CN119101214A

CN119101214A - A cycloolefin metathesis composition and polymerization method thereof

Info

Publication number: CN119101214A
Application number: CN202411571145.7A
Authority: CN
Inventors: 管升阳; 顾舜岩; 陈鹏州; 李和华; 孙国斌; 吉明磊; 陈翠萍
Original assignee: Daosheng Tianhe Material Technology Shanghai Co ltd
Current assignee: Daosheng Tianhe Material Technology Shanghai Co ltd
Priority date: 2024-11-06
Filing date: 2024-11-06
Publication date: 2024-12-10

Abstract

The present application relates to a cycloolefin metathesis composition and a polymerization method thereof, the cycloolefin metathesis composition including at least one cyclic olefin, a cyclic olefin metathesis catalyst in a molar ratio of less than 1/100000 with respect to the cyclic olefin, a peroxide inhibitor in a mass ratio of 0.1 to 10phr with respect to the cyclic olefin, a peroxide modifier in a mass ratio of 5 to 1000ppm with respect to the cyclic olefin, and an auxiliary catalyst [1, 3-bis (2, 4, 6-trimethylphenyl) -2-imidazolidine subunit ] (phenylmethylene) bipyridine ruthenium dichloride in an amount of 10% -20% of the cyclic olefin metathesis catalyst. The cyclic olefin double decomposition catalyst and the peroxide inhibitor are combined according to a certain proportion, so that the catalyst loading is reduced, the cost of the cyclic olefin double decomposition composition is reduced, and the mechanical property of the cyclic olefin double decomposition composition after curing is improved, thereby being better suitable for wide chemical application.

Description

Cycloolefin metathesis composition and polymerization method thereof

Technical Field

The present application relates to a cycloolefin resin, and more particularly, to a cycloolefin metathesis composition and a polymerization method thereof.

Background

Dicyclopentadiene (C ₁₀H₁₂, DCPD) is an important organic chemical raw material, mainly purified from C5 fraction or C9 fraction in petroleum cracking process. DCPD is an unsaturated compound containing two double bonds and a plurality of cyclic structures, can be subjected to polymerization reaction under certain conditions, is mainly used for unsaturated polyester, cycloolefin copolymer, polydicyclopentadiene and other purposes in industry, and has important application prospects in the fields of chemical industry and materials.

Polydicyclopentadiene (PDCPD), which is derived from DCPD by Ring Opening Metathesis Polymerization (ROMP), is a high performance thermosetting polymer. PDCPD has lower density, extremely high impact strength, better toughness, acid and alkali resistance and ageing resistance, so that the PDCPD is widely applied to various industrial fields of heavy equipment, automobiles, buildings and the like.

PDCPD curing is commonly performed by using two types of ruthenium or tungsten-molybdenum catalyst systems, and both types of catalysts complete curing through an olefin metathesis mechanism. The tungsten-molybdenum catalyst system is sensitive to water and oxygen, needs higher curing temperature and longer reaction time, and has more severe requirements on the production process. Ruthenium catalysts, especially Grubbs catalysts, have good water-oxygen compatibility and cure under mild conditions. Compared with tungsten-molybdenum catalyst, PDCPD prepared by ruthenium catalyst has better mechanical property and surface quality.

The relatively high price of ruthenium catalysts limits the industrial application prospects of such formulations. In the existing DCPD curing process, the problems of high peroxide content, high catalyst consumption, high curing temperature and the like exist. These problems result in high energy consumption, high raw material cost in the curing process, and severe requirements on reaction conditions, which are unfavorable for wide application in industrial production. In addition, high levels of peroxide may also initiate side reactions that affect the performance stability of the final product. Therefore, there is an urgent need for an improved scheme capable of reducing the impurity content, reducing the catalyst amount or using a mild curing temperature to improve the economical efficiency, environmental protection and product quality of the process. Meanwhile, the operation time of DCPD curing is adjusted by the aid on the premise of not affecting the performance of the cured product, so that diversified process selection and application directions can be provided for the DCPD.

Cross-reference 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 WO2002079126 A1;

U.S. patent application publication US 85101069 A2;

the relevant documents mentioned above are incorporated herein by reference in their entirety.

Disclosure of Invention

The application aims to provide a cycloolefin metathesis composition with low catalyst dosage, strong oxidation resistance and controllable curing time and a polymerization method thereof.

In order to solve the above technical problems, according to one aspect of the present application, there is provided a cycloolefin metathesis composition including at least one cyclic olefin, a cyclic olefin metathesis catalyst in which the molar ratio to the cyclic olefin is less than 1/100000, and a peroxide inhibitor in which the mass ratio to the cyclic olefin is 0.1 to 10phr, a peroxide modifier in which the mass ratio to the cyclic olefin is 5 to 1000 ppm, and an auxiliary catalyst [1, 3-bis (2, 4, 6-trimethylphenyl) -2-imidazolidine subunit ] (phenylmethylene) bipyridyl ruthenium dichloride in an amount of 10 to 20% of the cyclic olefin metathesis catalyst.

According to an embodiment of the present application, the at least one cyclic olefin may be selected from the group consisting of 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, 6-trimethyl-2-norbornene, 2, 3-dimethoxy-norbornene, norbornadiene, or a combination thereof. Preferably, the at least one cyclic olefin may be selected from cyclooctene, cyclooctadiene, cyclononadiene, norbornene, dicyclopentadiene, or a combination thereof. More preferably, the at least one cyclic olefin may be dicyclopentadiene. Still preferably, the at least one cyclic olefin may be a combination of dicyclopentadiene and tricyclopentadiene.

According to embodiments of the present application, the at least one cyclic olefin may be selected from the group consisting of cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, and cyclodecene.

According to embodiments of the present application, the cyclic olefin metathesis catalyst may comprise a metal carbene olefin metathesis catalyst, preferably the cyclic olefin metathesis catalyst may comprise a metal ruthenium carbene olefin metathesis catalyst. Preferably, the cyclic olefin metathesis catalyst is selected from the group consisting of [1, 3-bis (2, 4, 6-trimethylphenyl) -2-imidazolidinylene ] (o-isopropylidenylbenzylidene) ruthenium dichloride, [1, 3-bis (2, 4, 6-trimethylphenyl) -2-imidazolidinylidene ] (phenylmethylene) bipyridyl ruthenium 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 ] (tris (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) (tris (n-butylidene) phosphine).

According to embodiments of the present application, the peroxide inhibitor may be selected from the group consisting of bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide, dithiodipropionamide, hydrogenated hydroquinone, butylhydroxyanisole, 3, 5-di-tert-butyl-p-methylphenol, 2, 6-di-tert-butyl-p-methylphenol, 2-methylenebis (4-methyl-6-tert-butylphenol), pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or a combination thereof.

According to embodiments of the present application, the peroxide modifier may be selected from the group consisting of DI-tert-butyl peroxide (DI-tertiary butyl peroxide, luperox DI), DI-tert-butyl cumene peroxide (Di (tert-butylperoxyisopropyl) benzene, perkadox BC-FF), dicumyl peroxide (Dicumyl peroxide, perkadox 14S-FL), or any combination thereof.

According to an embodiment of the present application, the cyclic olefin metathesis catalyst may be a complex having a structure represented by formula G:

Wherein L ²、L³ is independently selected from neutral electron donor ligands, n is 0 or 1, X ¹、X² is halogen, R ¹ and R ² are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl and functional groups, R ³ and R ⁴ are aromatic groups, Q is a diatomic linkage having the structure-CR ⁵R⁶-CR⁷R⁸ -or-CR ⁵=CR⁷ -, wherein R ⁵、R⁶、R⁷ and R ⁸ are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl and functional groups, and any two or more of L ²、L³、X¹、X²、R¹、R²、R³ and R ⁴ together form one or more cyclic groups.

According to another aspect of the present application, there is provided a polymerization method of a cycloolefin metathesis composition, the cycloolefin metathesis composition being as described above, the polymerization method including the steps of:

S1, preparing a cyclic olefin solution;

s2, adding a peroxide inhibitor into the cyclic olefin solution, wherein the adding amount of the peroxide inhibitor is 0.1-10 phr relative to the mass ratio of the cyclic olefin;

s3, stirring for more than 24 hours in an inert gas atmosphere;

S4 dissolving a cyclic olefin metathesis catalyst having a molar ratio to cyclic olefin of less than 1/100000 in a dispersant, and dissolving the dissolved cyclic olefin metathesis catalyst solution in a cyclic olefin solution;

s5 is thermally cured for 3 to 5 hours at a temperature of 110 to 130 ℃;

Adding an oxide modifier in a mass ratio of 5 to 1000 ppm to the cyclic olefin solution before step S4, and

During step S4, a co-catalyst is added in an amount of 10% -20% of the cyclic olefin metathesis catalyst.

Compared with the prior art, the cycloolefin metathesis composition and the polymerization method thereof according to the embodiment of the application can realize 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), impurities in the resin that may cause catalyst failure are reduced by the addition of peroxide inhibitors to increase catalyst utilization efficiency. The catalyst dosage can be effectively reduced in the actual production process, or milder curing conditions are used, so that the purposes of reducing the production cost and being environment-friendly are achieved.

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

In yet another embodiment, in a cyclic olefin metathesis reaction catalyzed by an olefin metathesis catalyst (e.g., a cyclic olefin metathesis catalyst), the operating time is adjusted by the addition of a peroxide modifier, thereby effectively enhancing flexibility and freedom in operating time.

In general, the peroxide inhibitor and the second catalyst are added in amounts that, in the presence of the peroxide inhibitor or the second catalyst, can increase the degree of cure and mechanical properties of a cured product formed by the ROMP reaction, and thus greatly increase product properties, as compared to a Ring-opening metathesis polymerization (Ring-Opening Metathesis Polymerization, ROMP) reaction catalyzed by the same cyclic olefin metathesis catalyst in the absence of the added peroxide inhibitor and second catalyst.

By introducing various peroxide inhibitors into dicyclopentadiene (DCPD for short, hereinafter the same) the peroxide content is significantly reduced and the peroxide concentration in DCPD is greatly reduced. The improvement effectively reduces the requirement of ruthenium catalyst in the curing process, greatly reduces the dosage of the catalyst under the same condition, and remarkably improves the economy and the sustainability of the reaction.

In addition, if the catalyst dosage is kept unchanged, milder curing conditions can be considered, so that the energy consumption and the requirements on equipment are further reduced, and the application range of the curing process is widened. These improvements promote the environmental protection of the process and enhance the performance and production economy of the product.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following brief description of the drawings of the embodiments will make it apparent that the drawings in the following description relate only to some embodiments of the present application and are not limiting of the present application.

FIG. 1 is a dynamic thermo-mechanical analysis (DMA) chart of a cured product according to example 4j of the present application.

FIG. 2 is a graph of viscosity build curves according to examples 6a-6c of the present application.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Unless otherwise defined, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. As used herein, the word "comprising" and the like means that elements or items preceding the word are included in the element or item listed after the word and equivalents thereof without precluding other elements or items. As used herein, "attached" refers to an attachment that is either direct or indirect, i.e., through an intermediate, unless specifically indicated otherwise.

Unless otherwise indicated, the invention is not limited to specific reactants, substituents, catalysts, reaction conditions, etc., as these may vary. Meanwhile, the terminology used herein is for the purpose of describing particular embodiments only and should not be taken as limiting.

As used in the specification and claims, the terms "for example," "such as," "as," or "comprising," are intended to be used in a complementary manner to aid in understanding the invention, and not in any way limiting.

In the present description and claims, certain terms are mentioned, their specific definitions being as follows:

The term "alkyl" as used herein refers to straight, branched, or cyclic saturated hydrocarbon groups typically containing from 1 to about 24 carbon atoms, preferably from 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, octyl, cyclopentyl, cyclohexyl, and the like. The term "lower alkyl" refers to alkyl groups of 1 to 6 carbon atoms, and the term "cycloalkyl" refers to a cyclic alkyl group, typically 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 replaced with a heteroatom. Unless otherwise indicated, the terms "alkyl" and "lower alkyl" include straight-chain, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl and lower alkyl, respectively. The term "alkylene" refers to a difunctional linear, branched, or cyclic alkyl group.

The terms "cyclic" and "ring" as used herein refer to cycloaliphatic or aromatic groups which may or may not be substituted and/or contain heteroatoms, and may be monocyclic, bicyclic, or polycyclic. The term "cycloaliphatic" is used in a conventional sense to refer to an aliphatic cyclic moiety and may be monocyclic, bicyclic, or polycyclic with respect to an aromatic cyclic moiety.

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

The term "alkynyl" as used herein refers to straight or branched hydrocarbon groups of 2 to about 24 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Preferred alkynyl groups herein contain 2 to about 10 carbon atoms. The term "lower alkynyl" refers to alkynyl groups of 2 to 6 carbon atoms. The term "substituted alkynyl" refers to an alkynyl group substituted with one or more substituents, and the term "heteroalkynyl" refers to an alkynyl group in which at least one carbon atom is replaced 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.

The term "alkoxy" as used herein refers to an alkyl group attached through a single terminal ether linkage, e.g., an "alkoxy" group may be represented as an-O-alkyl group. "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, joined by a single terminal ether linkage, while "alkynyloxy" and "lower alkynyloxy" refer to alkynyl and lower alkynyl groups, respectively, joined by a single terminal ether linkage.

The term "aryl", as used herein, 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 from 5 to 24 carbon atoms and preferred aryl groups contain from 5 to 14 carbon atoms. Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl, naphthyl, biphenyl, diphenyl ether, diphenyl amine, benzophenone, and the like. "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.

The term "aryloxy" as used herein refers to an aryl group bound by a single terminal ether linkage. An "aryloxy" group may be represented as an-O-aryl group. Preferred aryloxy groups contain from 5 to 24 carbon atoms, and preferred aryloxy groups contain from 5 to 14 carbon atoms. Exemplary aryloxy groups include phenoxy, o/m/p halophenoxy, o/m/p methoxyphenoxy, 2, 4-dimethoxyphenoxy, 3,4, 5-trimethoxyphenoxy, and the like.

The term "alkylaryl" as used herein refers to an aryl group having an alkyl substituent, and the term "aralkyl" refers to an alkyl group having an aryl substituent. Preferred alkylaryl and arylalkyl groups contain from 6 to 24 carbon atoms, and preferred alkylaryl and arylalkyl groups contain from 6 to 16 carbon atoms. Exemplary alkylaryl groups include p-methylphenyl, 2, 4-dimethylphenyl, p-cyclohexylphenyl, 2, 7-dimethylnaphthyl, 3-ethyl-cyclopent-1, 4-diene, and the like. Exemplary aralkyl groups include benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenylbutyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like. The terms "alkylaryl" and "arylalkoxy" refer to substituents of formula-OR, wherein R refers to alkylaryl OR arylalkyl.

As used herein, the term "acyl" refers to a compound having the formula- (CO) -alkyl substituents of the- (CO) -aryl or- (CO) -aralkyl radical, the term "acyloxy" refers to a substituent having the formula-O (CO) -alkyl, -O (CO) -aryl, or-O (CO) -aralkyl. In addition, in the case of the optical fiber, the term "acyl" also refers to a compound having the formula- (CO) -aryl substituents of- (CO) -alkenyl or- (CO) -alkynyl, and the term "acyloxy" also refers to substituents having the formula-O (CO) -alkylaryl, -O (CO) -alkenyl, or-O (CO) -alkynyl.

The terms "halo" and "halogen" as used herein refer to fluorine, chlorine, bromine or iodine substituents.

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

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

The term "substituted" in "substituted hydrocarbyl", "substituted alkyl", "substituted aryl", and the like, refers to the substitution of at least one hydrogen atom in a hydrocarbyl, alkyl, aryl, or other group with a non-hydrogen substituent. Such substituents include, but are not limited to, functional groups referred to herein as "Fn", such as halo, hydroxy, mercapto, alkoxy, alkenyloxy, alkynyloxy, aryloxy, aralkoxy, acyl, acyloxy, alkoxycarbonyl, acyloxycarbonyl, halocarbonyl, alkyl/arylcarbonate, 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, N-aryl-substituted thiocarbamoyl, ureido, cyano, thiocyanoyl, formyl, thiocarbamoyl, amino, mono/dialkyl-substituted amino, mono/diaryl-substituted amino, alkylamido, alkylsulfinyl, arylimino, nitro, nitroso, sulfo, alkylthio, arylthio, alkylsulfinyl, alkylsulfonyl, dialkylsulfonyl, monoaryl, borono, phosphono, and phosphono. Other functional groups referred to herein as "Fn" include, but are not limited to, isocyanates and thioisocyanates.

The term "functionalized" in the terms of "functionalized hydrocarbyl", "functionalized alkyl", "functionalized olefin", "functionalized cyclic olefin" and the like, means that at least one hydrogen atom in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety is replaced with a functional group as described above. The term "functional group" is meant to include any functional species suitable for the purposes described herein. Where the particular group permits, the functional group may be further substituted with additional functional groups or hydrocarbyl moieties.

"Optional", "optional" or "optionally" means that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not. For example, the phrase "optionally substituted" refers to the presence or absence of a non-hydrogen substituent on a given atom, and thus, the description includes structures in which the non-hydrogen substituent is present or absent.

The addition of an olefin metathesis catalyst to a cycloolefin or its composition can initiate polymerization under suitable conditions, and the resulting resin composition has a sufficiently low viscosity to be fluid and can be used for the production run for a time called "run time". As the polymerization proceeds, the viscosity of the resin increases so that the resin is no longer free flowing, a so-called gel state. After the resin has reached the gel state, the polymerization reaction continues until no more monomer is consumed, the so-called cured state. The term "working time" as used herein is also understood to mean the "gel time", in particular the time taken to reach a viscosity of 2000 mPa s, measured by a viscometer or by other suitable technique, from the completion of the mixing of all the components of the composition.

Hereinafter, embodiments of the present application are described in detail.

The inventors found that pretreatment of cycloolefin resin with peroxide inhibitor can effectively reduce the peroxide content in the resin and make it possible to reduce the catalyst content in the composition or to make the curing conditions milder. This discovery will effectively reduce the cost of manufacturing and use of the composition. When a combination of peroxide inhibitor and resin is formulated, the content of peroxide inhibitor generally corresponds to the 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 '-methylenebis (4-methyl-6-tert-butylphenol), 2' -methylenebis (4-ethyl-6-tert-butylphenol), 4 '-methylenebis (2, 6-di-tert-butylphenol), 2' -ethylidenedi (4, 6-di-tert-butylphenol), 2 '-methylenebis (4-methyl-6- (1-methylcyclohexyl) phenol), 4,4' -metabisulfidenedi (6-tert-butyl-3-methylphenol), polybutylated bisphenol A, 4 '-thiobis (6-tert-butyl-3-methylphenol), 4' -methylenebis (2, 6-dimethylphenol), 1 '-thiobis (2-naphthol), and methylene bridged polyalkylphenols, 2' -thiobis (4-methyl-6-tert-butylphenol), 2 '-diisobutylidenedi (4, 6-dimethylphenol), 2' -methylenebis (4-methyl-6-cyclohexylphenol), the butylated reaction product of p-cresol and dicyclopentadiene, tetrakis (methylene-3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) methane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 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 (nonylphenyl phosphite), bis (2, 4-di-tert-butyl) pentaerythritol) bisphosphite, distearyl pentaerythritol bisphosphite, phosphite phenol and bisphenol, phosphite/phenol peroxide inhibitor blends, di-n-octadecyl (3, 5-di-tert-butyl-4-hydroxybenzyl) phosphonate, 1, 6-hexamethylenebis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3, 5-di-tert-butyl-4-hydroxyhydrocinnamate, tetra (2, 4-di-tert-butyl) pentaerythritol) bisphenylamine and 4' -diphenyl aniline.

The peroxide modifier is added into the resin, so that the operation time of the resin composition can be effectively prolonged, and more molding processes can be adapted. Generally, peroxides of alkyl, aryl, acyl are used. Suitable peroxides include, but are not limited to, butyl-4, 4-bis (t-butylperoxy) valerate (Trigonox 17-40B-PD), 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane (Trigonox 29-40B-PD), 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane (Trigonox 101), t-butylperoxy-2-ethylhexyl carbonate (Trigonox 117 Solar), t-amyl peroxy-2-ethylhexyl carbonate (Trigonox 131 Solar), 2, 5-dimethyl-2, 5-bis (T-butylperoxy) hexyne (Trigonox 145-E85), 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane (Trigonox 301), 3,5, 7-pentamethyl-1, 2, 4-trioxepane (Trigonox 311), di-T-butyl peroxide (Trigonox B), T-butylcumene peroxide (Trigonox T), T-butyl peroxyisopropyl carbonate (Trigonox BPIC-CP 75), Bis (t-butylperoxyisopropyl) benzene (Perkadox 14S-FL), dicumyl peroxide (Perkadox BC-FF), dibenzoyl peroxide (Perkadox L-40 RPS), bis (2, 4-dichlorobenzoyl) peroxide (Perkadox PD-50S-PS), bis (4-methylbenzoyl) peroxide (Perkadox PM-5 OS-PS), t-butyl peroxyneodecanoate (LUPEROX 10), 2, 5-dimethyl-2, 5-di-t-butylperoxy-3-hexyne (LUPEROX ^®), and the like, 2, 5-dimethyl-2, 5-di-tert-butylperoxy-3-hexyne (LUPEROX ^® 2,5-2, 5), bis (2-ethylhexyl) peroxydicarbonate (LUPEROX ^® S), di-sec-butyl peroxydicarbonate (LUPEROX ^®), a process for preparing the same, 2, 5-dimethyl-2, 5-di-tert-butylperoxy-3-hexyne (LUPEROX ^® 256), tert-butyl peroxy-2-ethylhexanoate (LUPEROX ^®), tert-butyl peroxy-3, 5-trimethylhexanoate (LUPEROX ^® 270 HP), and, DI-tert-butyl peroxide (LUPEROX ^® DI), DI-tert-amyl peroxide (LUPEROX ^® DTA), tert-butyl peroxybenzoate (LUPEROX ^® P). The peroxide may be added directly to the reaction mixture, maintaining its modifying activity for a longer shelf life.

The major component of the resin compositions disclosed herein is one or more cyclic olefins. In general, any cyclic olefin suitable for use in the olefin metathesis reactions disclosed herein may be used. Such cyclic olefins may be optionally substituted, optionally heteroatom-containing, optionally functionalized, monounsaturated, di-unsaturated or polyunsaturated hydrocarbons which may be monocyclic, bicyclic or polycyclic. The cyclic olefin may generally be any stressed or unstressed cyclic olefin provided that the cyclic olefin is capable of participating in a ROMP reaction, either alone or as part of a ROMP cyclic olefin composition. Some unstressed cyclic olefins, while generally not themselves capable of ROMP reactions, may be ROMP active where appropriate. For example, when present as a comonomer in a ROMP composition, the unstressed cyclic olefin may be ROMP active. Thus, as used herein and as will be understood by those of skill in the art, the term "unstressed cyclic olefins" refers to those unstressed cyclic olefins that can undergo ROMP reactions under any condition or in any ROMP composition, provided that the unstressed cyclic olefins are ROMP active.

In general, the cyclic olefin may be represented by the structure of formula a:

Wherein J and R ^A are as follows:

R ^A is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl, if substituted hydrocarbyl or substituted heterohydrocarbyl, wherein the substituent may be a functional group ("Fn") such as phosphino, amino, amido, imino, nitro, hydroxy, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxyl, mercapto, formyl, aminomethyl, epoxy, styryl, silyl, siloxy, silane or halogen.

J is a saturated or unsaturated alkylene, substituted alkylene, heteroatom-containing alkylene or substituted heteroatom-containing alkylene linkage. Two or more substituents attached to the ring atom of J may be linked to form a bicyclic or polycyclic alkene. J will generally contain about 5 to 14 ring atoms, typically 5 to 8 ring atoms per ring.

The monounsaturated cyclic olefin reactant encompassed by structural formula a may be represented by structural formula B:

Wherein b is an integer, typically ranging from 1 to 5, R ^A is as defined above, and R ^B1、R^B2、R^B3、R^B4、R^B5 and R ^B6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl. R ^B1、R^B2、R^B3、R^B4、R^B5 and R ^B6 may be hydrogen, hydroxy, alkyl, aryl, alkoxy, aryloxy, amino, amido, nitro, etc. In addition, any of R ^B1、R^B2、R^B3、R^B4、R^B5 and R ^B6 can be attached to any other group in the R ^B1、R^B2、R^B3、R^B4、R^B5 and R ^B6 groups to form a bicyclic or polycyclic olefin, and the attachment can include heteroatoms or functional groups such as ethers, esters, thioethers, amino groups, alkylamino groups, imino groups, or anhydrides. Examples of monounsaturated monocyclic olefins encompassed by structural formula B include, but are not limited to, cyclohexene, cyclooctene, cyclononene and substituted forms thereof such as 1-methylcyclopentene, 1-isopropylcyclohexene, 4-methylcyclopentene, 4-methoxycyclopentene, cyclopent-3-ene-mercapto, cyclopent-3-ene, 3-methylcyclohexene, 1, 5-dimethylcyclooctene, and the like.

The monocyclic diene reactant encompassed by structural formula a may be generally represented by structural formula C:

Wherein c and d are independently integers in the range of 2 to 4, preferably 2, R ^A is as defined above and R ^C1、R^C2、R^C3、R^C4、R^C5 and R ^C6 are as defined above for R ^B1 to R ^B6, wherein preferably R ^C3 and R ^C4 are non-hydrogen substituents. 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, 1, 3-cyclooctadiene.

The bicyclic and polycyclic olefin reactants encompassed by structural formula a may generally be represented by structural formula D:

Wherein R ^A is as defined above, R ^D1、R^D2、R^D3、R^D4、R^D5 and R ^D6 are as defined above for R ^B1 to R ^B6, and T is a methylene group, a heteroatom or a substituted heteroatom, preferably norbornene and oxanorbornene-type compounds. Examples of bicyclo and polycyclic olefin reactants therefore include, but are not limited to, dicyclopentadiene, tricyclopentadiene, dicyclohexyldiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5, 6-dimethyl-2-norbornene, 5-methoxycarbonylnorbornene, (endo ) -5, 6-dimethoxynorbornene, (endo, exo) -5, 6-dimethoxycarbonylnorbornene, 2, 3-dimethoxynorbornene and the like. Other examples of bicyclo and polycyclic olefins include, but are not limited to, higher oligomers of cyclopentadiene such as cyclopentadiene tetramer, pentamer, and the like, hydrocarbyl-substituted norbornene, 5-butyl-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, and the like.

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

One route for preparing substituted norbornenes employs a diels-alder reaction where cyclopentadiene or a substituent thereof is reacted with a dienophile at elevated temperatures to form a norbornene addition (reaction scheme 1).

Wherein R ^E1、R^E2、R^E3 and R ^E4 are as defined for R ^B1、R^B2、R^B3、R^B4、R^B5 and R ^B6.

Olefin metathesis catalyst

The olefin metathesis catalyst complex of the invention is preferably a ruthenium complex of the formula E.

Wherein L ¹、L²、L³ is a neutral ligand, n is 0 or 1, m is 0, 1 or 2, X ¹、X² is an anionic ligand, R ¹、R² is independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl and functional groups, wherein any two or more of X ¹、X²、L¹、L²、L³、R¹ and R ² are capable of together forming one or more cyclic groups.

The first group of catalysts, commonly referred to as first generation glabros (Grubbs) catalysts, has the structure of formula E. For the first group of catalysts, m is 0, 1 or 2, n is 0, and L ¹ and L ² are independently selected from the group consisting of phosphines, phosphonates, phosphinates, phosphites, ethers, amines, imines, carboxyls, pyridines, substituted pyridines, imidazoles, substituted imidazoles and thioethers. An exemplary ligand is a trisubstituted phosphine. Preferred trisubstituted phosphines have the formula PR ^H1R^H2R^H3 wherein R ^H1、R^H2、R^H3 are each independently aryl or alkyl. Preferably, L ¹ and L ² are independently selected from the group consisting of trimethylphosphine, triethylphosphine, tri-n-butylphosphine, tri (o-tolyl) phosphine, tri-t-butylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, triisopropylphosphine, triisobutylphosphine, trioctylphosphine, triphenylphosphine, tris (pentafluorophenyl) phosphine. X ¹ and X ² are anionic ligands, which may be the same or different, or are linked together to form a cyclic group, typically a five to eight membered ring. Preferably, X ¹ and X ² are each independently hydrogen, halogen or one of alkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, acyl, acyloxy, alkylsulfonyl, arylsulfonyl, alkylsulfanyl, arylsulfanyl, alkylsulfinyl or arylsulfinyl. More preferably, X ¹ and X ² are each halogen, triflate, formate, trimethylcarbonyl, phenoxy, methoxy, ethoxy, tosylate, mesylate. Most preferably, X ¹ and X ² are each chloro. R ¹ and R ² are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl. R ¹ and R ² may also be linked to form a cyclic group, 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.

A second group of catalysts, commonly referred to as second generation glabros catalysts, has the structure of formula E, wherein L ¹ is a carbene ligand having the structure of formula F.

Wherein R ³ and R ⁴ are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl. 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 within Q may also be joined to form additional cyclic structures that may be similarly substituted to provide fused ring structures of 2 to 4 cyclic groups.

Preferred complexes have the structure of formula G.

Preferably, Q is a polypeptide having the structure-CR ⁵R⁶-CR⁷R⁸ -or-CR ⁵=CR⁷ -, preferably-CR ⁵R⁶-CR⁷R⁸ -diatomic linkages, wherein R ⁵、R⁶、R⁷ and R ⁸ are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl, and functional groups. Examples of functional groups herein include carboxyl, alkoxy, aryloxy, alkoxycarbonyl, and acyloxy groups, optionally substituted with one or more moieties selected from alkyl, alkoxy, aryl, hydroxy, mercapto, formyl, and halogen. R ⁵、R⁶、R⁷ and R ⁸ are preferably independently selected from hydrogen, alkyl, substituted alkyl, heteroalkyl, substituted heteroalkyl, phenyl and substituted phenyl. Alternatively, any two of R ⁵、R⁶、R⁷ and R ⁸ may be linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure. R ³ and R ⁴ may be phenyl or phenyl substituted with one or more substituents selected from alkyl, substituted alkyl, heteroalkyl, substituted heteroalkyl, aryl, substituted aryl, heteroaryl, aralkyl, alkaryl, or halo. X ¹ and X ² are halogen.

A third group of catalysts is commonly referred to as "Grubbs-Huo Weida (Grubbs-Hoveyda)" catalysts. The glabros-Huo Weida catalyst can be described by formula H.

Wherein X ¹、X² and L ¹ are as defined above, Y is a heteroatom, and R ⁹、R¹⁰、R¹¹ and R ¹² are each independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylsulfanyl, sulfamoyl, mono/dialkylaminosulfonyl, alkylsulfonyl, nitro, alkylsulfinyl, trihaloalkyl, carboxyl, aldehyde, cyano, or hydroxyl. The combination of Y, Z, R ⁹、R¹⁰、R¹¹ and R ¹² is capable of linking to form a cyclic group. N is 0,1 or 2;n is 1 for the divalent heteroatom O or S and 2 for the trivalent heteroatom N or P. Z is a group selected from hydrogen, alkyl, aryl, substituted alkyl, substituted aryl.

Another group of olefin metathesis catalysts encompassed by structural formula F can be represented by structural formula I:

Wherein X ¹、X²、L¹ and L ² are as defined for the first and second sets of catalysts and R ¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷ and R ¹⁸ are 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.

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

in the above structural formula, ph represents phenyl, cy represents cyclohexyl, i-Pr represents isopropyl, mes represents mesityl (2, 4, 6-trimethylphenyl), DIPP represents 2, 6-diisopropylphenyl, and tBu represents tert-butyl.

In general, the transition metal complexes used herein as catalysts can be prepared by several different methods, see ：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 8510169 A2, the disclosure of each of which is incorporated herein by reference.

The metathesis catalysts described below may be used in olefin metathesis reactions according to techniques known in the art. The catalyst is typically 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 a number of factors such as the nature of the reactants, the nature of the additives and the reaction conditions employed. It will thus be appreciated that the amount of catalyst used can be optimised for each reaction and selected independently. In general, 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 of olefinic substrate (molar ratio).

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 copolymers (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.

In a preferred embodiment, the metathesis reactions disclosed herein can be carried out under a dry inert atmosphere. Such an atmosphere can be created using any inert gas, including gases such as nitrogen and argon. Preferably, the implementation is chosen under an atmosphere of nitrogen and argon, so as to enable the use of low-loading catalysts. The reactions disclosed herein may also be carried out under an oxygen-containing and/or water-containing atmosphere, and in one embodiment, the reactions are carried out under ambient conditions.

The reactions disclosed herein can all be accomplished in a solvent that is inert to the olefin metathesis reaction. Generally, organic solvents such as hydrocarbons, halogenated hydrocarbons, ethers, alcohols, and the like are used in the metathesis reactions herein. Examples include, but are not limited to, benzene, toluene, methylene chloride, 1, 2-dichloroethane, dichlorobenzene, tetrahydrofuran, diethyl ether, methanol, ethanol, or mixtures thereof. Preferably, it is carried out with little or no solvent.

The temperature of the metathesis reactions disclosed herein should be adjusted as desired and can be-78 ℃, -40 ℃, -10 ℃,0 ℃, 20 ℃,25 ℃, 35 ℃,70 ℃, 100 ℃, or 170 ℃.

Examples

The following list some examples, which further illustrate the invention, but should not in any way limit the scope of the invention.

In the following examples, the existence of experimental errors and deviations should be considered. As long as no other description is given, "DCPD" and "liquefied DCPD" (except "pure DCPD") refer to a modified liquid feedstock containing 10% to 15% by mass of tricyclopentadiene and small amounts of higher cyclopentadiene homologs, "ppm" refers to parts by mass of related substances per million parts by mass of DCPD, "phr" refers to parts by mass of related substances per hundred parts by mass of DCPD, "n/n, relative to monomer" refers to the ratio of the moles of pure DCPD of related substances to the mass of liquefied DCPD, and the curing procedure "a °c× b h" refers to continuous curing b h while maintaining a °c temperature.

Materials and test methods

All glassware and curing vessels were oven dried and the reaction was run at ambient conditions unless otherwise indicated. Unless otherwise indicated, all solvents and reagents were purchased from commercial suppliers and used directly.

Liquefied dicyclopentadiene (liquefied DCPD) is available from Guangdong New Yongdong petrochemical Co., inc., and contains 10% to 15% of tricyclopentadiene and a small amount of higher cyclopentadiene homologs.

Bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide was obtained from Guangzhou by new materials limited (peroxide inhibitor 1035). N, N '-dimethyl-3, 3' -dithiodipropionamide was obtained from Beijing Soy Corp. Tert-butyl-4-hydroxyanisole was obtained from Shanghai Meilin Biochemical technologies Co. 2, 2-methylenebis (4-methyl-6-t-butylphenol) was obtained from Shanghai Meilin Biochemical technologies Co., ltd (peroxide inhibitor 2246). Pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] was obtained from basf (china) limited (IRGANOX ^® 1010).

The metathesis catalyst was prepared by standard methods and included [1, 3-bis (2, 4, 6-trimethylphenyl) -2-imidazolidinylene ] (o-isopropylidenylbenzylidene) ruthenium dichloride (G627), [1, 3-bis (2, 4, 6-trimethylphenyl) -2-imidazolidinylidene ] (phenylmethylene) bipyridylium 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-imidazolidinylidene ] (tri (n-butyl) phosphine) ruthenium dichloride (G771), [1, 3-bis (2, 4, 6-trimethylphenyl) -2-imidazolidinylidene ] (phenylmethylene) (tricyclohexylphosphine) ruthenium dichloride (G849), and [1, 3-bis (2, 6-trimethylphenyl) -2-imidazolidinylidene (G871). The dispersing agent for the catalyst (3M ^TMNovec^TM DE) was obtained from 3M China and used directly.

Di-tert-butyl peroxide was obtained from Sigma Aldrich (Shanghai) trade Co., ltd (Luperox ^® DI) and used directly. Dicumyl peroxide was obtained from Noron chemical (Ningbo) Inc. (Perkadox BC-FF) and used directly. Di-tert-butylcumene hydroperoxide was obtained from Noron chemical (Ningbo) Inc. (Perkadox 14S-FL) and used directly.

The method for measuring the peroxide content in the DCPD raw material comprises the following implementation standard of GB/T12688.4-2011, industrial styrene test method and part 4, namely a method for measuring and titration of the peroxide content.

Glass transition temperature (Tg) was measured on TA DMA Q800 using thermal Dynamic Mechanical Analysis (DMA) (standard: ASTM D5023). Scanning temperature is 40-200 ℃ and 5 ℃ per minute. Test mode three point bending. The Tan delta value was taken as the measurement result of Tg.

Tensile properties were determined using standard techniques (standard: ISO 527-2:2012), all results being the average of 6 samples.

The operating time was measured on a Brookfield DVNXLVMJC viscometer and data analysis was performed by RheocalcT software. A 100g sample at a set temperature of 25 ℃ was measured using a No. 2 rotor set at 14 rpm. Data points were recorded at intervals of 2 s.

Example 1

The peroxide content in liquefied DCPD is reduced by the addition of peroxide inhibitors.

At normal temperature, a specified amount of each type of peroxide inhibitor was added to 150 g liquefied DCPD, and stirred under an inert gas atmosphere for 24: 24 h. The peroxide content of the obtained solution was measured (Table 1). It can be seen from table 1 that by adding peroxide inhibitors, the peroxide content is significantly reduced. The reduction of peroxide enhances the activity of the catalyst, so that the total amount of catalyst can be reduced.

TABLE 1 peroxide content of raw materials with various peroxide inhibitors in different addition amounts

Example 2

Curing of DCPD with the addition of peroxide inhibitors.

To 250g of liquefied DCPD, a prescribed amount of each type of peroxide inhibitor was added at room temperature, and stirred under an inert gas atmosphere for 24 h. 1/40000 (molar ratio relative to DCPD monomer) of the catalyst was weighed out and dissolved in the dispersant and in the liquefied DCPD. The solution was transferred to a curing mold and cured using a procedure of 120 ℃ x 4 h. The cured articles were measured for glass transition temperature (Tg, table 2) using dynamic thermo-mechanical analysis. Wherein, the tensile properties were also measured in examples 2i and 2j (for comparison of the results, see Table 4). As can be seen from table 2, the activity of the catalyst is enhanced and the catalytic effect is significantly enhanced with the addition of the peroxide inhibitor, and Tg is correspondingly increased, so that the amount of the catalyst can be reduced when the polymerization conditions are satisfied.

TABLE 2 Tg of cured product after addition of peroxide inhibitor

Example 3

Curing of DCPD with addition of peroxide inhibitors and reduced catalyst usage.

To 250g of liquefied DCPD, a prescribed amount of N, N '-dimethyl-3, 3' -dithiodipropionamide (the type of peroxide inhibitor used in the examples in tables 3 and 4) was added at ordinary temperature, and stirred under an inert gas atmosphere for 24 h. A specified amount of catalyst is weighed out and dissolved in the dispersant and dissolved in the liquefied DCPD. The solution was transferred to a curing mold and cured using a procedure of 120 ℃ x 4h. The cured articles were measured for glass transition temperature (Tg, table 3) using dynamic thermo-mechanical analysis. Among them, the tensile properties were also measured in examples 3d to 3e and 3j to 3l (Table 4). As can be seen from Table 3, the Tg increases with increasing peroxide addition under certain catalyst conditions, and the activity of the catalyst is enhanced and the catalytic effect is significantly enhanced under the addition of peroxide inhibitor, so that the catalyst dosage can be reduced under the condition of meeting polymerization conditions.

TABLE 3 addition of peroxide inhibitor and reduction of catalyst level of cured Tg

* "No data" refers to a situation that may not be readable within the measurement range 76 because the glass transition temperature is too low.

TABLE 4 tensile Properties of cured products with peroxide inhibitor added and catalyst level reduced

Example 4

DCPD curing with addition of peroxide inhibitors and reduced curing temperature.

To 250g of liquefied DCPD, a prescribed amount of N, N '-dimethyl-3, 3' -dithiodipropionamide (peroxide inhibitor) was added at ordinary temperature, and stirred under an inert gas atmosphere for 24 h. 1/40000 (molar ratio relative to DCPD monomer) of the catalyst was weighed out and dissolved in the dispersant and in the liquefied DCPD. The solution was transferred to a curing mold and cured using the indicated temperature for 4 hours. The cured articles were measured for glass transition temperature (Tg, table 5) using dynamic thermo-mechanical analysis. As can be seen from table 5, the activity of the catalyst is enhanced and the catalytic effect is remarkably enhanced in the case of adding the peroxide inhibitor, and thus the amount of the catalyst can be reduced in the case of satisfying the polymerization conditions.

TABLE 5 cured Tg of the cured product with addition of peroxide inhibitor and reduction of curing temperature

FIG. 1 is a dynamic thermo-mechanical analysis (DMA) chart of a cured product according to example 4j of the present application. As shown in FIG. 1, a cured product with a peroxide inhibitor added and a curing temperature lowered can obtain better dynamic thermo-mechanical properties.

Example 5

DCPD curing using a dual catalyst combination.

At normal temperature, 250G liquefied DCPD, 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 in the liquefied DCPD. The solution was transferred to a curing mold and cured using a procedure of 120 ℃ x 4h. The cured articles were measured for glass transition temperature (Tg, table 6) using dynamic thermo-mechanical analysis. As can be seen from the data set forth in Table 6, by reducing the total amount of catalyst, the cost of the cycloolefin metathesis composition can be reduced significantly, and the Tg threshold of the cured product can be lowered, thereby reducing the glass transition temperature and significantly reducing the energy consumption.

TABLE 6 influence of incorporation of different concentrations of G727 on Tg of low-load catalyst formulation cure

Example 6

Peroxide is added to extend the operating time.

A specified amount of peroxide was dissolved in 150g of liquefied DCPD at normal temperature. 1/40000 (molar ratio relative to DCPD monomer) of the procatalyst was weighed out and dissolved in the dispersant and liquefied DCPD. The viscosity of the mixture was measured using a rotational viscometer, and the operation was stopped when the viscosity increased to 2 Pa ·s, and the operation time was recorded (table 7). As can be seen from Table 7, the pot life of the cycloolefin metathesis polymer formed after polymerization is significantly improved by the addition of peroxide modifiers.

TABLE 7 influence of peroxide type and amount on Tg of DCPD cured product

FIG. 2 is a graph of viscosity build curves according to examples 6a-6c of the present application. As shown in fig. 2, the effect of peroxide type and amount on the viscosity change of the DCPD cured product tended.

Example 7

And adding a peroxide inhibitor, a peroxide modifier and curing DCPD under the condition of double catalysts.

IRGANOX 1010 peroxide inhibitor was added to 500g of liquefied DCPD at room temperature at a peroxide inhibitor to cyclic olefin mass ratio of 0.5phr. And stirred 24 h under an inert gas atmosphere. Luperox DI 1/100000 (molar ratio relative to DCPD monomer) was added to extend the run time. Subsequently 1/100000 (molar ratio relative to DCPD monomer) of the procatalyst G771 and 1/10 (relative to the procatalyst) of the G727 (second catalyst) were weighed out 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 the procedure of 120 ℃ x 4 h. The cured article was measured for glass transition temperature using dynamic thermo-mechanical analysis at 110 ℃. The other half of the samples were measured for viscosity of the mixture using a rotational viscometer, and the operation was stopped when the viscosity increased to 2 Pa s, and the operation time was recorded as 102min.

According to an aspect of the present application, there is provided a cycloolefin metathesis composition including at least one cyclic olefin, a cyclic olefin metathesis catalyst in a molar ratio of less than 1/100000 with respect to the cyclic olefin, a peroxide inhibitor in a mass ratio of 0.1 to 10phr with respect to the cyclic olefin, a cycloolefin metathesis composition may further include a peroxide modifier in a mass ratio of 5 to 1000ppm with respect to the cyclic olefin, and the cycloolefin metathesis composition may further include an auxiliary catalyst [1, 3-bis (2, 4, 6-trimethylphenyl) -2-imidazolidine dichloride ] in an amount of 10% to 20% of the cyclic olefin metathesis catalyst.

S1, preparing a cyclic olefin solution;

s3, stirring for more than 24 hours in an inert gas atmosphere;

s5 is thermally cured for 3 to 5 hours at a temperature of 110 to 130 ℃;

In another embodiment, in a cyclic olefin metathesis reaction catalyzed by an olefin metathesis catalyst (e.g., a cyclic olefin metathesis catalyst), catalyst utilization efficiency is improved by adding a highly active second catalyst.

In general, the peroxide inhibitor and the second catalyst are added in amounts that, in the presence of the peroxide inhibitor or the second catalyst, can increase the degree of cure and mechanical properties of the cured product formed by the ROMP reaction, and thus greatly increase product properties, as compared to ROMP reactions catalyzed by the same cyclic olefin metathesis catalyst in the absence of the added peroxide inhibitor and second catalyst.

By incorporating various peroxide inhibitors into dicyclopentadiene (DCPD), the peroxide content is significantly reduced, and the peroxide concentration in the DCPD is greatly reduced. The improvement effectively reduces the requirement of ruthenium catalyst in the curing process, greatly reduces the dosage of the catalyst under the same condition, and remarkably improves the economy and the sustainability of the reaction.

The foregoing is merely a specific implementation of the embodiment of the present application, but the protection scope of the embodiment of the present application is not limited to this, and any changes or substitutions within the technical scope disclosed in the embodiment of the present application should be covered in the protection scope of the embodiment of the present application. Therefore, the protection scope of the embodiments of the present application shall be subject to 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 cyclic olefin metathesis composition of claim 1, wherein the at least one cyclic olefin is selected from the group consisting of 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, norbornadiene, or a combination thereof.

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

4. The cyclic olefin metathesis composition of claim 1, wherein the cyclic olefin metathesis catalyst comprises a metal carbene olefin metathesis catalyst.

5. The cyclic olefin metathesis composition of claim 4, wherein the cyclic olefin metathesis catalyst comprises a metal ruthenium carbene olefin metathesis catalyst.

6. The cyclic olefin metathesis composition of 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 cyclic olefin metathesis composition of claim 1, wherein the peroxide inhibitor is selected from dithiodipropionate, 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 of 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 cyclic olefin metathesis composition of claim 1, wherein the cyclic olefin metathesis catalyst is a complex having a structure shown in Formula G:

wherein L ² and L ³ are independently selected from neutral electron donor ligands, n is 0 or 1, X ¹ and X ² are halogens, 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, and R ³ and R ⁴ are aromatic groups; Q is a diatomic linker having the structure -CR ⁵ R ⁶ -CR ⁷ R ⁸ - or - CR ⁵ =CR ⁷ -, wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently selected from hydrogen, hydrocarbon groups, substituted hydrocarbon groups, hydrocarbon groups containing heteroatoms, substituted hydrocarbon groups containing heteroatoms and functional groups; any two or more of L ² , L ³ , X ¹ , X ² , R ¹ , R ² , R ³ and R ⁴ 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; and

During step S4, an auxiliary catalyst is added in an amount of 10%-20% of the cyclic olefin metathesis catalyst.