g of liquefied DCPD and stirred in an inert gas atmosphere for 24 h. 1 / 40000 (molar ratio, relative to DCPD monomer) of the catalyst was weighed and dissolved in the dispersant and dissolved in the liquefied DCPD. The solution was transferred to a curing mold and cured using a 120 °C × 4 h program. The glass transition temperature (Tg, Table 2) of the cured product was determined using dynamic thermomechanical analysis. Among them, the tensile properties of Examples 2i and 2j were also determined (the results are compared in Table 4). It can be seen from Table 2 that when a peroxide inhibitor is added, the activity of the catalyst is enhanced, the catalytic effect is significantly enhanced, and the Tg is correspondingly increased, thereby reducing the amount of the catalyst when the polymerization conditions are met.

[0101] Table 2: Tg of cured product after adding peroxide inhibitor

[0102] Example 3 Curing of DCPD with addition of peroxide inhibitor and reduction of catalyst dosage.

[0103] At room temperature, a specified amount of N,N'-dimethyl-3,3'-dithiodipropionamide (the type of peroxide inhibitor used in the examples in Table 3 and Table 4) was added to 250g of liquefied DCPD and stirred in an inert gas atmosphere for 24 h. A specified amount of catalyst was weighed and dissolved in a dispersant and dissolved in liquefied DCPD. The solution was transferred to a curing mold and cured using a 120 °C × 4 h program. The glass transition temperature (Tg, Table 3) of the cured product was determined using dynamic thermomechanical analysis. Among them, the tensile properties of Examples 3d-3e and 3j-3l were also determined (Table 4). It can be seen from Table 3 that when the catalyst is constant, Tg increases with the increase in the amount of peroxide added; when the peroxide inhibitor is added, the activity of the catalyst is enhanced, the catalytic effect is significantly enhanced, and the amount of catalyst can be reduced when the polymerization conditions are met.

[0104] Table 3: Tg of cured products with added peroxide inhibitor and reduced catalyst dosage

[0105] *“No data” refers to the case where the glass transition temperature is too low to be read within the 76 measurement range.

[0106] Table 4: Tensile properties of cured products with added peroxide inhibitor and reduced catalyst dosage

[0107] Example 4 DCPD cure with the addition of a peroxide inhibitor and lower cure temperature.

[0108] At room temperature, add a specified amount of N,N'-dimethyl-3,3'-dithiodipropionamide (peroxide inhibitor) to 250g of liquefied DCPD and stir in an inert gas atmosphere for 24 hours. Weigh 1 / 40000 (molar ratio, relative to DCPD monomer) of the catalyst and dissolve it in the dispersant and in the liquefied DCPD. The solution is transferred to the curing mold and cured at a specified temperature for 4 hours. The glass transition temperature (Tg, Table 5) of the cured product is determined by dynamic thermomechanical analysis. As can be seen from Table 5, when the peroxide inhibitor is added, the activity of the catalyst is enhanced, the catalytic effect is significantly enhanced, and the amount of catalyst can be reduced when the polymerization conditions are met.

[0109] Table 5: Tg of cured products with addition of peroxide inhibitor and lower curing temperature

[0110] Figure 1 is a dynamic mechanical analysis (DMA) spectrum of the cured product according to Example 4j of the present application. Figure 1 As shown, adding peroxide inhibitor and lowering the curing temperature can obtain better dynamic thermomechanical properties.

[0111] Example 5 DCPD curing using a dual catalyst combination.

[0112] At room temperature, 250 g of liquefied DCPD was weighed, 1 / 100000 (molar ratio, relative to DCPD monomer) of the main catalyst and a specified amount of G727 were weighed and dissolved in the dispersant, and dissolved in the liquefied DCPD. The solution was transferred to a curing mold and cured using a 120 °C × 4 h program. The glass transition temperature (Tg, Table 6) of the cured product was determined using dynamic thermomechanical analysis. It can be seen from the data listed in Table 6 that by reducing the total amount of catalyst, the cost of the cycloolefin metathesis composition can be greatly reduced, and the threshold of the Tg of the cured product can be reduced, thereby reducing the glass transition temperature and greatly reducing energy consumption.

[0113] Table 6: Effect of different concentrations of G727 on the Tg of the cured product with low catalyst loading

[0114] Example 6 Peroxide is added to extend the working time.

[0115] At room temperature, a specified amount of peroxide was dissolved in 150 g of liquefied DCPD. 1 / 40000 (molar ratio, relative to DCPD monomer) of the main catalyst was weighed and dissolved in the dispersant and liquefied DCPD. The viscosity of the mixture was measured using a rotational viscometer. When the viscosity increased to 2 Pa·s, the operation was stopped and the operation time was recorded (Table 7). As can be seen from Table 7, the addition of the peroxide modifier significantly improved the operability time of the cycloolefin metathesis polymer formed after polymerization.

[0116] Table 7: Effect of peroxide type and dosage on Tg of DCPD cured product

[0117] Figure 2 is the viscosity growth curve according to Examples 6a-6c of the present application. Figure 2 As shown in the figure, the influence trend of peroxide type and dosage on the viscosity change of DCPD cured product.

[0118] Example 7 Curing of DCPD under the conditions of adding peroxide inhibitor, peroxide modifier and dual catalyst.

[0119] At room temperature, IRGANOX® 1010 peroxide inhibitor was added to 500g of liquefied DCPD, and the mass ratio of the peroxide inhibitor to the cyclic olefin was 0.5phr. Stirred for 24 h in an inert gas atmosphere. Luperox® DI 1 / 100000 (molar ratio, relative to DCPD monomer) was added to extend the operation time. Then 1 / 100000 (molar ratio, relative to DCPD monomer) of the main catalyst G771 and 1 / 10 of the amount of G727 (second catalyst) (relative to the main catalyst) were weighed and dissolved in the dispersant and dissolved in the liquefied DCPD. Half of the sample solution was transferred to the curing mold and cured using a 120 °C × 4 h program. The glass transition temperature of the cured product was determined by dynamic thermomechanical analysis to be 110 °C. The viscosity of the mixture was measured using a rotational viscometer for the other half of the sample. The operation was stopped when the viscosity increased to 2 Pa·s, and the operation time was recorded as 102min.

[0120] According to one aspect of the present application, a cyclic olefin metathesis composition is provided, comprising: at least one cyclic olefin; a cyclic olefin metathesis catalyst, the molar ratio of which relative to the cyclic olefin is less than 1 / 100000; a peroxide inhibitor, the mass ratio of which relative to the cyclic olefin is 0.1-10 phr; the cyclic olefin metathesis composition may also include a peroxide modifier, the mass ratio of which relative to the cyclic olefin is 5-1000 ppm; and the cyclic olefin metathesis composition may also include an auxiliary catalyst [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl](phenylmethylene)bipyridinedichloride ruthenium, the content of which is 10%-20% of the cyclic olefin metathesis catalyst.

[0121] According to an embodiment of the present application, at least one cyclic olefin can be selected from cyclooctene, cyclooctadiene, cyclononadiene, dicyclopentadiene, tricyclopentadiene, 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-ethoxycarbonyl-1-norbornene, 5-methyl-5-methoxy-carbonylnorbornene, 5,5,6-trimethyl-2-norbornene, 2,3-dimethoxynorbornene, norbornene or a combination thereof. Preferably, at least one cyclic olefin can be selected from cyclooctene, cyclooctadiene, cyclononadiene, norbornene, dicyclopentadiene or a combination thereof. More preferably, the at least one cyclic olefin may be dicyclopentadiene. Still more preferably, the at least one cyclic olefin may be a combination of dicyclopentadiene and tricyclopentadiene.

[0122] According to an embodiment of the present application, the at least one cyclic olefin may be selected from cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, and cyclodecene.

[0123] According to an embodiment of the present application, the cyclic olefin metathesis catalyst may include a metal carbene olefin isotope catalyst, preferably, the cyclic olefin metathesis catalyst may include a metal ruthenium carbene olefin isotope catalyst. Preferably, the cyclic olefin metathesis catalyst may be selected from [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl] The group consisting of (o-isopropoxybenzylidene) dichloride, [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](phenylmethylene) bipyridine dichloride, [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-methyl-2-butenylidene)(tricyclohexylphosphine) dichloride, [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tri(n-butyl)phosphine) dichloride, [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](phenylmethylene)(tricyclohexylphosphine) dichloride and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](phenylindenylidene)(tri(n-butyl)phosphine) dichloride.

[0124] According to an embodiment of the present application, the peroxide inhibitor can be selected from thiodipropionic acid diester, bis(3,5-di-tert-butyl-4-hydroxyphenyl) sulfide, disulfide dipropionamide, hydrogenated hydroquinone, butylated hydroxyanisole, 3,5-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-p-cresol, 2,2-methylenebis(4-methyl-6-tert-butylphenol), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] or a combination thereof.

[0125] According to an embodiment of the present application, the peroxide modifier may be selected from di-tertiarybutyl peroxide (Luperox® DI), di-tert-butylperoxyisopropylbenzene (Perkadox BC-FF), dicumyl peroxide (Perkadox 14S-FL), or any combination thereof.

[0126] According to an embodiment of the present application, the cyclic olefin metathesis catalyst may be a complex having a structure shown in Formula G:

[0127] Among them, L 2 , L 3 are independently selected from neutral electron donor ligands, n is 0 or 1, X 1 , X 2 is halogen, R 1 and R 2 are independently selected from hydrogen, hydrocarbon groups, substituted hydrocarbon groups, hydrocarbon groups containing heteroatoms, substituted hydrocarbon groups containing heteroatoms, and functional groups, R 3 and R 4 is an aromatic group; Q is a group having the structure -CR 5 R 6 -CR 7 R 8 -or- CR 5 =CR 7 - diatomic connection, where R 5 , R 6 , R 7 and R 8 L is independently selected from hydrogen, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon group containing a heteroatom, a substituted hydrocarbon group containing a heteroatom, and a functional group; 2 , L 3 , X 1 , X 2 , R 1 , R 2 , R 3 and R 4 Any two or more of them together form one or more cyclic groups.

[0128] According to another aspect of the present application, a polymerization method of a cycloolefin metathesis composition is provided, wherein the cycloolefin metathesis composition is the cycloolefin metathesis composition as described above, and the polymerization method comprises the following steps: S1 prepares a cyclic olefin solution; S2: adding a peroxide inhibitor to the cyclic olefin solution, wherein the amount of the peroxide inhibitor added is 0.1 to 10 phr relative to the mass ratio of the cyclic olefin; S3 was stirred in an inert gas atmosphere for more than 24 hours; S4: dissolving a cyclic olefin metathesis catalyst in a molar ratio of less than 1 / 100000 relative to the cyclic olefin in a dispersant, and dissolving the dissolved cyclic olefin metathesis catalyst solution in the cyclic olefin solution; S5 is heat cured at 110°C-130°C for 3-5 hours; Before step S4, adding an oxide modifier in a mass ratio of 5-1000 ppm relative to the cyclic olefin to the cyclic olefin solution; and During step S4, a co-catalyst is added in an amount of 10%-20% of the cyclic olefin metathesis catalyst.

[0129] Compared with the prior art, the cycloolefin metathesis composition and polymerization method thereof according to the embodiments of the present application can achieve at least the following beneficial effects: In one embodiment, in a cyclic olefin metathesis reaction catalyzed by an olefin metathesis catalyst (e.g., a cyclic olefin metathesis catalyst), a peroxide inhibitor is added to reduce impurities in the resin that may cause the catalyst to fail so as to improve the catalyst utilization efficiency. In the actual production process, the amount of catalyst used can be effectively reduced, or milder curing conditions can be used, thereby achieving the purpose of reducing production costs and being environmentally friendly.

[0130] In another embodiment, in a cyclic olefin metathesis reaction catalyzed by an olefin metathesis catalyst (eg, a cyclic olefin metathesis catalyst), a highly active second catalyst is added to improve catalyst utilization efficiency.

[0131] In yet another embodiment, in a cyclic olefin metathesis reaction catalyzed by an olefin metathesis catalyst (eg, a cyclic olefin metathesis catalyst), the operation time is adjusted by adding a peroxide modifier, thereby effectively enhancing the flexibility and freedom in the operation time.

[0132] Generally, the amount of the peroxide inhibitor and the second catalyst added can improve the degree of cure and mechanical properties of the cured product formed by the ROMP reaction in the presence of the peroxide inhibitor or the second catalyst, compared to the ROMP reaction catalyzed by the same cyclic olefin metathesis catalyst in the absence of the added peroxide inhibitor and the second catalyst, thereby greatly improving the product performance.

[0133] By introducing a variety of peroxide inhibitors into dicyclopentadiene (DCPD), the peroxide content was significantly reduced, and the peroxide concentration in DCPD was greatly reduced. This improvement effectively reduced the demand for ruthenium catalysts during the curing process, greatly reduced the amount of catalyst used under the same conditions, and significantly improved the economy and sustainability of the reaction.

[0134] In addition, if the amount of catalyst remains unchanged, milder curing conditions can also be considered, further reducing energy consumption and equipment requirements, and broadening the application range of the curing process. These improvements improve the environmental friendliness of the process, enhance product performance and production economy.

[0135] The above is only a specific implementation of the embodiment of the present application, but the protection scope of the embodiment of the present application is not limited thereto, and any changes or replacements within the technical scope disclosed in the embodiment of the present application should be included in the protection scope of the embodiment of the present application. Therefore, the protection scope of the embodiment of the present application should be based on the protection scope of the claims.

Claims

1. A cycloolefin metathesis composition comprising: at least one cyclic olefin; A cyclic olefin metathesis catalyst, the molar ratio of which relative to the cyclic olefin is less than 1 / 100000; A peroxide inhibitor, with a mass ratio of 0.1 to 10 phr relative to the cyclic olefin; a peroxide modifier, in an amount of 5-1000 ppm relative to the cyclic olefin; and The auxiliary catalyst [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl](phenylmethylene)bipyridine ruthenium dichloride has a content of 10%-20% of the cyclic olefin metathesis catalyst.

2. The cycloolefin metathesis composition according to claim 1, wherein The at least one cyclic olefin is selected from cyclooctene, cyclooctadiene, cyclononadiene, dicyclopentadiene, tricyclopentadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-phenyl norbornene, 5-benzyl norbornene, 5-acetyl norbornene, 5-methoxycarbonyl norbornene, 5-ethoxycarbonyl-1-norbornene, 5-methyl-5-methoxy-carbonyl norbornene, 5,5,6-trimethyl-2-norbornene, 2,3-dimethoxynorbornene, norbornadiene, or a combination thereof.

3. The cycloolefin metathesis composition according to claim 1, wherein The at least one cyclic olefin is selected from cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, and cyclodecene.

4. The cycloolefin metathesis composition according to claim 1, wherein The cyclic olefin metathesis catalyst includes a metal carbene olefin metathesis catalyst.

5. The cycloolefin metathesis composition according to claim 4, wherein The cyclic olefin metathesis catalyst comprises a metal ruthenium carbene olefin metathesis catalyst.

6. The cycloolefin metathesis composition according to claim 5, wherein The cyclic olefin metathesis catalyst is selected from [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyl] One or more of (o-isopropoxybenzylidene) ruthenium dichloride, [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene] (phenylmethylene) dipyridinium dichloride, [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene] (3-methyl-2-butenylidene) (tricyclohexylphosphine) ruthenium dichloride, [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene] (benzylidene) (tri(n-butyl)phosphine) ruthenium dichloride, [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene] (phenylmethylene) (tricyclohexylphosphine) ruthenium dichloride and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene] (phenylindenylidene) (tri(n-butyl)phosphine) ruthenium dichloride.

7. The cycloolefin metathesis composition according to claim 1, wherein The peroxide inhibitor is selected from thiodipropionic acid diester, bis(3,5-di-tert-butyl-4-hydroxyphenyl) sulfide, disulfide dipropionamide, hydrogenated hydroquinone, butylated hydroxyanisole, 3,5-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-p-cresol, 2,2-methylenebis(4-methyl-6-tert-butylphenol), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] or a combination thereof.

8. The cycloolefin metathesis composition according to claim 1, wherein The peroxide modifier is selected from di-tert-butyl peroxide, di-tert-butyl peroxide isopropylbenzene, diisopropylbenzene peroxide or any combination thereof.

9. The cycloolefin metathesis composition according to claim 1, wherein The cyclic olefin metathesis catalyst is a complex having a structure shown in Formula G: Among them, L 2 , L 3 are independently selected from neutral electron donor ligands, n is 0 or 1, X 1 , X 2 is halogen, R 1 and R 2 are independently selected from hydrogen, hydrocarbon groups, substituted hydrocarbon groups, hydrocarbon groups containing heteroatoms, substituted hydrocarbon groups containing heteroatoms, and functional groups, R 3 and R 4 is an aromatic group; Q is a group having the structure -CR 5 R 6 -CR 7 R 8 -or- CR 5 =CR 7 - diatomic connection, where R 5 , R 6 , R 7 and R 8 L is independently selected from hydrogen, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon group containing a heteroatom, a substituted hydrocarbon group containing a heteroatom, and a functional group; 2 , L 3 , X 1 , X 2 , R 1 , R 2 , R 3 and R 4 Any two or more of them together form one or more cyclic groups.

10. A method for polymerizing a cycloolefin metathesis composition, wherein the cycloolefin metathesis composition is the cycloolefin metathesis composition according to claim 1, the method comprising the following steps: S1 prepares a cyclic olefin solution; S2: adding a peroxide inhibitor to the cyclic olefin solution, wherein the amount of the peroxide inhibitor added is 0.1 to 10 phr relative to the mass ratio of the cyclic olefin; S3 was stirred in an inert gas atmosphere for more than 24 hours; S4: dissolving a cyclic olefin metathesis catalyst having a molar ratio of less than 1 / 100000 relative to the cyclic olefin in a dispersant, and dissolving the dissolved cyclic olefin metathesis catalyst solution in the cyclic olefin solution; S5 is heat cured at 110°C-130°C for 3-5 hours; Before step S4, an oxide modifier is added to the cyclic olefin solution at a mass ratio of 5-1000 ppm relative to the cyclic olefin; as well as During step S4, an auxiliary catalyst is added in an amount of 10%-20% of the cyclic olefin metathesis catalyst.

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