Organopolysiloxane compounds and polymers thereof, self-supporting films, and molded articles

Abstract

The present application provides an organic polysiloxane compound having a cyclic olefin skeleton at only a single terminal of a polysiloxane chain, which is not a crosslinking system and is capable of being compounded with a cyclic olefin, a polymer thereof, a self-supporting film, and a molded article. The organic polysiloxane compound is represented by formula (1). A is a monovalent alicyclic hydrocarbon group having a carbon number of 4 to 60 having at least one carbon-carbon double bond, and T is a group represented by formula (2). R 1 and R 2 are independently an alkyl group having a carbon number of 1 to 10 or an aryl group having a carbon number of 6 to 10, R 3 is an alkyl group having a carbon number of 4 to 10, x is an integer of 1 to 3, and n is an integer of 1 or more.

Description

Technical Field

[0001] This invention relates to an organopolysiloxane compound having a cyclic olefin backbone capable of being compounded with cyclic olefin monomers. Furthermore, it relates to a polymer, a self-supporting membrane, and molded articles formed by reacting the organopolysiloxane compound with a raw material containing cyclic olefin monomers. Background Technology

[0002] Organopolysiloxane compounds are compounds with a main chain backbone containing siloxane bonds (-Si-O-Si-) and organic substituents at the ends or side chains. They exhibit excellent heat resistance, weather resistance, electrical properties, water resistance, and mold release properties derived from siloxane bonds. These organopolysiloxane compounds can be characterized by compounding with common organic polymers, thus making them suitable for modifying organic polymers.

[0003] Typically, as a method for compounding organopolysiloxane compounds with organic polymers, a copolymerization method is used, incorporating organopolysiloxane compounds with reactive functional groups into the polymerization system of the organic polymer.

[0004] Patent Document 1 discloses a branched polysiloxane compound having a methacryloyl group as a reactive functional group. Patent Document 2 discloses an organopolysiloxane compound having multiple cyclic olefin backbones at both ends of the polysiloxane chain and in the side chains of the polysiloxane chain.

[0005] However, organopolysiloxane compounds with a cyclic olefin backbone at only a single end of the polysiloxane chain have not been studied.

[0006] [Existing Technical Documents]

[0007] [Patent Literature]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 2008-274278

[0009] [Patent Document 2] Japanese Patent Application Publication No. 2003-212973 Summary of the Invention

[0010] [The problem the invention aims to solve]

[0011] As a subject of this invention, an organopolysiloxane compound having a cyclic olefin backbone only at a single end of the polysiloxane chain is provided that can be compounded with cyclic olefins without becoming a crosslinking system.

[0012] [Technical means to solve the problem]

[0013] The inventors of this invention have conducted diligent research to solve the aforementioned problems. As a result, they discovered that by reacting a polysiloxane obtained through the reaction of an organometallic compound with a cyclic siloxane with a chlorosilane compound having a cyclic olefin backbone, it is possible to synthesize an organopolysiloxane compound having a cyclic olefin backbone only at a single end of the polysiloxane chain. Furthermore, it was found that by adding the obtained cyclic olefin-containing organopolysiloxane to a polymerization system of cyclic olefin monomers for polymerization, surface modification of the cyclic olefin polymer can be achieved.

[0014] The present invention provides the following organopolysiloxane compounds.

[0015] Item 1. An organopolysiloxane compound, which is an organopolysiloxane compound represented by formula (1).

[0016]

[0017] In formula (1), A is a monovalent alicyclic hydrocarbon group with 4 to 60 carbon atoms having at least one carbon-carbon double bond, and T is the group represented by formula (2).

[0018]

[0019] In equation (2), R 1 and R 2 Independently, it is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R 3 For alkyl groups having 4 to 10 carbon atoms, x is an integer from 1 to 3, and n is an integer greater than or equal to 1. In the formula, in R... 1 Or R 3 When multiple R exist, they can be the same or different. 2 They can be the same or different.

[0020] Item 2. The organopolysiloxane compound according to Item 1, wherein A in formula (1) is the base represented by formula (3).

[0021]

[0022] In formula (3), Y is a trivalent group containing a hydrocarbon group with 2 to 36 carbon atoms, a substituted hydrocarbon group with 3 to 58 carbon atoms, a hydrocarbon group containing heteroatoms with 2 to 36 carbon atoms, or a hydrocarbon group containing substituted heteroatoms with 2 to 58 carbon atoms. These trivalent groups may have at least one cyclic structure and may have unsaturated bonds.

[0023] Item 3. The organopolysiloxane compound according to Item 1 or Item 2, wherein A in formula (1) is a base represented by formula (4a), formula (4b), formula (4c) or formula (4d).

[0024]

[0025] In equations (4a) to (4d), R 5 Independently, it is either hydrogen or a monovalent hydrocarbon group with 1 to 4 carbon atoms that may have unsaturated bonds, R 6 Independently, it is a divalent group comprising a hydrocarbon group having 1 to 4 carbon atoms, a substituted hydrocarbon group having 3 to 20 carbon atoms, a hydrocarbon group containing a heteroatom having 1 to 4 carbon atoms, or a hydrocarbon group containing a substituted heteroatom having 1 to 20 carbon atoms. These divalent groups may have unsaturated bonds, R 7 It is a methine (CH) or a trivalent heteroelement, L is a divalent hydrocarbon group with 2 to 10 carbon atoms that may have unsaturated bonds, Z is a methylene or 1,2-ethanediyl group, and m is an integer from 0 to 3.

[0026] Item 4. The organopolysiloxane compound according to Item 3, wherein A in formula (1) according to Item 1 is a base represented by formula (4a), formula (4b), formula (4c) or formula (4d), and R in formula (4a) or formula (4c) 5 For hydrogen, L is 1,2-ethanediyl, m is 0, and R in formula (4b) or formula (4d) 5 For hydrogen, R 6 For carbonyl, R 7 Nitrogen is 1,3-propanediyl.

[0027] Item 5. The organopolysiloxane compound according to Item 4, wherein A in formula (1) according to Item 1 is a base represented by formula (4a) or formula (4b), and x in formula (2) according to Item 1 is 2 or 3.

[0028] Item 6. A polymer obtained by polymerizing an organopolysiloxane compound according to any one of items 1 to 5 with a cycloolefin monomer.

[0029] Item 7. The polymer according to Item 6, wherein it is obtained by polymerization in the presence of a metasomatic polymerization catalyst.

[0030] Item 8. A self-supporting membrane comprising the polymer according to Item 6 or Item 7.

[0031] Item 9. A molded article comprising the polymer according to item 6 or item 7.

[0032] [The effects of the invention]

[0033] This invention provides organopolysiloxane compounds that are useful for surface modification of cyclic olefin polymers and have a cyclic olefin backbone only at a single end of the polysiloxane chain. Detailed Implementation

[0034] The embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments.

[0035] The terms used in this specification have the following meanings.

[0036] In this specification, "alkyl" refers to a saturated, straight-chain, branched, or cyclic hydrocarbon having a specific number of carbon atoms.

[0037] In this specification, "halogen" or "halogen" refers to chlorine, fluorine, bromine, or iodine.

[0038] In this specification, "heteroatoms" or "heteroele elements" refers to nitrogen, oxygen, phosphorus, or sulfur.

[0039] The organopolysiloxane compounds of the present invention are characterized by being represented by formula (1).

[0040]

[0041] In formula (1), A is a monovalent alicyclic hydrocarbon group with 4 to 60 carbon atoms having at least one carbon-carbon double bond, and T is the group represented by formula (2).

[0042]

[0043] In equation (2), R 1 and R 2 Independently, it is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R 3 For alkyl groups having 4 to 10 carbon atoms, x is an integer from 1 to 3, and n is an integer greater than or equal to 1. In the formula, in R... 1 Or R 3 When multiple R exist, they can be the same or different. 2 They can be the same or different.

[0044] In formula (1), the monovalent alicyclic hydrocarbon group with carbon-carbon double bonds, having 4 to 60 carbon atoms, is, for example, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cyclododecenyl, cyclotetradecenyl, cyclohexadecenyl, cyclooctadecenyl, cycloeicodecenyl, cyclododecenyl, cycloticodecenyl, cyclohexadecenyl, cyclooctadecenyl, norbornenyl, norbornadienyl, dicyclopentenyl, dicyclopentadienyl, dicyclohexenyl, dicyclohexadienyl, tricyclodecenyl, tetracyclododecenyl, tetracyclododecadienyl, etc. At least one hydrogen atom of these groups may be substituted by an alkyl group, a halogen, a heteroatom, a haloalkyl group, or a heteroatom-substituted alkyl group. The monovalent alicyclic hydrocarbon group having carbon-carbon double bonds preferably has 4 to 30 carbon atoms, more preferably 5 to 15.

[0045] R in equation (2) 1 and R 2The alkyl groups having 1 to 10 carbon atoms include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, isohexyl, tert-hexyl, 2-methylpentyl, 3,3-dimethylbutyl, isohexyl, 3-methylhexyl, 2,2'-dimethylpentyl, 3,3-dimethylpentyl, 2,3-dimethylpentyl, 2-ethylpentyl, 3-ethylpentyl. Tert-heptyl, isooctyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 2,3-dimethylhexyl, 2-ethylhexyl, 3-ethylhexyl, isononyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl, 2,2-dimethylheptyl, 3,3-dimethylheptyl, 4,4-dimethylheptyl, 2,3-dimethylheptyl, 2,4-dimethylheptyl, 2 5-Dimethylheptyl, 2,6-Dimethylheptyl, 3,4-Dimethylheptyl, 3,5-Dimethylheptyl, 2-Ethylheptyl, 3-Ethylheptyl, 4-Ethylheptyl, Neononyl, Isodecyl, 2-Methylnonyl, 3-Methylnonyl, 4-Methylnonyl, 5-Methylnonyl, 2,2-Dimethyloctyl, 3,3-Dimethyloctyl, 4,4-Dimethyloctyl, 2,3-Dimethyloctyl, 2,4-Dimethyloctyl, 2,5 -Dimethyloctyl, 2,6-dimethyloctyl, 3,4-dimethyloctyl, 3,5-dimethyloctyl, 3,6-dimethyloctyl, 4,5-dimethyloctyl, 2-ethyloctyl, 3-ethyloctyl, 4-ethyloctyl, 3-propylheptyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, cyclooctyl, methylcycloheptyl, cyclononyl, methylcyclooctyl, cyclodecyl, methylcyclononyl, etc., wherein the alkyl group preferably has 1 to 4 carbon atoms.

[0046] Aryl groups with 6 to 10 carbon atoms include, for example, phenyl, benzyl, 2-toluyl, 3-toluyl, 4-toluyl, ethylphenyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, propylphenyl, isopropylphenyl, 1,2,3-trimethylphenyl, 1,2,4-trimethylphenyl, 1,3,5-trimethylphenyl, butylphenyl, isobutylphenyl, tert-butylphenyl, 1,2,3,4-tetramethylphenyl, 1,2,3,5-tetramethylphenyl, 1,2,4,5-tetramethylphenyl, 1-naphthyl, 2-naphthyl, etc.

[0047] R in equation (2) 3Alkyl groups having 4 to 10 carbon atoms include, for example, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, isohexyl, tert-hexyl, 2-methylpentyl, 3,3-dimethylbutyl, isohexyl, 3-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 2,3-dimethylpentyl, 2-ethylpentyl, 3-ethylpentyl, tert-heptyl, isooctyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 2,3-dimethylhexyl, 2-ethylhexyl, 3-ethylhexyl, isononyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl, 2,2-dimethylheptyl, 3,3-dimethylheptyl, 4,4-dimethylheptyl, 2 3-Dimethylheptyl, 2,4-Dimethylheptyl, 2,5-Dimethylheptyl, 2,6-Dimethylheptyl, 3,4-Dimethylheptyl, 3,5-Dimethylheptyl, 2-Ethylheptyl, 3-Ethylheptyl, 4-Ethylheptyl, Neononyl, Isodecyl, 2-Methylnonyl, 3-Methylnonyl, 4-Methylnonyl, 5-Methylnonyl, 2,2-Dimethyloctyl, 3,3-Dimethyloctyl, 4,4-Dimethyloctyl, 2,3-Dimethyloctyl, 2,4-Dimethyloctyl, 2,5-Dimethyloctyl, 2,6-Dimethyloctyl, 3,4-Dimethyloctyl, 3,5-Dimethyloctyl, 3,6-Dimethyloctyl, 4,5-Dimethyloctyl, 2-Ethyloctyl, 3-Ethyloctyl, 4-Ethyloctyl, 3-Propylheptyl, wherein the alkyl group preferably has 4 carbon atoms.

[0048] In formula (2), n is preferably 10 to 150, and more preferably 15 to 80.

[0049] In formula (1), the monovalent alicyclic hydrocarbon group of A is preferably the group represented by formula (3).

[0050]

[0051] In formula (3), Y is a trivalent group containing a hydrocarbon group with 2 to 36 carbon atoms, a substituted hydrocarbon group with 3 to 58 carbon atoms, a hydrocarbon group containing heteroatoms with 2 to 36 carbon atoms, or a hydrocarbon group containing substituted heteroatoms with 2 to 58 carbon atoms. These trivalent groups may have at least one cyclic structure and may have unsaturated bonds.

[0052] Examples of hydrocarbon groups with 2 to 36 carbon atoms include ethylene, propylene, butene, pentene, hexene, hepten, octene, decene, dodecene, tetradecene, hexadecene, octadecene, eicosene, dodecene, tetradecene, hexadecene, cyclopentane, cyclopentene, octahydro-1H-indene, 2,3,3a,4,7,7a-hexahydro-1H-indene, octahydro-1H-4,7-methylbridged indene, etc. The number of carbon atoms in the hydrocarbon group is preferably 2 to 28, more preferably 3 to 10.

[0053] The substituted hydrocarbon group having carbon numbers 3 to 58 is formed by at least one hydrogen atom of the hydrocarbon group having carbon numbers 2 to 36 via methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, isohexyl, tert-hexyl, 2-methylpentyl, 3-methylpentyl, 3,3-dimethylbutyl, isohexyl, 3-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 2,3-dimethylpentyl, 2- Ethylpentyl, 3-ethylpentyl, tert-heptyl, isooctyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 2,3-dimethylhexyl, 2-ethylhexyl, 3-ethylhexyl, isononyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl, 2,2-dimethylheptyl, 3,3-dimethylheptyl, 4,4-dimethylheptyl, 2,3-dimethylheptyl, 2,4-dimethylheptyl 2,5-Dimethylheptyl, 2,6-Dimethylheptyl, 3,4-Dimethylheptyl, 3,5-Dimethylheptyl, 2-Ethylheptyl, 3-Ethylheptyl, 4-Ethylheptyl, Neononyl, Isodecyl, 2-Methylnonyl, 3-Methylnonyl, 4-Methylnonyl, 5-Methylnonyl, 2,2-Dimethyloctyl, 3,3-Dimethyloctyl, 4,4-Dimethyloctyl, 2,3-Dimethyloctyl, 2,4-Dimethyloctyl, 2,5-Dimethyloctyl, 2, It is formed by alkyl substitution of 6-dimethyloctyl, 3,4-dimethyloctyl, 3,5-dimethyloctyl, 3,6-dimethyloctyl, 4,5-dimethyloctyl, 2-ethyloctyl, 3-ethyloctyl, 4-ethyloctyl, 3-propylheptyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, cyclooctyl, methylcycloheptyl, cyclononyl, methylcyclooctyl, cyclodecyl, methylcyclononyl, etc., wherein the number of carbon atoms of the substituted hydrocarbon group is preferably 3 to 48, more preferably 4 to 30.

[0054] The heteroatom-containing hydrocarbon group with 2 to 36 carbon atoms is formed by substituting at least one carbon atom of the hydrocarbon group with 2 to 36 carbon atoms with a substituent containing a heteroatom, such as carbonyl (>C=O), amide (-CONH2, -CONH-, CON<), sulfonyl (>SO2), sulfide (-S-), thiocarbonyl (>C=S), sulfonic acid oxy (-S(=O)-), etc. The number of carbon atoms in the heteroatom-containing hydrocarbon group is preferably 2 to 28, more preferably 3 to 10.

[0055] The hydrocarbon group containing substituted heteroatoms with 2 to 58 carbon atoms is formed by substituting at least one carbon or hydrogen of the hydrocarbon group with 2 to 36 carbon atoms with a substituent containing heteroatoms, such as hydroxyl (-OH), alkoxy (-OR), carbonyl (>C=O), carboxyl (-COOH), ester (-COOR), amino (-NH2), imino (=NH), azo (-N=N-), nitro (-NO2), nitroso (-NO), amide (-CONH2), cyano (-C≡N), thiol (-SH), thioether (-SR), sulfonyl (>SO2), sulfonyl (-SO3H), sulfide (-S-), thiocarbonyl (>C=S), sulfonic acid oxy (-S(=O)-), etc. The hydrocarbon group containing substituted heteroatoms preferably has 3 to 48 carbon atoms, more preferably 4 to 30 carbon atoms.

[0056] In formula (1), the monovalent alicyclic hydrocarbon group of A is more preferably represented by formula (4a), formula (4b), formula (4c) or formula (4d).

[0057]

[0058] In equations (4a) to (4d), R 5 Independently, it is either hydrogen or a monovalent hydrocarbon group with 1 to 4 carbon atoms that may have unsaturated bonds, R 6 Independently, it is a divalent group comprising a hydrocarbon group having 1 to 4 carbon atoms, a substituted hydrocarbon group having 3 to 20 carbon atoms, a hydrocarbon group containing a heteroatom having 1 to 4 carbon atoms, or a hydrocarbon group containing a substituted heteroatom having 1 to 20 carbon atoms. These divalent groups may have unsaturated bonds, R 7 It is a methine (CH) or a trivalent heteroelement, L is a divalent hydrocarbon group with 2 to 10 carbon atoms that may have unsaturated bonds, Z is a methylene or 1,2-ethanediyl group, and m is an integer from 0 to 3.

[0059] R 5 The monovalent hydrocarbon groups with 1 to 4 carbon atoms that have unsaturated bonds can be, for example, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, vinyl, allyl, butenyl, isopropenyl, isobutylenyl, butadieneyl, etc.

[0060] R 6 Examples of hydrocarbon groups with 1 to 4 carbon atoms include methylene, 1,1-ethanediyl, 1,2-ethanediyl, 1,1-propanediyl, 1,2-propanediyl, 1,3-propanediyl, 1,1-butanediyl, 1,2-butanediyl, 1,3-butanediyl, and 1,4-butanediyl.

[0061] Substituted hydrocarbon groups having 3 to 20 carbon atoms include, for example, 2,2-propanediyl, 1-methylpropane-1,1-diyl, 1-methylpropane-1,2-diyl, 1-methylpropane-1,3-diyl, 2-methylpropane-1,1-diyl, 2-methylpropane-1,2-diyl, 2-methylpropane-1,3-diyl, 1,1-dimethylethane-1,2-diyl, 1-methylbutane-1,1-diyl, 1-methylbutane-1,2-diyl, 1-methylbutane-1,3-diyl, 1-methylbutane-1,4-diyl, 2-methylbutane-1,1-diyl, 2-methylbutane-1,2-diyl, 2-methylbutane-1,3-diyl, 2-methylbutane-1,4-diyl, and 2,2-dimethylpropane-1,1-diyl. -diyl, 2,2-dimethylpropane-1,3-diyl, 1-methylpentane-1,1-diyl, 1-methylpentane-1,2-diyl, 1-methylpentane-1,3-diyl, 1-methylpentane-1,4-diyl, 1-methylpentane-1,5-diyl, 2-methylpentane-1,1-diyl, 2-methylpentane-1,2-diyl, 2-methylpentane-1,3-diyl, 2-methylpentane-1,4-diyl, 2-methylpentane-1,5-diyl, 3-methylpentane-1,1-diyl, 3-methylpentane-1,2-diyl, 3-methylpentane-1,3-diyl, 3-methylpentane-1,4-diyl, 3-methylpentane-1,5-diyl, 1,1-dimethylbutane-1,2-diyl, 1, 1-Dimethylbutane-1,3-diyl, 1,1-dimethylbutane-1,4-diyl, 2,2-dimethylbutane-1,1-diyl, 2,2-dimethylbutane-1,3-diyl, 2,2-dimethylbutane-1,4-diyl, 1-methylhexane-1,1-diyl, 1-methylhexane-1,2-diyl, 1-methylhexane-1,3-diyl, 1-methylhexane-1,4-diyl, 1-methylhexane-1,5-diyl, 1-methylhexane-1,6-diyl, 2-methylhexane-1,1-diyl, 2-methylhexane-1,2-diyl, 2-methylhexane-1,3-diyl, 2-methylhexane-1,4-diyl, 2-methylhexane-1,5-diyl, 2-methylhexane-1,6-diyl 3-Methylhexane-1,1-diyl, 3-methylhexane-1,2-diyl, 3-methylhexane-1,3-diyl, 3-methylhexane-1,4-diyl, 3-methylhexane-1,5-diyl, 3-methylhexane-1,6-diyl, 1,1-dimethylpentane-1,2-diyl, 1,1-dimethylpentane-1,3-diyl, 1,1-dimethylpentane-1,4-diyl, 1,1-dimethylpentane-1,5-diyl, 2,2-dimethylpentane-1,1-diyl, 2,2-dimethylpentane-1,3-diyl, 2,2-dimethylpentane-1,4-diyl, 2,2-dimethylpentane-1,5-diyl, 3,3-dimethylpentane-1,1-diyl, 3,3-dimethylpentane-1,2-Diyl, 3,3-dimethylpentane-1,4-diyl, 3,3-dimethylpentane-1,5-diyl, 1-ethylpentane-1,1-diyl, 1-ethylpentane-1,2-diyl, 1-ethylpentane-1,3-diyl, 1-ethylpentane-1,4-diyl, 1-ethylpentane-1,5-diyl, 2-ethylpentane-1,1-diyl, 2-ethylpentane-1,2-diyl, 2-ethylpentane-1,3-diyl, 2-ethylpentane-1,4-diyl, 2-ethylpentane-1,5-diyl, 3-ethylpentane-1,1-diyl, 3-ethylpentane-1,2-diyl, 3-ethylpentane-1,3-diyl, 3-ethylpentane-1,4-diyl, 3-ethylpentane-1,5-diyl, 1 1-Dimethylpentane-1,2-diyl, 1,1-dimethylpentane-1,3-diyl, 1,1-dimethylpentane-1,4-diyl, 1,1-dimethylpentane-1,5-diyl, 2,2-dimethylpentane-1,1-diyl, 2,2-dimethylpentane-1,3-diyl, 2,2-dimethylpentane-1,4-diyl, 2,2-dimethylpentane-1,5-diyl, 3,3-dimethylpentane-1,1-diyl, 3,3-dimethylpentane-1,2-diyl, 3,3-dimethylpentane-1,4-diyl, 3,3-dimethylpentane-1,5-diyl, 1-methylheptane-1,1-diyl, 1-methylheptane-1,2-diyl, 1-methylheptane-1,3-diyl, 1-methylheptane Alkane-1,4-diyl, 1-methylheptane-1,5-diyl, 1-methylheptane-1,6-diyl, 1-methylheptane-1,7-diyl, 2-methylheptane-1,1-diyl, 2-methylheptane-1,2-diyl, 2-methylheptane-1,3-diyl, 2-methylheptane-1,4-diyl, 2-methylheptane-1,5-diyl, 2-methylheptane-1,6-diyl, 2-methylheptane-1,7-diyl, 3-methylheptane-1,1-diyl, 3-methylheptane-1,2-diyl, 3-methylheptane-1,3-diyl, 3-methylheptane-1,4-diyl, 3-methylheptane-1,5-diyl, 3-methylheptane-1,6-diyl, 3-methylheptane-1,7-diyl, 4-methylheptane-1,4-diyl, 1-methylheptane-1,5-diyl, 1-methylheptane-1,6-diyl, 3-methylheptane-1,7-diyl, 4-methylheptane-1,4-diyl, 1-methylheptane-1,5-diyl, 1-methylheptane-1,6-diyl, 1-methylheptane-1,7-diyl, 1-methylheptane-1,4 ...6-diyl, 1-methylh 1,1-diyl heptane-1,2-diyl, 4-methylheptane-1,3-diyl, 4-methylheptane-1,4-diyl, 4-methylheptane-1,5-diyl, 4-methylheptane-1,6-diyl, 4-methylheptane-1,7-diyl, 1,1-dimethylhexane-1,2-diyl, 1,1-dimethylhexane-1,3-diyl, 1,1-dimethylhexane-1,4-diyl, 1,1-dimethylhexane-1,5-diyl, 1,1-dimethylhexane-1,6-diyl, 2,2-dimethylhexane-1,1-diyl, 2,2-dimethylhexane-1,3-diyl, 2,2-dimethylhexane-1,4-diyl, 2,2-dimethylhexane-1,5-diyl, 2,2-Dimethylhexane-1,6-diyl, 3,3-dimethylhexane-1,1-diyl, 3,3-dimethylhexane-1,2-diyl, 3,3-dimethylhexane-1,4-diyl, 3,3-dimethylhexane-1,5-diyl, 3,3-dimethylhexane-1,6-diyl, 1-ethylhexane-1,1-diyl, 1-ethylhexane-1,2-diyl, 1-ethylhexane-1,3-diyl, 1-ethylhexane-1,4-diyl, 1-ethylhexane-1,5-diyl, 1-ethylhexane-1,6-diyl, 2-ethylhexane-1,1-diyl, 2-ethylhexane-1,2-diyl, 2-ethylhexane-1,3-diyl, 2-ethylhexane-1,4-diyl, 2-ethylhexane-1, 5-Diyl, 2-Ethylhexane-1,6-Diyl, 3-Ethylhexane-1,1-Diyl, 3-Ethylhexane-1,2-Diyl, 3-Ethylhexane-1,3-Diyl, 3-Ethylhexane-1,4-Diyl, 3-Ethylhexane-1,5-Diyl, 3-Ethylhexane-1,6-Diyl, 1-Methyloctane-1,1-Diyl, 1-Methyloctane-1,2-Diyl, 1-Methyloctane-1,3-Diyl, 1-Methyloctane-1,4-Diyl, 1-Methyloctane-1,5-Diyl, 1-Methyloctane-1,6-Diyl, 1-Methyloctane-1,7-Diyl, 1-Methyloctane-1,8-Diyl, 2-Methyloctane-1,1-Diyl, 2-Methyloctane-1,2-Diyl, 2-Methyloctane- 1,3-Diyl, 2-Methyloctane-1,4-Diyl, 2-Methyloctane-1,5-Diyl, 2-Methyloctane-1,6-Diyl, 2-Methyloctane-1,7-Diyl, 2-Methyloctane-1,8-Diyl, 3-Methyloctane-1,1-Diyl, 3-Methyloctane-1,2-Diyl, 3-Methyloctane-1,3-Diyl, 3-Methyloctane-1,4-Diyl, 3-Methyloctane-1,5-Diyl, 3-Methyloctane-1,6-Diyl, 3-Methyloctane-1,7-Diyl, 3-Methyloctane-1,8-Diyl, 4-Methyloctane-1,1-Diyl, 4-Methyloctane-1,2-Diyl, 4-Methyloctane-1,3-Diyl, 4-Methyloctane-1,4-Diyl, 4-Methyloctane Alkane-1,5-diyl, 4-methyloctane-1,6-diyl, 4-methyloctane-1,7-diyl, 4-methyloctane-1,8-diyl, 1,1-dimethylheptane-1,2-diyl, 1,1-dimethylheptane-1,3-diyl, 1,1-dimethylheptane-1,4-diyl, 1,1-dimethylheptane-1,5-diyl, 1,1-dimethylheptane-1,6-diyl, 1,1-dimethylheptane-1,7-diyl, 2,2-dimethylheptane-1,1-diyl, 2,2-dimethylheptane-1,3-diyl, 2,2-dimethylheptane-1,4-diyl, 2,2-dimethylheptane-1,5-diyl, 2,2-dimethylheptane-1,6-diyl, 2,2-dimethylheptane-1,6-diyl, 2,2-dimethylheptane-1,7-Diyl, 3,3-Dimethylheptane-1,1-diyl, 3,3-Dimethylheptane-1,2-diyl, 3,3-Dimethylheptane-1,4-diyl, 3,3-Dimethylheptane-1,5-diyl, 3,3-Dimethylheptane-1,6-diyl, 3,3-Dimethylheptane-1,7-diyl, 4,4-Dimethylheptane-1,1-diyl, 4,4-Dimethylheptane-1,2-diyl, 4,4-Dimethylheptane-1,3-diyl, 4,4-Dimethylheptane-1,5-diyl, 4,4-Dimethylheptane-1,6-diyl, 4,4-Dimethylheptane-1,7-diyl, 1-Ethylheptane-1,1-diyl, 1-Ethylheptane-1,2-diyl, 1-Ethylheptane-1,3- Diyl, 1-ethylheptane-1,4-diyl, 1-ethylheptane-1,5-diyl, 1-ethylheptane-1,6-diyl, 1-ethylheptane-1,7-diyl, 2-ethylheptane-1,1-diyl, 2-ethylheptane-1,2-diyl, 2-ethylheptane-1,3-diyl, 2-ethylheptane-1,4-diyl, 2-ethylheptane-1,5-diyl, 2-ethylheptane-1,6-diyl, 2-ethylheptane-1,7-diyl, 3-ethylheptane-1,1-diyl, 3-ethylheptane-1,2-diyl, 3-ethylheptane-1,3-diyl, 3-ethylheptane-1,4-diyl, 3-ethylheptane-1,5-diyl, 3-ethylheptane-1,6-diyl, 3-ethylheptane-1 ,7-diyl, 4-ethylheptane-1,1-diyl, 4-ethylheptane-1,2-diyl, 4-ethylheptane-1,3-diyl, 4-ethylheptane-1,4-diyl, 4-ethylheptane-1,5-diyl, 4-ethylheptane-1,6-diyl, 4-ethylheptane-1,7-diyl, 2,2,4,4-tetramethylpentane-1,5-diyl, 1-methylnonane-1,1-diyl, 1-methylnonane-1,2-diyl, 1-methylnonane-1,3-diyl, 1-methylnonane-1,4-diyl, 1-methylnonane-1,5-diyl, 1-methylnonane-1,6-diyl, 1-methylnonane-1,7-diyl, 1-methylnonane-1,8-diyl, 1-methylnonane-1,9-diyl 2-Methylnonane-1,1-diyl, 2-Methylnonane-1,2-diyl, 2-Methylnonane-1,3-diyl, 2-Methylnonane-1,4-diyl, 2-Methylnonane-1,5-diyl, 2-Methylnonane-1,6-diyl, 2-Methylnonane-1,7-diyl, 2-Methylnonane-1,8-diyl, 2-Methylnonane-1,9-diyl, 3-Methylnonane-1,1-diyl, 3-Methylnonane-1,2-diyl, 3-Methylnonane-1,3-diyl, 3-Methylnonane-1,4-diyl, 3-Methylnonane-1,5-diyl, 3-Methylnonane-1,6-diyl, 3-Methylnonane-1,7-diyl, 3-Methylnonane-1,8-diyl, 3-Methylnonane-1,1-diyl9-Diyl, 4-Methylnonane-1,1-Diyl, 4-Methylnonane-1,2-Diyl, 4-Methylnonane-1,3-Diyl, 4-Methylnonane-1,4-Diyl, 4-Methylnonane-1,5-Diyl, 4-Methylnonane-1,6-Diyl, 4-Methylnonane-1,7-Diyl, 4-Methylnonane-1,8-Diyl, 4-Methylnonane-1,9-Diyl, 5-Methylnonane-1,1-Diyl, 5-Methylnonane-1,2-Diyl, 5-Methylnonane-1,3-Diyl, 5-Methylnonane-1,4-Diyl, 5-Methylnonane-1,5-Diyl, 5-Methylnonane-1,6-Diyl, 5-Methylnonane-1,7-Diyl, 5-Methylnonane-1,8-Diyl, 5-Methylnonane Alkane-1,9-diyl, 1,1-dimethyloctane-1,2-diyl, 1,1-dimethyloctane-1,3-diyl, 1,1-dimethyloctane-1,4-diyl, 1,1-dimethyloctane-1,5-diyl, 1,1-dimethyloctane-1,6-diyl, 1,1-dimethyloctane-1,7-diyl, 1,1-dimethyloctane-1,8-diyl, 2,2-dimethyloctane-1,1-diyl, 2,2-dimethyloctane-1,3-diyl, 2,2-dimethyloctane-1,4-diyl, 2,2-dimethyloctane-1,5-diyl, 2,2-dimethyloctane-1,6-diyl, 2,2-dimethyloctane-1,7-diyl, 2,2-dimethyloctane-1,8-diyl, 3, 3-Dimethyloctane-1,1-diyl, 3,3-dimethyloctane-1,2-diyl, 3,3-dimethyloctane-1,4-diyl, 3,3-dimethyloctane-1,5-diyl, 3,3-dimethyloctane-1,6-diyl, 3,3-dimethyloctane-1,7-diyl, 3,3-dimethyloctane-1,8-diyl, 4,4-dimethyloctane-1,1-diyl, 4,4-dimethyloctane-1,2-diyl, 4,4-dimethyloctane-1,3-diyl, 4,4-dimethyloctane-1,5-diyl, 4,4-dimethyloctane-1,6-diyl, 4,4-dimethyloctane-1,7-diyl, 4,4-dimethyloctane-1,8-diyl, 1-ethyloctane-1,1-diyl 1-Ethyloctane-1,2-diyl, 1-Ethyloctane-1,3-diyl, 1-Ethyloctane-1,4-diyl, 1-Ethyloctane-1,5-diyl, 1-Ethyloctane-1,6-diyl, 1-Ethyloctane-1,7-diyl, 1-Ethyloctane-1,8-diyl, 2-Ethyloctane-1,1-diyl, 2-Ethyloctane-1,2-diyl, 2-Ethyloctane-1,3-diyl, 2-Ethyloctane-1,4-diyl, 2-Ethyloctane-1,5-diyl, 2-Ethyloctane-1,6-diyl, 2-Ethyloctane-1,7-diyl, 2-Ethyloctane-1,8-diyl, 3-Ethyloctane-1,1-diyl, 3-Ethyloctane-1,2-diyl, 3-Ethyloctane-1,3-Diyl, 3-ethyloctane-1,4-diyl, 3-ethyloctane-1,5-diyl, 3-ethyloctane-1,6-diyl, 3-ethyloctane-1,7-diyl, 3-ethyloctane-1,8-diyl, 4-ethyloctane-1,1-diyl, 4-ethyloctane-1,2-diyl, 4-ethyloctane-1,3-diyl, 4-ethyloctane-1,4-diyl, 4-ethyloctane-1,5-diyl, 4-ethyloctane-1,6-diyl, 4-ethyloctane-1,7-diyl, 4-ethyloctane-1,8-diyl, etc., wherein the number of carbon atoms in the substituted hydrocarbon group is preferably 3 to 10, more preferably 3 to 6.

[0062] The hydrocarbon group containing heteroatoms with 1 to 4 carbon atoms, such as methylene, 1,1-ethanediyl, 1,2-ethanediyl, 1,1-propanediyl, 1,2-propanediyl, 1,3-propanediyl, 1,1-butanediyl, 1,2-butanediyl, 1,3-butanediyl, 1,4-butanediyl, etc., is formed by substituting at least one carbon carbonyl group of the hydrocarbon group with heteroatoms, such as carbonyl (>C=O), amide (-CONH2, -CONH-, CON<), sulfonyl (>SO2), sulfide (-S-), thiocarbonyl (>C=S), sulfonic acid oxy (-S(=O)-).

[0063] A hydrocarbon group containing a substituted heteroatom and having 1 to 20 carbon atoms, such as methylene, 1,1-ethanediyl, 1,2-ethanediyl, 1,1-propanediyl, 1,2-propanediyl, 1,3-propanediyl, 1,1-butanediyl, 1,2-butanediyl, 1,3-butanediyl, 1,4-butanediyl, etc., wherein at least one carbon or hydrogen atom is substituted by a hydroxyl (-OH), alkoxy (-OR), carbonyl (>C=O), carboxyl (-COOH), ester (-COOR), amino (-NH2), or imine group. It is formed by substituting with substituents containing heteroatoms, such as hydroxyl (=NH), azo (-N=N-), nitro (-NO2), nitroso (-NO), amide (-CONH2), cyano (-C≡N), thiol (-SH), thioether (-SR), sulfonyl (>SO2), sulfonyl (-SO3H), sulfide (-S-), thiocarbonyl (>C=S), sulfonic acid oxy (-S(=O)-), etc., wherein the hydrocarbon group containing the substituted heteroatoms preferably has 1 to 10 carbon atoms, more preferably 1 to 4.

[0064] In the basis represented by equation (4b) or equation (4d), there are two R... 6 With R 7 The ring has 5 or more elements, preferably 5 to 15, more preferably 5 to 7, and particularly preferably 5.

[0065] The divalent hydrocarbon group in L, which may have 2 to 10 unsaturated bonds, includes, for example: 1,2-ethanediyl, prop-1-en-1,2-diyl, prop-1-en-1,3-diyl, prop-1-en-2,3-diyl, but-1-en-1,2-diyl, but-1-en-1,3-diyl, but-1-en-1,4-diyl, but-1-en-2,3-diyl, but-1-en-2,4-diyl, but-1-en-3,4-diyl, but-2-en-1,2-diyl, but-2-en-1,3-diyl, but-2-en-1,4-diyl, but-2-en-2,3-diyl, but-2-en-2,4-diyl, but-2-en-3,4-diyl, pent-1-en-1,2-diyl, pent-1-en -1,3-diyl, pent-1-en-1,4-diyl, pent-1-en-1,5-diyl, pent-1-en-2,3-diyl, pent-1-en-2,4-diyl, pent-1-en-2,5-diyl, pent-2-en-3,4-diyl, pent-1-en-3,5-diyl, pent-1-en-4,5-diyl, pent-2-en-1,2-diyl , pent-2-en-1,3-diyl, pent-2-en-1,4-diyl, pent-2-en-1,5-diyl, pent-2-en-2,3-diyl, pent-2-en-2,4-diyl, pent-2-en-2,5-diyl, pent-2-en-3,4-diyl, pent-2-en-3,5-diyl, pent-2-en-4,5-diyl, hex-1-en- 1,2-Diyl, Hex-1-en-1,3-Diyl, Hex-1-en-1,4-Diyl, Hex-1-en-1,5-Diyl, Hex-1-en-1,6-Diyl, Hex-1-en-2,3-Diyl, Hex-1-en-2,4-Diyl, Hex-1-en-2,5-Diyl, Hex-1-en-2,6-Diyl, Hex-1-en-3,4-Diyl Hex-1-en-3,5-diyl, hex-1-en-3,6-diyl, hex-1-en-4,5-diyl, hex-1-en-4,6-diyl, hex-1-en-5,6-diyl, hex-2-en-1,2-diyl, hex-2-en-1,3-diyl, hex-2-en-1,4-diyl, hex-2-en-1,5-diyl, hex-2-en-1 ,6-diyl, hex-2-en-2,3-diyl, hex-2-en-2,4-diyl, hex-2-en-2,5-diyl, hex-2-en-2,6-diyl, hex-2-en-3,4-diyl, hex-2-en-3,5-diyl, hex-2-en-3,6-diyl, hex-2-en-4,5-diyl, hex-2-en-4,6-diyl, hex -2-en-5,6-diyl, hex-3-en-1,2-diyl, hex-3-en-1,3-diyl, hex-3-en-1,4-diyl, hex-3-en-1,5-diyl, hex-3-en-1,6-diyl, hex-3-en-2,3-diyl, hex-3-en-2,4-diyl, hex-3-en-2,5-diyl, hex-3-en-2,6-Diyl, Hex-3-en-3,4-diyl, Hex-3-en-3,5-diyl, Hex-3-en-3,6-diyl, Hex-3-en-4,5-diyl, Hex-3-en-4,6-diyl, Hex-3-en-5,6-diyl, Hepten-1-en-1,2-diyl, Hepten-1-en-1,3-diyl, Hepten-1-en-1,4-diyl, Hepten-1 -en-1,5-diyl, hept-1-en-1,6-diyl, hept-1-en-1,7-diyl, hept-1-en-2,3-diyl, hept-1-en-2,4-diyl, hept-1-en-2,5-diyl, hept-1-en-2,6-diyl, hept-1-en-2,7-diyl, hept-1-en-3,4-diyl, hept-1-en-3,5-diyl heptyl, hept-1-en-3,6-diyl, hept-1-en-3,7-diyl, hept-1-en-4,5-diyl, hept-1-en-4,6-diyl, hept-1-en-4,7-diyl, hept-1-en-5,6-diyl, hept-1-en-5,7-diyl, hept-1-en-6,7-diyl, hept-2-en-1,2-diyl, hept-2-en- 1,3-Diyl, hept-2-en-1,4-diyl, hept-2-en-1,5-diyl, hept-2-en-1,6-diyl, hept-2-en-1,7-diyl, hept-2-en-2,3-diyl, hept-2-en-2,4-diyl, hept-2-en-2,5-diyl, hept-2-en-2,6-diyl, hept-2-en-2,7-diyl, hept -2-en-3,4-diyl, hept-2-en-3,5-diyl, hept-2-en-3,6-diyl, hept-2-en-3,7-diyl, hept-2-en-4,5-diyl, hept-2-en-4,6-diyl, hept-2-en-4,7-diyl, hept-2-en-5,6-diyl, hept-2-en-5,7-diyl, hept-2-en-6,7 -diyl, hept-3-en-1,2-diyl, hept-3-en-1,3-diyl, hept-3-en-1,4-diyl, hept-3-en-1,5-diyl, hept-3-en-1,6-diyl, hept-3-en-1,7-diyl, hept-3-en-2,3-diyl, hept-3-en-2,4-diyl, hept-3-en-2,5-diyl, hept-3- Hept-2,6-diyl, hept-3-en-2,7-diyl, hept-3-en-3,4-diyl, hept-3-en-3,5-diyl, hept-3-en-3,6-diyl, hept-3-en-3,7-diyl, hept-3-en-4,5-diyl, hept-3-en-4,6-diyl, hept-3-en-4,7-diyl, hept-3-en-5,6-diyl Hepten-3-en-5,7-diyl, Hepten-3-en-6,7-diyl, Octen-1-en-1,2-diyl, Octen-1-en-1,3-diyl, Octen-1-en-1,4-diyl, Octen-1-en-1,5-diyl, Octen-1-en-1,6-diyl, Octen-1-en-1,7-diyl, Octen-1-en-1,8-diyl, Octen-1-en-2,3-Diyl, oct-1-en-2,4-diyl, oct-1-en-2,5-diyl, oct-1-en-2,6-diyl, oct-1-en-2,7-diyl, oct-1-en-2,8-diyl, oct-1-en-3,4-diyl, oct-1-en-3,5-diyl, oct-1-en-3,6-diyl, oct-1-en-3,7-diyl, oct-1 -en-3,8-diyl, oct-1-en-4,5-diyl, oct-1-en-4,6-diyl, oct-1-en-4,7-diyl, oct-1-en-4,8-diyl, oct-1-en-5,6-diyl, oct-1-en-5,7-diyl, oct-1-en-5,8-diyl, oct-1-en-6,7-diyl, oct-1-en-6,8-diyl Oct-1-en-7,8-diyl, Oct-2-en-1,2-diyl, Oct-2-en-1,3-diyl, Oct-2-en-1,4-diyl, Oct-2-en-1,5-diyl, Oct-2-en-1,6-diyl, Oct-2-en-1,7-diyl, Oct-2-en-1,8-diyl, Oct-2-en-2,3-diyl, Oct-2-en- 2,4-Diyl, oct-2-en-2,5-diyl, oct-2-en-2,6-diyl, oct-2-en-2,7-diyl, oct-2-en-2,8-diyl, oct-2-en-3,4-diyl, oct-2-en-3,5-diyl, oct-2-en-3,6-diyl, oct-2-en-3,7-diyl, oct-2-en-3,8-diyl, oct- -2-en-4,5-diyl, oct-2-en-4,6-diyl, oct-2-en-4,7-diyl, oct-2-en-4,8-diyl, oct-2-en-5,6-diyl, oct-2-en-5,7-diyl, oct-2-en-5,8-diyl, oct-2-en-6,7-diyl, oct-2-en-6,8-diyl, oct-2-en-7,8 -diyl, oct-3-en-1,2-diyl, oct-3-en-1,3-diyl, oct-3-en-1,4-diyl, oct-3-en-1,5-diyl, oct-3-en-1,6-diyl, oct-3-en-1,7-diyl, oct-3-en-1,8-diyl, oct-3-en-2,3-diyl, oct-3-en-2,4-diyl, oct-3- 2,5-diyl octyl-3-en-2,6-diyl octyl-3-en-2,7-diyl octyl-3-en-2,8-diyl octyl-3,4-diyl octyl-3-en-3,5-diyl octyl-3,6-diyl octyl-3,7-diyl octyl-3,8-diyl octyl-3-en-4,5-diyl Oct-3-en-4,6-diyl, Oct-3-en-4,7-diyl, Oct-3-en-4,8-diyl, Oct-3-en-5,6-diyl, Oct-3-en-5,7-diyl, Oct-3-en-5,8-diyl, Oct-3-en-6,7-diyl, Oct-3-en-6,8-diyl, Oct-3-en-7,8-diyl, Oct-4-en-1,2-Diyl, oct-4-en-1,3-diyl, oct-4-en-1,4-diyl, oct-4-en-1,5-diyl, oct-4-en-1,6-diyl, oct-4-en-1,7-diyl, oct-4-en-1,8-diyl, oct-4-en-2,4-diyl, oct-4-en-2,5-diyl, oct-4-en-2,6-diyl, oct-4 -en-2,7-diyl, oct-4-en-2,8-diyl, oct-4-en-3,4-diyl, oct-4-en-3,5-diyl, oct-4-en-3,6-diyl, oct-4-en-3,7-diyl, oct-4-en-3,8-diyl, oct-4-en-4,5-diyl, oct-4-en-4,6-diyl, oct-4-en-4,7-diyl Oct-4-en-4,8-diyl, Oct-4-en-5,6-diyl, Oct-4-en-5,7-diyl, Oct-4-en-5,8-diyl, Oct-4-en-6,7-diyl, Oct-4-en-6,8-diyl, Oct-4-en-7,8-diyl, Non-1-en-1,2-diyl, Non-1-en-1,3-diyl, Non-1-en- 1,4-Diyl, non-1-en-1,5-diyl, non-1-en-1,6-diyl, non-1-en-1,7-diyl, non-1-en-1,8-diyl, non-1-en-1,9-diyl, non-1-en-2,3-diyl, non-1-en-2,4-diyl, non-1-en-2,5-diyl, non-1-en-2,6-diyl, nonyl -1-en-2,7-diyl, non-1-en-2,8-diyl, non-1-en-2,9-diyl, non-1-en-3,4-diyl, non-1-en-3,5-diyl, non-1-en-3,6-diyl, non-1-en-3,7-diyl, non-1-en-3,8-diyl, non-1-en-3,9-diyl, non-1-en-4,5 -diyl, non-1-en-4,6-diyl, non-1-en-4,7-diyl, non-1-en-4,8-diyl, non-1-en-4,9-diyl, non-1-en-5,6-diyl, non-1-en-5,7-diyl, non-1-en-5,8-diyl, non-1-en-5,9-diyl, non-1-en-6,7-diyl, non-1- Non-6,8-diyl, non-1-en-6,9-diyl, non-1-en-7,8-diyl, non-1-en-7,9-diyl, non-1-en-8,9-diyl, non-2-en-1,2-diyl, non-2-en-1,3-diyl, non-2-en-1,4-diyl, non-2-en-1,5-diyl, non-2-en-1,6-diyl Non-2-en-1,7-diyl, non-2-en-1,8-diyl, non-2-en-1,9-diyl, non-2-en-2,3-diyl, non-2-en-2,4-diyl, non-2-en-2,5-diyl, non-2-en-2,6-diyl, non-2-en-2,7-diyl, non-2-en-2,8-diyl, non-2-en-2,9-diyl, non-2-ene-3,4-diyl, non-2-ene-3,5-diyl, non-2-ene-3,6-diyl, non-2-ene-3,7-diyl, non-2-ene-3,8-diyl, non-2-ene-3,9-diyl, non-2-ene-4,5-diyl, non-2-ene-4,6-diyl, non-2-ene-4,7-diyl, non-2 -en-4,8-diyl, non-2-en-4,9-diyl, non-2-en-5,6-diyl, non-2-en-5,7-diyl, non-2-en-5,8-diyl, non-2-en-5,9-diyl, non-2-en-6,7-diyl, non-2-en-6,8-diyl, non-2-en-6,9-diyl, non-2-en-7,8-diyl nonyl, non-2-en-7,9-diyl, non-2-en-8,9-diyl, non-3-en-1,2-diyl, non-3-en-1,3-diyl, non-3-en-1,4-diyl, non-3-en-1,5-diyl, non-3-en-1,6-diyl, non-3-en-1,7-diyl, non-3-en-1,8-diyl, non-3-en- 1,9-diyl, non-3-en-2,3-diyl, non-3-en-2,4-diyl, non-3-en-2,5-diyl, non-3-en-2,6-diyl, non-3-en-2,7-diyl, non-3-en-2,8-diyl, non-3-en-2,9-diyl, non-3-en-3,4-diyl, non-3-en-3,5-diyl, nonyl -3-en-3,6-diyl, non-3-en-3,7-diyl, non-3-en-3,8-diyl, non-3-en-3,9-diyl, non-3-en-4,5-diyl, non-3-en-4,6-diyl, non-3-en-4,7-diyl, non-3-en-4,8-diyl, non-3-en-4,9-diyl, non-3-en-5,6 -diyl, non-3-en-5,7-diyl, non-3-en-5,8-diyl, non-3-en-5,9-diyl, non-3-en-6,7-diyl, non-3-en-6,8-diyl, non-3-en-6,9-diyl, non-3-en-7,8-diyl, non-3-en-7,9-diyl, non-3-en-8,9-diyl, non-4- Non-1,2-diyl, non-4-en-1,3-diyl, non-4-en-1,4-diyl, non-4-en-1,5-diyl, non-4-en-1,6-diyl, non-4-en-1,7-diyl, non-4-en-1,8-diyl, non-4-en-1,9-diyl, non-4-en-2,3-diyl, non-4-en-2,4-diyl Non-4-ene-2,5-diyl, non-4-ene-2,6-diyl, non-4-ene-2,7-diyl, non-4-ene-2,8-diyl, non-4-ene-2,9-diyl, non-4-ene-3,4-diyl, non-4-ene-3,5-diyl, non-4-ene-3,6-diyl, non-4-ene-3,7-diyl, non-4-ene-3,8-Diyl, non-4-en-3,9-diyl, non-4-en-4,5-diyl, non-4-en-4,6-diyl, non-4-en-4,7-diyl, non-4-en-4,8-diyl, non-4-en-4,9-diyl, non-4-en-5,6-diyl, non-4-en-5,7-diyl, non-4-en-5,8-diyl, non- 4-en-5,9-diyl, non-4-en-6,7-diyl, non-4-en-6,8-diyl, non-4-en-6,9-diyl, non-4-en-7,8-diyl, non-4-en-7,9-diyl, non-4-en-8,9-diyl, dec-1-en-1,2-diyl, dec-1-en-1,3-diyl, dec-1-en-1,4- Diyl, dec-1-en-1,5-diyl, dec-1-en-1,6-diyl, dec-1-en-1,7-diyl, dec-1-en-1,8-diyl, dec-1-en-1,9-diyl, dec-1-en-1,10-diyl, dec-1-en-2,3-diyl, dec-1-en-2,4-diyl, dec-1-en-2,5-diyl, dec-1- 2,6-diyl dec-1-en-2,7-diyl dec-1-en-2,8-diyl dec-1-en-2,9-diyl dec-1-en-2,10-diyl dec-1-en-3,4-diyl dec-1-en-3,5-diyl dec-1-en-3,6-diyl dec-1-en-3,7-diyl dec-1-en-3,8-diyl dec-1-en-3,9-diyl, dec-1-en-3,10-diyl, dec-1-en-4,5-diyl, dec-1-en-4,6-diyl, dec-1-en-4,7-diyl, dec-1-en-4,8-diyl, dec-1-en-4,9-diyl, dec-1-en-4,10-diyl, dec-1-en-5,6-diyl, dec-1 -en-5,7-diyl, dec-1-en-5,8-diyl, dec-1-en-5,9-diyl, dec-1-en-5,10-diyl, dec-1-en-6,7-diyl, dec-1-en-6,8-diyl, dec-1-en-6,9-diyl, dec-1-en-6,10-diyl, dec-1-en-7,8-diyl, dec-1-en-7,9 -diyl, dec-1-en-7,10-diyl, dec-1-en-8,9-diyl, dec-1-en-8,10-diyl, dec-1-en-9,10-diyl, dec-2-en-1,2-diyl, dec-2-en-1,3-diyl, dec-2-en-1,4-diyl, dec-2-en-1,5-diyl, dec-2-en-1,6-diyl, decyl -2-en-1,7-diyl, dec-2-en-1,8-diyl, dec-2-en-1,9-diyl, dec-2-en-1,10-diyl, dec-2-en-2,3-diyl, dec-2-en-2,4-diyl, dec-2-en-2,5-diyl, dec-2-en-2,6-diyl, dec-2-en-2,7-diyl, dec-2-en-2,8-Diyl, Dec-2-en-2,9-Diyl, Dec-2-en-2,10-Diyl, Dec-2-en-3,4-Diyl, Dec-2-en-3,5-Diyl, Dec-2-en-3,6-Diyl, Dec-2-en-3,7-Diyl, Dec-2-en-3,8-Diyl, Dec-2-en-3,9-Diyl, Dec-2-en-3,10-Diyl dec-2-en-4,5-diyl, dec-2-en-4,6-diyl, dec-2-en-4,7-diyl, dec-2-en-4,8-diyl, dec-2-en-4,9-diyl, dec-2-en-4,10-diyl, dec-2-en-5,6-diyl, dec-2-en-5,7-diyl, dec-2-en-5,8-diyl, dec-2-en -5,9-diyl, dec-2-en-5,10-diyl, dec-2-en-6,7-diyl, dec-2-en-6,8-diyl, dec-2-en-6,9-diyl, dec-2-en-6,10-diyl, dec-2-en-7,8-diyl, dec-2-en-7,9-diyl, dec-2-en-7,10-diyl, dec-2-en-8,9 -diyl, dec-2-en-8,10-diyl, dec-2-en-9,10-diyl, dec-3-en-1,2-diyl, dec-3-en-1,3-diyl, dec-3-en-1,4-diyl, dec-3-en-1,5-diyl, dec-3-en-1,6-diyl, dec-3-en-1,7-diyl, dec-3-en-1,8-diyl, decyl -3-en-1,9-diyl, dec-3-en-1,10-diyl, dec-3-en-2,3-diyl, dec-3-en-2,4-diyl, dec-3-en-2,5-diyl, dec-3-en-2,6-diyl, dec-3-en-2,7-diyl, dec-3-en-2,8-diyl, dec-3-en-2,9-diyl, dec-3-en-2 10-diyl, dec-3-en-3,4-diyl, dec-3-en-3,5-diyl, dec-3-en-3,6-diyl, dec-3-en-3,7-diyl, dec-3-en-3,8-diyl, dec-3-en-3,9-diyl, dec-3-en-3,10-diyl, dec-3-en-4,5-diyl, dec-3-en-4,6-diyl dec-3-en-4,7-diyl, dec-3-en-4,8-diyl, dec-3-en-4,9-diyl, dec-3-en-4,10-diyl, dec-3-en-5,6-diyl, dec-3-en-5,7-diyl, dec-3-en-5,8-diyl, dec-3-en-5,9-diyl, dec-3-en-5,10-diyl, dec-3- En-6,7-diyl, Dec-3-en-6,8-diyl, Dec-3-en-6,9-diyl, Dec-3-en-6,10-diyl, Dec-3-en-7,8-diyl, Dec-3-en-7,9-diyl, Dec-3-en-7,10-diyl, Dec-3-en-8,9-diyl, Dec-3-en-8,10-diyl, Dec-3-en-9,10-Diyl, Dec-4-en-1,2-Diyl, Dec-4-en-1,3-Diyl, Dec-4-en-1,4-Diyl, Dec-4-en-1,5-Diyl, Dec-4-en-1,6-Diyl, Dec-4-en-1,7-Diyl, Dec-4-en-1,8-Diyl, Dec-4-en-1,9-Diyl, Dec-4-en-1,10-Diyl dec-4-en-2,3-diyl, dec-4-en-2,4-diyl, dec-4-en-2,5-diyl, dec-4-en-2,6-diyl, dec-4-en-2,7-diyl, dec-4-en-2,8-diyl, dec-4-en-2,9-diyl, dec-4-en-2,10-diyl, dec-4-en-3,4-diyl, dec-4-en -3,5-diyl, dec-4-en-3,6-diyl, dec-4-en-3,7-diyl, dec-4-en-3,8-diyl, dec-4-en-3,9-diyl, dec-4-en-3,10-diyl, dec-4-en-4,5-diyl, dec-4-en-4,6-diyl, dec-4-en-4,7-diyl, dec-4-en-4,8- Diyl, dec-4-en-4,9-diyl, dec-4-en-4,10-diyl, dec-4-en-5,6-diyl, dec-4-en-5,7-diyl, dec-4-en-5,8-diyl, dec-4-en-5,9-diyl, dec-4-en-5,10-diyl, dec-4-en-6,7-diyl, dec-4-en-6,8-diyl, dec- 4-en-6,9-diyl, dec-4-en-6,10-diyl, dec-4-en-7,8-diyl, dec-4-en-7,9-diyl, dec-4-en-7,10-diyl, dec-4-en-8,9-diyl, dec-4-en-8,10-diyl, dec-4-en-9,10-diyl, dec-5-en-1,2-diyl, dec-5- 1,3-diyl dec-5-en-1,4-diyl dec-5-en-1,5-diyl dec-5-en-1,6-diyl dec-5-en-1,7-diyl dec-5-en-1,8-diyl dec-5-en-1,9-diyl dec-5-en-1,10-diyl dec-5-en-2,3-diyl dec-5-en-2,4- Diyl, dec-5-en-2,5-diyl, dec-5-en-2,6-diyl, dec-5-en-2,7-diyl, dec-5-en-2,8-diyl, dec-5-en-2,9-diyl, dec-5-en-2,10-diyl, dec-5-en-3,4-diyl, dec-5-en-3,5-diyl, dec-5-en-3,6-diyl, dec- 5-en-3,7-diyl, dec-5-en-3,8-diyl, dec-5-en-3,9-diyl, dec-5-en-3,10-diyl, dec-5-en-4,5-diyl, dec-5-en-4,6-diyl, dec-5-en-4,7-diyl, dec-5-en-4,8-diyl, dec-5-en-4,9-diyl, dec-5-en-4,10-Diyl, Dec-5-en-5,6-diyl, Dec-5-en-5,7-diyl, Dec-5-en-5,8-diyl, Dec-5-en-5,9-diyl, Dec-5-en-5,10-diyl, Dec-5-en-6,7-diyl, Dec-5-en-6,8-diyl, Dec-5-en-6,9-diyl, Dec-5-en-6,10-diyl dec-5-en-7,8-diyl, dec-5-en-7,9-diyl, dec-5-en-7,10-diyl, dec-5-en-8,9-diyl, dec-5-en-8,10-diyl, dec-5-en-9,10-diyl, prop-1-yne-1,3-diyl, but-1-yne-1,3-diyl, but-1-yne-1,4-diyl, but-1 - Acrylonitrile-3,4-diyl, Butyronitrile-1,4-diyl, Pentyl-1,3-diyl, Pentyl-1,4-diyl, Pentyl-1,5-diyl, Pentyl-1,4-diyl, Pentyl-1,5-diyl, Pentyl-1,4-diyl, Pentyl-1,5-diyl, Pentyl-1,4-diyl, Pentyl-1,5-diyl, Pentyl-1,5-diyl, Pentyl-2-diyl-1,4-diyl, Pentyl-2-diyl-1,5-diyl Diyl, Pentyl-2-yne-4,5-diyl, Hex-1-yne-1,3-diyl, Hex-1-yne-1,4-diyl, Hex-1-yne-1,5-diyl, Hex-1-yne-1,6-diyl, Hex-1-yne-3,4-diyl, Hex-1-yne-3,5-diyl, Hex-1-yne-3,6-diyl, Hex-1-yne-4,5-diyl, Hex-1-yne -4,6-diyl, hex-1-yne-5,6-diyl, hex-2-yne-1,4-diyl, hex-2-yne-1,5-diyl, hex-2-yne-1,6-diyl, hex-2-yne-4,5-diyl, hex-2-yne-4,6-diyl, hex-2-yne-5,6-diyl, hex-3-yne-1,2-diyl, hex-3-yne-1,5-diyl Hex-3-yne-1,6-diyl, Hex-3-yne-2,5-diyl, Hex-3-yne-2,6-diyl, Hex-3-yne-5,6-diyl, Hep-1-yne-1,3-diyl, Hep-1-yne-1,4-diyl, Hep-1-yne-1,5-diyl, Hep-1-yne-1,6-diyl, Hep-1-yne-1,7-diyl, Hep-1-yne- 3,4-Diyl, Hepta-1-yne-3,5-Diyl, Hepta-1-yne-3,6-Diyl, Hepta-1-yne-3,7-Diyl, Hepta-1-yne-4,5-Diyl, Hepta-1-yne-4,6-Diyl, Hepta-1-yne-4,7-Diyl, Hepta-1-yne-5,6-Diyl, Hepta-1-yne-5,7-Diyl, Hepta-1-yne-6,7-Diyl Hepta-2-yne-1,4-diyl, hepta-2-yne-1,5-diyl, hepta-2-yne-1,6-diyl, hepta-2-yne-1,7-diyl, hepta-2-yne-4,5-diyl, hepta-2-yne-4,6-diyl, hepta-2-yne-4,7-diyl, hepta-2-yne-5,6-diyl, hepta-2-yne-5,7-diyl, hepta-2-yne-67-Diyl, Hepta-3-yne-1,2-Diyl, Hepta-3-yne-1,5-Diyl, Hepta-3-yne-1,6-Diyl, Hepta-3-yne-1,7-Diyl, Hepta-3-yne-2,5-Diyl, Hepta-3-yne-2,6-Diyl, Hepta-3-yne-2,7-Diyl, Hepta-3-yne-5,6-Diyl, Hepta-3-yne-5,7-Diyl, Hepta-3 -yne-6,7-diyl, oct-1-yne-1,3-diyl, oct-1-yne-1,4-diyl, oct-1-yne-1,5-diyl, oct-1-yne-1,6-diyl, oct-1-yne-1,7-diyl, oct-1-yne-1,8-diyl, oct-1-yne-3,4-diyl, oct-1-yne-3,5-diyl, oct-1-yne-3,6-diyl 3,7-diyl, 3,8-diyl, 4,5-diyl, 4,6-diyl, 4,7-diyl, 4,8-diyl, 5,6-diyl, 5,7-diyl, 5,8-diyl, 5,8-diyl 6,7-diyl, oct-1-yne-6,8-diyl, oct-1-yne-7,8-diyl, oct-2-yne-1,4-diyl, oct-2-yne-1,5-diyl, oct-2-yne-1,6-diyl, oct-2-yne-1,7-diyl, oct-2-yne-1,8-diyl, oct-2-yne-4,5-diyl, oct-2-yne-4,6-diyl, oct- -2-yne-4,7-diyl, oct-2-yne-4,8-diyl, oct-2-yne-5,6-diyl, oct-2-yne-5,7-diyl, oct-2-yne-5,8-diyl, oct-2-yne-6,7-diyl, oct-2-yne-6,8-diyl, oct-2-yne-7,8-diyl, oct-3-yne-1,2-diyl, oct-3-yne-1,5 -diyl, oct-3-yne-1,6-diyl, oct-3-yne-1,7-diyl, oct-3-yne-1,8-diyl, oct-3-yne-2,5-diyl, oct-3-yne-2,6-diyl, oct-3-yne-2,7-diyl, oct-3-yne-2,8-diyl, oct-3-yne-5,6-diyl, oct-3-yne-5,7-diyl, oct-3- Acrylonitrile-5,8-diyl, Octyl-3-yne-6,7-diyl, Octyl-3-yne-6,8-diyl, Octyl-3-yne-7,8-diyl, Octyl-4-yne-1,2-diyl, Octyl-4-yne-1,3-diyl, Octyl-4-yne-1,6-diyl, Octyl-4-yne-1,7-diyl, Octyl-4-yne-1,8-diyl, Octyl-4-yne-2,3-diyl Oct-4-yne-2,6-diyl, Oct-4-yne-2,7-diyl, Oct-4-yne-2,8-diyl, Oct-4-yne-3,6-diyl, Oct-4-yne-3,7-diyl, Oct-4-yne-3,8-diyl, Oct-4-yne-6,7-diyl, Oct-4-yne-6,8-diyl, Oct-4-yne-7,8-diyl, Non-1-yne-1,3-Diyl, non-1-yne-1,4-diyl, non-1-yne-1,5-diyl, non-1-yne-1,6-diyl, non-1-yne-1,7-diyl, non-1-yne-1,8-diyl, non-1-yne-1,9-diyl, non-1-yne-3,4-diyl, non-1-yne-3,5-diyl, non-1-yne-3,6-diyl, non-1 -yne-3,7-diyl, nonyl-1-yne-3,8-diyl, nonyl-1-yne-3,9-diyl, nonyl-1-yne-4,5-diyl, nonyl-1-yne-4,6-diyl, nonyl-1-yne-4,7-diyl, nonyl-1-yne-4,8-diyl, nonyl-1-yne-4,9-diyl, nonyl-1-yne-5,6-diyl, nonyl-1-yne-5,7-diyl nonyl-1-yne-5,8-diyl, nonyl-1-yne-5,9-diyl, nonyl-1-yne-6,7-diyl, nonyl-1-yne-6,8-diyl, nonyl-1-yne-6,9-diyl, nonyl-1-yne-7,8-diyl, nonyl-1-yne-7,9-diyl, nonyl-1-yne-8,9-diyl, nonyl-2-yne-1,4-diyl, nonyl-2-yne- 1,5-Diyl, nonyl-2-yne-1,6-diyl, nonyl-2-yne-1,7-diyl, nonyl-2-yne-1,8-diyl, nonyl-2-yne-1,9-diyl, nonyl-2-yne-4,5-diyl, nonyl-2-yne-4,6-diyl, nonyl-2-yne-4,7-diyl, nonyl-2-yne-4,8-diyl, nonyl-2-yne-4,9-diyl, nonyl -2-yne-5,6-diyl, non-2-yne-5,7-diyl, non-2-yne-5,8-diyl, non-2-yne-5,9-diyl, non-2-yne-6,7-diyl, non-2-yne-6,8-diyl, non-2-yne-6,9-diyl, non-2-yne-7,8-diyl, non-2-yne-7,9-diyl, non-2-yne-8,9 -diyl, nonyl-3-yne-1,2-diyl, nonyl-3-yne-1,5-diyl, nonyl-3-yne-1,6-diyl, nonyl-3-yne-1,7-diyl, nonyl-3-yne-1,8-diyl, nonyl-3-yne-1,9-diyl, nonyl-3-yne-2,5-diyl, nonyl-3-yne-2,6-diyl, nonyl-3-yne-2,7-diyl, nonyl-3- 2,8-diyl-yn, 2,9-diyl-nonyl-3-yn, 5,6-diyl-nonyl-3-yn, 5,7-diyl-nonyl-3-yn, 5,8-diyl-nonyl-3-yn, 5,9-diyl-nonyl-3-yn, 6,7-diyl-nonyl-3-yn, 6,8-diyl-nonyl-3-yn, 6,9-diyl-nonyl-3-yn, 7,8-diyl-nonyl-3-yn Non-3-yne-7,9-diyl, non-3-yne-8,9-diyl, non-4-yne-1,2-diyl, non-4-yne-1,3-diyl, non-4-yne-1,6-diyl, non-4-yne-1,7-diyl, non-4-yne-1,8-diyl, non-4-yne-1,9-diyl, non-4-yne-2,3-diyl, non-4-yne-2,6-Dimethyl, nonyl-4-yne-2,7-dimethyl, nonyl-4-yne-2,8-dimethyl, nonyl-4-yne-2,9-dimethyl, nonyl-4-yne-3,6-dimethyl, nonyl-4-yne-3,7-dimethyl, nonyl-4-yne-3,8-dimethyl, nonyl-4-yne-3,9-dimethyl, nonyl-4-yne-6,7-dimethyl, nonyl-4-yne-6,8-dimethyl, nonyl-4 -yne-6,9-diyl, non-4-yne-7,8-diyl, non-4-yne-7,9-diyl, non-4-yne-8,9-diyl, dec-1-yne-1,3-diyl, dec-1-yne-1,3-diyl, dec-1-yne-1,4-diyl, dec-1-yne-1,5-diyl, dec-1-yne-1,6-diyl, dec-1-yne-1,7-diyl 1,8-diyl-decyl-1,8-diyl-decyl-1,9-diyl-decyl-1,10-diyl-decyl-3,4-diyl-decyl-3,5-diyl-decyl-3,6-diyl-decyl-3,7-diyl-decyl-3,8-diyl-decyl-3,9-diyl-decyl-1-yne -3,10-diyl, dec-1-yne-4,5-diyl, dec-1-yne-4,6-diyl, dec-1-yne-4,7-diyl, dec-1-yne-4,8-diyl, dec-1-yne-4,9-diyl, dec-1-yne-4,10-diyl, dec-1-yne-5,6-diyl, dec-1-yne-5,7-diyl, dec-1-yne-5,8-diyl decyl-1-yne-5,9-diyl, decyl-1-yne-5,10-diyl, decyl-1-yne-6,7-diyl, decyl-1-yne-6,8-diyl, decyl-1-yne-6,9-diyl, decyl-1-yne-6,10-diyl, decyl-1-yne-7,8-diyl, decyl-1-yne-7,9-diyl, decyl-1-yne-7,10-diyl, decyl-1 - Acyn-8,9-diyl, Dec-1-acyn-8,10-diyl, Dec-1-acyn-9,10-diyl, Dec-2-acyn-1,4-diyl, Dec-2-acyn-1,5-diyl, Dec-2-acyn-1,6-diyl, Dec-2-acyn-1,7-diyl, Dec-2-acyn-1,8-diyl, Dec-2-acyn-1,9-diyl, Dec-2-acyn-1,1 0-diyl, dec-2-yne-4,5-diyl, dec-2-yne-4,6-diyl, dec-2-yne-4,7-diyl, dec-2-yne-4,8-diyl, dec-2-yne-4,9-diyl, dec-2-yne-4,10-diyl, dec-2-yne-5,6-diyl, dec-2-yne-5,7-diyl, dec-2-yne-5,8-diyl, dec- 2-Acyn-5,9-diyl, Dec-2-Acyn-5,10-diyl, Dec-2-Acyn-6,7-diyl, Dec-2-Acyn-6,8-diyl, Dec-2-Acyn-6,9-diyl, Dec-2-Acyn-6,10-diyl, Dec-2-Acyn-7,8-diyl, Dec-2-Acyn-7,9-diyl, Dec-2-Acyn-7,10-diyl, Dec-2-Acyn-8,9-Diyl, Dec-2-yne-8,10-Diyl, Dec-2-yne-9,10-Diyl, Dec-3-yne-1,2-Diyl, Dec-3-yne-1,5-Diyl, Dec-3-yne-1,6-Diyl, Dec-3-yne-1,7-Diyl, Dec-3-yne-1,8-Diyl, Dec-3-yne-1,9-Diyl, Dec-3-yne-1,10-Diyl Dec-3-yne-2,5-diyl, Dec-3-yne-2,6-diyl, Dec-3-yne-2,7-diyl, Dec-3-yne-2,8-diyl, Dec-3-yne-2,9-diyl, Dec-3-yne-2,10-diyl, Dec-3-yne-5,6-diyl, Dec-3-yne-5,7-diyl, Dec-3-yne-5,8-diyl, Dec-3-yne -5,9-diyl, dec-3-yne-5,10-diyl, dec-3-yne-6,7-diyl, dec-3-yne-6,8-diyl, dec-3-yne-6,9-diyl, dec-3-yne-6,10-diyl, dec-3-yne-7,8-diyl, dec-3-yne-7,9-diyl, dec-3-yne-7,10-diyl, dec-3-yne-8,9 -diyl, dec-3-yne-8,10-diyl, dec-3-yne-9,10-diyl, dec-4-yne-1,2-diyl, dec-4-yne-1,3-diyl, dec-4-yne-1,6-diyl, dec-4-yne-1,7-diyl, dec-4-yne-1,8-diyl, dec-4-yne-1,9-diyl, dec-4-yne-1,10-diyl, Dec-4-yne-2,3-diyl, Dec-4-yne-2,6-diyl, Dec-4-yne-2,7-diyl, Dec-4-yne-2,8-diyl, Dec-4-yne-2,9-diyl, Dec-4-yne-2,10-diyl, Dec-4-yne-3,6-diyl, Dec-4-yne-3,7-diyl, Dec-4-yne-3,8-diyl, Dec-4-yne- 3,9-Diyl, Dec-4-yne-3,10-Diyl, Dec-4-yne-6,7-Diyl, Dec-4-yne-6,8-Diyl, Dec-4-yne-6,9-Diyl, Dec-4-yne-6,10-Diyl, Dec-4-yne-7,8-Diyl, Dec-4-yne-7,9-Diyl, Dec-4-yne-7,10-Diyl, Dec-4-yne-8,9- Dimethyl, Dec-4-yne-8,10-dimethyl, Dec-4-yne-9,10-dimethyl, Dec-5-yne-1,2-dimethyl, Dec-5-yne-1,3-dimethyl, Dec-5-yne-1,4-dimethyl, Dec-5-yne-1,7-dimethyl, Dec-5-yne-1,8-dimethyl, Dec-5-yne-1,9-dimethyl, Dec-5-yne-1,10-dimethyl, Dec -5-yne-2,3-diyl, dec-5-yne-2,4-diyl, dec-5-yne-2,7-diyl, dec-5-yne-2,8-diyl, dec-5-yne-2,9-diyl, dec-5-yne-2,10-diyl, dec-5-yne-3,4-diyl, dec-5-yne-3,7-diyl, dec-5-yne-3,8-diyl, dec-5-yne-3,The hydrocarbon groups, such as 9-diyl, dec-5-yne-3,10-diyl, dec-5-yne-4,7-diyl, dec-5-yne-4,8-diyl, dec-5-yne-4,9-diyl, dec-5-yne-4,10-diyl, dec-5-yne-7,8-diyl, dec-5-yne-7,9-diyl, dec-5-yne-7,10-diyl, dec-5-yne-8,9-diyl, dec-5-yne-8,10-diyl, and dec-5-yne-9,10-diyl, may have unsaturated divalent hydrocarbon groups with 2 to 6 carbon atoms, more preferably 2 to 4.

[0066] From the viewpoint of raw material availability, in the monovalent alicyclic hydrocarbon group of A represented by formula (4a), formula (4b), formula (4c) or formula (4d), R in formula (4a) or formula (4c) 5 The hydrogen is 1,2-ethanediyl, and the m is 0, more preferably R in formula (4b) or formula (4d). 5 For hydrogen, R 6 For carbonyl, R 7 Nitrogen is 1,3-propanediyl.

[0067] The organopolysiloxane compound of the present invention is synthesized by the following steps: a step of reacting an organometallic compound with a cyclic siloxane to generate a metal silane alkoxide; a subsequent step of reacting a cyclotrisiloxane or a cyclotetrasiloxane with a metal silane alkoxide to generate a compound represented by formula (5); a step of stopping the polymerization of the compound represented by formula (5) by adding water or acid as needed, thereby generating a compound represented by formula (5'); and then, a step of reacting the compound represented by formula (6) (a chlorosilane compound having a cyclic olefin skeleton) with the compound represented by formula (5) or formula (5').

[0068]

[0069] In equations (5) and (5'), R 2 It is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R 3 It is an alkyl group with 4 to 10 carbon atoms, where n is an integer greater than or equal to 1, and there are multiple R groups. 2 They can be the same or different. Additionally, M in formula (5) is a monovalent metal. In formula (6), A is a monovalent alicyclic hydrocarbon group with 4 to 60 carbon atoms having at least one carbon-carbon double bond, and R... 1 It is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, where X is a halogen and I is an integer from 1 to 3.

[0070] Specific examples of organometallic compounds used in the synthesis of organopolysiloxane compounds include: methyllithium, ethyllithium, propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, or sodium phenyl. Among these, methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, or phenyllithium are preferred, and n-butyllithium is particularly preferred.

[0071] Specific examples of cyclic siloxanes used in the synthesis of organopolysiloxane compounds include: trimethylcyclotrisiloxane, hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, pentamethylvinylcyclotrisiloxane, trimethyltrivinylcyclotrisiloxane, trimethyltriphenylcyclotrisiloxane, hexaphenylcyclotrisiloxane, tris(trifluoropropyl)trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, heptamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, or tetra(trifluoropropyl)tetramethylcyclotetrasiloxane. Among these, trimethylcyclotrisiloxane and tetramethylcyclotetrasiloxane are preferred.

[0072] As the reaction solvent for the synthesis of organopolysiloxane compounds, a nonpolar or low-polarity aprotic solvent is used. Specific examples of nonpolar aprotic solvents include hexane, cyclohexane, heptane, toluene, and xylene. Specific examples of low-polarity aprotic solvents include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetrahydrofuran (THF), 4-methyltetrahydropyran, cyclopentyl methyl ether (CPME), and 1,4-dioxane. Among these, a nonpolar solvent is preferred for easy control of reactivity, and toluene is particularly preferred considering the solubility of the product.

[0073] When using a nonpolar solvent as a reaction solvent in the synthesis of organopolysiloxane compounds, a highly polar aprotic solvent can be added as a reactant to promote the polymerization reaction. Specific examples of highly polar aprotic solvents include: N,N-dimethylformamide (DMF), N,N-diethylformamide (DEF), dimethoxyethane, dimethyl sulfoxide (DMSO), and N-methyl-2-pyrrolidone (NMP). Among these, N,N-dimethylformamide (DMF) is preferred considering its ease of removal by washing with water.

[0074] Specific examples of cyclotrisiloxanes or cyclotetrasiloxanes that react with the generated metal silane alkoxides include: trimethylcyclotrisiloxane, hexamethylcyclotrisiloxane, pentamethylvinylcyclotrisiloxane, hexaethylcyclotrisiloxane, trimethyltrivinylcyclotrisiloxane, trimethyltriphenylcyclotrisiloxane, hexaphenylcyclotrisiloxane, tris(trifluoropropyl)trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, heptamethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, or tetra(trifluoropropyl)tetramethylcyclotetrasiloxane. Among these, trimethylcyclotrisiloxane, hexamethylcyclotrisiloxane, trimethyltriphenylcyclotrisiloxane, hexaphenylcyclotrisiloxane, tris(trifluoropropyl)trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane or tetra(trifluoropropyl)tetramethylcyclotetrasiloxane are preferred, with hexamethylcyclotrisiloxane or octamethylcyclotetrasiloxane being particularly preferred.

[0075] In the compound represented by formula (5), M is not particularly limited as long as it is a monovalent metal. Specifically, lithium or sodium can be listed, with lithium being the preferred one.

[0076] As needed, for the compound represented by formula (5), polymerization can be stopped by adding water or acid. Therefore, when using an acid, there is no particular limitation as long as the acid used is a Brønsted acid or an aqueous solution thereof. Specifically, formic acid, acetic acid, nitric acid, sulfuric acid, and hydrochloric acid can be listed, among which acetic acid is preferred.

[0077] In the compound represented by formula (6), the halogen of X is particularly preferably chlorine.

[0078] In the process of reacting the compound represented by formula (6) with the compound represented by formula (5) or formula (5'), in order to capture the hydrochloric acid (HCl) produced by the reaction of chlorosilane with water or silanol, it is preferable to add an organic base. Specific examples of the organic base used include trimethylamine, pyridine, diisopropylethylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), etc., but triethylamine is preferred if boiling point or basicity is taken into consideration.

[0079] The compound represented by formula (6) can also be a commercially available product, or it can be synthesized by the hydrosilylation reaction of the compound represented by formula (7) and the compound represented by formula (8).

[0080]

[0081] In formula (7), A' is a monovalent alicyclic hydrocarbon group with 4 to 58 carbon atoms having at least one carbon-carbon double bond, and R 8 R is a hydrocarbon group having at least one unsaturated bond at the end. In formula (8), R 1 It is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, where X is a halogen and I is an integer from 1 to 3.

[0082] The monovalent alicyclic hydrocarbon group with carbon-carbon double bonds in A', having 4 to 58 carbon atoms, includes, for example, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cyclododecenyl, cyclotetradecenyl, cyclohexadecenyl, cyclooctadecenyl, cycloeicodecenyl, cyclododecenyl, cycloticodecenyl, cyclohexadecenyl, cyclooctadecenyl, norbornenyl, norbornadienyl, dicyclopentenyl, dicyclopentadienyl, dicyclohexenyl, dicyclohexadienyl, tricyclodecenyl, tetracyclododecenyl, tetracyclododecadienyl, etc. At least one hydrogen atom of these groups may be substituted by an alkyl group, a halogen, a heteroatom, a haloalkyl group, or a heteroatom-substituted alkyl group. The monovalent alicyclic hydrocarbon group having carbon-carbon double bonds preferably has 4 to 30 carbon atoms, more preferably 5 to 15.

[0083] R 8 The hydrocarbon group having at least one unsaturated bond at the end is, for example, vinyl, allyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, 1-decenyl, isopropenyl, isobutenyl, butadienyl, etc. The number of carbon atoms in the hydrocarbon group having at least one unsaturated bond at the end is preferably 2 to 20, more preferably 2 to 10.

[0084] In the case of synthesizing the compound represented by formula (6) by a hydrosilylation reaction, a hydrosilylation reaction catalyst is used. Platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts are commonly used as hydrosilylation reaction catalysts. Among these, from the viewpoint of reactivity or solubility in the reaction system, Speier catalysts or Karstedt catalysts, which are platinum-based catalysts, are preferred.

[0085] The compound represented by formula (1) can be complexed with cyclic olefin monomers via ring-opening metathesis polymerization (ROMP) or addition polymerization. The compound represented by formula (1) can be used to impart organopolysiloxane source functionality by addition and copolymerization with cyclic olefin monomers in a ROMP reaction system or in an addition polymerization reaction system with olefin monomers or cyclic olefin monomers. As methods of addition polymerization, coordination polymerization or cationic polymerization can be listed.

[0086] The cyclic olefin monomers that can be used in the ROMP representing the compound of formula (1) are not particularly limited. Specific examples include: 2-norbornene, 5-ethylidene-2-norbornene, 5-norbornene-2-carboxylic acid, 5-norbornene-2-formonitrile, 5-norbornene-2-methylamine, 5-norbornene-2-methanol, 3a,4,7,7a-tetrahydroindene, tetracyclododecadiene, 1,4-dihydro-1,4-methylbridged naphthalene, 5-norbornene-2,3-dicarboxyimide, dicyclopentadiene, 2,5-norbornadiene, 5-norbornene-2,3-dicarboxylic anhydride, tetracyclo[6.2.1.1] 3,6 .0 2,7 Dodecyl-4-ene, 5,6-dihydrocyclopentadiene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclobutadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, cyclononadiene, cyclodecadiene, etc.

[0087] In the case of obtaining copolymers of the compound represented by formula (1) with cyclic olefin monomers via ROMP, a metathesis polymerization catalyst is used. Hereafter, cyclic olefin polymers synthesized using ROMP are sometimes referred to as ROMP polymers.

[0088] There are no particular limitations on the metasomatic polymerization catalysts used in ROMP. Specific examples include: first-generation Grubbs catalysts, second-generation Grubbs catalysts, Hoveyda-type Grubbs catalysts, and third-generation Grubbs catalysts.

[0089] As described in Japanese Patent No. 5613981, in ROMP, a molecular weight adjuster can be added to the reaction system to adjust the molecular weight of the obtained polymer.

[0090] There are no particular limitations on the molecular weight modifiers used. Specific examples include: α-olefins such as 1-butene, 1-pentene, 1-hexene, and 1-octene; styrene such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether, and allyl glycidyl ether; halogenated vinyl compounds such as allyl chloride; oxygenated vinyl compounds such as glycidyl methacrylate; nitrogen-containing vinyl compounds such as acrylamide; non-conjugated dienes such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, and 2,5-dimethyl-1,5-hexadiene; and conjugated dienes such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene.

[0091] The cyclic olefin monomers that can be used in the ROMP of the compound represented by formula (1) can be one or more. Cyclic olefin polymers are widely used in optical parts, packaging materials for pharmaceuticals or food, substrates for electronic devices, etc., and can be used in appropriate combinations according to the application.

[0092] The ratio of the compound represented by formula (1) to the cyclic olefin monomer used as the raw material of the polymer (cyclic olefin polymer) of the present invention is not particularly limited and can be adjusted. However, if the total amount of the compound represented by formula (1) and the cyclic olefin monomer is set to 100, even at around 0.1% to 10% by weight, the waterproof or slip-resistant effect can be imparted.

[0093] The polymers of the present invention can be processed into films or molded articles using conventional methods. One film-forming method involves dissolving the polymer in a solvent, coating the solution, and then drying it to obtain a self-supporting film. Another method for manufacturing molded articles is injection molding.

[0094] There are no particular limitations on the solvents that can be used to dissolve the polymers of the present invention. Specific examples include cyclic ether solvents, primarily cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), and 4-methyltetrahydropyran (MTHP); halogenated hydrocarbon solvents, primarily chloroform, dichloromethane, and dichlorobenzene; and ethylene glycol ether solvents, primarily propylene glycol-1-monomethyl ether-2-acetate (PGMEA) and propylene glycol-1-monomethyl ether (PGME). From the viewpoint of solubility or drying speed during film formation, CPME is preferred.

[0095] In the coordination polymerization of the compound represented by formula (1), monoolefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, isobutene, 2-methyl-1-butene, and 2-methyl-1-pentene, or dienes such as 1,3-butadiene, 2-methyl-1,3-butadiene, and 1,3-pentadiene, or acyclic olefin monomers represented by aromatic olefin monomers such as styrene, 2-phenyl-1-propene, and vinylnaphthalene, or 2-norbornene, 5- Ethylene-2-norbornene, 5-norbornene-2-carboxylic acid, 5-norbornene-2-formonitrile, 5-norbornene-2-methylamine, 5-norbornene-2-methanol, 3a,4,7,7a-tetrahydroindene, tetracyclododecadiene, 1,4-dihydro-1,4-methylbridged naphthalene, 5-norbornene-2,3-dicarboxyimide, dicyclopentadiene, 2,5-norbornene, 5-norbornene-2,3-dicarboxylic anhydride, tetracyclo[6.2.1.1] 3,6 .0 2,7 Cycloolefin monomers, primarily dodecyl-4-ene, 5,6-dihydrocyclopentadiene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclobutadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, cyclononadiene, and cyclodecadiene, are used as copolymer monomers.

[0096] In the coordination polymerization of the compound represented by formula (1), a catalyst containing transition metal compounds such as titanium (Ti), zirconium (Zr), chromium (Cr), cobalt (Co), nickel (Ni), palladium (Pd), and zinc (Zn) is used as the coordination polymerization catalyst.

[0097] In the cationic polymerization of the compound represented by formula (1), monoolefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, isobutene, 2-methyl-1-butene, and 2-methyl-1-pentene, or dienes such as 1,3-butadiene, 2-methyl-1,3-butadiene, and 1,3-pentadiene, or acyclic olefin monomers represented by aromatic olefin monomers such as styrene, 2-phenyl-1-propene, and vinylnaphthalene, or ethylene oxide, propylene oxide, oxetane, 1,4-dioxane, 1,3,5-trioxane, cyclohexane oxide, styrene oxide, and epidermis can be used. Cyclic ether monomers primarily composed of chlorohydrin, glycidyl phenyl ether, furan, and tetrahydrofuran, or monomers primarily composed of 2-norbornene, 5-ethylidene-2-norbornene, 5-norbornene-2-carboxylic acid, 5-norbornene-2-carboxylonitrile, 5-norbornene-2-methylamine, 5-norbornene-2-methanol, 3a,4,7,7a-tetrahydroindene, tetracyclododecadiene, 1,4-dihydro-1,4-methylbridged naphthalene, 5-norbornene-2,3-dicarboxyimide, dicyclopentadiene, 2,5-norbornene, 5-norbornene-2,3-dicarboxylic anhydride, and tetracyclo[6.2.1.1] 3,6 .0 2,7Cycloolefin monomers, primarily dodecyl-4-ene, 5,6-dihydrocyclopentadiene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclobutadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, cyclononadiene, and cyclodecadiene, are used as copolymer monomers.

[0098] In the cationic polymerization of the compound represented by formula (1), any commonly used catalyst can be used as the cationic polymerization catalyst, such as metal halide such as AlCl3, AlBr3, BCl3, BF3, TiCl4, TiBr4, FeCl3, FeCl2, SnCl2, SnCl4, or protonic acid such as HCl, HF, HBr, or oxyacid such as H2SO4, H3BO3, HClO4, CH3COOH3.

[0099] [Example]

[0100] The present invention will now be described in more detail by way of examples, but the present invention is not limited to these examples in any way.

[0101] <Determination of molecular weight>

[0102] The molecular weight of organopolysiloxane compounds was determined by gel permeation chromatography (GPC), and the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) was used as the molecular weight distribution (Mw / Mn). Polydimethylsiloxane was used as a standard sample to determine the converted molecular weight of polydimethylsiloxane.

[0103] Furthermore, the determination of the equivalent molecular weight of polystyrene based on the GPC method was carried out under the following test conditions.

[0104] a) Measurement equipment: High Performance Liquid Chromatograph (HPLC) LC-2000Plus series manufactured by Nippon Seiko Co., Ltd.

[0105] b) Pipe string: Shodex KF-804L (two pipes connected in series) manufactured by Resonac (stock) (formerly Showa Denko (stock)).

[0106] c) Oven temperature: 40℃

[0107] d) Eluent: Toluene 0.7 mL / min

[0108] e) Detector: RI-2031

[0109] f) Standard sample: polydimethylsiloxane

[0110] g) Injection volume: 20 μL

[0111] h) Concentration: 0.025 g / 10 mL

[0112] i) Sample preparation: Toluene was used as a solvent and dissolved at room temperature.

[0113] The molecular weight of the polymer obtained through ROMP was determined by gel permeation chromatography (GPC), and the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) was used as the molecular weight distribution (Mw / Mn). Polystyrene was used as a standard sample to determine the converted molecular weight of polystyrene.

[0114] Furthermore, the determination of the equivalent molecular weight of polystyrene based on the GPC method was carried out under the following test conditions.

[0115] a) Measurement equipment: HPLC LC-2000Plus series manufactured by Nippon Spectros Technology Co., Ltd.

[0116] b) Pipeline: Shodex KF-805L manufactured by Resonac (stock) (formerly Showa Denko (stock)) and Shodex KF-804L manufactured by Resonac (stock) (formerly Showa Denko (stock)) (two pipes connected in series).

[0117] c) Oven temperature: 40℃

[0118] d) Elution buffer: THF 1.0 mL / min

[0119] e) Detector: RI-2031

[0120] f) Standard sample: Polystyrene

[0121] g) Injection volume: 20 μL

[0122] h) Concentration: 0.025 g / 10 mL

[0123] i) Sample preparation: THF was used as a solvent and dissolved at room temperature.

[0124] <Analysis of Compounds>

[0125] <Nuclear Magnetic Resonance (NMR) spectroscopy>

[0126] Using a 500 MHz NMR measuring apparatus manufactured by Nippon Electron Ltd., for 1 H-NMR and29 Si-NMR involves dissolving the sample in dichloroform (manufactured by Fujifilm and Koichi Chemical Co., Ltd.) and measuring it at room temperature.

[0127] <Example 1>

[0128] (Synthesis of organopolysiloxane compound (1-1) with x=1 in formula (2))

[0129] In a 100 mL four-necked flask equipped with a reflux cooler, thermometer, and septum cap, 10.07 g of hexamethylcyclotrisiloxane and 14 mL of toluene were introduced, and the flask was sealed with nitrogen. The flask was placed in an oil bath maintained at 30°C, and the temperature was raised. Then, when the liquid temperature reached 30°C, 3.0 mL of n-butyllithium (1.6 M hexane solution) was added, followed by 1.25 mL of DMF, and polymerization was initiated. After 2 hours and 30 minutes of reaction, 0.46 g of triethylamine and 0.97 g of 5-norbornene-2-yl(ethyl)chlorodimethylsilane were introduced. After 18 hours of reaction, 50 mL of distilled water and 50 mL of heptane were added to terminate the reaction. After the reaction was complete, the reaction mixture was transferred to a separatory funnel. The separatory funnel was used to separate the aqueous layer and the organic layer, and the aqueous layer was discarded. Then, 50 mL of 1 N hydrochloric acid was added to wash the organic layer. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. Then, 50 mL of saturated sodium bicarbonate solution was added to wash the organic layer. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. Then, 50 mL of distilled water was added to wash the organic layer. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. The organic layer was dried with anhydrous sodium sulfate, filtered, and transferred to a rotary evaporator for distillation at 55°C and 1 kPa to remove the solvent. The obtained oil (9.01 g) had the following GPC data: Mn = 2540, Mw = 2820, Mw / Mn = 1.11.

[0130] The following shows the process of the final product. 1 H-NMR and 29 Chemical shifts obtained by Si-NMR measurements.

[0131] 1 H-NMR: (ppm); 6.20~6.01 (2H), 2.89~2.85 (2H), 1.46~1.38 (12H), 1.05~0.98 (6H), 0.67~0.63 (4H), 0.30~-0.07 (166H).

[0132] 29 Si-NMR: (ppm); 8.95, -5.55, -18.51, -20.33~-20.81.

[0133] Based on these NMR measurements, the obtained compound was confirmed to have the structure of formula (1-1). In formula (1-1), Me is a methyl group, and the average value of n is 27.

[0134]

[0135] <Example 2>

[0136] (Synthesis of organopolysiloxane compound (1-2) with x=2 in formula (2))

[0137] In a 100 mL four-necked flask equipped with a reflux cooler, thermometer, and septum cap, 10.07 g of hexamethylcyclotrisiloxane and 14 mL of toluene were introduced, and the flask was sealed with nitrogen. The flask was placed in an oil bath maintained at 30 °C, and the temperature was raised. Then, when the liquid temperature reached 30 °C, 3.0 mL of n-butyllithium (1.6 M hexane solution) was introduced, followed by 1.25 mL of DMF, and polymerization was initiated. After 2 hours and 30 minutes of reaction, 0.46 g of triethylamine and 0.53 g of 5-norbornene-2-yl(ethyl)dichloromethylsilane were introduced. After 18 hours of reaction, 50 mL of distilled water and 50 mL of heptane were introduced to terminate the reaction. After the reaction was complete, the reaction mixture was transferred to a separatory funnel. The separatory funnel was used to separate the aqueous layer and the organic layer, and the aqueous layer was discarded. Then, 50 mL of 1 N hydrochloric acid was added to wash the organic layer. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. Then, 50 mL of saturated sodium bicarbonate solution was added to wash the organic layer. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. Then, 50 mL of distilled water was added to wash the organic layer. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. The organic layer was dried with anhydrous sodium sulfate, filtered, and transferred to a rotary evaporator for distillation at 55°C and 1 kPa to remove the solvent. The obtained oil (9.37 g) had the following GPC data: Mn = 4340, Mw = 4620, Mw / Mn = 1.06.

[0138] The following shows the process of the final product. 1 H-NMR and 29 Chemical shifts obtained by Si-NMR measurements.

[0139] 1 H-NMR: (ppm); 6.20~6.01 (2H), 2.89~2.85 (2H), 1.46~1.38 (20H), 1.05~0.98 (12H), 0.67~0.63 (8H), 0.25~-0.05 (332H).

[0140] 29 Si-NMR: (ppm); 9.14, 8.82, -19.02, -19.80~-20.91, -36.06.

[0141] Based on these NMR measurements, the obtained compound was confirmed to have the structure of formula (1-2). In formula (1-2), Me is a methyl group, and the average value of n is 28.

[0142]

[0143] <Example 3>

[0144] (Synthesis of organopolysiloxane compounds (1-3) with x=3 in formula (2))

[0145] In a 100 mL four-necked flask equipped with a reflux cooler, thermometer, and septum cap, 10.07 g of hexamethylcyclotrisiloxane and 14 mL of toluene were introduced, and the flask was sealed with nitrogen. The flask was placed in an oil bath maintained at 30 °C, and the temperature was raised. Then, when the liquid temperature reached 30 °C, 3.0 mL of n-butyllithium (1.6 M hexane solution) was added, followed by 1.25 mL of DMF, and polymerization was initiated. After 2 hours and 30 minutes of reaction, 0.46 g of triethylamine and 0.40 g of 5-norbornene-2-yl(ethyl)trichlorosilane were introduced. After 18 hours of reaction, 50 mL of distilled water and 50 mL of heptane were added to terminate the reaction. After the reaction was complete, the reaction mixture was transferred to a separatory funnel. The separatory funnel was used to separate the aqueous layer and the organic layer, and the aqueous layer was discarded. Then, 50 mL of 1 N hydrochloric acid was added to wash the organic layer. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. Then, 50 mL of saturated sodium bicarbonate solution was added to wash the organic layer. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. Then, 50 mL of distilled water was added to wash the organic layer. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. The organic layer was dried with anhydrous sodium sulfate, filtered, and transferred to a rotary evaporator for distillation at 55°C and 1 kPa to remove the solvent. The obtained oil (9.22 g) had the following GPC data: Mn=5230, Mw=5980, Mw / Mn=1.14.

[0146] The following shows the process of the final product.1 H-NMR and 29 Chemical shifts obtained by Si-NMR measurements.

[0147] 1 H-NMR: (ppm); 6.20~6.01 (2H), 2.89~2.85 (2H), 1.46~1.38 (28H), 1.05~0.98 (18H), 0.67~0.63 (12H), 0.25~-0.05 (549H).

[0148] 29 Si-NMR: (ppm); 9.12, -8.59, -19.02, -20.18~-20.60, -61.04.

[0149] Based on these NMR measurements, the obtained compound was confirmed to have the structure of formula (1-3). In formula (1-3), Me is a methyl group, and the average value of n is 30.

[0150]

[0151] <Example 4>

[0152] (Synthesis of ROMP polymer formed by reacting compound (1-1) with dicyclopentadiene)

[0153] Inside a glove box, dicyclopentadiene (1.0 g), dehydrated cyclohexene (19.2 g), compound (1-1) (10.2 mg), and 1-hexene (4.5 mg) were added to a threaded perfluoroalkoxyalkane (PFA) container equipped with a magnetic stirrer. Subsequently, 64.2 mg of Grubbs second-generation catalyst was added and polymerization was initiated, stirred at room temperature for 2 hours. After adding ethyl vinyl ether to the reaction solution, the reaction solution was added dropwise to 200 mL of methanol to obtain a precipitate. The supernatant was removed by decantation, and the precipitate was dissolved in THF. This solution was then added dropwise to 200 mL of methanol to obtain a precipitate. The process of removing the supernatant, dissolving in THF, and obtaining the precipitate was repeated twice to recover 0.92 g of the polymer of compound (1-1) and dicyclopentadiene.

[0154] The results of GPC analysis of the obtained polymer were as follows: number average molecular weight (Mn) was 27,000, weight average molecular weight (Mw) was 48,000, and molecular weight distribution (Mw / Mn) was 1.78.

[0155] <Example 5>

[0156] (Synthesis of ROMP polymers formed by reacting compounds (1-2) with dicyclopentadiene)

[0157] Inside a glove box, 1.0 g of dicyclopentadiene, 19.2 g of dehydrated cyclohexene, 10.7 mg of compounds (1-2), and 5.2 mg of 1-hexene were added to a threaded PFA container including a magnetic stirrer. Then, 57.6 mg of Grubbs second-generation catalyst was added and polymerization was initiated, stirred at room temperature for 2 hours. After adding ethyl vinyl ether to the reaction solution, the reaction solution was added dropwise to 200 mL of methanol to obtain a precipitate. The supernatant was removed by decantation, and the precipitate was dissolved in THF. This solution was then added dropwise to 200 mL of methanol to obtain a precipitate. The process of removing the supernatant, dissolving in THF, and obtaining the precipitate was repeated twice to recover 1.04 g of the polymer of compounds (1-2) and dicyclopentadiene.

[0158] The results of GPC analysis of the obtained polymer were as follows: number average molecular weight (Mn) was 26,000, weight average molecular weight (Mw) was 41,000, and molecular weight distribution (Mw / Mn) was 1.58.

[0159] <Example 6>

[0160] (Synthesis of ROMP polymers formed by reacting compounds (1-3) with dicyclopentadiene)

[0161] Inside a glove box, 1.0 g of dicyclopentadiene, 19.2 g of dehydrated cyclohexene, 9.8 mg of compounds (1-3), and 6.7 mg of 1-hexene were added to a threaded PFA container including a magnetic stirrer. Then, 62.3 mg of Grubbs second-generation catalyst was added and polymerization was initiated, stirred at room temperature for 2 hours. After adding ethyl vinyl ether to the reaction solution, the reaction solution was added dropwise to 200 mL of methanol to obtain a precipitate. The supernatant was removed by decantation, and the precipitate was dissolved in THF. This solution was then added dropwise to 200 mL of methanol to obtain a precipitate. The process of removing the supernatant, dissolving in THF, and obtaining the precipitate was repeated twice to recover 0.95 g of the polymer of compounds (1-3) and dicyclopentadiene.

[0162] The results of GPC analysis of the obtained polymer were as follows: number average molecular weight (Mn) was 15,000, weight average molecular weight (Mw) was 32,000, and molecular weight distribution (Mw / Mn) was 2.13.

[0163] <Comparative Example 1>

[0164] (Synthesis of ROMP polymers with dicyclopentadiene alone)

[0165] Inside a glove box, 1.0 g of dicyclopentadiene, 19.2 g of dehydrated cyclohexene, and 4.3 mg of 1-hexene were added to a threaded PFA container including a magnetic stirrer. Then, 61.5 mg of Grubbs second-generation catalyst was added and polymerization was initiated, stirred at room temperature for 2 hours. After adding ethyl vinyl ether to the reaction solution, the reaction solution was added dropwise to 200 mL of methanol to obtain a precipitate. The supernatant was removed by decantation, and the precipitate was dissolved in THF. This solution was then added dropwise to 200 mL of methanol to obtain a precipitate. This process of removing the supernatant, dissolving in THF, and obtaining the precipitate was repeated twice to recover 1.09 g of dicyclopentadiene polymer alone.

[0166] The results of GPC analysis of the obtained polymer were as follows: number average molecular weight (Mn) was 12,000, weight average molecular weight (Mw) was 23,000, and molecular weight distribution (Mw / Mn) was 1.92.

[0167] <Contact Angle Measurement>

[0168] Contact angle measurements were performed on the polymers obtained in Examples 4-6 and the dicyclopentadiene polymer obtained in Comparative Example 1. A cast film was used as the sample for contact angle measurement; this film was obtained by dropping a solution in which each polymer was dissolved in cyclopentyl methyl ether (CPME) onto a glass substrate and allowing it to dry. Purified water was used as the probe solution for contact angle measurement. After forming a droplet of 1.5 μL of purified water at the tip of the injection needle, the needle was moved towards the sample side to allow the droplet to fall onto the sample surface. A still image of the droplet falling onto the sample surface was taken, and based on the taken still image, the outline of the droplet was assumed to be a perfect circle, and the contact angle was determined using the θ / 2 method. Ten measurements were performed on the same sample, and the average value was taken as the contact angle. If the contact angle value was 90° or higher, it was recorded as ◎; if it was 60° or higher but less than 90°, it was recorded as ○; and if it was less than 60°, it was recorded as ×.

[0169] <Results of contact angle measurement>

[0170] The contact angle measurements of the polymers obtained in Examples 4 through 6 and dicyclopentadiene obtained in Comparative Example 1 are shown in Table 1. The contact angle of the polymer in Example 4 was 88.1°. The contact angle of the polymer in Example 5 was 84.7°. The contact angle of the polymer in Example 6 was 97.2°. The contact angle of the polymer in Comparative Example 1 was 50.6°.

[0171] [Table 1]

[0172]

[0173] The contact angle measurements shown in Table 1 demonstrate that copolymerizing the organopolysiloxane compounds obtained by the present invention with cyclic olefin monomers improves the water resistance of cyclic olefin polymers. In particular, the polymer of Example 6, copolymerized from the organopolysiloxane compounds (1-3) obtained in Example 3 with cyclic olefin monomers, exhibits excellent water resistance improvement, thus demonstrating a greater improvement in water resistance resulting from increasing the number of polysiloxane chains introduced.

[0174] <Evaluation of the slipperiness of water>

[0175] The water slippage properties of the polymers obtained in Examples 4-6 and the dicyclopentadiene polymer obtained in Comparative Example 1 were evaluated. For the evaluation samples, a cast film prepared in the same manner as the contact angle measurement was used. A DropMaster 500 (manufactured by Kyowa Interface Science Co., Ltd.) was used for the evaluation. Purified water was used as the probe solution. After forming a 5 μL water droplet at the tip of the injection needle, the injection needle was moved sideways, causing the water droplet to fall onto the sample surface. This operation was repeated three times, resulting in a total of 15 μL of water droplets. The sample stage was tilted at a tilt rate of 2 degrees / second. A case where the contact point on the retreating side of the water droplet moved 1 mm was defined as "slippage property." A case where the contact point on the advancing side of the water droplet could not move 1 mm at a tilt angle of 90 degrees was defined as "no slippage property." A case of slippage property was marked as ○, and a case of no slippage property was marked as ×.

[0176] <Results of the evaluation of water slippage>

[0177] The results of the slippage evaluation of the polymers obtained in Examples 4 to 6 and the dicyclopentadiene-only polymer obtained in Comparative Example 1 are shown in Table 2. The polymers obtained in Examples 4 to 6 exhibited slippage properties, while the dicyclopentadiene-only polymer obtained in Comparative Example 1 did not.

[0178] [Table 2]

[0179]

[0180] The results of the water slippage evaluation shown in Table 2 demonstrate that slippage properties can be imparted to cyclic olefin polymers by copolymerizing the organopolysiloxane compounds obtained by the present invention with cyclic olefin monomers.

[0181] <Preparation of self-standing membranes for optical measurement>

[0182] Self-standing optical measuring films used in the determination of total transmittance (TT) and haze values ​​described below were prepared. Cyclopentyl methyl ether (CPME) was used as the solvent, and the polymer was added to the solvent until saturation. The clear solution obtained by filtering the saturated solution was used as the casting solution. The casting solution was coated onto an aluminum cup with a diameter of 45 mm, and the solution was peeled off from the aluminum cup after standing and air drying, thereby obtaining self-standing optical measuring films for various polymers. Regarding the film thickness of these self-standing films, the film thickness was measured at 10 points, and the average value was taken as the film thickness. The film thickness was measured using a digital length measuring machine (DIGIMICRO, Nikon Corporation).

[0183] <Example 7>

[0184] A self-standing membrane for optical measurement was prepared using the polymer described in Example 4. The thickness of the obtained self-standing membrane was 13 μm.

[0185] <Example 8>

[0186] A self-standing membrane for optical measurement was prepared using the polymer described in Example 5. The thickness of the obtained self-standing membrane was 14 μm.

[0187] <Example 9>

[0188] A self-standing membrane for optical measurement was prepared using the polymer described in Example 6. The thickness of the obtained self-standing membrane was 14 μm.

[0189] <Comparative Example 2>

[0190] A self-standing membrane for optical measurement was prepared using the polymer described in Comparative Example 1. The thickness of the obtained self-standing membrane was 15 μm.

[0191] <Determination of Total Light Transmittance (TT)>

[0192] The total light transmittance (TT) of the self-standing membranes composed of the polymers described in Examples 7 to 9 and the self-standing membrane composed of the dicyclopentadiene-only polymer described in Comparative Example 2 was measured according to Japanese Industrial Standards (JIS) K7361-1. For the measurement, an NDH7000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) was used.

[0193] <Results of Total Light Transmittance (TT) Measurement>

[0194] The TT values ​​of the self-standing membranes composed of the polymers described in Examples 7 to 9 and the self-standing membrane composed of the polymer consisting solely of dicyclopentadiene described in Comparative Example 2 are as follows: Example 7: TT = 90%, Example 8: TT = 90%, Example 9: TT = 90%, Comparative Example 2: TT = 91%.

[0195] <Determination of Haze Value>

[0196] The haze values ​​of the self-standing membranes composed of the polymers described in Examples 7 to 9 and the self-standing membrane composed of the polymer consisting solely of dicyclopentadiene described in Comparative Example 2 were measured according to JIS K7136. An NDH7000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) was used for the measurement.

[0197] <Results of Haze Measurement>

[0198] The haze values ​​of the self-standing membranes composed of the polymers described in Examples 7 to 9 and the self-standing membrane composed of the polymer consisting solely of dicyclopentadiene described in Comparative Example 2 are as follows: Example 7: Haze value = 16%; Example 8: Haze value = 20%; Example 9: Haze value = 16%; Comparative Example 2: Haze value = 18%.

[0199] <Measurement results of self-standing membranes for optical measurement>

[0200] The measurement results of film thickness, TT, and haze value of the self-standing membranes composed of the polymers described in Examples 7 to 9 and the self-standing membrane composed of the polymer dicyclopentadiene alone described in Comparative Example 2 are shown in Table 3.

[0201] [Table 3]

[0202]

[0203] The results of optical measurements of the self-supporting membrane shown in Table 3 demonstrate that by copolymerizing the organopolysiloxane compound obtained by the present invention with cyclic olefin monomers, it is possible to improve water resistance or modify surface properties such as slip resistance without significantly impairing the optical properties of the cyclic olefin polymer.

[0204] [Industry availability]

[0205] The organopolysiloxane compounds obtained by this invention show the effect of improving the water resistance of cyclic olefin polymers by copolymerizing with cyclic olefin monomers, and are therefore expected to be used as additives for improving the water resistance or stain resistance of cyclic olefin polymers.

Claims

1. An organopolysiloxane compound, which is an organopolysiloxane compound represented by formula (1), In formula (1), A is a monovalent alicyclic hydrocarbon group with 4 to 60 carbon atoms having at least one carbon-carbon double bond, and T is the group represented by formula (2). In equation (2), R 1 and R 2 Independently, it is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R 3 For alkyl groups having 4 to 10 carbon atoms, x is an integer from 1 to 3, and n is an integer greater than or equal to 1. In the formula, in R... 1 Or R 3 When multiple R exist, they can be the same or different. 2 They can be the same or different.

2. The organopolysiloxane compound according to claim 1, wherein, In equation (1), A is the basis represented by equation (3). In formula (3), Y is a trivalent group containing a hydrocarbon group with 2 to 36 carbon atoms, a substituted hydrocarbon group with 3 to 58 carbon atoms, a hydrocarbon group containing heteroatoms with 2 to 36 carbon atoms, or a hydrocarbon group containing substituted heteroatoms with 2 to 58 carbon atoms. These trivalent groups may have at least one cyclic structure and may have unsaturated bonds.

3. The organopolysiloxane compound according to claim 1, wherein, In equation (1), A is the basis represented by equation (4a), equation (4b), equation (4c), or equation (4d). In equations (4a) to (4d), R 5 Independently, it is either hydrogen or a monovalent hydrocarbon group with 1 to 4 carbon atoms that may have unsaturated bonds, R 6 Independently, it is a divalent group comprising a hydrocarbon group having 1 to 4 carbon atoms, a substituted hydrocarbon group having 3 to 20 carbon atoms, a hydrocarbon group containing a heteroatom having 1 to 4 carbon atoms, or a hydrocarbon group containing a substituted heteroatom having 1 to 20 carbon atoms. These divalent groups may have unsaturated bonds, R 7 It is a methine (CH) or a trivalent heteroelement, L is a divalent hydrocarbon group with 2 to 10 carbon atoms that may have unsaturated bonds, Z is a methylene or 1,2-ethanediyl group, and m is an integer from 0 to 3.

4. The organopolysiloxane compound according to claim 3, wherein, In equation (1), A is the basis represented by equation (4a), equation (4b), equation (4c) or equation (4d), and R in equation (4a) or equation (4c) 5 For hydrogen, L is 1,2-ethanediyl, m is 0, and R in formula (4b) or formula (4d) 5 For hydrogen, R 6 For carbonyl, R 7 Nitrogen is 1,3-propanediyl.

5. The organopolysiloxane compound according to claim 4, wherein, In equation (1), A is the basis represented by equation (4a) or equation (4b), and in equation (2), x is 2 or 3.

6. A polymer obtained by polymerizing an organopolysiloxane compound as described in any one of claims 1 to 5 with a cycloolefin monomer.

7. The polymer according to claim 6, wherein, It is obtained by polymerization in the presence of a metasomatic polymerization catalyst.

8. A self-supporting membrane comprising the polymer as described in claim 6.

9. A molded article comprising the polymer as claimed in claim 6.

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