Polymerizable compositions of cyclic olefin monomers and related ring-opening metathesis polymerization processes

Abstract

The present invention provides a polymerizable monomer composition containing a cyclic olefin monomer having a large ring strain, which facilitates handling during processing without chemical activation and without the risk of premature and uncontrollable ROMP reactions. [Solution] A polymerizable composition is provided comprising a monomer containing a cyclic olefin monomer having a ring strain greater than 85 kJ / mol, preferably greater than 100 kJ / mol; one or more 18-electron shroc alkylidene adducts selected from complexes of 14-electron shroc alkylidene compounds and bidentate ligands; and an inert solvent in an amount of less than 10% by weight, preferably less than 5% by weight, relative to the weight of the polymerizable composition. Furthermore, a ring-opening metathesis polymerization process and polymerized articles that can be obtained by the process are also provided.

Description

[Technical Field]

[0001] The present invention relates to a polymerizable composition comprising a monomer including a cyclic olefin monomer. The present invention also relates to a ring-opening metathesis polymerization (ROMP) process using the polymerizable composition. Finally, the present invention relates to a novel polymerized article that can be obtained by the ROMP process. [Background technology]

[0002] The production of polymers and copolymers by ring-opening metathesis polymerization (ROMP) of cyclic olefin monomers is well known in the art. A suitable example is the production of polydicyclopentadiene polymers (PDCPDs) using dicyclopentadiene monomers and metathesis catalyst systems. Examples of other monomers that can be copolymerized with DCPDs include monocyclic olefins containing three or more carbon atoms and one or more double bonds. Typical examples include cyclooctadiene (COD) monomer, tricyclopentadiene (TCPD) monomer, and ethylidene norbornene (ENB) monomer.

[0003] The cyclic olefin monomers (ROMPs) can be catalyzed by organometallic complexes having a transition metal atom as the central atom. Examples of transition metals include tantalum, molybdenum, tungsten, ruthenium, and osmium. Alkylidene complexes of molybdenum (Mo) and tungsten (W) are called Schrock catalysts and are one of the most promising catalysts in olefin metathesis reactions, such as the group of Mo(VI) and W(VI) alkylidene complexes.

[0004] While such catalysts can be effective in catalyzing ROMP of cyclic olefin monomers, they are known in the art to often lack stability in air. Therefore, these catalysts are more difficult to handle, and their usefulness is often limited, especially in processes that cannot be carried out under inert conditions.

[0005] International Publication No. 2012 / 116695 proposes a solution to overcome the lack of stability in air by complex formation between the catalyst and bidentate heterocycles such as 1,10-phenanthroline or 2,2'-bipyridine, the entire contents of which are incorporated herein by reference. In this process, for example, an 18-electron molybdenum or tungsten alkylidene complex is formed by a 14-electron molybdenum or tungsten alkylidene complex (referred to as the "parent complex" in the said document) and 1,10-phenanthroline or 2,2'-bipyridine as a neutral bidentate ligand. However, it was found that catalysts exhibiting such stability in air lacked catalytic activity and required chemical activation by exposure to Lewis acids such as MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, or Zn(trifluoroacetate)2. The need to add such Lewis acids is undesirable in many production processes, for example, due to the formation of undesirable byproducts, and should be avoided if possible.

[0006] International Publication No. 2021 / 239891 discloses a shrock alkylidene complex containing a phenanthrene ligand. The inventors of International Publication No. 2021 / 239891 disclose a shrock alkylidene complex in which, when the complex is dissolved in a solvent, the volume is measured at 25°C, resulting in a volume of 5 L·mol. -1 ~250,000 L·mol -1 It has been found that complexes with a finite stability constant within a certain range can possess both stability in air and catalytic activity in olefin metathesis reactions without the need to remove bidentate ligands using Lewis acids, and therefore without the unnecessary formation of corresponding byproducts. Such complexes are thought to be self-activating upon dissolution.

[0007] However, with such catalysts, it is considered difficult to control the ROMP kinetics, particularly with respect to the polymerization of a composition containing at least a cyclic olefin monomer having a ring strain greater than 85 kJ / mol. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] Therefore, an object of the present invention is to provide a polymerizable composition of a monomer containing a cyclic olefin monomer having a large ring strain, which enables easy handling in processing without chemical activation and without causing the risk of early and uncontrollable ROMP reactions. Another object of the present invention is to provide a trouble-free molding operation and a practical production method that can be easily scaled up. A further object is to provide a ring-opening metathesis polymerization (ROMP) process using the polymerizable composition and a novel polymerized article obtainable by using this ROMP process according to the present invention. MEANS FOR SOLVING THE PROBLEMS

[0009] These objects and other objects are achieved by the polymerizable composition according to claim 1. The polymerizable composition is · a monomer containing a cyclic olefin monomer having a ring strain greater than 85 kJ / mol, preferably greater than 100 kJ / mol, and · a 14-electron Schrock alkylidene compound and a compound of formula (I):

Chemical formula

[0010] According to the present invention, the catalyst system comprises one or more 18-electron shroc alkylidene adducts as described in the claims. The inventors have found that the 18-electron shroc alkylidene adduct described in the claims maintains a non-dissociative state for a certain period, at least up to room temperature, in a composition comprising the 18-electron shroc alkylidene compound and a cyclic olefin monomer having a ring strain greater than 85 kJ / mol. This allows for uniform mixing of the 18-electron shroc alkylidene adduct in the composition without the occurrence of premature ROMP reactions. Such premature ROMP reactions may lead to catalyst embedding and incomplete polymerization. However, surprisingly, the same 18-electron shroc alkylidene adduct described in the claims as described above is considered to ultimately exhibit autocatalytic activity at room temperature, even when the composition does not contain an inert solvent. The inventors have found that this occurs only when the composition contains a monomer comprising a cyclic olefin monomer having a ring strain greater than 85 kJ / mol, preferably greater than 100 kJ / mol, as described in the claims.

[0011] Thus, the compositions described in the claims are considered to be easily prepared at room temperature and capable of polymerization in a controlled manner without chemical activation. This is extremely important when the reaction is carried out on an industrial scale, because such a reaction must be controllable. Furthermore, actively heating the compositions to temperatures above room temperature is not obviously ruled out, but is considered unnecessary.

[0012] In compositions containing at least a cyclic olefin monomer having a ring strain greater than 85 kJ / mol, the parent compound, a 14-electron shrok alkylidene compound, is considered to be highly active. Therefore, directly adding the parent compound, a 14-electron shrok alkylidene compound, to the composition results in uncontrollable ROMP. Thus, the above finding is all the more surprising.

[0013] In another aspect of the present invention, (a) the step of providing a polymerizable composition as described in the claims, (b) The step of subjecting the polymerizable composition to ring-opening metathesis polymerization. A ring-opening metathesis polymerization (ROMP) process is provided, which includes [the specified element].

[0014] In yet another aspect of the present invention, a novel polymerized article is provided which can be obtained by the ring-opening metathesis polymerization process described in the claims, the polymerized article containing a total amount of metallic Mo and W of 5 to 100 ppm relative to the weight of the polymerized article. [Modes for carrying out the invention]

[0015] The present invention • A monomer comprising a cyclic olefin monomer having a ring strain greater than 85 kJ / mol, preferably greater than 100 kJ / mol, • 14-electron shrock alkylidene compounds and formula (I): [ka] [In the formula, R a , R b , R c , R d , R e , R f , R g , and R h H, halogen, nitro, cyano, trifluoromethyl, C1-C 12 -Alkoxycarbonyl, C1~C 12 -alkyl, 5-18 member aryl, C1-C 12 - Independently selected from the group consisting of alkyloxy and di(C1~C4-alkyl)amino, or the group R d and R e They bond to each other to form a 6-membered ring, and at that time, R d and R e These combine to form the base C(R i )=C(R j ) forms, and here, R i and R jH, halogen, nitro, cyano, trifluoromethyl, C1-C 12 -Alkoxycarbonyl, C1~C 12 -alkyl, 5-18 member aryl, C1-C 12 One or more 18-electron shrock alkylidene adducts selected from complexes with bidentate ligands independently selected from the group consisting of -alkyloxy and di(C1-C4-alkyl)amino, Here, the one or more 18-electron shlock alkylidene adducts were determined according to the protocol specified in the experimental section, at 250,000 L·mol in deuterated benzene (C6D6) at 25°C. -1 Larger, preferably 300,000 L·mol -1 Larger, more preferably 400,000 L·mol -1 Larger, and more preferably 500,000 L·mol -1 One or more 18-electron shrock alkylidene adducts having a larger stability constant K, • Less than 10% by weight, preferably less than 5% by weight, of the polymerizable composition, an inert solvent and / or carrier A polymerizable composition containing the following is provided.

[0016] As used herein, the term "inert solvent" refers to a solvent that does not react under ROMP polymerization conditions.

[0017] As defined herein, an 18-electron shlock alkylidene adduct is a complex of a 14-electron shlock alkylidene compound with a bidentate ligand of formula (I). Therefore, as defined herein, an 18-electron shlock alkylidene adduct includes both a 14-electron shlock alkylidene compound and a bidentate ligand of formula (I). This means that the expression "one or more 18-electron shlock alkylidene adducts selected from complexes of 14-electron shlock alkylidene compounds with a bidentate ligand of formula (I)" is identical and interchangeable with "one or more 18-electron shlock alkylidene adducts selected from complexes of 14-electron shlock alkylidene compounds having a bidentate ligand of formula (I)".

[0018] The compositions of the present invention particularly comprise an 18-electron shroc alkylidene adduct having relatively high stability and a monomer, wherein the monomer comprises at least partially a cyclic olefin monomer, which preferably has at least two carbon-carbon double bonds and a ring strain greater than 85 kJ / mol. The combination of the relatively high stability of the 18-electron shroc alkylidene adduct and the large ring strain of the cyclic olefin monomer, which preferably has at least two carbon-carbon double bonds, plays an important role in achieving the above-mentioned objectives of the present invention.

[0019] In one preferred embodiment, one or more 18-electron shlock alkylidene adducts are derived from formula (II): [ka] [In the formula, M is Mo or W, A is O, or NR 3 And, R 1 and R 2 H, C1~C 12 - Independently selected from the group consisting of alkyl and 5-18 membered aryl, where C1-C 12 -alkyl and the 5-18 member aryl are C1-C 12- Alkyl group, 5-18 membered aryl group, C1-C 12 - May be substituted with one or more of the alkyloxy group, di(C1~C4-alkyl)amino group, halogen group, trifluoromethyl group, cyano group, and nitro group, however R 1 and R 2 It is assumed that they cannot become hydrogen at the same time. R 3 C1~C 12 -Selected from the group consisting of alkyl and 5-18 membered aryls, where C1-C 12 -alkyl and the 5-18 member aryl are C1-C 12 - Alkyl group, 5-18 membered aryl group, C1-C 12 - May be substituted with one or more of the following: alkoxy group, di(C1-C4-alkyl)amino group, halogen group, trifluoromethyl group, cyano group, and nitro group. X and Y are halogens, methanesulfonyloxy, trifluoromethanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy, pyrrolyl, indolyl, pyrazolyl, C1-C 12 -Alkyloxy, 5-18 member aryloxy, tri(C1-C) 12 -alkyl)silyloxy, tri(C6~C 18 -aryl)silyloxy, di(C1~C 12 -alkyl)(C6~C 18 -aryl)silyloxy, (C1~C 12 -alkyl) di(C6~C 18 -aryl)silyloxy, and tri(C1~C 12 These are independently selected from the group consisting of -alkyloxy)silyloxy, and these are C1~C 12 - Alkyl group, 5-18 membered aryl group, C1-C 12 - May be substituted with one or more alkyloxy groups, di(C1-C4-alkyl)amino groups, halogen groups, trifluoromethyl groups, cyano groups, and nitro groups, or groups X and Y together form formula (III-A), (III-B), or (III-C): [ka] forms the structure, where R A 、R B 、R C 、R D 、R E 、R F 、R G 、and R H is independently selected from the group consisting of H, halogen, nitro, cyano, trifluoromethyl, C1 - C 12 -alkoxycarbonyl, C1 - C 12 -alkyl, 5 - 18-membered aryl, C1 - C 12 -alkyloxy, and di(C1 - C4-alkyl)amino] A polymerizable composition selected from the group represented by

[0020] In the context of this application, the following terms have the following meanings: · 「C1 - C 12 -alkyl」 represents an unbranched, branched, or cyclic alkyl group having 1 to 12 carbon atoms; · 「5 - 18-membered aryl」 represents a monocyclic, bicyclic or tricyclic carbocyclic or heterocyclic aromatic group, and the aromatic group can have 0 to 5 substituents selected from the list of C1 - C 12 -alkyl, C1 - C 12 [[ID=四十一]]-alkoxy, di(C1 - C4-alkyl)amino, halogen, cyano, and nitro; · 「di(C1 - C4-alkyl)amino」 represents an amino group having 2 unbranched, branched, or cyclic alkyl substituents, and the 2 alkyl substituents each have 1 to 4 carbon atoms and may be the same or different; · 「halogen」 includes fluorine, chlorine, bromine, and iodine.

[0021] Preferred alkyl groups within the scope of the present invention are, but are not limited to, unbranched, branched, or cyclic alkyl groups having 1 to 12 carbon atoms, such as methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, hexafluoroisopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, trifluoro-tert-butyl, hexafluoro-tert-butyl, nonafluoro-tert-butyl, 1-ethylpropyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and adamantyl.

[0022] Preferred aryl groups within the scope of the present invention can be selected from phenyl, naphthyl, anthryl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, di(isopropyl)phenyl, tri(isopropyl)phenyl, tert-butylphenyl, di(tert-butyl)phenyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, trifluoromethylphenyl, bis(trifluoromethyl)phenyl, fluorophenyl, difluorophenyl, chlorophenyl, dichlorophenyl, bromophenyl, iodophenyl, pentafluorophenyl, dimethylaminophenyl, phenylphenyl, diphenylphenyl, (methoxycarbonyl)phenyl, (ethoxycarbonyl)phenyl, and (tert-butoxycarbonyl)phenyl. Furthermore, heterocyclic aryl groups having up to two heteroatoms selected from N, O, and / or S, such as furyl, thienyl, thiazolyl, oxazolyl, indolyl, isothiazolyl, isoxazolyl, pyrazolyl, imidazolyl, pyridyl, pyrimidinyl, pyridadinyl, pyrazinyl, benzofuranyl, benzothiophenyl, benzimidazolyl, and carbazolyl, are also included in the scope of the present invention.

[0023] Preferred di(C1-C4-alkyl)amino groups within the scope of the present invention can be selected from N,N-dimethylamino, N,N-diethylamino, N-ethyl-N-methylamino, N-methyl-Nn-propylamino, N-isopropyl-Nn-propylamino, N,N-diisopropylamino, Nn-butyl-N-methylamino, and N-tert-butyl-N-methylamino.

[0024] In another preferred embodiment of the present invention, a polymerizable composition as defined herein, comprising one or more 18-electron shroc alkylidene adducts of formulas (II-A) and (II-B): [ka] [In the formula, M, A, X, Y, R 1 , and R 2 This is as defined above. Polymerizable compositions selected from are provided.

[0025] In formula (II-A), preferred examples of 2,2'-bipyridines (2,2'-dipyridyls) that can be used as ligands to stabilize a 14-electron shrock alkylidene complex of molybdenum or tungsten within the scope of the present invention include 2,2'-bipyridine, 5,5'-dimethyl-2,2'-dipyridyl, 4,4'-dimethyl-2,2'-dipyridyl, 6,6'-dimethyl-2,2'-dipyridyl, 4,4'-dimethoxy-2,2'-bipyridine, 2,2'-biquinoline, 4,4'-di-tert-butyl-2,2'-dipyridyl, and 2,2'-bipyridinyl-4,4'-dicarboxylate di Examples include methyl esters, 4,4'-diphenyl-2,2'-dipyridyl, 6,6'-dibromo-2,2'-dipyridyl, 4,4'-dinonyl-2,2'-dipyridyl, 2,2'-biquinolinyl-4,4'-dicarboxylate dibutyl ester, 2,2'-biquinolinyl-4,4'-dicarboxylate diheptyl ester, 6-methyl-2,2'-dipyridyl, 2-(2-pyridinyl)quinoline, 2-pyridine-2-yl-4-pyrroridine-1-ylquinoline, 4-piperidine-1-yl-2-pyridine-2-ylquinoline, and 4-morpholine-4-yl-2-pyridine-2-ylquinoline.

[0026] In formula (II-B), preferred examples of 1,10-phenanthrolines that can be used as ligands to stabilize a 14-electron shrock alkylidene complex of molybdenum or tungsten within the scope of the present invention include 1,10-phenanthroline, 4-methyl-1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 2,9-dimethyl[1,10]phenanthroline, 5,6-dimethyl-1,10-phenanthroline, and 5 Examples include chloro[1,10]phenanthroline, 4,7-dichloro-1,10-phenanthroline, 4,7-dichloro-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 4,7-diphenyl[1,10]phenanthroline, 2,9-dimethyl-4,7-diphenyl[1,10]phenanthroline, 5-nitro-1,10-phenanthroline, and 4,7-dimethoxy-1,10-phenanthroline.

[0027] In yet another preferred embodiment, a polymerizable composition, wherein R 3 is selected from the group consisting of C1-C 10 -alkyl or phenyl, and the C1-C 10 -alkyl or the phenyl may be substituted with one or more of a C1-C 10 -alkyl group, a phenyl group, a C1-C 10 -alkoxy group, a halogen group, a trifluoromethyl group, a cyano group, and a nitro group, is provided.

[0028] In another embodiment, R 3 is of formulas (IV-A) and (IV-B): [Chemical formula] [wherein, R 4 , R 5 , and R 6 are independently selected from the group consisting of H, halogen, trifluoromethyl, methyl, ethyl, propyl, butyl, isopropyl, and tert-butyl] is selected from.

[0029] According to another embodiment, a polymerizable composition, wherein R 1 and R 2 are independently selected from the group consisting of H, C1-C 10 -alkyl, and phenyl, and the C1-C 10 -alkyl and the phenyl may be substituted with one or more of a C1-C 10 -alkyl group, a phenyl group, a C1-C 10 -alkyloxy group, a halogen group, a trifluoromethyl group, a cyano group, and a nitro group, is provided.

[0030] According to yet another embodiment, a polymerizable composition, wherein R 1 is H, and R 2 is of formula (V): [Chemical formula] [In the formula, R 7 [It is methyl or phenyl.] A polymerizable composition is provided, which is derived from [the specified method].

[0031] In yet another embodiment, a polymerizable composition in which X is selected from formula (VI-A) and Y is formula (VI-B): [ka] [In the formula, R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 [The element is independently selected from the group consisting of H, methyl, and trifluoromethyl.] Polymerizable compositions selected from are provided.

[0032] Another embodiment is a polymerizable composition in which X and Y are of formula (VII) [ka] [In the formula, R 14 It is a halogen. This relates to polymerizable compositions selected independently of the above.

[0033] With respect to compounds X and Y, X may be the same as Y, or X and Y may be different. X is preferably selected from pyrrole, pyrazole, optionally substituted pyrrole, and optionally substituted pyrazole, where substitution is preferably C 1~5 -alkyl, C 1~5 -This is done with one or more of alkoxy or phenyl. Y is OR 15 You can choose from, and here, R 15 is alkyl, preferably C 1~10 - Alkyl, aryl, optionally substituted alkyl, or optionally substituted aryl. In one embodiment, R 15 C 1~5 -Selected from alkyl, the C 1~5-Alkyl is independently substituted with one or more halogens or phenyls; or R 15 is phenyl, and that phenyl is C 1~5 -alkyl, C substituted with one or more halogens 1~5 -alkyl, C 1~5 It is independently substituted with one or more of the following: -alkoxy, phenyl, halogen, -(CH2)4- which forms a condensed ring with phenyl, -(CH=CH-CH=CH)- which forms a condensed ring with phenyl, or O-silyl.

[0034] The term "silyl" may refer to any silyl group that forms a covalent bond between silicon and oxygen. Suitable silyl groups include, for example, t-butyldimethylsilyl (TBS, TBDMS), trimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS), tert-butyldiphenylsilyl (TBDPS), and triphenylsilyl.

[0035] In one preferred embodiment, the polymerizable composition is such that X and Y are of formula (VIII): [ka] A polymerizable composition is provided, which is derived from [the specified method].

[0036] In another embodiment, a polymerizable composition in which X is selected from formula (IX-A) and Y is formula (IX-B): [ka] Polymerizable compositions selected from are provided.

[0037] A particularly preferred polymerizable composition according to one embodiment of the present invention comprises one or more 18-electron shlock alkylidene adducts of formula (II-C) and formula (II-D): [ka] [In the formula, M is Mo or W, preferably Mo, and iPr represents isopropyl.] It is characterized by being selected from.

[0038] In the polymerizable composition according to one embodiment, the cyclic olefin monomer having a ring strain greater than 85 kJ / mol is preferably selected from the group consisting of dicyclopentadiene (DCPD), norbornene or its derivatives, norbornadiene or its derivatives, and combinations thereof.

[0039] In another embodiment, cyclic olefin monomers having a ring strain greater than 85 kJ / mol are selected from the group consisting of dicyclopentadiene, norbornene, norbornadiene, substituted norbornene, cyclobutene, cyclopentadiene, tricyclopentadiene, tetracyclododecene, hexacycloheptadecene, and Diels-Alder adducts of tetracyclododecene and cyclopentadiene.

[0040] Non-limiting examples of substituted norbornenes with ring strains greater than 85 kJ / mol include alkyl-substituted norbornenes, alkenyl-substituted norbornenes, norbornenes with aromatic rings, 5-methoxycarbonyl norbornene, 5-ethoxycarbonyl norbornene, 5-methyl-5-methoxycarbonyl norbornene, norbornenyl-2-methylpropionate, norbornene-5,6-dicarboxylic acid anhydride, 5-hydroxymethyl norbornene, 5,6-di(hydroxymethyl) norbornene, 5,5-di(hydroxymethyl) norbornene, 5,6-dicarboxynorbornene, 5-methoxycarbonyl-6-carboxynorbornene, 5-cyanonorbornene, and N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide.

[0041] Non-limiting examples of alkyl-substituted norbornene having a ring strain greater than 85 kJ / mol include 5-methylnorbornene, 5-ethylnorbornene, 5-cyclohexylnorbornene, and 5-cyclopentylnorbornene.

[0042] Non-limiting examples of alkenyl-substituted norbornenes with ring strains greater than 85 kJ / mol include 5-methylidene norbornene, 5-ethylidene norbornene, 5-vinyl norbornene, 5-cyclohexenyl norbornene, and 5-cyclopentenyl norbornene.

[0043] A non-limiting example of norbornene with an aromatic ring and a ring strain greater than 85 kJ / mol is 5-phenylnorbornene.

[0044] Non-limiting examples of tetracyclododecene having a ring strain greater than 85 kJ / mol include tetracyclododecene, alkyl-substituted tetracyclododecene, alkenyl-substituted tetracyclododecene, tetracyclododecene with an aromatic ring, 8-ethoxycarbonyltetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, tetracyclododecene-8,9-dicarboxylic anhydride, 8-cyanotetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid imide, and 8-chlorotetracyclododecene.

[0045] Non-limiting examples of alkyl-substituted tetracyclododecenes having a ring strain greater than 85 kJ / mol include 8-methyltetracyclododecene and 8-cyclohexyltetracyclododecene.

[0046] Non-limiting examples of alkenyl-substituted tetracyclododecenes having ring strains greater than 85 kJ / mol include 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, and 8-cyclohexenyltetracyclododecene.

[0047] A non-limiting example of a tetracyclododecene having an aromatic ring and a ring strain greater than 85 kJ / mol is 8-phenyltetracyclododecene.

[0048] Suitable norbornene derivatives are disclosed, for example, in Formula (II) on pages 3-5 of International Publication No. 2020 / 072776, which are incorporated herein by reference in their entirety.

[0049] Norbornene monomers are given by the following formula (1): [ka] It is a compound having a norbornene structure represented by .

[0050] Examples of norbornene monomers include norbornene monomers that do not have a ring that condenses with the norbornene ring in the molecule; and polycyclic norbornene monomers with three or more rings. These monomers can be used individually or in mixtures of two or more types. Specific examples of norbornene monomers that do not have a ring fused with the norbornene ring in the molecule include unsubstituted or alkylated norbornene, e.g., norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5-cyclohexylnorbornene, and 5-cyclopentylnorbornene; norbornene with an alkenyl group, e.g., 5-ethylidenenorbornene, 5-vinylnorbornene, 5-propenylnorbornene, 5-cyclohexenylnorbornene, and 5-cyclopentenylnorbornene; norbornene with an aromatic ring, e.g., 5-phenylnorbornene; and polar groups containing an oxygen atom. Norbornene having a nitrogen atom, for example, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, norvonenyl-2-methylpropionate, norvonenyl-2-methyloctanate, 5-hydroxymethylnorbornene, 5,6-di(hydroxymethyl)norbornene, 5,5-di(hydroxymethyl)norbornene, 5-hydroxy-i-propylnorbornene, 5,6-dicarboxynorbornene, and 5-methoxycarbonyl-6-carboxynorbornene; norbornene having a polar group containing a nitrogen atom, for example, 5-cyanonorbornene.

[0051] Polycyclic norbornene monomers with three or more rings refer to norbornene monomers that contain a norbornene ring within the molecule and one or more rings fused with the norbornene ring. A specific example is shown in formula (2) below: [ka] [In the formula, R 16 ~R 19Each of these is independently a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 20 carbon atoms which may have substituents; or a substituent containing a silicon atom, an oxygen atom, or a nitrogen atom, where R 17 and R 18 They are clustered together and joined to each other, forming a ring. A monomer represented by the following formula (3): [ka] [In the formula, R 20 ~R 23 Each of these is independently a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 20 carbon atoms which may have substituents; or a substituent containing a silicon atom, an oxygen atom, or a nitrogen atom, where R 20 and R 21 , or R 22 and R 23 [m is often linked to each other to form a ring; m is 1 or 2] Examples of monomers represented by [the formula shown] include [the following].

[0052] Examples of monomers represented by formula (2) include dicyclopentadiene, methyldicyclopentadiene, and tricyclo[5.2.1.0 2,6 Deca-8-ene, tetracyclo[9.2.1.0 2,10 .0 3,8 ] Tetradeca-3,5,7,12-tetraene (also known as 1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene), tetracyclo[10.2.1.0 2,11 .0 4,9 Examples include pentadeca-4,6,8,13-tetraene (also known as 1,4-methano-1,4,4a,9,9a,10-hexahydroanthracene).

[0053] Dicyclopentadiene has two stereoisomers: endo-dicyclopentadiene (Equation 4) and exo-dicyclopentadiene (Equation 5). When referring to dicyclopentadiene, it actually means the endo-dicyclopentadiene form. Currently, the main component of industrially available dicyclopentadiene is endo-dicyclopentadiene, and the exo-dicyclopentadiene content can be around 0-2% by mass. [ka]

[0054] Examples of monomers represented by formula (3) include: tricyclopentadiene and tetracyclododecene, where m is 1; and hexacycloheptadecene, where m is 2. Specific examples of tetracyclododecene include unsubstituted or alkyl-containing tetracyclododecene, e.g., tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and 8-cyclopentyltetracyclododecene; tetracyclododecene with an extra-ring double bond, e.g., 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, and 8-cyclopentenyltetracyclododecene; tetracyclododecene with an aromatic ring, e.g., 8-phenyltetracyclododecene; and tetracyclododecene with substituents containing an oxygen atom. Examples include tetracyclododecene, such as 8-methoxycarbonyltetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, and tetracyclododecene-8,9-dicarboxylic acid anhydride; tetracyclododecene having substituents containing a nitrogen atom, such as 8-cyanotetracyclododecene and tetracyclododecene-8,9-dicarboxylic acid imide; tetracyclododecene having substituents containing a halogen atom, such as 8-chlorotetracyclododecene; and tetracyclododecene having substituents containing a silicon atom, such as 8-trimethoxysilyltetracyclododecene; and so on.

[0055] Specific examples of hexacycloheptadecenes include unsubstituted or alkyl-containing hexacycloheptadecenes, such as hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, and 12-cyclopentylhexacycloheptadecene; and hexacycloheptadecenes having a double bond outside the ring, such as 12-methyl Dene hexacycloheptadecene, 12-ethylidene hexacycloheptadecene, 12-vinyl hexacycloheptadecene, 12-propenyl hexacycloheptadecene, 12-cyclohexenyl hexacycloheptadecene, and 12-cyclopentenyl hexacycloheptadecene; hexacycloheptadecene having an aromatic ring, e.g., 12-phenyl hexacycloheptadecene; hexacycloheptadecene having substituents containing an oxygen atom Examples include hexacycloheptadecenes, such as 12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene-12,13-dicarboxylic acid, and hexacycloheptadecene-12,13-dicarboxylic acid anhydride; hexacycloheptadecenes having substituents containing a nitrogen atom, such as 12-cyanohexacycloheptadecene and hexacycloheptadecene-12,13-dicarboxylic acid imide; hexacycloheptadecenes having substituents containing a halogen atom, such as 12-chlorohexacycloheptadecene; and hexacycloheptadecenes having substituents containing a silicon atom, such as 12-trimethoxysilylhexacycloheptadecene.

[0056] These norbornene monomers can be used individually or in combination of two or more.

[0057] Among these norbornene monomers, polycyclic norbornene monomers with three or more rings are preferred, and tricyclic, tetracyclic, or pentacyclic norbornene monomers are more preferred, from the viewpoint of being readily available, having excellent reactivity, and yielding resin molded articles with excellent heat resistance.

[0058] Furthermore, from the viewpoint of obtaining thermosetting ring-opening polymers, it is desirable to use a crosslinkable norbornene monomer having two or more reactive double bonds (a norbornene monomer that produces a ring-opening polymer having crosslinkable reactive double bonds), such as a symmetrical cyclopentadiene trimer, together with another norbornene monomer (a norbornene monomer that produces a ring-opening polymer without crosslinkable reactive double bonds). When using a crosslinkable norbornene monomer, it is desirable that the proportion of the crosslinkable norbornene monomer used be 2 to 30% by mass of the total norbornene monomers.

[0059] Furthermore, monomers capable of ring-opening copolymerization with norbornene monomers can be used within the limits that do not impair the objectives of the present invention. Examples of such monomers include monocyclic cycloolefins, such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, and cyclododecene.

[0060] In addition to cyclic olefin monomers having a ring strain greater than 85 kJ / mol, the polymerizable composition according to one embodiment further comprises cyclic olefin monomers selected from the group consisting of cyclopentene, 1,4-cyclohexadiene, cycloheptene, cis-cyclooctene, cis,cis-1,5-cyclooctadiene, 1,3,5,7-cyclooctatetraene, cyclododecene, trans,trans,cis-1,5,9-cyclododecatriene, their derivatives, and combinations thereof.

[0061] In useful embodiments, the composition may also include chain transfer agents, such as substituted linear olefins. Suitable chain transfer agents include vinylnorbornene, 1-hexene, 2-hexene, and other aliphatic olefins; styrene, divinylbenzene, and other vinyl aromatic olefins; olefins having alicyclic hydrocarbon groups, such as vinylcyclohexane; vinyl ethers; methyl vinyl ketones, substituted (meth)acrylic acids and their salts, such as vinyl(meth)acrylate, allyl(meth)acrylate, and compounds, such as allyltrivinylsilane, allylmethyldivinylsilane, allyldimethylvinylsilane, and 4-vinylaniline. These chain transfer agents may be used alone or in combination and are generally added in an amount ranging from 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of monomer.

[0062] Other additives, such as flame retardants, light stabilizers, pigments, dyes, and other colorants, as well as foaming agents, may also be added to this composition. Suitable flame retardants include, but are not limited to, phosphorus, nitrogen, and halogen-containing flame retardants, metal hydroxides, such as aluminum hydroxide, and antimony compounds, such as antimony trioxide. Granular inorganic fillers may also be included, but are not limited to, calcium carbonate, calcium hydroxide, calcium silicate, calcium sulfate, aluminum trioxide, magnesium hydroxide, titanium dioxide, zinc oxide, barium titanate, silica, alumina, clay, and carbon black.

[0063] In preferred embodiments, fillers can be added to the composition according to the present invention as a base material. Both inorganic and organic fillers can be used without limitation, but inorganic fillers are preferred. Suitable inorganic fillers include, for example, metal particles of iron, copper, nickel, gold, silver, aluminum, lead, and tungsten; carbon particles, such as carbon black, graphite, activated carbon, and carbon microballoons; inorganic oxide particles, such as silica, alumina, titanium oxide, iron oxide, zinc oxide, and magnesium oxide; inorganic carbonate particles, such as calcium carbonate and magnesium carbonate; calcium sulfate; inorganic silicate particles, such as talc, clay, mica, kaolin, fly ash, montmorillonite, calcium silicate, and glass particles; and titanate, aluminum nitride, and silicon carbide particles. Specific examples of fibrous inorganic fillers include glass fibers, wollastonite, potassium titanate, xonolite, basic magnesium sulfate, aluminum borate, tetrapod-type zinc oxide, gypsum fibers, phosphate fibers, alumina fibers, and whiskers, whisker-shaped calcium carbonate, whisker-shaped boehmite, etc. Furthermore, fibrous inorganic fillers may be subjected to hydrophobic treatment on their surface, similar to the granular inorganic fillers described above.

[0064] Suitable organic fillers include, for example, wood, starch, lignin, organic pigments, and polymer particles such as polystyrene, polyamide, polyolefin, polyethylene, and polypropylene, polyvinyl chloride, elastomers, and / or waste polymer particles. Functional fillers, such as piezoelectric ceramics, fillers that alter electrostatic / conductive properties, such as carbon nanotubes, and rheological modifiers may also be added. According to the present invention, a sizing composition can be imparted to the filler.

[0065] In one preferred embodiment, a polymerizable composition is provided, further comprising, for example, up to 20% by weight, more preferably up to 10% by weight, of an elastomer relative to the weight of the polymerizable composition, wherein the elastomer is preferably selected from the group consisting of styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), ethylene-propylene rubber (EPR), ethylene-propylene-diene monomer rubber (EPDM), polyolefin elastomer (POE), trans-polyoctenomer rubber (TOR), and combinations thereof. The trans-polyoctenomer rubber (TOR) may be cyclic polybutadiene-based or cyclic isoprene-based. It can be produced by ring-opening metathesis polymerization (ROMP) starting from 1,5-cyclooctadiene and via cyclooctene as an intermediate. Because the double bonds of the cyclooctene monomer are retained, the resulting trans-polyoctenomer typically contains one double bond for every eight carbon atoms.

[0066] According to another embodiment of the present invention, the composition further comprises reinforcing fibers as an adhesive substrate. Suitable reinforcing fibers used in the present invention can be selected from a wide range. For example, inorganic fibers such as glass fibers, carbon and graphite fibers, alumina fibers, tungsten fibers, molybdenum fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, and silica fibers can be used. Other suitable fibers include organic fibers such as aramid fibers, ultra-high molecular weight polyethylene fibers, liquid crystal and other polyester fibers, as well as natural fibers and reinforcing materials. Preferred reinforcing fibers include glass and carbon fibers, of which E glass fibers, R glass fibers, S glass fibers, and S2 glass fibers are most preferably used.

[0067] Reinforcement fibers can be applied in any physical form, namely as monofilaments and multifilaments, or in the form of strands and yarns, as woven fabrics, or according to any other textile structure, as short fibers, as continuous fibers, or in the form of pre-impregnated sheets ("prepregs"). Any combination of different types of fibers is possible. The amount of reinforcement fibers can be selected within a wide range, but the appropriate amount is generally in the range of 30 to 70 volume%, with a fiber volume fraction of 55 to 65 volume% being preferred for most applications.

[0068] In another embodiment of the present invention, reinforcing fibers are provided with a coupling agent incorporated into a sizing composition. The sizing composition is configured to provide improved adhesion of the composition to an adhesive substrate, such as the reinforcing fibers. The adhesive substrate is preferably sizing treatment with a commercially available silane compound that does not interfere with the olefin metathesis catalyst used and exhibits compatibility with cyclic olefin polymers, particularly polycyclopentadiene.

[0069] Sizing formulations applied to substrates, particularly reinforcing fibers, typically further contain a coupling agent, a film-forming agent, and optionally a lubricant. The film-forming agent usually includes a film-forming polymer. Any component of a sizing formulation that does not substantially inhibit metathesis catalysis and / or substantially hinder the polymerization reaction of cyclic olefins is considered compatible with this composition and can generally be used in the present invention.

[0070] A film-forming agent that is compatible with and / or does not inhibit ring-opening metathesis polymerization (ROMP) is preferably used, and this film-forming agent includes epoxy, polyester, polyurethane, polyolefin and / or polyvinyl acetate. Other common film-forming agents that do not adversely affect the performance of the cyclic olefin metathesis catalyst can also be used. The film-forming agent is usually used as a nonionic aqueous emulsion, and combinations of different film-forming agents can be used as needed.

[0071] In one preferred embodiment, particularly when reinforcing fibers are used, the polymerizable composition further comprises a vinyl-containing monomer and a polymerization initiator for the vinyl-containing monomer, preferably comprising a (meth)acrylic monomer and a peroxide initiator. This composition can promote adhesion to substrates such as reinforcing fibers and polyolefin substrates. Preferred unsaturated compounds include ethylene unsaturated compounds, which are understood to mean vinyl aromatic compounds, e.g., styrene, α-methylstyrene, p-methylstyrene, aminostyrene, hydroxystyrene, divinylbenzene, vinyltoluene; allyl compounds, e.g., monoallyl esters and / or ethers, and diallyl esters and / or ethers; vinyl ethers and vinyl ester compounds, e.g., vinyl benzoate; and (meth)acrylic compounds, e.g., (meth)acrylic acid and its esters. Particularly preferred polyfunctional unsaturated compounds include acrylic and / or methacrylic compounds. Suitable (meth)acrylic compounds include, but are not limited to, ethylene glycol di(meth)acrylate, propanediol di(meth)acrylate, butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and other bifunctional compounds, as well as trimethylolpropane tri(meth)acrylate, trimethylolethane(tri)methacrylate, trimethylolpropanepropylene oxide-modified tri(meth)acrylate, and other trifunctional compounds. Combinations of unsaturated compounds may also be used.

[0072] Suitable curing agents for vinyl-containing monomers include radical sources such as peroxides, hydroperoxides, peresters and / or perketone compounds, including cyclic and linear compounds. Linear (hydro)peroxides are particularly preferred as curing agents. Suitable peroxides, but are not limited to, include alkyl peroxides, aryl peroxides, and aralkyl or alkaryl peroxides. Secondary and tertiary aliphatic and aromatic hydroperoxides, such as tert-butyl hydroperoxide, tert-amyl hydroperoxide, and cumene hydroperoxide are particularly preferred.

[0073] In another embodiment of the present invention, particularly when reinforcing fibers are used, the composition further comprises the adhesion-promoting composition disclosed in International Publication No. 2015 / 130802, which is incorporated herein by reference in its entirety. The adhesion-promoting composition comprises an isocyanate-containing monomer, preferably a pre-reacted mixture comprising at least one compound containing at least two isocyanate groups and at least one compound containing a heteroatom-containing functional group and a metathesis-active olefin, wherein the adhesion-promoting composition has storage stability and / or storage stability within the resin when added to a resin composition, particularly a cyclic olefin resin composition, such as a ROMP composition.

[0074] The amount of monomer in the composition can be selected within a wide range, but is preferably at least 20% by weight, preferably at least 50% by weight, and more preferably at least 90% by weight of the polymerizable composition. The remaining amount consists of fillers and other additives in the composition.

[0075] The amount of cyclic monomer in the composition can also be selected within a wide range. According to one embodiment of the present invention, the cyclic olefin monomer in the polymerizable composition accounts for at least 80 mol%, preferably at least 90 mol%, of the monomer.

[0076] In yet another embodiment, the polymerizable composition is provided such that a cyclic olefin monomer having a ring strain greater than 85 kJ / mol accounts for at least 50 mol%, preferably 50 to 100 mol%, for example, 50 to 80 mol%, of the monomer.

[0077] In polymerizable compositions, combinations of different cyclic olefin monomers can be used. A preferred embodiment of the polymerizable composition is characterized in that the monomers include dicyclopentadiene (DCPD), cis,cis-1,5-cyclooctadiene (COD), and optionally ethylidene norbornene (ENB) and / or tricyclopentadiene (TCPD).

[0078] Particularly preferred are dicyclopentadiene (DCPD), cis,cis-1,5-cyclooctadiene (COD), tricyclopentadiene (TCPD), and ethylidene norbornene (ENB) in the following amounts: • 50-90 mol% dicyclopentadiene; • 0-30 mol% cis,cis-1,5-cyclooctadiene; and • 0-20 mol% ethylidene norbornene and / or tricyclopentadiene The polymerizable composition is such that the total percentage of dicyclopentadiene, cis,cis-1,5-cyclooctadiene, and ethylidene norbornene and / or tricyclopentadiene is 100 mol% of the monomers.

[0079] In addition to the monomer, the polymerizable composition further comprises a catalyst system containing one or more 18-electron shroc alkylidene adducts as described in the claims, in an amount suitable for catalyzing the metathesis ring-opening polymerization of the cyclic olefin monomer. In a preferred embodiment, the molar ratio of the cyclic olefin monomer to one or more 18-electron shroc alkylidene adducts is 500 to 200,000, preferably 10,000 to 150,000, and more preferably 20,000 to 80,000.

[0080] The polymerizable composition may further contain a catalyst inhibitor. The catalyst inhibitor can extend the working time before polymerization begins. Suitable polymerization inhibitors include, but are not limited to, phosphite compounds, such as those disclosed in European Patent No. 2460587, which are incorporated herein by reference in their entirety.

[0081] As disclosed above, polymerizable compositions have been shown to exhibit autocatalytic activity at room temperature and do not require chemical activation. Therefore, a preferred embodiment of the present invention relates to a polymerizable composition that does not contain a Lewis acid reagent.

[0082] Even more preferable is a polymerizable composition according to an embodiment in which the polymerizable composition does not contain MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, and Zn(trifluoroacetate)2.

[0083] In one embodiment, the polymerizable composition does not contain MgCl2. In one embodiment, the polymerizable composition does not contain MgBr2. In one embodiment, the polymerizable composition does not contain MgI2. In one embodiment, the polymerizable composition does not contain MnCl2. In one embodiment, the polymerizable composition does not contain MnBr2. In one embodiment, the polymerizable composition does not contain MnI2. In one embodiment, the polymerizable composition does not contain FeCl3. In one embodiment, the polymerizable composition does not contain AlCl3. In one embodiment, the polymerizable composition does not contain CuCl2. In one embodiment, the polymerizable composition does not contain ZnCl2. In one embodiment, the polymerizable composition does not contain ZnBr2. In one embodiment, the polymerizable composition does not contain ZnI2. In one embodiment, the polymerizable composition does not contain Zn(triflate)2. In one embodiment, the polymerizable composition does not contain Zn(trifluoroacetate)2. In one embodiment, the polymerizable composition does not contain chlorosilane.

[0084] In another aspect, the present invention also relates to a ring-opening metathesis polymerization process. According to the present invention, the ring-opening metathesis polymerization process is (a) the step of providing a polymerizable composition as described in the claims, (b) The step of subjecting the polymerizable composition to ring-opening metathesis polymerization. Includes.

[0085] According to another embodiment, it may be advantageous to carry out the ring-opening metathesis polymerization process by suspending or dissolving one or more 18-electron shlock alkylidene adducts in an inert carrier, preferably an inert liquid carrier, prior to step (a), and then adding the resulting suspension or solution to the other components of the polymerizable composition.

[0086] Suitable inert liquid or solid carriers include linear aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, alkylbenzene, or liquid paraffin, as well as alicyclic hydrocarbons such as cyclopentane, cyclohexane, alkyl-substituted cyclohexane, di- and tricycloheptane, and cyclooctane, and aromatic hydrocarbons such as benzene, toluene, and xylene; nitrogen-containing solvents such as nitromethane, nitrobenzene, and acetonitrile, and oxygen-containing solvents such as diethyl ether and tetrahydrofuran. Ketones such as cyclohexanone, cyclopentanone, and methyl ethyl ketone (MEK) can also be used, as can esters such as ethyl acetate and alkyl maleic acid. Paraffin wax can also be used.

[0087] As already explained above, the ring-opening metathesis polymerization process does not require activation by adding a Lewis acid reagent. Therefore, according to one preferred embodiment, the ring-opening metathesis polymerization process is characterized by not adding a Lewis acid reagent, and more preferably not adding MgCl2, MgBr2, MgI2, MnCl2, MnBr2, MnI2, FeCl3, AlCl3, CuCl2, ZnCl2, ZnBr2, ZnI2, Zn(triflate)2, and Zn(trifluoroacetate)2.

[0088] In one embodiment, MgCl2 is not added. In one embodiment, MgBr2 is not added. In one embodiment, MgI2 is not added. In one embodiment, MnCl2 is not added. In one embodiment, MnBr2 is not added. In one embodiment, MnI2 is not added. In one embodiment, FeCl3 is not added. In one embodiment, AlCl3 is not added. In one embodiment, CuCl2 is not added. In one embodiment, ZnCl2 is not added. In one embodiment, ZnBr2 is not added. In one embodiment, ZnI2 is not added. In one embodiment, Zn(triflate)2 is not added. In one embodiment, Zn(trifluoroacetate)2 is not added. In one embodiment, chlorosilane is not added.

[0089] Methods for producing polymerized articles from polymerizable compositions by a ring-opening metathesis polymerization process are not limited to those described above, but may include those molded by conventional manufacturing techniques such as casting, centrifugal injection, pultrusion, injection pultrusion, filament winding, rotational molding, 3D printing, and open mold molding. This composition can also be used for semi-finished products such as prepregs and sheet molding compounds (SMCs).

[0090] When a closed-mold process is used to manufacture polymerized articles, the preferred ring-opening metathesis polymerization process is carried out under an inert atmosphere, preferably an N2 atmosphere.

[0091] Another preferred embodiment of the present invention relates to a ring-opening metathesis polymerization process, wherein step (a) comprises injecting a polymerizable composition into a closed mold. The mold may be empty before the injection of the polymerizable composition. However, more preferably, the mold contains reinforcing fibers before the polymerizable composition is injected in the process. Such techniques include reaction injection molding (RIM), resin transfer molding (RTM), vacuum-assisted resin infusion (VARI), Seeman composite resin infusion molding process (SCRIMP), reinforced reaction injection molding (RRIM), structural reaction injection molding (SRIM), thermal expansion transfer molding (TERM), resin injection recirculation molding (RICM), and controlled atmospheric pressure resin infusion (CAPRI).

[0092] Exposing the composition to conditions effective for promoting ROMP of cyclic olefin monomers may include actively heating the composition to a suitable polymerization temperature at a pressure optionally exceeding 0.1 MPa for a suitable period of time. In one embodiment of the ROMP process, the heating temperature is in the range of room temperature to 200°C, more preferably 50°C to 200°C, and even more preferably 120°C to 150°C. The heating time is preferably in the range of 0.1 to 180 minutes, or even longer depending on the size of the article to be manufactured. The pressure applied during molding can be selected according to the manufacturing method used, and may be as low as 0.1 to 0.5 MPa when RTM is used, for example. Vacuum or reduced pressure may also be used.

[0093] Active heating of this composition can be carried out according to methods well known to those skilled in the art. When a processing method using a mold is used to form an article, heating usually involves heating the mold to a temperature of, for example, 40 to 80°C. For example, a process using a resin bath to wet reinforcing fibers usually involves heating the resin bath.

[0094] Another aspect of the present invention relates to polymer articles manufactured from polymer articles. Polymer articles can be used in a variety of applications, including, but are not limited to, aerospace components, marine components, automotive components, sporting goods, electrical components, medical components, and military components. In useful embodiments, the polymer article may be a turbine component, such as a turbine blade component or a turbine blade. Examples of aerospace components, but are not limited to, fuselage skins, wings, fairings, doors, access panels, and stiffeners. Examples of automotive components, but are not limited to, body panels, fenders, spoilers, protective plates, hoods, pillars, leaf springs, and doors. Other examples of suitable articles include bridges, pipes, pressure vessels, and containers. Examples of military components, but are not limited to, include bulletproof armor plates and other structures for protecting personnel or equipment. Examples of suitable sporting goods include tennis rackets, hockey sticks, and golf club shafts.

[0095] Polymerized articles produced from polymerizable compositions are advantageous in that they contain relatively small amounts of the catalyst system described in the claims. Therefore, a polymerized article according to one preferred embodiment, which can be obtained by the ring-opening metathesis polymerization process described in the claims, contains a total amount of metallic Mo and W of 5 to 100 ppm relative to the weight of the polymerized article. Conventional ROMP articles typically contain much larger amounts of catalyst-derived Mo and W, often as much as ten times more.

[0096] The present invention has been described above with reference to the specific embodiments discussed above. It will be understood that these embodiments can take various modifications and alternative forms that are well known to those skilled in the art.

[0097] Furthermore, in order to properly understand this specification and the claims, it should be understood that the verb "to comprise" and its conjugations are used in an unrestrictive sense, meaning that the items following the word are included, but not that items not specifically mentioned are excluded. Also, when an element is referred to by the indefinite article "a" or "an," it does not preclude the possibility that there are multiple such elements unless the context clearly requires that there be only one or one such element. Therefore, the indefinite article "a" or "an" usually means "at least one." [Examples]

[0098] Experiment Section The present invention will now be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" refer to weight unless otherwise specified.

[0099] Overview The 14-electron shrock alkylidene and 18-electron shrock alkylidene adducts used as catalysts in the following examples were prepared according to methods disclosed in the literature. Their chemical structures are as follows: [ka]

[0100] The stability constants K of catalysts 2, 3, and 4 (18-electron shrok alkylidene adducts) were determined in deuterated benzene (C6D6) at 25°C. The higher the stability of the adduct, the less likely it is to dissociate when dissolved in deuterated benzene (C6D6) at 25°C. Therefore, a high stability constant K, expressed in L / mol units, corresponds to a low degree of dissociation. The stability constant K is measured after dissolving the 18-electron shrok alkylidene adduct in deuterated benzene (C6D6) at a concentration of 0.01 M at 25°C. This is given by the following formula:

number

[0101] However, the above method may not be entirely accurate for very stable 18-electron schrock alkylidene adducts. This is because the alkylidene peak may be small and almost unobservable. In such cases, the stability constant is estimated to be greater than 1,000,000 L / mol.

[0102] Catalysts 2 and 3 had a stability constant K greater than 1,000,000 L / mol in deuterated benzene (C6D6) at 25°C. Catalyst 4 had a stability constant K of 9,000 L / mol in deuterated benzene (C6D6) at 25°C.

[0103] All process steps were carried out under an inert atmosphere (using Schlenk technique or an argon glove box). Molecular sieves were activated by heating them overnight at 200°C under vacuum before use. Solvents were purchased as 99+% or HPLC grade and dehydrated with molecular sieves. Deuterated solvents were purchased from Eurosotop, dehydrated with 3 Å molecular sieves, and stored in a glove box.

[0104] A catalyst stock solution was prepared at a concentration of 0.037 M using chlorobenzene as the solvent. The catalyst stock solution was stored at -30°C in a glove box freezer. • Catalyst 1: 0.037M (28.3 mg in 1 mL of chlorobenzene); • Catalyst 2: 0.037M (34.1 mg in 1 mL of chlorobenzene); • Catalyst 3: 0.037M (35.0 mg in 1 mL of chlorobenzene); and • Catalyst 4: 0.037M (40.0 mg in 1 mL of chlorobenzene).

[0105] The following monomer / monomer mixtures were used in the experiment: a) DCPD: 100% dicyclopentadiene; b) COD: 100% cis,cis-1,5-cyclooctadiene; c) DCPD / TCPD: A mixture of dicyclopentadiene and tricyclopentadiene, with a tricyclopentadiene content of approximately 5-10% by weight; and d) DCPD / ENB / COD: Dicyclopentadiene, ethylidene norbornene, and cis,cis-1,5-cyclooctadiene, with a cis,cis-1,5-cyclooctadiene content of approximately 28% by weight and an ethylidene norbornene content of approximately 3.5-7% by weight.

[0106] Dicyclopentadiene is a highly reactive monomer with a ring strain of approximately 27 kcal / mol (113 kJ / mol). See I. Njoroge et al., Langmuir, 2017, 33(49), pp 13903-13912. cis,cis-1,5-cyclooctadiene has a ring strain of <<85 kJ / mol.

[0107] These monomers were dehydrated through a 3 Å molecular sieve for at least 24 hours. These monomers were then filtered through a glass filter (Porosity 4) and stored in a glove box. The COD was refluxed in the presence of calcium hydride for 24 hours, then distilled and collected under an argon atmosphere. The distilled COD was then further dehydrated through a 3 Å molecular sieve for at least 24 hours, filtered through a glass filter (Porosity 4), and stored in a glove box.

[0108] Example 1 Eleven experiments were conducted, in which monomers or monomer mixtures were subjected to ring-opening metathesis polymerization (ROMP) in the presence of a catalyst.

[0109] Experiment III was carried out using, for example, the following protocol: The catalyst solution (stock solution of catalyst 2, 0.037 M, 0.1 mL, 0.0037 mmol) was weighed using an Eppendorf micropipette (10-100 μL) and added to a 20 mL scintillation vial. The monomer mixture DCPD / TCPD (9.922 mL, 9.780 g, 74 mmol) was weighed into a second scintillation vial. The monomer mixture was drawn up with a syringe and poured into the catalyst solution. The mixture was gently shaken to ensure homogeneous mixing. The vial was then capped and the reaction was allowed to proceed without stirring until the exothermic reaction stopped and the mixture cooled to room temperature. The conversion rate of the resulting solid polymer was determined by thermogravimetric analysis. The resulting polymer samples were also analyzed by differential scanning calorimetry.

[0110] Experiment VII was carried out using, for example, the following protocol: The catalyst solution (stock solution of catalyst 2, 0.037 M, 0.053 mL, 0.00196 mmol) was weighed using an Eppendorf micropipette (10-100 μL) and added to a 20 mL scintillation vial. The monomer mixture DCPD / ENB / COD (5.24 mL, 5.01 g, 40.1 mmol) was weighed into a second scintillation vial. The monomer mixture was drawn up with a syringe and poured into the catalyst solution. The mixture was gently shaken to ensure homogeneous mixing. The vial was then capped and the reaction was allowed to proceed without stirring until the exothermic reaction stopped and the mixture cooled to room temperature. The conversion rate of the resulting solid polymer was determined by thermogravimetric analysis. The resulting polymer samples were also analyzed by differential scanning calorimetry.

[0111] Other experiments were conducted using similar protocols. The results are shown in Table 1. The initial temperature is the temperature of the reaction mixture immediately after the monomer or monomer mixture was poured into the catalyst solution.

[0112] Due to the exothermic reaction of the ring-opening metathesis polymerization reaction, the temperature rose after the reaction started. The start time was defined as the point at which the reaction mixture lost its fluidity and the temperature began to rise rapidly.

[0113] As can be inferred from Table 1, catalysts 2 and 3 (18-electron shlock alkylidene adducts) enable the ring-opening metathesis polymerization of cyclic olefin monomers with large ring strains with a high monomer conversion rate, resulting in a sufficiently high glass transition temperature (T g A polymer having the following characteristics is obtained.

[0114] [Table 1]

[0115] Comparative Example 2 Eight comparative experiments (XII-XIX) were conducted using protocols similar to those applied to Example 1. The results are shown in Table 2. The 14-electron shrock alkylidene catalyst 1 (without adduct) and the 18-electron shrock alkylidene adduct 4, with a stability constant K << 250,000 L / mol, exhibited excessively high activity in ring-opening metathesis polymerization of cyclic olefin monomers with large ring strains, such as DCPD or DCPD-containing monomer mixtures. As a result, the catalyst was immediately embedded, and little polymer was formed. On the other hand, the 14-electron shrock alkylidene catalyst 1 and the 18-electron shrock alkylidene adduct 4 could be used for ring-opening metathesis polymerization of cyclic olefin monomers with much smaller ring strains, such as COD.

[0116] [Table 2]

Claims

1. A polymerizable composition, A monomer comprising a cyclic olefin monomer having a ring strain greater than 85 kJ / mol, preferably greater than 100 kJ / mol, Equation (I): 【Chemistry 1】 [wherein, R ｊ , R ｂ , R ｃ , R ｄ , R ｅ , R ｆ , R ｇ , and R ｈ are each independently selected from the group consisting of H, halogen, nitro, cyano, trifluoromethyl, C １ -C １２ -alkoxycarbonyl, C １ -C １２ -alkyl, 5- to 18-membered aryl, C １ -C １２ -alkyloxy, and di(C １ -C ４ -alkyl)amino, or groups R ｄ and R ｅ are bonded to each other to form a 6-membered ring, wherein R ｄ and R ｅ together form the group C(R ｉ )=C(R ｊ ), where R ｉ and R ｊ are each independently selected from the group consisting of H, halogen, nitro, cyano, trifluoromethyl, C １ -C １２ -alkoxycarbonyl, C １ -C １２ -alkyl, 5- to 18-membered aryl, C １ -C １２ -alkyloxy, and di(C １ -C ４ -alkyl)amino] One or more 18-electron shrock alkylidene adducts selected from complexes of 14-electron shrock alkylidene compounds having a bidentate ligand, Here, the one or more 18-electron shlock alkylidene adducts are determined according to the protocol specified in the detailed description of the invention, and deuterated benzene (C) at 25°C. ６ D ６ ) 250,000 L·mol －１ Larger, preferably 500,000 L·mol －１ One or more 18-electron shrock alkylidene adducts having a larger stability constant K, - Less than 10% by weight, preferably less than 5% by weight, of the polymerizable composition and an inert solvent A polymerizable composition containing the following:

2. The one or more 18-electron suloc alkylidene adducts are defined by formula (II): 【Chemistry 2】 [In the formula, M is Mo or W, A is O, or N-R ３ And, R １ and R ２ H, C １ ~C １２ - Independently selected from the group consisting of alkyl and 5- to 18-membered aryl, where C １ ~C １２ - Alkyl and the 5- to 18-membered aryls are C １ ~C １２ - Alkyl group, 5-18 membered aryl group, C １ ~C １２ - Alkyloxy group, di(C) １ ~C ４ - It may be substituted with one or more of the following: an alkyl)amino group, a halogen group, a trifluoromethyl group, a cyano group, and a nitro group, however, R １ and R ２ It is assumed that they cannot become hydrogen at the same time. R ３ C １ ~C １２ - Selected from the group consisting of alkyl and 5- to 18-membered aryl, where C １ ~C １２ - Alkyl and the 5- to 18-membered aryls are C １ ~C １２ - Alkyl group, 5-18 membered aryl group, C １ ~C １２ - Alkoxy group, di(C) １ ~C ４ - It may be substituted with one or more of the following: an alkyl)amino group, a halogen group, a trifluoromethyl group, a cyano group, and a nitro group. X and Y are halogens, methanesulfonyloxy, trifluoromethanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy, pyrrolyl, indolyl, pyrazolyl, C １ ~C １２ - Alkyloxy, 5-18 member aryloxy, tri(C) １ ~C １２ -Alkyl)silyloxy, tri(C ６ ~C １８ -aryl)silyloxy, di(C １ ~C １２ -Alkyl) (C ６ ~C １８ -aryl)silyloxy, (C １ ~C １２ -Alkyl)di(C ６ ~C １８ -aryl)silyloxy, and tri(C １ ~C １２ They are independently selected from the group consisting of -alkyloxy)silyloxy, and these are C １ ~C １２ - Alkyl group, 5-18 membered aryl group, C １ ~C １２ - Alkyloxy group, di(C) １ ~C ４ - Alkyl) may be substituted with one or more of the following: amino group, halogen group, trifluoromethyl group, cyano group, and nitro group, or groups X and Y together form formula (III-A), (III-B), or (III-C): 【Transformation 3】 It forms a structure, and here, R Ａ 、R Ｂ 、R Ｃ 、R Ｄ 、R Ｅ 、R Ｆ 、R Ｇ 、and R Ｈ are independently selected from the group consisting of H, halogen, nitro, cyano, trifluoromethyl, C １ ~C １２ -alkoxycarbonyl, C １ ~C １２ -alkyl, 5- to 18-membered aryl, C １ ~C １２ -alkyloxy, and di(C １ ~C ４ -alkyl)amino] A polymerizable composition according to claim 1, selected from the group represented by .

3. The one or more 18-electron shlock alkylidene adducts are of formulas (II-A) and (II-B): 【Chemistry 4】 [In the formula, M, A, X, Y, R １ , and R ２ This is as defined in claim 2. A polymerizable composition according to claim 1 or 2, selected from the above.

4. The one or more 18-electron shlock alkylidene adducts are defined by formulas (II-C) and (II-D): 【Transformation 5】 [In the formula, M is Mo or W, preferably Mo, and iPr represents isopropyl.] A polymerizable composition according to any one of claims 1 to 3, selected from the above.

5. The polymerizable composition according to any one of claims 1 to 4, wherein the cyclic olefin monomer having a ring strain greater than 85 kJ / mol is selected from the group consisting of dicyclopentadiene (DCPD), norbornene or its derivatives, norbornadiene or its derivatives, and combinations thereof.

6. A polymerizable composition according to any one of claims 1 to 5, further comprising a cyclic olefin monomer selected from the group consisting of cyclopentene, 1,4-cyclohexadiene, cycloheptene, cis-cyclooctene, cis,cis-1,5-cyclooctadiene, 1,3,5,7-cyclooctatetraene, cyclododecene, trans,trans,cis-1,5,9-cyclododecatriene, derivatives thereof, and combinations thereof.

7. The polymerizable composition according to any one of claims 1 to 6, wherein the monomer accounts for at least 20% by weight, preferably at least 50% by weight, and more preferably at least 90% by weight of the polymerizable composition.

8. The polymerizable composition according to any one of claims 1 to 7, wherein the cyclic olefin monomer accounts for at least 80 mol%, preferably at least 90 mol%, of the monomer.

9. The polymerizable composition according to any one of claims 1 to 8, wherein the monomer comprises dicyclopentadiene (DCPD), cis,cis-1,5-cyclooctadiene (COD), and optionally ethylidene norbornene (ENB) and / or tricyclopentadiene (TCPD).

10. The polymerizable composition according to any one of claims 1 to 9, wherein the molar ratio of the cyclic olefin monomer to one or more 18-electron shrock alkylidene adducts is 500 to 200,000, preferably 10,000 to 150,000, and more preferably 20,000 to 80,000.

11. The polymerizable composition may include MgCl ２ MgBr ２ MgI ２ , MnCl ２ MnBr ２ MnI ２ FeCl ３ AlCl ３ CuCl ２ ZnCl ２ , ZnBr ２ , ZnI ２ , Zn (triflat) ２ , and Zn (trifluoroacetate) ２ A polymerizable composition according to any one of claims 1 to 10, which does not contain the following.

12. (a) the step of providing a polymerizable composition according to any one of claims 1 to 11, (b) The step of subjecting the polymerizable composition to ring-opening metathesis polymerization. A ring-opening metathesis polymerization process, including

13. MgCl ２ MgBr ２ MgI ２ , MnCl ２ MnBr ２ MnI ２ FeCl ３ AlCl ３ CuCl ２ ZnCl ２ , ZnBr ２ , ZnI ２ , Zn (triflat) ２ , and Zn (trifluoroacetate) ２ The ring-opening metathesis polymerization process according to claim 12, wherein no additives are added.

14. The ring-opening metathesis polymerization process according to claim 12 or 13, wherein step (a) comprises injecting the polymerizable composition into a mold, casting the polymerizable composition into a mold, and / or supplying the polymerizable composition into a bath for wetting reinforcing fibers.

15. A polymerized article that can be obtained by a ring-opening metathesis polymerization process according to any one of claims 12 to 14, the polymerized article comprising a total amount of metal Mo and W in an amount of 5 to 100 ppm relative to the weight of the polymerized article.

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