Organopolysiloxane compounds and their polymers

Abstract

To provide a polysiloxane compound having a cycloolefin skeleton at only one end of a polysiloxane chain, which can be compounded with cycloolefins without forming a crosslinking system. [Solution] The organopolysiloxane compound is represented by formula (1). TIFF2026142546000024.tif1246 A is a monovalent alicyclic hydrocarbon group having 4 to 60 carbon atoms and having at least one carbon-carbon double bond, and T is a group represented by formula (2). TIFF2026142546000025.tif30118 R 1 and R 2 R is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. 3 x is an alkyl group 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.

Description

[Technical Field]

[0001] The present invention relates to organopolysiloxane compounds having a cycloolefin skeleton that can be compounded with cycloolefin monomers. Furthermore, it relates to polymers obtained by reacting the organopolysiloxane compound with a raw material containing a cycloolefin monomer. [Background technology]

[0002] Organopolysiloxane compounds are compounds with a main chain skeleton consisting of siloxane bonds (-Si-O-Si-) and organic substituents at the terminals or side chains. They exhibit excellent properties such as heat resistance, weather resistance, electrical properties, water repellency, and mold release properties derived from the siloxane bonds. Because these characteristics can be imparted to general-purpose organic polymers by compounding them, they are used in the modification of organic polymers.

[0003] Generally, a method for compounding organopolysiloxane compounds with organic polymers involves incorporating the organopolysiloxane compound, which has reactive functional groups, into the polymerization system of the organic polymer and copolymerizing it.

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

[0005] However, organopolysiloxane compounds that have a cycloolefin skeleton at only one end of the polysiloxane chain have not been studied. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2008-274278 [Patent Document 2] Japanese Unexamined Patent Publication No. 2003-212973 [Summary of the Invention] [Problem to be Solved by the Invention]

[0007] An object of the present invention is to provide an organopolysiloxane compound having a cycloolefin skeleton only at one terminal of a polysiloxane chain, which can be combined with cycloolefin without forming a crosslinked system. [Means for Solving the Problem]

[0008] The inventors of the present invention have conducted intensive studies to solve the above problems. As a result, they have found that by reacting a polysiloxane obtained by the reaction of an organometallic compound with a cyclic siloxane with a chlorosilane compound having a cycloolefin skeleton, an organopolysiloxane compound having a cycloolefin skeleton only at one terminal of a polysiloxane chain can be synthesized. They have also found that surface modification of a cycloolefin polymer can be achieved by adding the obtained cycloolefin-containing organopolysiloxane to a polymerization system of a cycloolefin monomer and performing polymerization.

[0009] According to the present invention, the following organopolysiloxane compound is provided.

[0010] Item 1. An organopolysiloxane compound represented by formula (1). TIFF2026142546000001.tif1347 In formula (1), A is a monovalent alicyclic hydrocarbon group having 4 to 60 carbon atoms and having at least one carbon-carbon double bond, and T is a group represented by formula (2). TIFF2026142546000002.tif30117 In formula (2), R 1 and R 2 are each independently alkyl having 1 to 10 carbon atoms or aryl having 6 to 10 carbon atoms, and R 3is alkyl having 4 to 10 carbon atoms, x is an integer of 1 to 3, n is an integer of 1 or more, and in the formula, R 1 or R 3 when there are a plurality of them, they may be the same or different, and when there are a plurality of R 2 they may be the same or different from each other.

[0011] Item 2. The organopolysiloxane compound according to Item 1, wherein A in formula (1) is a group represented by formula (3). TIFF2026142546000003.tif2049 In formula (3), Y is a trivalent group selected from a hydrocarbon group having 2 to 36 carbon atoms, a substituted hydrocarbon group having 3 to 58 carbon atoms, a heteroatom-containing hydrocarbon group having 2 to 36 carbon atoms, or a substituted heteroatom-containing hydrocarbon group having 2 to 58 carbon atoms, these trivalent groups may have at least one cyclic structure, and these trivalent groups may have an unsaturated bond.

[0012] Item 3. The organopolysiloxane compound according to Item 1 or 2, wherein A in formula (1) is a group represented by formula (4a), formula (4b), formula (4c), or formula (4d). TIFF2026142546000004.tif65166 In formulas (4a) to (4d), R 5 is each independently hydrogen or a monovalent hydrocarbon group having 1 to 4 carbon atoms which may have an unsaturated bond, and R 6 is each independently a divalent group selected from a hydrocarbon group having 1 to 4 carbon atoms, a substituted hydrocarbon group having 3 to 20 carbon atoms, a heteroatom-containing hydrocarbon group having 1 to 4 carbon atoms, or a substituted heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms, these divalent groups may have an unsaturated bond, R 7 is methine (CH) or a trivalent heteroelement, L is a divalent hydrocarbon group having 2 to 10 carbon atoms which may have an unsaturated bond, Z is methylene or 1,2-ethanediyl, and m is an integer of 0 to 3.

[0013] Item 4. In formula (1) described in Item 1, A is a group represented by formula (4a), formula (4b), formula (4c), or formula (4d), and R in formula (4a) or formula (4c) 5 is hydrogen, L is 1,2-ethanediyl, m is 0, and R in formula (4b) or formula (4d) 5 is hydrogen, R 6 is a carbonyl group, and R 7 The organopolysiloxane compound according to item 3, wherein L is nitrogen and L is 1,3-propanediyl.

[0014] Item 5. The organopolysiloxane compound according to Item 4, wherein A in formula (1) described in Item 1 is a group represented by formula (4a) or formula (4b), and x in formula (2) described in Item 1 is 2 or 3. Item 6. A polymer obtained by polymerizing an organopolysiloxane compound described in any one of items 1 to 5 with a cycloolefin monomer. Item 7. The polymer according to item 6, obtained by polymerization in the presence of a metathesis polymerization catalyst. Item 8. A self-supporting film comprising the polymer described in Item 6 or Item 7. Article 9. A molded article comprising the polymer described in Article 6 or Article 7. [Effects of the Invention]

[0015] According to the present invention, an organopolysiloxane compound having a cycloolefin skeleton at only one end of a polysiloxane chain, which is useful for surface modification of cycloolefin polymers, can be obtained. [Modes for carrying out the invention]

[0016] The following describes embodiments of the present invention, but the present invention is not limited to the following embodiments.

[0017] The terms used in this specification have the following meanings:

[0018] In this specification, “alkyl” means a saturated, linear, branched, or cyclic hydrocarbon having a specific number of carbon atoms.

[0019] In this specification, "halogen" or "halo" means chloro, fluoro, bromo, or iodine.

[0020] In this specification, “heteroatom” or “heteroelement” means nitrogen, oxygen, phosphorus, or sulfur.

[0021] The organopolysiloxane compound of the present invention is characterized by being represented by formula (1). TIFF2026142546000005.tif1141 In formula (1), A is a monovalent alicyclic hydrocarbon group having 4 to 60 carbon atoms and having at least one carbon-carbon double bond, and T is the group represented by formula (2). TIFF2026142546000006.tif28111 In formula (2), R 1 and R 2 R is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. 3 R is an alkyl group having 4 to 10 carbon atoms, x is an integer from 1 to 3, n is an integer greater than or equal to 1, and in the formula, 1 or R 3 If there are multiple Rs, they may be the same or different, and there are multiple Rs. 2 They may be the same or different.

[0022] In formula (1), A is a monovalent alicyclic hydrocarbon group having 4 to 60 carbon atoms and a carbon-carbon double bond. Examples include cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cyclododecenyl, cyclotetradecenyl, cyclohexadecenyl, cyclooctadecenyl, cycloeicocenyl, cyclodococenyl, cyclotetracocenyl, cyclohexacocenyl, cyclooctacocenyl, norborneyl, norbornadienyl, dicyclopentenyl, dicyclopentadienyl, dicyclohexenyl, dicyclohexadienyl, tricyclodecenyl, tetracyclododecenyl, tetracyclododecadienyl, and at least one hydrogen atom of these groups may be replaced by an alkyl, halogen, heteroatom, haloalkyl, or heteroatom-substituted alkyl group. The number of carbon atoms in the monovalent alicyclic hydrocarbon group having a carbon-carbon double bond is preferably 4 to 30, and more preferably 5 to 15.

[0023] R in equation (2) 1 and R 2In this context, 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, isoheptyl, 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, 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 Examples include 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, and methylcyclononyl, and the number of carbon atoms in the alkyl group is preferably 1 to 4.

[0024] Examples of aryl compounds having 6 to 10 carbon atoms include phenyl, benzyl, 2-tolyl, 3-tolyl, 4-tolyl, 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, and 2-naphthyl.

[0025] R in equation (2) 3Alkyls with 4 to 10 carbon atoms in this context 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, isoheptyl, 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-dimethylheptyl These are ethyloctyl, 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, and 3-propylheptyl, and the number of carbon atoms in the alkyl group is preferably 4.

[0026] In formula (2), n is preferably 10 to 150, and more preferably 15 to 80.

[0027] In formula (1), the monovalent alicyclic hydrocarbon group of A is preferably the group represented by formula (3). TIFF2026142546000007.tif2048 In formula (3), Y is a trivalent group consisting of a hydrocarbon group having 2 to 36 carbon atoms, a substituted hydrocarbon group having 3 to 58 carbon atoms, a heteroatom-containing hydrocarbon group having 2 to 36 carbon atoms, or a substituted heteroatom-containing hydrocarbon group having 2 to 58 carbon atoms, and these trivalent groups may have at least one cyclic structure, and these trivalent groups may have an unsaturated bond.

[0028] Examples of hydrocarbon groups having 2 to 36 carbon atoms include ethylene, propylene, butylene, pentene, hexene, heptene, octene, decene, dodecene, tetradecene, hexadecene, octadecene, eicosene, docosene, tetracosene, hexacosene, cyclopentane, cyclopentene, octahydro-1H-indene, 2,3,3a,4,7,7a-hexahydro-1H-indene, octahydro-1H-4,7-methanoindene, and others. The number of carbon atoms in the hydrocarbon group is preferably 2 to 28, and more preferably 3 to 10.

[0029] Substitutive hydrocarbon groups with 3 to 58 carbon atoms have at least one hydrogen atom of the above hydrocarbon groups with 2 to 36 carbon atoms, such as 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, isoheptyl, 3-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, and 2,3-dimethyl Pentyl, 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, 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, These are alkyl-substituted hydrocarbons such as 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, and methylcyclononyl, and the number of carbon atoms in the substituted hydrocarbon group is preferably 3 to 48, more preferably 4 to 30.

[0030] A heteroatom-containing hydrocarbon group having 2 to 36 carbon atoms is one in which at least one carbon atom of the above-mentioned hydrocarbon group having 2 to 36 carbon atoms is substituted with a substituent containing a heteroatom, such as a carbonyl group (>C=O), an amide group (-CONH2, -CONH-, CON<), a sulfonyl group (>SO2), a sulfide group (-S-), a thiocarbonyl group (>C=S), or a sulfoxy group (-S(=O)-). The number of carbon atoms in the heteroatom-containing hydrocarbon group is preferably 2 to 28, and more preferably 3 to 10. A substituted heteroatom-containing hydrocarbon group having 2 to 58 carbon atoms is one in which at least one carbon or hydrogen of the above-mentioned hydrocarbon group having 2 to 36 carbon atoms is substituted with a substituent containing a heteroatom such as a hydroxyl group (-OH), alkoxy group (-OR), carbonyl group (>C=O), carboxyl group (-COOH), ester group (-COOR), amino group (-NH2), imino group (=NH), azo group (-N=N-), nitro group (-NO2), nitroso group (-NO), amide group (-CONH2), cyano group (-C≡N), thiol group (-SH), thioether group (-SR), sulfonyl group (>SO2), sulfo group (-SO3H), sulfide group (-S-), thiocarbonyl group (>C=S), or sulfoxy group (-S(=O)-). The number of carbon atoms in the substituted heteroatom-containing hydrocarbon group is preferably 3 to 48, and more preferably 4 to 30.

[0031] In formula (1), the monovalent alicyclic hydrocarbon group of A is more preferably a group represented by formula (4a), formula (4b), formula (4c), or formula (4d). TIFF2026142546000008.tif64163 In formulas (4a) to (4d), R 5 R is independently a monovalent hydrocarbon group having 1 to 4 carbon atoms, which may have hydrogen or an unsaturated bond. 6 R is independently a divalent group consisting of a hydrocarbon group having 1 to 4 carbon atoms, a substituted hydrocarbon group having 3 to 20 carbon atoms, a heteroatom-containing hydrocarbon group having 1 to 4 carbon atoms, or a substituted heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms, and these divalent groups may have unsaturated bonds. 7is methine (CH) or a trivalent heteroatom, L is a divalent hydrocarbon group having 2 to 10 carbon atoms which may have unsaturated bonds, Z is methylene or 1,2-ethanediyl, and m is an integer from 0 to 3.

[0032] R 5 Examples of monovalent hydrocarbon groups having 1 to 4 carbon atoms that may have an unsaturated bond include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, vinyl, allyl, butenyl, isopropenyl, isobutenyl, and butadienyl.

[0033] R 6 Examples of hydrocarbon groups having 1 to 4 carbon atoms in this context 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.

[0034] Substitutive hydrocarbon groups with 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, 2,2-dimethylpropane-1,1-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-di Il, 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 Dimethylpentane-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-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-1,1-diyl, 4-methylheptane -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 Tan-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-1,7-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 L, 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-1,9-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-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 n-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-E Examples include 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., and the number of carbon atoms in the substituted hydrocarbon group is preferably 3 to 10, more preferably 3 to 6.

[0035] Heteroatom-containing hydrocarbon groups having 1 to 4 carbon atoms are, for example, hydrocarbon groups 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, and 1,4-butanediyl, in which at least one carbon atom is substituted with a substituent containing a heteroatom, such as a carbonyl group (>C=O), an amide group (-CONH2, -CONH-, CON<), a sulfonyl group (>SO2), a sulfide group (-S-), a thiocarbonyl group (>C=S), or a sulfoxy group (-S(=O)-).

[0036] Hydrocarbon groups containing substituted heteroatoms with 1 to 20 carbon atoms include, for example, 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, in which at least one carbon or hydrogen of the hydrocarbon group is a hydroxyl group (-OH), alkoxy group (-OR), carbonyl group (>C=O), carboxyl group (-COOH), ester group (-COOR), amino group (-NH2), etc. The hydrocarbon group is substituted with substituents containing heteroatoms such as mino group (=NH), azo group (-N=N-), nitro group (-NO2), nitroso group (-NO), amide group (-CONH2), cyano group (-C≡N), thiol group (-SH), thioether group (-SR), sulfonyl group (>SO2), sulfo group (-SO3H), sulfide group (-S-), thiocarbonyl group (>C=S), and sulfoxy group (-S(=O)-). The number of carbon atoms in the substituted heteroatom-containing hydrocarbon group is preferably 1 to 10, more preferably 1 to 4.

[0037] In the group represented by formula (4b) or formula (4d), two R 6 and R 7 The number of members in the ring containing is 5 or more, preferably 5 to 15, more preferably 5 to 7, and particularly preferably 5.

[0038] In L, divalent hydrocarbon groups having 2 to 10 carbon atoms that may have unsaturated bonds include, for example, 1,2-ethanediyl, prop-1-ene-1,2-diyl, prop-1-ene-1,3-diyl, prop-1-ene-2,3-diyl, buta-1-ene-1,2-diyl, buta-1-ene-1,3-diyl, buta-1-ene-1,4-diyl, buta-1-ene-2,3-diyl, buta-1-ene-2,4-diyl, buta-1-ene-3,4-diyl, buta-2-ene-1,2-diyl, buta-2-ene-1,3-diyl, buta-2-ene-1,4-diyl Lu, Buta-2-en-2,3-jiil, Buta-2-en-2,4-jiil, Buta-2-en-3,4-jiil, Penta-1-en-1,2-jiil, Penta-1-en-1,3-jiil, Penta-1-en-1,4-jiil, Penta-1-en-1,5-jiil, Penta-1-en-2,3-jiil, Penta-1-en-2,4-jiil, Penta-1-en-2,5-jiil, Penta-2-en-3,4-jiil, Penta-1-en-3,5-jiil, Penta-1-en-4,5-jiil, Penta-2-en-1,2-jiil, Penta-2-en-1 ,3-jile, pent-2-en-1,4-jile, pent-2-en-1,5-jile, pent-2-en-2,3-jile, pent-2-en-2,4-jile, pent-2-en-2,5-jile, pent-2-en-3,4-jile, pent-2-en-3,5-jile, pent-2-en-4,5-jile, hexa-1-en-1,2-jile, hexa-1-en-1,3-jile, hexa-1-en-1,4-jile, hexa-1-en-1,5-jile, hexa-1-en-1,6-jile, hexa-1-en-2,3-jile, hex Sa-1-en-2,4-jiil, Hexa-1-en-2,5-jiil, Hexa-1-en-2,6-jiil, Hexa-1-en-3,4-jiil, Hexa-1-en-3,5-jiil, Hexa-1-en-3,6-jiil, Hexa-1-en-4,5-jiil, Hexa-1-en-4,6-jiil, Hexa-1-en-5,6-jiil, Hexa-2-en-1,2-jiil, Hexa-2-en-1,3-jiil, Hexa-2-en-1,4-jiil, Hexa-2-en-1,5-jiil, Hexa-2-en-1,6-jiil, Hexa-2-en-2,3-Jil, Hexa-2-En-2,4-Jil, Hexa-2-En-2,5-Jil, Hexa-2-En-2,6-Jil, Hexa-2-En-3,4-Jil, Hexa-2-En-3,5-Jil, Hexa-2-En-3,6-Jil, Hexa-2-En-4,5-Jil, Hexa-2-En-4,6-Jil, Hexa-2-En-5,6-Jil, Hexa-3-En-1,2-Jil, Hexa-3-En-1,3-Jil, Hexa-3-En-1,4-Jil, Hexa-3-En-1,5-Jil, Hexa-3-En-1,6-Jil, Hex Sa-3-en-2,3-jiil, Hexa-3-en-2,4-jiil, Hexa-3-en-2,5-jiil, Hexa-3-en-2,6-jiil, Hexa-3-en-3,4-jiil, Hexa-3-en-3,5-jiil, Hexa-3-en-3,6-jiil, Hexa-3-en-4,5-jiil, Hexa-3-en-4,6-jiil, Hexa-3-en-5,6-jiil, Hepta-1-en-1,2-jiil, Hepta-1-en-1,3-jiil, Hepta-1-en-1,4-jiil, Hepta-1-en-1,5-jiil, Hepta-1-en-1, 6-Jil, Hepta-1-En-1,7-Jil, Hepta-1-En-2,3-Jil, Hepta-1-En-2,4-Jil, Hepta-1-En-2,5-Jil, Hepta-1-En-2,6-Jil, Hepta-1-En-2,7-Jil, Hepta-1-En-3,4-Jil, Hepta-1-En-3,5-Jil, Hepta-1-En-3,6-Jil, Hepta-1-En-3,7-Jil, Hepta-1-En-4,5-Jil, Hepta-1-En-4,6-Jil, Hepta-1-En-4,7-Jil, Hepta-1-En-5,6-Jil, Hep Ta-1-en-5,7-jiil, Hepta-1-en-6,7-jiil, Hepta-2-en-1,2-jiil, Hepta-2-en-1,3-jiil, Hepta-2-en-1,4-jiil, Hepta-2-en-1,5-jiil, Hepta-2-en-1,6-jiil, Hepta-2-en-1,7-jiil, Hepta-2-en-2,3-jiil, Hepta-2-en-2,4-jiil, Hepta-2-en-2,5-jiil, Hepta-2-en-2,6-jiil, Hepta-2-en-2,7-jiil, Hepta-2-en-3,4-jiil, Hepta-2-en-3,5-Jil, Hepta-2-En-3,6-Jil, Hepta-2-En-3,7-Jil, Hepta-2-En-4,5-Jil, Hepta-2-En-4,6-Jil, Hepta-2-En-4,7-Jil, Hepta-2-En-5,6-Jil, Hepta-2-En-5,7-Jil, Hepta-2-En-6,7-Jil, Hepta-3-En-1,2-Jil, Hepta-3-En-1,3-Jil, Hepta-3-En-1,4-Jil, Hepta-3-En-1,5-Jil, Hepta-3-En-1,6-Jil, Hepta-3-En-1,7-Jil, Hep Ta-3-en-2,3-jiil, hepta-3-en-2,4-jiil, hepta-3-en-2,5-jiil, hepta-3-en-2,6-jiil, hepta-3-en-2,7-jiil, hepta-3-en-3,4-jiil, hepta-3-en-3,5-jiil, hepta-3-en-3,6-jiil, hepta-3-en-3,7-jiil, hepta-3-en-4,5-jiil, hepta-3-en-4,6-jiil, hepta-3-en-4,7-jiil, hepta-3-en-5,6-jiil, hepta-3-en-5,7-jiil, hepta-3-en-6, 7-Jil, Octa-1-En-1,2-Jil, Octa-1-En-1,3-Jil, Octa-1-En-1,4-Jil, Octa-1-En-1,5-Jil, Octa-1-En-1,6-Jil, Octa-1-En-1,7-Jil, Octa-1-En-1,8-Jil, Octa-1-En-2,3-Jil, Octa-1-En-2,4-Jil, Octa-1-En-2,5-Jil, Octa-1-En-2,6-Jil, Octa-1-En-2,7-Jil, Octa-1-En-2,8-Jil, Octa-1-En-3,4-Jil, Oct Ta-1-en-3,5-jiil, Octa-1-en-3,6-jiil, Octa-1-en-3,7-jiil, Octa-1-en-3,8-jiil, Octa-1-en-4,5-jiil, Octa-1-en-4,6-jiil, Octa-1-en-4,7-jiil, Octa-1-en-4,8-jiil, Octa-1-en-5,6-jiil, Octa-1-en-5,7-jiil, Octa-1-en-5,8-jiil, Octa-1-en-6,7-jiil, Octa-1-en-6,8-jiil, Octa-1-en-7,8-jiil, Octa-2-en-1,2-Jil, Octa-2-En-1,3-Jil, Octa-2-En-1,4-Jil, Octa-2-En-1,5-Jil, Octa-2-En-1,6-Jil, Octa-2-En-1,7-Jil, Octa-2-En-1,8-Jil, Octa-2-En-2,3-Jil, Octa-2-En-2,4-Jil, Octa-2-En-2,5-Jil, Octa-2-En-2,6-Jil, Octa-2-En-2,7-Jil, Octa-2-En-2,8-Jil, Octa-2-En-3,4-Jil, Octa-2-En-3,5-Jil, Oct Ta-2-en-3,6-jiil, Octa-2-en-3,7-jiil, Octa-2-en-3,8-jiil, Octa-2-en-4,5-jiil, Octa-2-en-4,6-jiil, Octa-2-en-4,7-jiil, Octa-2-en-4,8-jiil, Octa-2-en-5,6-jiil, Octa-2-en-5,7-jiil, Octa-2-en-5,8-jiil, Octa-2-en-6,7-jiil, Octa-2-en-6,8-jiil, Octa-2-en-7,8-jiil, Octa-3-en-1,2-jiil, Octa-3-en-1, 3-Jil, Octa-3-En-1,4-Jil, Octa-3-En-1,5-Jil, Octa-3-En-1,6-Jil, Octa-3-En-1,7-Jil, Octa-3-En-1,8-Jil, Octa-3-En-2,3-Jil, Octa-3-En-2,4-Jil, Octa-3-En-2,5-Jil, Octa-3-En-2,6-Jil, Octa-3-En-2,7-Jil, Octa-3-En-2,8-Jil, Octa-3-En-3,4-Jil, Octa-3-En-3,5-Jil, Octa-3-En-3,6-Jil, Oct Ta-3-en-3,7-jiil, Octa-3-en-3,8-jiil, Octa-3-en-4,5-jiil, Octa-3-en-4,6-jiil, Octa-3-en-4,7-jiil, Octa-3-en-4,8-jiil, Octa-3-en-5,6-jiil, Octa-3-en-5,7-jiil, Octa-3-en-5,8-jiil, Octa-3-en-6,7-jiil, Octa-3-en-6,8-jiil, Octa-3-en-7,8-jiil, Octa-4-en-1,2-jiil, Octa-4-en-1,3-jiil, Octa-4-en-1,4-Jil, Octa-4-En-1,5-Jil, Octa-4-En-1,6-Jil, Octa-4-En-1,7-Jil, Octa-4-En-1,8-Jil, Octa-4-En-2,4-Jil, Octa-4-En-2,5-Jil, Octa-4-En-2,6-Jil, Octa-4-En-2,7-Jil, Octa-4-En-2,8-Jil, Octa-4-En-3,4-Jil, Octa-4-En-3,5-Jil, Octa-4-En-3,6-Jil, Octa-4-En-3,7-Jil, Octa-4-En-3,8-Jil, Octa-4- En-4,5-jiil, Octa-4-En-4,6-jiil, Octa-4-En-4,7-jiil, Octa-4-En-4,8-jiil, Octa-4-En-5,6-jiil, Octa-4-En-5,7-jiil, Octa-4-En-5,8-jiil, Octa-4-En-6,7-jiil, Octa-4-En-6,8-jiil, Octa-4-En-7,8-jiil, Nona-1-En-1,2-jiil, Nona-1-En-1,3-jiil, Nona-1-En-1,4-jiil, Nona-1-En-1,5-jiil, Nona-1-En-1,6-jiil, Nona-1-E n-1,7-jiil, nona-1-en-1,8-jiil, nona-1-en-1,9-jiil, nona-1-en-2,3-jiil, nona-1-en-2,4-jiil, nona-1-en-2,5-jiil, nona-1-en-2,6-jiil, nona-1-en-2,7-jiil, nona-1-en-2,8-jiil, nona-1-en-2,9-jiil, nona-1-en-3,4-jiil, nona-1-en-3,5-jiil, nona-1-en-3,6-jiil, nona-1-en-3,7-jiil, nona-1-en-3,8-jiil, nona-1-en-3,9-jiil, Nona-1-En-4,5-Jil, Nona-1-En-4,6-Jil, Nona-1-En-4,7-Jil, Nona-1-En-4,8-Jil, Nona-1-En-4,9-Jil, Nona-1-En-5,6-Jil, Nona-1-En-5,7-Jil, Nona-1-En-5,8-Jil, Nona-1-En-5,9-Jil, Nona-1-En-6,7-Jil, Nona-1-En-6,8-Jil, Nona-1-En-6,9-Jil, Nona-1-En-7,8-Jil, Nona-1-En-7,9-Jil, Nona-1-En-8,9-Jil, Nona-2-En-1,2-Jil, Nona-2-En-1, 3-Jil, Nona-2-En-1, 4-Jil, Nona-2-En-1, 5-Jil, Nona-2-En-1, 6-Jil, Nona-2-En-1, 7-Jil, Nona-2-En-1, 8-Jil, Nona-2-En-1, 9-Jil, Nona-2-En-2, 3-Jil, Nona-2-En-2, 4-Jil, Nona-2-En-2, 5-Jil, Nona-2-En-2, ,6-Jil, Nona-2-En-2,7-Jil, Nona-2-En-2,8-Jil, Nona-2-En-2,9-Jil, Nona-2-En-3,4-Jil, Nona-2-En-3,5-Jil, Nona-2-En-3,6-Jil, Nona-2-En-3,7-Jil, Nona-2-En-3,8-Jil, Nona-2-En-3,9-Jil, Nona-2-En-4,5-Jil, Nona-2-En-4,6-Jil, Nona-2-En-4,7-Jil, Nona-2-En-4,8-Jil, Nona-2-En-4,9-Jil, Nona-2-En-5,6-Jil, No Na-2-en-5,7-jiil, Non-na-2-en-5,8-jiil, Non-na-2-en-5,9-jiil, Non-na-2-en-6,7-jiil, Non-na-2-en-6,8-jiil, Non-na-2-en-6,9-jiil, Non-na-2-en-7,8-jiil, Non-na-2-en-7,9-jiil, Non-na-2-en-8,9-jiil, Non-na-3-en-1,2-jiil, Non-na-3-en-1,3-jiil, Non-na-3-en-1,4-jiil, Non-na-3-en-1,5-jiil, Non-na-3-en-1,6-jiil, Non-na-3-en-1,7-jiil, Non-na-3-en-1 ,8-Jil, Nona-3-En-1,9-Jil, Nona-3-En-2,3-Jil, Nona-3-En-2,4-Jil, Nona-3-En-2,5-Jil, Nona-3-En-2,6-Jil, Nona-3-En-2,7-Jil, Nona-3-En-2,8-Jil, Nona-3-En-2,9-Jil, Nona-3-En-3,4-Jil, Nona-3-En-3,5-Jil, Nona-3-En-3,6-Jil, Nona-3-En-3,7-Jil, Nona-3-En-3,8-Jil, Nona-3-En-3,9-Jil, Nona-3-En-4,5-Jil, No Na-3-en-4,6-jiil, Non-3-en-4,7-jiil, Non-3-en-4,8-jiil, Non-3-en-4,9-jiil, Non-3-en-5,6-jiil, Non-3-en-5,7-jiil, Non-3-en-5,8-jiil, Non-3-en-5,9-jiil, Non-3-en-6,7-jiil, Non-3-en-6,8-jiil, Non-3-en-6,9-jiil, Non-3-en-7,8-jiil, Non-3-en-7,9-jiil, Non-3-en-8,9-jiil, Non-4-en-1,2-jiil, Non-4-en-1,3-Jil, Nona-4-En-1,4-Jil, Nona-4-En-1,5-Jil, Nona-4-En-1,6-Jil, Nona-4-En-1,7-Jil, Nona-4-En-1,8-Jil, Nona-4-En-1,9-Jil, Nona-4-En-2,3-Jil, Nona-4-En-2,4-Jil, Nona-4-En-2,5-Jil, Nona-4-En-2,6-Jil, Nona-4-En-2,7-Jil, Nona-4-En-2,8-Jil, Nona-4-En-2,9-Jil, Nona-4-En-3,4-Jil, Nona-4-En-3,5-Jil, Nona -4-En-3,6-Jil, Non-4-En-3,7-Jil, Non-4-En-3,8-Jil, Non-4-En-3,9-Jil, Non-4-En-4,5-Jil, Non-4-En-4,6-Jil, Non-4-En-4,7-Jil, Non-4-En-4,8-Jil, Non-4-En-4,9-Jil, Non-4-En-5,6-Jil, Non-4-En-5,7-Jil, Non-4-En-5,8-Jil, Non-4-En-5,9-Jil, Non-4-En-6,7-Jil, Non-4-En-6,8-Jil, Non-4-En-6,9 -Jil, Nona-4-En-7,8-Jil, Nona-4-En-7,9-Jil, Nona-4-En-8,9-Jil, Deka-1-En-1,2-Jil, Deka-1-En-1,3-Jil, Deka-1-En-1,4-Jil, Deka-1-En-1,5-Jil, Deka-1-En-1,6-Jil, Deka-1-En-1,7-Jil, Deka-1-En-1,8-Jil, Deka-1-En-1,9-Jil, Deka-1-En-1,10-Jil, Deka-1-En-2,3-Jil, Deka-1-En-2,4-Jil, Deka-1-En-2,5-Jil, Deka- 1-En-2,6-Jil, Deca-1-En-2,7-Jil, Deca-1-En-2,8-Jil, Deca-1-En-2,9-Jil, Deca-1-En-2,10-Jil, Deca-1-En-3,4-Jil, Deca-1-En-3,5-Jil, Deca-1-En-3,6-Jil, Deca-1-En-3,7-Jil, Deca-1-En-3,8-Jil, Deca-1-En-3,9-Jil, Deca-1-En-3,10-Jil, Deca-1-En-4,5-Jil, Deca-1-En-4,6-Jil, Deca-1-En-4,7-Jil, Deca-1-En-4,8-Jil, Deca-1-En-4,9-Jil, Deca-1-En-4,10-Jil, Deca-1-En-5,6-Jil, Deca-1-En-5,7-Jil, Deca-1-En-5,8-Jil, Deca-1-En-5,9-Jil, Deca-1-En-5,10-Jil, Deca-1-En-6,7-Jil, Deca-1-En-6,8-Jil, Deca-1-En-6,9-Jil, Deca-1-En-6,10-Jil, Deca-1-En-7,8-Jil, Deca-1-En-7,9-Jil, Deca-1-En-7,10-Jil, Deca-1-En-8,9-Jil Iru, Deca-1-En-8,10-Jiru, Deca-1-En-9,10-Jiru, Deca-2-En-1,2-Jiru, Deca-2-En-1,3-Jiru, Deca-2-En-1,4-Jiru, Deca-2-En-1,5-Jiru, Deca-2-En-1,6-Jiru, Deca-2-En-1,7-Jiru, Deca-2-En-1,8-Jiru, Deca-2-En-1,9-Jiru, Deca-2-En-1,10-Jiru, Deca-2-En-2,3-Jiru, Deca-2-En-2,4-Jiru, Deca-2-En-2,5-Jiru, Deca-2-En-2,6-Jiru, De Ka-2-En-2,7-Jil, Deka-2-En-2,8-Jil, Deka-2-En-2,9-Jil, Deka-2-En-2,10-Jil, Deka-2-En-3,4-Jil, Deka-2-En-3,5-Jil, Deka-2-En-3,6-Jil, Deka-2-En-3,7-Jil, Deka-2-En-3,8-Jil, Deka-2-En-3,9-Jil, Deka-2-En-3,10-Jil, Deka-2-En-4,5-Jil, Deka-2-En-4,6-Jil, Deka-2-En-4,7-Jil, Deka-2-En-4,8-Jil, Deka-2-E n-4,9-jiil, deka-2-en-4,10-jiil, deka-2-en-5,6-jiil, deka-2-en-5,7-jiil, deka-2-en-5,8-jiil, deka-2-en-5,9-jiil, deka-2-en-5,10-jiil, deka-2-en-6,7-jiil, deka-2-en-6,8-jiil, deka-2-en-6,9-jiil, deka-2-en-6,10-jiil, deka-2-en-7,8-jiil, deka-2-en-7,9-jiil, deka-2-en-7,10-jiil, deka-2-en-8,9-jiil, deka-2-en-8,10-Jil, Deca-2-En-9, 10-Jil, Deca-3-En-1, 2-Jil, Deca-3-En-1, 3-Jil, Deca-3-En-1, 4-Jil, Deca-3-En-1, 5-Jil, Deca-3-En-1, 6-Jil, Deca-3-En-1, 7-Jil, Deca-3-En-1, 8-Jil, Deca-3-En-1, 9-Jil, Deca-3-En-1, 10-Jil, Deca-3-En-2, 3-Jil, Deca-3-En-2, 4-Jil, Deca-3-En-2, 5-Jil, Deca-3-En-2, 6-Jil, Deca-3-En-2, 7-Jil Ru, Deka-3-En-2,8-Jil, Deka-3-En-2,9-Jil, Deka-3-En-2,10-Jil, Deka-3-En-3,4-Jil, Deka-3-En-3,5-Jil, Deka-3-En-3,6-Jil, Deka-3-En-3,7-Jil, Deka-3-En-3,8-Jil, Deka-3-En-3,9-Jil, Deka-3-En-3,10-Jil, Deka-3-En-4,5-Jil, Deka-3-En-4,6-Jil, Deka-3-En-4,7-Jil, Deka-3-En-4,8-Jil, Deka-3-En-4,9-Jil, Deka- 3-En-4,10-Jil, Deca-3-En-5,6-Jil, Deca-3-En-5,7-Jil, Deca-3-En-5,8-Jil, Deca-3-En-5,9-Jil, Deca-3-En-5,10-Jil, Deca-3-En-6,7-Jil, Deca-3-En-6,8-Jil, Deca-3-En-6,9-Jil, Deca-3-En-6,10-Jil, Deca-3-En-7,8-Jil, Deca-3-En-7,9-Jil, Deca-3-En-7,10-Jil, Deca-3-En-8,9-Jil, Deca-3-En-8,10-Jil, Deca-3- En-9,10-jiil, Deca-4-En-1,2-jiil, Deca-4-En-1,3-jiil, Deca-4-En-1,4-jiil, Deca-4-En-1,5-jiil, Deca-4-En-1,6-jiil, Deca-4-En-1,7-jiil, Deca-4-En-1,8-jiil, Deca-4-En-1,9-jiil, Deca-4-En-1,10-jiil, Deca-4-En-2,3-jiil, Deca-4-En-2,4-jiil, Deca-4-En-2,5-jiil, Deca-4-En-2,6-jiil, Deca-4-En-2,7-jiil, Deca-4-En-2,8-Jil, Deca-4-En-2, 9-Jil, Deca-4-En-2, 10-Jil, Deca-4-En-3, 4-Jil, Deca-4-En-3, 5-Jil, Deca-4-En-3, 6-Jil, Deca-4-En-3, 7-Jil, Deca-4-En-3, 8-Jil, Deca-4-En-3, 9-Jil, Deca-4-En-3, 10-Jil, Deca-4-En-4, 5-Jil, Deca-4-En-4, 6-Jil, Deca-4-En-4, 7-Jil, Deca-4-En-4, 8-Jil, Deca-4-En-4, 9-Jil, Deca-4-En-4, 10-Jil Ru, Deka-4-En-5,6-Jiru, Deka-4-En-5,7-Jiru, Deka-4-En-5,8-Jiru, Deka-4-En-5,9-Jiru, Deka-4-En-5,10-Jiru, Deka-4-En-6,7-Jiru, Deka-4-En-6,8-Jiru, Deka-4-En-6,9-Jiru, Deka-4-En-6,10-Jiru, Deka-4-En-7,8-Jiru, Deka-4-En-7,9-Jiru, Deka-4-En-7,10-Jiru, Deka-4-En-8,9-Jiru, Deka-4-En-8,10-Jiru, Deka-4-En-9,10-Jiru, Deca-5-En-1,2-Jil, Deca-5-En-1,3-Jil, Deca-5-En-1,4-Jil, Deca-5-En-1,5-Jil, Deca-5-En-1,6-Jil, Deca-5-En-1,7-Jil, Deca-5-En-1,8-Jil, Deca-5-En-1,9-Jil, Deca-5-En-1,10-Jil, Deca-5-En-2,3-Jil, Deca-5-En-2,4-Jil, Deca-5-En-2,5-Jil, Deca-5-En-2,6-Jil, Deca-5-En-2,7-Jil, Deca-5-En-2,8-Jil, Deca-5-E n-2,9-jiil, deka-5-en-2,10-jiil, deka-5-en-3,4-jiil, deka-5-en-3,5-jiil, deka-5-en-3,6-jiil, deka-5-en-3,7-jiil, deka-5-en-3,8-jiil, deka-5-en-3,9-jiil, deka-5-en-3,10-jiil, deka-5-en-4,5-jiil, deka-5-en-4,6-jiil, deka-5-en-4,7-jiil, deka-5-en-4,8-jiil, deka-5-en-4,9-jiil, deka-5-en-4,10-jiil, deka-5-en-5,6-Jil, Deca-5-En-5, 7-Jil, Deca-5-En-5, 8-Jil, Deca-5-En-5, 9-Jil, Deca-5-En-5, 10-Jil, Deca-5-En-6, 7-Jil, Deca-5-En-6, 8-Jil, Deca-5-En-6, 9-Jil, Deca-5-En-6, 10-Jil, Deca-5-En-7, 8-Jil, Deca-5-En-7, 9-Jil, Deca-5-En-7,10-Jil, Deca-5-En-8,9-Jil, Deca-5-En-8,10-Jil, Deca-5-En-9,10-Jil, Propa-1-In-1,3-Jil, Buta-1-In-1,3-Jil, Buta-1-In-1,4-Jil, Buta-1-In-3,4-Jil, Buta-2-In-1,4-Jil, Penta-1-In-1,3-Jil, Penta-1-In-1,4-Jil, Penta-1-In-1,5-Jil, Penta-1-In-3,4-Jil, Penta-1-In-3,5-Jil, Penta-1-In-4,5-Jil Lu, Penta-2-in-1,4-jiil, Penta-2-in-1,5-jiil, Penta-2-in-4,5-jiil, Hexa-1-in-1,3-jiil, Hexa-1-in-1,4-jiil, Hexa-1-in-1,5-jiil, Hexa-1-in-1,6-jiil, Hexa-1-in-3,4-jiil, Hexa-1-in-3,5-jiil, Hexa-1-in-3,6-jiil, Hexa-1-in-4,5-jiil, Hexa-1-in-4,6-jiil, Hexa-1-in-5,6-jiil, Hexa-2-in-1,4-jiil, Hexa-2-in -1,5-ziil, hexa-2-in-1,6-ziil, hexa-2-in-4,5-ziil, hexa-2-in-4,6-ziil, hexa-2-in-5,6-ziil, hexa-3-in-1,2-ziil, hexa-3-in-1,5-ziil, hexa-3-in-1,6-ziil, hexa-3-in-2,5-ziil, hexa-3-in-2,6-ziil, hexa-3-in-5,6-ziil, hept-1-in-1,3-ziil, hept-1-in-1,4-ziil, hept-1-in-1,5-ziil, hept-1-in-1,6-ziil, Hepta-1-in-1,7-jiil, Hepta-1-in-3,4-jiil, Hepta-1-in-3,5-jiil, Hepta-1-in-3,6-jiil, Hepta-1-in-3,7-jiil, Hepta-1-in-4,5-jiil, Hepta-1-in-4,6-jiil, Hepta-1-in-4,7-jiil, Hepta-1-in-5,6-jiil, Hepta-1-in-5,7-jiil, Hepta-1-in-6,7-jiil, Hepta-2-in-1,4-jiil, Hepta-2-in-1,5-jiil, Hepta-2-in-1,6-jiil, Hepta-2-in-1,7-Jil, Hepta-2-in-4,5-Jil, Hepta-2-in-4,6-Jil, Hepta-2-in-4,7-Jil, Hepta-2-in-5,6-Jil, Hepta-2-in-5,7-Jil, Hepta-2-in-6,7-Jil, Hepta-3-in-1,2-Jil, Hepta-3-in-1,5-Jil, Hepta-3-in-1,6-Jil, Hepta-3-in-1,7-Jil, Hepta-3-in-2,5-Jil, Hepta-3-in-2,6-Jil, Hepta-3-in-2,7-Jil, Hepta-3-in-5,6-Jil, Hep Ta-3-in-5,7-jiil, Hepta-3-in-6,7-jiil, Octa-1-in-1,3-jiil, Octa-1-in-1,4-jiil, Octa-1-in-1,5-jiil, Octa-1-in-1,6-jiil, Octa-1-in-1,7-jiil, Octa-1-in-1,8-jiil, Octa-1-in-3,4-jiil, Octa-1-in-3,5-jiil, Octa-1-in-3,6-jiil, Octa-1-in-3,7-jiil, Octa-1-in-3,8-jiil, Octa-1-in-4,5-jiil, Octa-1-in-4, 6-Jill, Octa-1-in-4,7-Jill, Octa-1-in-4,8-Jill, Octa-1-in-5,6-Jill, Octa-1-in-5,7-Jill, Octa-1-in-5,8-Jill, Octa-1-in-6,7-Jill, Octa-1-in-6,8-Jill, Octa-1-in-7,8-Jill, Octa-2-in-1,4-Jill, Octa-2-in-1,5-Jill, Octa-2-in-1,6-Jill, Octa-2-in-1,7-Jill, Octa-2-in-1,8-Jill, Octa-2-in-4,5-Jill, Oct Octa-2-in-4,6-jiil, Octa-2-in-4,7-jiil, Octa-2-in-4,8-jiil, Octa-2-in-5,6-jiil, Octa-2-in-5,7-jiil, Octa-2-in-5,8-jiil, Octa-2-in-6,7-jiil, Octa-2-in-6,8-jiil, Octa-2-in-7,8-jiil, Octa-3-in-1,2-jiil, Octa-3-in-1,5-jiil, Octa-3-in-1,6-jiil, Octa-3-in-1,7-jiil, Octa-3-in-1,8-jiil, Octa-3-in-2,5-Jill, Octa-3-in-2,6-Jill, Octa-3-in-2,7-Jill, Octa-3-in-2,8-Jill, Octa-3-in-5,6-Jill, Octa-3-in-5,7-Jill, Octa-3-in-5,8-Jill, Octa-3-in-6,7-Jill, Octa-3-in-6,8-Jill, Octa-3-in-7,8-Jill, Octa-4-in-1,2-Jill, Octa-4-in-1,3-Jill, Octa-4-in-1,6-Jill, Octa-4-in-1,7-Jill, Octa-4-in-1,8-Jill, Octa-4- In-2,3-jiil, Octa-4-in-2,6-jiil, Octa-4-in-2,7-jiil, Octa-4-in-2,8-jiil, Octa-4-in-3,6-jiil, Octa-4-in-3,7-jiil, Octa-4-in-3,8-jiil, Octa-4-in-6,7-jiil, Octa-4-in-6,8-jiil, Octa-4-in-7,8-jiil, Nona-1-in-1,3-jiil, Nona-1-in-1,4-jiil, Nona-1-in-1,5-jiil, Nona-1-in-1,6-jiil, Nona-1-in-1,7-jiil, Nona-1-i n-1,8-jiil, nona-1-in-1,9-jiil, nona-1-in-3,4-jiil, nona-1-in-3,5-jiil, nona-1-in-3,6-jiil, nona-1-in-3,7-jiil, nona-1-in-3,8-jiil, nona-1-in-3,9-jiil, nona-1-in-4,5-jiil, nona-1-in-4,6-jiil, nona-1-in-4,7-jiil, nona-1-in-4,8-jiil, nona-1-in-4,9-jiil, nona-1-in-5,6-jiil, nona-1-in-5,7-jiil, nona-1-in-5,8-jiil, Non-1-in-5,9-jiil, Non-1-in-6,7-jiil, Non-1-in-6,8-jiil, Non-1-in-6,9-jiil, Non-1-in-7,8-jiil, Non-1-in-7,9-jiil, Non-1-in-8,9-jiil, Non-2-in-1,4-jiil, Non-2-in-1,5-jiil, Non-2-in-1,6-jiil, Non-2-in-1,7-jiil, Non-2-in-1,8-jiil, Non-2-in-1,9-jiil, Non-2-in-4,5-jiil, Non-2-in-4,6-jiil, Non-2-in-4,7-Jil, Non-2-In-4, 8-Jil, Non-2-In-4, 9-Jil, Non-2-In-5, 6-Jil, Non-2-In-5, 7-Jil, Non-2-In-5, 8-Jil, Non-2-In-5, 9-Jil, Non-2-In-6, 7-Jil, Non-2-In-6, 8-Jil, Non-2-In-6, 9-Jil, Non-2-In-7, 8-Jil, Non-2-In-7, 9-Jil, Non-2-In-8, 9-Jil, Non-3-In-1, 2-Jil, Non-3-In-1, 5-Jil, Non-3-In-1, 6-Jil, Non -3-in-1,7-jiil, nona-3-in-1,8-jiil, nona-3-in-1,9-jiil, nona-3-in-2,5-jiil, nona-3-in-2,6-jiil, nona-3-in-2,7-jiil, nona-3-in-2,8-jiil, nona-3-in-2,9-jiil, nona-3-in-5,6-jiil, nona-3-in-5,7-jiil, nona-3-in-5,8-jiil, nona-3-in-5,9-jiil, nona-3-in-6,7-jiil, nona-3-in-6,8-jiil, nona-3-in-6,9-jiil, nona-3-in-7, 8-Jil, Non-3-In-7,9-Jil, Non-3-In-8,9-Jil, Non-4-In-1,2-Jil, Non-4-In-1,3-Jil, Non-4-In-1,6-Jil, Non-4-In-1,7-Jil, Non-4-In-1,8-Jil, Non-4-In-1,9-Jil, Non-4-In-2,3-Jil, Non-4-In-2,6-Jil, Non-4-In-2,7-Jil, Non-4-In-2,8-Jil, Non-4-In-2,9-Jil, Non-4-In-3,6-Jil, Non-4-In-3,7-Jil, Non -4-in-3,8-jiil, nona-4-in-3,9-jiil, nona-4-in-6,7-jiil, nona-4-in-6,8-jiil, nona-4-in-6,9-jiil, nona-4-in-7,8-jiil, nona-4-in-7,9-jiil, nona-4-in-8,9-jiil, deca-1-in-1,3-jiil, deca-1-in-1,3-jiil, deca-1-in-1,4-jiil, deca-1-in-1,5-jiil, deca-1-in-1,6-jiil, deca-1-in-1,7-jiil, deca-1-in-1,8-jiil, deca-1-in-1,9-Jil, Deca-1-in-1, 10-Jil, Deca-1-in-3, 4-Jil, Deca-1-in-3, 5-Jil, Deca-1-in-3, 6-Jil, Deca-1-in-3, 7-Jil, Deca-1-in-3, 8-Jil, Deca-1-in-3, 9-Jil, Deca-1-in-3, 10-Jil, Deca-1-in-4, 5-Jil, Deca-1-in-4, 6-Jil, Deca-1-in-4, 7-Jil, Deca-1-in-4, 8-Jil, Deca-1-in-4, 9-Jil, Deca-1-in-4, 10-Jil, Deca-1-in-5, 6-Jil Deca-1-in-5,7-jiil, Deca-1-in-5,8-jiil, Deca-1-in-5,9-jiil, Deca-1-in-5,10-jiil, Deca-1-in-6,7-jiil, Deca-1-in-6,8-jiil, Deca-1-in-6,9-jiil, Deca-1-in-6,10-jiil, Deca-1-in-7,8-jiil, Deca-1-in-7,9-jiil, Deca-1-in-7,10-jiil, Deca-1-in-8,9-jiil, Deca-1-in-8,10-jiil, Deca-1-in-9,10-jiil, Deca-2-in-1,4-jiil, De Ka-2-in-1,5-jiil, Deca-2-in-1,6-jiil, Deca-2-in-1,7-jiil, Deca-2-in-1,8-jiil, Deca-2-in-1,9-jiil, Deca-2-in-1,10-jiil, Deca-2-in-4,5-jiil, Deca-2-in-4,6-jiil, Deca-2-in-4,7-jiil, Deca-2-in-4,8-jiil, Deca-2-in-4,9-jiil, Deca-2-in-4,10-jiil, Deca-2-in-5,6-jiil, Deca-2-in-5,7-jiil, Deca-2-in-5,8-jiil, Deca-2-in -5,9-jiil, Deca-2-in-5,10-jiil, Deca-2-in-6,7-jiil, Deca-2-in-6,8-jiil, Deca-2-in-6,9-jiil, Deca-2-in-6,10-jiil, Deca-2-in-7,8-jiil, Deca-2-in-7,9-jiil, Deca-2-in-7,10-jiil, Deca-2-in-8,9-jiil, Deca-2-in-8,10-jiil, Deca-2-in-9,10-jiil, Deca-3-in-1,2-jiil, Deca-3-in-1,5-jiil, Deca-3-in-1,6-jiil, Deca-3-in-1,7-Jill, Deca-3-in-1, 8-Jill, Deca-3-in-1, 9-Jill, Deca-3-in-1, 10-Jill, Deca-3-in-2, 5-Jill, Deca-3-in-2, 6-Jill, Deca-3-in-2, 7-Jill, Deca-3-in-2, 8-Jill, Deca-3-in-2, 9-Jill, Deca-3-in-2, 10-Jill, Deca-3-in-, 5,6-jiil, Deca-3-in-5,7-jiil, Deca-3-in-5,8-jiil, Deca-3-in-5,9-jiil, Deca-3-in-5,10-jiil, Deca-3-in-6,7-jiil, Deca-3-in-6,8-jiil, Deca-3-in-6,9-jiil, Deca-3-in-6,10-jiil, Deca-3-in-7,8-jiil, Deca-3-in-7,9-jiil, Deca-3-in-7,10-jiil, Deca-3-in-8,9-jiil, Deca-3-in-8,10-jiil, Deca-3-in-9,10-jiil, Deca-4-in-1,2 -Jill, Deca-4-in-1,3-Jill, Deca-4-in-1,6-Jill, Deca-4-in-1,7-Jill, Deca-4-in-1,8-Jill, Deca-4-in-1,9-Jill, Deca-4-in-1,10-Jill, Deca-4-in-2,3-Jill, Deca-4-in-2,6-Jill, Deca-4-in-2,7-Jill, Deca-4-in-2,8-Jill, Deca-4-in-2,9-Jill, Deca-4-in-2,10-Jill, Deca-4-in-3,6-Jill, Deca-4-in-3,7-Jill, Deca-4-in-3,8-Jill, De Ka-4-in-3,9-jiil, Deka-4-in-3,10-jiil, Deka-4-in-6,7-jiil, Deka-4-in-6,8-jiil, Deka-4-in-6,9-jiil, Deka-4-in-6,10-jiil, Deka-4-in-7,8-jiil, Deka-4-in-7,9-jiil, Deka-4-in-7,10-jiil, Deka-4-in-8,9-jiil, Deka-4-in-8,10-jiil, Deka-4-in-9,10-jiil, Deka-5-in-1,2-jiil, Deka-5-in-1,3-jiil, Deka-5-in-1,4-jiil, Deka-5 -In-1,7-Jill, Deca-5-In-1,8-Jill, Deca-5-In-1,9-Jill, Deca-5-In-1,10-Jill, Deca-5-In-2,3-Jill, Deca-5-In-2,4-Jill, Deca-5-In-2,7-Jill, Deca-5-In-2,8-Jill, Deca-5-In-2,9-Jill, Deca-5-In-2,10-Jill, Deca-5-In-3,4-Jill, Deca-5-In-3,7-Jill, Deca-5-In-3,8-Jill, Deca-5-In-3,9-Jill, Deca-5-In-3,10-Jill, Deca-5-In-4,These include 7-diyl, deca-5-in-4,8-diyl, deca-5-in-4,9-diyl, deca-5-in-4,10-diyl, deca-5-in-7,8-diyl, deca-5-in-7,9-diyl, deca-5-in-7,10-diyl, deca-5-in-8,9-diyl, deca-5-in-8,10-diyl, deca-5-in-9,10-diyl, etc., and the number of carbon atoms in the divalent hydrocarbon group, which may have unsaturated bonds, is preferably 2 to 6, more preferably 2 to 4.

[0039] 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 is hydrogen, L is 1,2-ethanediyl, m is 0, and R in formula (4b) or formula (4d) 5 is hydrogen, R 6 is a carbonyl group, and R 7 It is more preferable that is nitrogen and L is 1,3-propanediyl.

[0040] The organopolysiloxane compounds of the present invention are synthesized by the steps of: reacting an organometallic compound with a cyclic siloxane to produce a metal silanolate; subsequently reacting a cyclotrisiloxane or cyclotetrasiloxane with the metal silanolate to produce a compound represented by formula (5); optionally stopping the polymerization of the compound represented by formula (5) by adding water or acid to produce a compound represented by formula (5'); and further reacting a compound represented by formula (6) (a chlorosilane compound having a cycloolefin skeleton) with a compound represented by formula (5) or formula (5'). TIFF2026142546000009.tif2784 TIFF2026142546000010.tif2683 TIFF2026142546000011.tif1367 In equations (5) and (5'), R 2 R is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.3 R is an alkyl group with 4 to 10 carbon atoms, n is an integer greater than or equal to 1, and there are multiple R groups. 2 These may be the same or different. Also, M in formula (5) is a monovalent metal. In formula (6), A is a monovalent alicyclic hydrocarbon group having 4 to 60 carbon atoms and having at least one carbon-carbon double bond, and R 1 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, X is a halogen, and I is an integer from 1 to 3.

[0041] Specific examples of organometallic compounds used in the synthesis of organopolysiloxane compounds include methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, phenyllithium, or sodium phenyl. Of these, methyllithium, n-butyllithium, s-butyllithium, t-butyllithium, or phenyllithium are preferred, with n-butyllithium being particularly preferred.

[0042] 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 tetrakis(trifluoropropyl)tetramethylcyclotetrasiloxane. Of these, trimethylcyclotrisiloxane and tetramethylcyclotetrasiloxane are preferred.

[0043] When synthesizing organopolysiloxane compounds, nonpolar or low-polarity aprotic solvents are used as reaction solvents. 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. Of these, nonpolar solvents are preferred to facilitate control of reaction activity, and toluene is particularly preferred considering the solubility of the product.

[0044] When a nonpolar solvent is used as the reaction solvent in the synthesis of organopolysiloxane compounds, a highly polar aprotic solvent may be added as a reactant to accelerate 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). Of these, N,N-dimethylformamide (DMF) is preferred due to its ease of removal by washing with water.

[0045] Specific examples of cyclotrisiloxanes or cyclotetrasiloxanes to be reacted with the generated metal silanolate include trimethylcyclotrisiloxane, hexamethylcyclotrisiloxane, pentamethylvinylcyclotrisiloxane, hexaethylcyclotrisiloxane, trimethyltrivinylcyclotrisiloxane, trimethyltriphenylcyclotrisiloxane, hexaphenylcyclotrisiloxane, tris(trifluoropropyl)trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, heptamethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, or tetrakis(trifluoropropyl)tetramethylcyclotetrasiloxane. Of these, trimethylcyclotrisiloxane, hexamethylcyclotrisiloxane, trimethyltriphenylcyclotrisiloxane, hexaphenylcyclotrisiloxane, tris(trifluoropropyl)trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, or tetrakis(trifluoropropyl)tetramethylcyclotetrasiloxane are preferred, and hexamethylcyclotrisiloxane or octamethylcyclotetrasiloxane are particularly preferred.

[0046] In the compound represented by formula (5), M is not particularly limited as long as it is a monovalent metal, but specifically, lithium or sodium are examples, of which lithium is preferred.

[0047] Polymerization is stopped by adding water or an acid to the compound represented by formula (5) as needed. When an acid is used for this purpose, the acid used is not particularly limited as long as it is a Brønsted acid or an aqueous solution thereof, but specific examples of acids include formic acid, acetic acid, nitric acid, sulfuric acid, and hydrochloric acid, of which acetic acid is preferred.

[0048] In the compound represented by formula (6), the halogen X is particularly preferably chlorine.

[0049] In the step of reacting the compound represented by formula (6) with the compound represented by formula (5) or formula (5'), it is preferable to add an organic base for the purpose of capturing hydrochloric acid (HCl) produced by the reaction of chlorosilane with water or silanol. Specific examples of organic bases that can be used include trimethylamine, pyridine, diisopropylethylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, 1,8-diazabicyclo[5.4.0]undeca-7-ene (DBU), and 1,5-diazabicyclo[4.3.0]nona-5-ene (DBN). However, considering the boiling point and strength of the base, it is preferable to use triethylamine.

[0050] While commercially available compounds can be used for the compound represented by formula (6), the compound represented by formula (6) may also be synthesized by a hydrosilylation reaction between the compound represented by formula (7) and the compound represented by formula (8). TIFF2026142546000012.tif1353 TIFF2026142546000013.tif1483 In formula (7), A' is a monovalent alicyclic hydrocarbon group having 4 to 58 carbon atoms and having at least one carbon-carbon double bond, R 8 R is a hydrocarbon group having at least one unsaturated bond at its terminal end. In formula (8), R 1 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, X is a halogen, and I is an integer from 1 to 3. Examples of monovalent alicyclic hydrocarbon groups having 4 to 58 carbon atoms and a carbon-carbon double bond in A' include cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cyclododecenyl, cyclotetradecenyl, cyclohexadecenyl, cyclooctadecenyl, cycloeicocenyl, cyclodococenyl, cyclotetracocenyl, cyclohexacocenyl, cyclooctacocenyl, norborneyl, norbornadienyl, dicyclopentenyl, dicyclopentadienyl, dicyclohexenyl, dicyclohexadienyl, tricyclodecenyl, tetracyclododecenyl, and tetracyclododecadienyl. At least one hydrogen atom of these groups may be replaced by an alkyl, halogen, heteroatom, haloalkyl, or heteroatom-substituted alkyl group. The number of carbon atoms in the monovalent alicyclic hydrocarbon group having a carbon-carbon double bond is preferably 4 to 30, and more preferably 5 to 15. R 8 Examples of hydrocarbon groups having at least one unsaturated bond at their terminus include vinyl, allyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, 1-decenyl, isopropenyl, isobutenyl, and butadienyl. The number of carbon atoms in the hydrocarbon group having at least one unsaturated bond at its terminus is preferably 2 to 20, and more preferably 2 to 10.

[0051] When synthesizing the compound represented by formula (6) by a hydrosilylation reaction, a hydrosilylation catalyst is used. Platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts are commonly used as hydrosilylation catalysts. Among these, platinum-based catalysts such as Speier catalysts and Karstedt catalysts are preferred from the viewpoint of reactivity and solubility in the reaction system.

[0052] The compound represented by formula (1) can be compounded with cycloolefin monomers by ring-opening metathesis polymerization (ROMP) or addition polymerization. The compound represented by formula (1) can be used to impart organopolysiloxane-derived functions by copolymerizing it by adding it to a ROMP reaction system of cycloolefin monomers or an addition polymerization reaction system with olefin monomers or cycloolefin monomers. Addition polymerization methods include coordination polymerization and cationic polymerization.

[0053] The cycloolefin monomers that can be used in ROMP with the compound represented by formula (1) are not particularly limited, but specific examples include 2-norbornene, 5-ethylidene-2-norbornene, 5-norbornene-2-carboxylic acid, 5-norbornene-2-carbonitrile, 5-norbornene-2-methylamine, 5-norbornene-2-methanol, 3a,4,7,7a-tetrahydroindene, tetracyclododecadiene, 1,4-dihydro-1,4-methanonaphthalene, 5-norbornene-2,3-dicarboximide, dicyclopentadiene, 2,5-norbornadiene, 5-norbornene-2,3-dicarboxylic acid anhydride, tetracyclo[6.2.1.1 3,6 .0 2,7 Examples include dodeca-4-ene, 5,6-dihydrocyclopentadiene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclobutadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, cyclononadiene, and cyclodecadien.

[0054] When obtaining copolymers of the compound represented by formula (1) and cycloolefin monomers using ROMP, a metathesis polymerization catalyst is used. Hereafter, cycloolefin polymers synthesized using ROMP may be referred to as ROMP polymers.

[0055] The metathesis polymerization catalyst used in ROMP is not particularly limited, but specific examples include first-generation Grubbs catalysts, second-generation Grubbs catalysts, Hoveyda-type Grubbs catalysts, and third-generation Grubbs catalysts.

[0056] As described in Japanese Patent No. 5613981, in ROMP, a molecular weight adjusting agent may be added to the reaction system for the purpose of adjusting the molecular weight of the resulting polymer.

[0057] The molecular weight modifier used is not particularly limited, but specific examples include α-olefins such as 1-butene, 1-pentene, 1-hexene, and 1-octene, and styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether, and allyl glycidyl ether, halogen-containing vinyl compounds such as allyl chloride; oxygen-containing 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, or 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.

[0058] The cycloolefin monomers that can be used in ROMP with the compound represented by formula (1) may be one type or two or more types. Cycloolefin polymers are widely used in optical components, pharmaceutical and food packaging materials, and electronic device substrates, and can be used in appropriate combinations depending on the application.

[0059] The ratio of the compound represented by formula (1) to the cycloolefin monomer used as a raw material for the polymer (cycloolefin polymer) of the present invention is not particularly limited and can be adjusted. However, even if the total amount of the compound represented by formula (1) and the cycloolefin monomer is set to 100, a ratio of about 0.1 to 10% by weight can impart water-repellent and slippery effects.

[0060] The polymer of the present invention can be processed into films or molded articles using commonly used methods. One method for forming a film involves dissolving the polymer in a solvent, coating the solution, and then drying it to obtain a self-supporting film. One method for manufacturing molded articles is injection molding.

[0061] The solvents that can be used to dissolve the polymer of the present invention are not particularly limited, but specific examples include cyclic ether solvents such as cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), and 4-methyltetrahydropyran (MTHP); halogenated hydrocarbon solvents such as chloroform, dichloromethane, and dichlorobenzene; and glycol ether solvents such as propylene glycol-1-monomethyl ether 2-acetate (PGMEA) and propylene glycol-1-monomethyl ether (PGME). Using CPME is preferable from the viewpoint of solubility and drying speed during film formation.

[0062] In the coordination polymerization of the compound represented by formula (1), monoolefins such as ethene, propene, 1-butene, 1-pentene, 1-hexene, isobutene, 2-methyl-1-butene, and 2-methyl-1-pentene, diolefins such as 1,3-butadiene, 2-methyl-1,3-butadiene, and 1,3-pentadiene, acyclic olefin monomers such as styrene, 2-phenyl-1-propene, and vinylnaphthalene, and aromatic olefin monomers such as 2-norbornene and 5-ethylidene 2-norbornene, 5-norbornene-2-carboxylic acid, 5-norbornene-2-carbonitride, 5-norbornene-2-methylamine, 5-norbornene-2-methanol, 3a,4,7,7a-tetrahydroindene, tetracyclododecadiene, 1,4-dihydro-1,4-methanonaphthalene, 5-norbornene-2,3-dicarboximide, dicyclopentadiene, 2,5-norbornadiene, 5-norbornene-2,3-dicarboxylic acid anhydride, tetracyclo[6.2.1.1 3,6 .0 2,7It can be used as a monomer for copolymerizing cycloolefin monomers, including dodeca-4-ene, 5,6-dihydrocyclopentadiene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclobutadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, cyclononadiene, and cyclodecadiene.

[0063] 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.

[0064] In the cationic polymerization of the compound represented by formula (1), monoolefins such as ethene, propene, 1-butene, 1-pentene, 1-hexene, isobutene, 2-methyl-1-butene, and 2-methyl-1-pentene, diolefins such as 1,3-butadiene, 2-methyl-1,3-butadiene, and 1,3-pentadiene, acyclic olefin monomers represented by aromatic olefin monomers such as styrene, 2-phenyl-1-propene, and vinylnaphthalene, and ethylene oxide, propylene oxide, trimethylene oxide, 1,4-dioxane, 1,3,5-trioxane, cyclohexane oxide, styrene oxide, and epichlorohydrate are used. Ruhydrin, glycidylphenyl ether, furan, tetrahydrofuran and other cyclic ether monomers, as well as 2-norbornene, 5-ethylidene-2-norbornene, 5-norbornene-2-carboxylic acid, 5-norbornene-2-carbonitride, 5-norbornene-2-methylamine, 5-norbornene-2-methanol, 3a,4,7,7a-tetrahydroindene, tetracyclododecadiene, 1,4-dihydro-1,4-methanonaphthalene, 5-norbornene-2,3-dicarboximide, dicyclopentadiene, 2,5-norbornenadiene, 5-norbornene-2,3-dicarboxylic acid anhydride, tetracyclo[6.2.1.1 3,6 .0 2,7It can be used as a monomer for copolymerizing cycloolefin monomers, including dodeca-4-ene, 5,6-dihydrocyclopentadiene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclobutadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, cyclononadiene, and cyclodecadiene.

[0065] For the cationic polymerization of the compound represented by formula (1), any commonly used catalyst can be used as the cationic polymerization catalyst. This includes metal halides such as AlCl3, AlBr3, BCl3, BF3, TiCl4, TiBr4, FeCl3, FeCl2, SnCl2, and SnCl4, as well as protic acids such as HCl, HF, and HBr, and oxo acids such as H2SO4, H3BO3, HClO4, and CH3COOH3. [Examples]

[0066] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by these examples.

[0067] <Measuring molecular weight> The molecular weight of organopolysiloxane compounds was measured by gel permeation chromatography (GPC), and the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) was defined as the molecular weight distribution (Mw / Mn). Polydimethylsiloxane was used as a standard sample, and the molecular weight in terms of polydimethylsiloxane was measured. Furthermore, the polystyrene-equivalent molecular weight measurement by the GPC method was performed under the following measurement conditions. a) Measuring instrument: HPLC LC-2000Plus series manufactured by JASCO Corporation b) Column: Shodex KF-804L manufactured by Resonaq Corporation (formerly Showa Denko Corporation) (two connected in series) c) Oven temperature: 40°C d) Eluent: Toluene 0.7 mL / min e) Detector: RI-2031 f) Standard sample: polydimethylsiloxane g) Injection volume: 20 μL h) Concentration: 0.025 g / 10 mL i) Sample preparation: Toluene was used as the solvent, and the sample was dissolved at room temperature.

[0068] The molecular weight of the polymer obtained by ROMP was measured by gel permeation chromatography (GPC), and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was defined as the molecular weight distribution (Mw / Mn). Polystyrene was used as a standard sample, and the polystyrene-equivalent molecular weight was measured. The polystyrene-equivalent molecular weight measurement by GPC was performed under the following measurement conditions. a) Measuring instrument: HPLC LC-2000Plus series manufactured by JASCO Corporation b) Column: Shodex KF-805L manufactured by Resonac Corporation (formerly Showa Denko K.K.) and Shodex KF-804L manufactured by Resonac Corporation (formerly Showa Denko K.K.) (two columns connected in series) c) Oven temperature: 40°C d) Eluent: THF, 1.0 mL / min e) Detector: RI-2031 f) Standard sample: polystyrene g) Injection volume: 20 μL h) Concentration: 0.025 g / 10 mL i) Sample preparation: THF was used as the solvent, and the sample was dissolved at room temperature.

[0069] <Analysis of Compound> <NMR (Nuclear Magnetic Resonance Spectrum)> Using a 500 MHz NMR measurement apparatus manufactured by JEOL Ltd., 1 1H-NMR and 29 For 29Si-NMR, a measurement sample was dissolved in deuterated chloroform (manufactured by FUJIFILM Wako Pure Chemical Corporation) and measured at room temperature.

[0070] <Example 1> (Synthesis of organopolysiloxane compound (1-1) where x=1 in formula (2)) 10.07 g of hexamethylcyclotrisiloxane and 14 mL of toluene were introduced into a 100 mL four-necked flask fitted with a reflux condenser, thermometer, and septum cap, and the flask was nitrogen-sealed. The flask was placed in an oil bath maintained at 30°C and the temperature was raised. When the liquid temperature reached 30°C, 3.0 mL of n-butyllithium (1.6 M hexane solution) was introduced, and 1.25 mL of DMF was added to initiate polymerization. After reacting for 2 hours and 30 minutes, 0.46 g of triethylamine and 0.97 g of 5-norbornene-2-yl(ethyl)chlorodimethylsilane were introduced. After reacting for 18 hours, the reaction was terminated by introducing 50 mL of distilled water and 50 mL of heptane. After the reaction was complete, the reaction mixture was introduced into a separatory funnel. The aqueous layer and organic layer were separated in the separatory funnel, and the aqueous layer was discarded. Next, 50 mL of 1N hydrochloric acid was added, and the organic layer was washed. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. Next, 50 mL of saturated sodium bicarbonate aqueous solution was added, and the organic layer was washed. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. Next, 50 mL of distilled water was added, and the organic layer was washed. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. The organic layer was dried over anhydrous sodium sulfate, filtered, and transferred to a rotary evaporator, where the solvent was removed by distillation at 55°C at 1 kPa. The obtained oil (9.01 g) had GPC data: Mn=2540, Mw=2820, Mw / Mn=1.11.

[0071] Final product 1 H-NMR and 29 The chemical shifts obtained by Si-NMR measurements are shown below. 1 H-NMR: δ(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). 29 Si-NMR: δ(ppm);8.95, -5.55, -18.51, -20.33~-20.81.

[0072] From these NMR measurement results, it was confirmed that the obtained compound has the structure of formula (1-1). In formula (1-1), Me is methyl, and on average, n is 27. TIFF2026142546000014.tif27145

[0073] <Example 2> (Synthesis of organopolysiloxane compounds (1-2) where x=2 in equation (2)) 10.07 g of hexamethylcyclotrisiloxane and 14 mL of toluene were introduced into a 100 mL four-necked flask fitted with a reflux condenser, thermometer, and septum cap, and the flask was nitrogen-sealed. The flask was placed in an oil bath maintained at 30°C and the temperature was raised. When the liquid temperature reached 30°C, 3.0 mL of n-butyllithium (1.6 M hexane solution) was introduced, and 1.25 mL of DMF was added to initiate polymerization. After reacting for 2 hours and 30 minutes, 0.46 g of triethylamine and 0.53 g of 5-norbornene-2-yl(ethyl)dichloromethylsilane were introduced. After reacting for 18 hours, the reaction was terminated by introducing 50 mL of distilled water and 50 mL of heptane. After the reaction was complete, the reaction mixture was introduced into a separatory funnel. The aqueous layer and organic layer were separated in the separatory funnel, and the aqueous layer was discarded. Next, 50 mL of 1N hydrochloric acid was added, and the organic layer was washed. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. Next, 50 mL of saturated sodium bicarbonate aqueous solution was added, and the organic layer was washed. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. Next, 50 mL of distilled water was added, and the organic layer was washed. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. The organic layer was dried over anhydrous sodium sulfate, filtered, and transferred to a rotary evaporator, where the solvent was removed by distillation at 55°C at 1 kPa. The obtained oil (9.37 g) had GPC data: Mn=4340, Mw=4620, Mw / Mn=1.06.

[0074] Final product 1 H-NMR and 29 The chemical shifts obtained by Si-NMR measurements are shown below. 1H-NMR: δ(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). 29 Si-NMR: δ(ppm);9.14, 8.82, -19.02, -19.80~-20.91, -36.06.

[0075] From these NMR measurement results, it was confirmed that the obtained compound has the structure of formula (1-2). In formula (1-2), Me is methyl, and on average, n is 28. TIFF2026142546000015.tif28144

[0076] <Example 3> (Synthesis of organopolysiloxane compounds (1-3) where x=3 in equation (2)) 10.07 g of hexamethylcyclotrisiloxane and 14 mL of toluene were introduced into a 100 mL four-necked flask fitted with a reflux condenser, thermometer, and septum cap, and the flask was nitrogen-sealed. The flask was placed in an oil bath maintained at 30°C and the temperature was raised. When the liquid temperature reached 30°C, 3.0 mL of n-butyllithium (1.6 M hexane solution) was introduced, and 1.25 mL of DMF was added to initiate polymerization. After reacting for 2 hours and 30 minutes, 0.46 g of triethylamine and 0.40 g of 5-norbornene-2-yl(ethyl)trichlorosilane were introduced. After reacting for 18 hours, the reaction was terminated by introducing 50 mL of distilled water and 50 mL of heptane. After the reaction was complete, the reaction mixture was introduced into a separatory funnel. The aqueous layer and organic layer were separated in the separatory funnel, and the aqueous layer was discarded. Next, 50 mL of 1N hydrochloric acid was added, and the organic layer was washed. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. Next, 50 mL of saturated sodium bicarbonate aqueous solution was added, and the organic layer was washed. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. Next, 50 mL of distilled water was added, and the organic layer was washed. After washing, the aqueous and organic layers were separated using a separatory funnel, and the aqueous layer was discarded. The organic layer was dried over anhydrous sodium sulfate, filtered, and transferred to a rotary evaporator, where the solvent was removed by distillation at 55°C at 1 kPa. The obtained oil (9.22 g) had GPC data: Mn=5230, Mw=5980, Mw / Mn=1.14.

[0077] Final product 1 H-NMR and 29 The chemical shifts obtained by Si-NMR measurements are shown below. 1 H-NMR: δ(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). 29 Si-NMR: δ(ppm);9.12, -8.59, -19.02, -20.18~-20.60, -61.04.

[0078] From these NMR measurement results, it was confirmed that the obtained compound has the structure of formula (1-3). In formula (1-3), Me is methyl, and on average, n is 30. TIFF2026142546000016.tif30139

[0079] <Example 4> (Synthesis of ROMP polymer by reacting compound (1-1) with dicyclopentadiene) In a glove box, 1.0 g of dicyclopentadiene, 19.2 g of anhydrous cyclohexene, 10.2 mg of compound (1-1), and 4.5 mg of 1-hexene were added to a screw-top PFA container equipped with a magnetic stirrer. Next, 64.2 mg of Grubbs second-generation catalyst was added to initiate polymerization, and the mixture was stirred at room temperature for 2 hours. Ethyl vinyl ether was added to the reaction solution, and then the reaction solution was added dropwise to 200 mL of methanol to obtain a precipitate. After removing the supernatant by decantation, the precipitate was dissolved in THF, and this solution was added dropwise to 200 mL of methanol to obtain a precipitate. This procedure of removing the supernatant, dissolving in THF, and obtaining the precipitate was repeated two more times, and 0.92 g of the polymer of compound (1-1) and dicyclopentadiene was recovered.

[0080] GPC analysis of the obtained polymer revealed a number-average molecular weight (Mn) of 27,000, a weight-average molecular weight (Mw) of 48,000, and a molecular weight distribution (Mw / Mn) of 1.78.

[0081] <Example 5> (Synthesis of ROMP polymer by reacting compound (1-2) with dicyclopentadiene) In a glove box, 1.0 g of dicyclopentadiene, 19.2 g of anhydrous cyclohexene, 10.7 mg of compound (1-2), and 5.2 mg of 1-hexene were added to a screw-top PFA container equipped with a magnetic stirrer. Next, 57.6 mg of Grubbs second-generation catalyst was added to initiate polymerization, and the mixture was stirred at room temperature for 2 hours. Ethyl vinyl ether was added to the reaction solution, and then the reaction solution was added dropwise to 200 mL of methanol to obtain a precipitate. After removing the supernatant by decantation, the precipitate was dissolved in THF, and this solution was added dropwise to 200 mL of methanol to obtain a precipitate. This procedure of removing the supernatant, dissolving in THF, and obtaining the precipitate was repeated two more times, and 1.04 g of the polymer of compound (1-2) and dicyclopentadiene was recovered.

[0082] GPC analysis of the obtained polymer revealed a number-average molecular weight (Mn) of 26,000, a weight-average molecular weight (Mw) of 41,000, and a molecular weight distribution (Mw / Mn) of 1.58.

[0083] <Example 6> (Synthesis of ROMP polymers by reacting compounds (1-3) with dicyclopentadiene) In a glove box, 1.0 g of dicyclopentadiene, 19.2 g of anhydrous cyclohexene, 9.8 mg of compound (1-3), and 6.7 mg of 1-hexene were added to a screw-top PFA container equipped with a magnetic stirrer. Next, 62.3 mg of Grubbs second-generation catalyst was added to initiate polymerization, and the mixture was stirred at room temperature for 2 hours. Ethyl vinyl ether was added to the reaction solution, and then the reaction solution was added dropwise to 200 mL of methanol to obtain a precipitate. After removing the supernatant by decantation, the precipitate was dissolved in THF, and this solution was added dropwise to 200 mL of methanol to obtain a precipitate. This procedure of removing the supernatant, dissolving in THF, and obtaining the precipitate was repeated two more times, and 0.95 g of the polymer of compound (1-3) and dicyclopentadiene was recovered.

[0084] GPC analysis of the obtained polymer revealed a number-average molecular weight (Mn) of 15,000, a weight-average molecular weight (Mw) of 32,000, and a molecular weight distribution (Mw / Mn) of 2.13.

[0085] <Comparative Example 1> (Synthesis of ROMP polymers using dicyclopentadiene alone) In a glove box, 1.0 g of dicyclopentadiene, 19.2 g of anhydrous cyclohexene, and 4.3 mg of 1-hexene were added to a screw-top PFA container equipped with a magnetic stirrer. Next, 61.5 mg of Grubbs second-generation catalyst was added to initiate polymerization, and the mixture was stirred at room temperature for 2 hours. Ethyl vinyl ether was added to the reaction solution, and then the reaction solution was added dropwise to 200 mL of methanol to obtain a precipitate. After removing the supernatant by decantation, the precipitate was dissolved in THF, and this solution was added dropwise to 200 mL of methanol to obtain a precipitate. This procedure of removing the supernatant, dissolving in THF, and obtaining the precipitate was repeated two more times, and 1.09 g of the polymer of dicyclopentadiene alone was recovered.

[0086] GPC analysis of the obtained polymer revealed a number-average molecular weight (Mn) of 12,000, a weight-average molecular weight (Mw) of 23,000, and a molecular weight distribution (Mw / Mn) of 1.92.

[0087] <Contact angle measurement> Contact angle measurements were performed on the polymers obtained in Examples 4-6 and the dicyclopentadiene polymer obtained in Comparative Example 1. For the contact angle measurements, a cast film was used, obtained by dissolving each polymer in cyclopentyl methyl ether (CPME), dropping the solution onto a glass substrate, and drying it. Purified water was used as the probe solution for the contact angle measurements. A 1.5 μL droplet of purified water was formed on the tip of a syringe needle, and the needle was moved toward the sample to deposit the droplet onto the sample surface. A still image of the droplet on the sample surface was taken, and based on the captured still image, the contact angle was determined using the θ / 2 method, assuming the droplet's contour shape was a perfect circle. Ten measurements were performed on the same sample, and the average value was taken as the contact angle. A contact angle of 90° or greater was marked with ◎, 60° or greater and less than 90° with ○, and less than 60° with ×.

[0088] <Results of contact angle measurement> Table 1 shows the results of contact angle measurements for the polymers obtained in Examples 4-6 and the dicyclopentadiene polymer obtained in Comparative Example 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°.

[0089] [Table 1] TIFF2026142546000017.tif37170

[0090] The contact angle measurement results shown in Table 1 demonstrate that copolymerizing the organopolysiloxane compound obtained by the present invention with a cycloolefin monomer can improve the water repellency of the cycloolefin polymer. In particular, the polymer of Example 6, obtained by copolymerizing the organopolysiloxane compound (1-3) obtained in Example 3 with a cycloolefin monomer, showed excellent water repellency improvement, indicating that increasing the number of polysiloxane chains introduced can further improve water repellency.

[0091] <Evaluation of water sliding properties> The water sliding properties of the polymers obtained in Examples 4-6 and the dicyclopentadiene polymer obtained in Comparative Example 1 were evaluated. Cast films prepared in the same manner as for contact angle measurement were used as evaluation samples. A DropMaster 500 (manufactured by Kyowa Interface Science Co., Ltd.) was used for evaluation. Purified water was used as the probe solution. After forming a 5 μL water droplet on the tip of a syringe needle, the droplet was deposited onto the sample surface by moving the syringe needle. This operation was repeated three times to deposit a total of 15 μL of water droplets. The sample stage was then tilted at a tilt speed of 2 degrees / second, and if it was confirmed that the contact point on the receding side of the water droplet moved 1 mm, it was judged as "sliding property present." If the contact point on the advancing side of the water droplet did not move 1 mm when the tilt angle reached 90 degrees, it was judged as "sliding property absent." ○ was used to indicate sliding property present, and × to indicate absent sliding property.

[0092] <Results of water sliding performance evaluation> Table 2 shows the results of the sliding properties evaluation of the polymers obtained in Examples 4-6 and the dicyclopentadiene-only polymer obtained in Comparative Example 1. The polymers obtained in Examples 4-6 exhibited sliding properties, while the dicyclopentadiene-only polymer obtained in Comparative Example 1 did not.

[0093] [Table 2] TIFF2026142546000018.tif41170

[0094] The results of the water sliding performance evaluation shown in Table 2 demonstrate that sliding properties can be imparted to cycloolefin polymers by copolymerizing the organopolysiloxane compound obtained by the present invention with cycloolefin monomers.

[0095] <Creation of self-supporting films for optical measurements> Self-supporting optical measurement films were prepared for use in measuring total light transmittance (TT) and haze values ​​as described below. Cyclopentyl methyl ether (CPME) was used as the solvent, and polymers were added to the solvent until saturated. The clear solution obtained by filtering this saturated solution was used as the casting solution. The casting solution was applied to a 45 mm diameter aluminum cup, allowed to stand and air dry, and then peeled off the aluminum cup to obtain self-supporting optical measurement films of various polymers. The film thickness of these self-supporting films was measured at 10 points, and the average value was taken as the film thickness. Film thickness was measured using a digital length measuring instrument (DIGIMICRO, manufactured by Nikon Corporation).

[0096] <Example 7> A self-supporting film for optical measurement was prepared using the polymer described in Example 4. The thickness of the obtained self-supporting film was 13 μm.

[0097] <Example 8> A self-supporting film for optical measurement was prepared using the polymer described in Example 5. The thickness of the obtained self-supporting film was 14 μm.

[0098] <Example 9> A self-supporting film for optical measurement was prepared using the polymer described in Example 6. The thickness of the obtained self-supporting film was 14 μm.

[0099] <Comparative Example 2> A self-supporting film for optical measurement was prepared using the polymer described in Comparative Example 1. The thickness of the obtained self-supporting film was 15 μm.

[0100] <Measurement of total light transmittance (TT)> The total light transmittance (TT) of the self-supporting films made of the polymers described in Examples 7-9 and the self-supporting film made of the dicyclopentadiene polymer alone described in Comparative Example 2 was measured in accordance with JIS K7361-1. An NDH7000 (manufactured by Nippon Denshoku Industries Ltd.) was used for the measurement.

[0101] <Results of measurement of total light transmittance (TT)> The TT values ​​for the self-supporting membranes made of the polymers described in Examples 7 to 9 and the self-supporting membrane made of the dicyclopentadiene polymer alone described in Comparative Example 2 were as follows: Example 7: TT = 90%, Example 8: TT = 90%, Example 9: TT = 90%, Comparative Example 2: TT = 91%.

[0102] <Haze value measurement> The haze values ​​of the self-supporting films made from the polymers described in Examples 7-9 and the self-supporting films made from the dicyclopentadiene polymer alone described in Comparative Example 2 were measured in accordance with JIS K7136. An NDH7000 (manufactured by Nippon Denshoku Industries Ltd.) was used for the measurements.

[0103] <Haze value measurement results> The haze values ​​of the self-supporting membranes made from the polymers described in Examples 7 to 9 and the self-supporting membrane made from the dicyclopentadiene polymer alone described in Comparative Example 2 were as follows: Example 7: haze value = 16%, Example 8: haze value = 20%, Example 9: haze value = 16%, Comparative Example 2: haze value = 18%.

[0104] <Measurement results of self-supporting films for optical measurement> Table 3 shows the measurement results for film thickness, TT, and haze value of the self-supporting films made of the polymers described in Examples 7 to 9 and the self-supporting films made of the dicyclopentadiene polymer alone described in Comparative Example 2. [Table 3] TIFF2026142546000019.tif37170

[0105] The results of optical measurements of the self-supporting films shown in Table 3 demonstrate that copolymerizing the organopolysiloxane compound obtained by the present invention with a cycloolefin monomer can modify surface properties such as improving water repellency and imparting slipperiness without significantly impairing the optical properties of the cycloolefin polymer. [Industrial applicability]

[0106] The organopolysiloxane compounds obtained by this invention showed the effect of enhancing the water repellency of cycloolefin polymers when copolymerized with cycloolefin monomers. Therefore, they are expected to be used as additives to improve the water repellency and antifouling properties of cycloolefin polymers.

Claims

1. An organopolysiloxane compound represented by formula (1). In formula (1), A is a monovalent alicyclic hydrocarbon group having 4 to 60 carbon atoms and having at least one carbon-carbon double bond, and T is a group represented by formula (2). In formula (2), R １ and R ２ R is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. ３ R is an alkyl group having 4 to 10 carbon atoms, x is an integer from 1 to 3, n is an integer greater than or equal to 1, and in the formula, １ or R ３ If there are multiple R's, they may be the same or different, and there are multiple R's. ２ They may be the same or different.

2. The organopolysiloxane compound according to claim 1, wherein A in formula (1) is a group represented by formula (3). In formula (3), Y is a trivalent group consisting of a hydrocarbon group having 2 to 36 carbon atoms, a substituted hydrocarbon group having 3 to 58 carbon atoms, a heteroatom-containing hydrocarbon group having 2 to 36 carbon atoms, or a substituted heteroatom-containing hydrocarbon group having 2 to 58 carbon atoms, and these trivalent groups may have at least one cyclic structure, and these trivalent groups may have an unsaturated bond.

3. The organopolysiloxane compound according to claim 1, wherein A in formula (1) is a group represented by formula (4a), formula (4b), formula (4c), or formula (4d). In formulas (4a) to (4d), R ５ each independently represent hydrogen or a monovalent hydrocarbon group having 1 to 4 carbon atoms which may have an unsaturated bond, and R ６ each independently represent a divalent group selected from the group consisting of a hydrocarbon group having 1 to 4 carbon atoms, a substituted hydrocarbon group having 3 to 20 carbon atoms, a heteroatom-containing hydrocarbon group having 1 to 4 carbon atoms, and a substituted heteroatom-containing hydrocarbon group having 1 to 20 carbon atoms, and said divalent groups may have an unsaturated bond, and R ７ represents methine (CH) or a trivalent heteroatom, L represents a divalent hydrocarbon group having 2 to 10 carbon atoms which may have an unsaturated bond, Z represents methylene or 1,2-ethanediyl, and m is an integer of 0 to 3.

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

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

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

7. The polymer according to claim 6, obtained by polymerization in the presence of a metathesis polymerization catalyst.

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

9. A molded article comprising the polymer described in claim 6.

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