Diol compound having a norbornane skeleton and a cyclohexadione skeleton and method for producing the same

Abstract

To provide a novel compound that is a diol compound that is easily produced by using an easily acquirable compound as a raw material, is very useful as a synthetic intermediate of various compounds, and becomes a raw material of various polymers.SOLUTION: A diol compound represented by formula (1) is provided. [In formula (1), at least one hydrogen in the norbornane skeleton may be independently substituted by at least one substituent selected from the group consisting of a halogen, a sulfur-containing monovalent group, an oxygen-containing monovalent group, a nitrogen-containing monovalent group, an alkyl having 1 to 20 carbon atoms, an alkenyl having 1 to 20 carbon atoms, an alkynyl having 1 to 20 carbon atoms, an alkoxy having 1 to 20 carbon atoms, a saturated or unsaturated cyclic hydrocarbon group having 3 to 20 carbon atoms, a saturated or unsaturated heterocyclic hydrocarbon group having 3 to 20 carbon atoms, and a group obtained by substituting at least one hydrogen atom in these groups by a halogen, and at least one carbon may independently be substituted by a heteroatom.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a diol compound useful as a paint additive, adhesive or resin raw material, and a method for producing the same, and more particularly to a novel diol compound having a norbornane skeleton and a cyclohexadione skeleton in the molecule, and a method for producing the same. [Background technology]

[0002] Alcohol compounds having a norbornane skeleton and an aliphatic cyclic skeleton are known to have excellent characteristics when used as adhesives or resin raw materials (Patent Documents 1 and 2).

[0003] However, the only derivatives reported for 1,4:5,8-dimethano-1,4,4a,5,8,8a,9a,10a-octahydroanthracene-9,10-dione (Non-Patent Document 1), which is obtained by adding cyclopentadiene to benzoquinone, are tetracarboxylic acids and tetracarboxylic anhydrides (Patent Document 3), or compounds in which the ketone moiety is converted to alcohols or ethers (Patent Documents 4 and 5, Non-Patent Documents 2 to 6). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2017-047555 [Patent Document 2] Japanese Patent Application Publication No. 5-125329 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-184898 [Patent Document 4] International Publication No. 2017-209197 [Patent Document 5] International Publication No. 2017-209199 [Non-patent literature]

[0005] [Non-Patent Document 1] Organic synthesis, 2005, 82, 1. [Non-patent document 2] J. Org. Chem. 1991, 56, 5253. [Non-patent document 3] J. Org. Chem. 1995, 60, 4399. [Non-patent document 4] Tetrahedron, 1997, Vol.53, 11257. [Non-Patent Document 5] Beilstein J. Org. Chem. 2015, 11, 2159. [Non-patent document 6] Eur. J. Org. Chem. 2017, 6793. Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention provides a novel diol compound having a norbornane skeleton and a cyclohexadione skeleton. [Means for solving the problem]

[0007] As a result of extensive investigations, the present inventors have found that a diol can be efficiently produced from a tricyclic compound by using a hydrogenation reaction, and have thus completed the present invention.

[0008] [1] A diol compound represented by formula (1): TIFF0007823429000001.tif3387 [In formula (1), at least one hydrogen atom in the norbornane skeleton may be independently replaced with one substituent selected from the group consisting of a halogen atom, a monovalent group containing sulfur, a monovalent group containing oxygen, a monovalent group containing nitrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a saturated or unsaturated cyclic hydrocarbon group having 3 to 20 carbon atoms, a saturated or unsaturated heterocyclic group having 3 to 20 carbon atoms, and a group in which at least one hydrogen atom in any of these groups has been replaced with a halogen atom, and at least one carbon atom may be independently replaced with a heteroatom.]

[0009] [2] A method for producing the diol compound according to item [1] by a hydrogenation reaction.

[0010] [3] A method for producing a diol compound according to item [2], comprising a step of hydrogenating 9,10-dioxotetradecahydro-1,4:5,8-dimethanoanthracene-2,6-dicarbaldehyde or 9,10-dioxotetradecahydro-1,4:5,8-dimethanoanthracene-2,7-dicarbaldehyde represented by formula (2). TIFF0007823429000002.tif3784 [In formula (2), at least one hydrogen atom in the norbornane skeleton may be independently replaced with one substituent selected from the group consisting of a halogen atom, a monovalent group containing sulfur, a monovalent group containing oxygen, a monovalent group containing nitrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a saturated or unsaturated cyclic hydrocarbon group having 3 to 20 carbon atoms, a saturated or unsaturated heterocyclic group having 3 to 20 carbon atoms, and a group in which at least one hydrogen atom in any of these groups has been replaced with a halogen atom, and at least one carbon atom in the norbornane skeleton may be independently replaced with a heteroatom.]

[0011] [4] A method for producing a diol compound according to item [2], comprising the step of converting a diolefin compound represented by formula (3) into a dialdehyde compound by an oxo reaction, and subsequently hydrogenating the resulting reaction product without isolating it. TIFF0007823429000003.tif3457 [In formula (3), at least one hydrogen atom in the norbornene skeleton may be independently replaced with one substituent selected from the group consisting of a halogen atom, a monovalent group containing sulfur, a monovalent group containing oxygen, a monovalent group containing nitrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a saturated or unsaturated cyclic hydrocarbon group having 3 to 20 carbon atoms, a saturated or unsaturated heterocyclic group having 3 to 20 carbon atoms, and a group in which at least one hydrogen atom in any of these groups has been replaced with a halogen atom, and at least one carbon atom in the norbornane skeleton may be independently replaced with a heteroatom.]

[0012] [5] A method for producing a diol compound according to item [3] or [4], using a nickel catalyst, palladium catalyst, iron catalyst, copper catalyst, rhodium catalyst, ruthenium catalyst, platinum catalyst, cobalt catalyst, or manganese catalyst under an atmosphere containing hydrogen gas.

[0013] [6] A method for producing a diol compound according to item [3] or [4], wherein a boron hydride reagent, an aluminum hydride reagent, or a lithium hydride reagent is used as a hydrogenation reagent.

[0014] [7] The diol compound according to item [1], which is a cis isomer represented by formula (4), a trans isomer represented by formula (5), or an isomer mixture in which the mixing ratio of the cis isomer represented by formula (4) to the trans isomer represented by formula (5) is 0.001:100 to 100:0.001. TIFF0007823429000004.tif3483 TIFF0007823429000005.tif3384

[0015] [8] A polymer obtained by polymerization using the diol compound according to item [1].

[0016] [9] A polyester resin obtained by polymerization using the diol compound according to item [1].

[0017]

[10] A polycarbonate resin obtained by polymerization using the diol compound according to item [1].

[0018]

[11] A compound represented by formula (6): TIFF0007823429000006.tif65164 In the formula, when there are a plurality of the same symbols, they may have the same structure or each may independently have a different structure. P is independently any of the polymerizable groups of formula (P1), (P2), (P3), or (P4); R d is hydrogen, halogen, methyl, ethyl or trifluoromethyl.

[0019]

[12] In equation (P1), (P2) or (P4), R d The compound according to item

[11] , wherein is hydrogen.

[0020]

[13] In the formula (6) described in item

[11] , P has at least one structural unit represented by group (PM1), (PM2), (PM3), or (PM4), and a polymer obtained from the compound described in item

[11] or

[12] . In the formula TIFF0007823429000007.tif46139, when there are multiple identical symbols, they may have the same structure or each may independently have a different structure. d is hydrogen, halogen, methyl, ethyl or trifluoromethyl. [Effects of the Invention]

[0021] According to the present invention, it is possible to provide a novel diol compound having a norbornane skeleton and a cyclohexadione skeleton by an industrially simple, convenient and economically excellent method. [Brief explanation of the drawings]

[0022] [Figure 1] 1 shows the results of 1H-NMR measurement of the mixture of compound (4) and compound (5) obtained in Example 1. [Figure 2]1 shows the results of 13C-NMR measurement of the mixture of compound (4) and compound (5) obtained in Example 1. [Figure 3] 1 is a GC chart of GC / MASS measurement of a mixture of compound (4) and compound (5) obtained in Example 1. [Figure 4] 1 is a MASS chart of GC / MASS measurement of a mixture of compound (4) and compound (5) obtained in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0023] <Compound> The diol compound of the present invention is represented by formula (1). Hereinafter, the compound of the present invention represented by formula (1) will also be referred to as "compound (1)." In this specification, compounds represented by other formulas may also be expressed in the same manner. TIFF0007823429000008.tif3387 [In formula (1), at least one hydrogen atom in the norbornane skeleton may be independently replaced with one substituent selected from the group consisting of a halogen atom, a monovalent group containing sulfur, a monovalent group containing oxygen, a monovalent group containing nitrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a saturated or unsaturated cyclic hydrocarbon group having 3 to 20 carbon atoms, a saturated or unsaturated heterocyclic group having 3 to 20 carbon atoms, and a group in which at least one hydrogen atom in any of these groups has been replaced with a halogen atom, and at least one carbon atom in the norbornane skeleton may be independently replaced with a heteroatom.]

[0024] The diol compound having a norbornane skeleton and a cyclohexadione skeleton represented by compound (1) exhibits excellent characteristics when used as an adhesive or resin raw material, and can also be widely used as a reaction intermediate.

[0025] The diol compound represented by compound (1) exists as a cis isomer represented by formula (4) or a trans isomer represented by formula (5) depending on the position of methanol addition, and may be either a single positional isomer or a mixture of these positional isomers. In the case of a mixture, the mixture is an isomer mixture in which the mixing ratio of the cis isomer of compound (4) to the trans isomer of compound (5) is 0.001:100 to 100:0.001. TIFF0007823429000009.tif3585 TIFF0007823429000010.tif3384

[0026] <Manufacturing method> The diol compound represented by compound (1) can be produced by hydrogenating 9,10-dioxotetradecahydro-1,4:5,8-dimethanoanthracene-2,6-dicarbaldehyde or 9,10-dioxotetradecahydro-1,4:5,8-dimethanoanthracene-2,7-dicarbaldehyde represented by formula (2). TIFF0007823429000011.tif3784 [In formula (2), at least one hydrogen atom in the norbornane skeleton may be independently replaced with one substituent selected from the group consisting of a halogen atom, a monovalent group containing sulfur, a monovalent group containing oxygen, a monovalent group containing nitrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a saturated or unsaturated cyclic hydrocarbon group having 3 to 20 carbon atoms, a saturated or unsaturated heterocyclic group having 3 to 20 carbon atoms, and a group in which at least one hydrogen atom in any of these groups has been replaced with a halogen atom, and at least one carbon atom in the norbornane skeleton may be independently replaced with a heteroatom.]

[0027] The catalyst used in the hydrogenation reaction of this embodiment is a metal catalyst that can hydrogenate compound (2) in an atmosphere containing hydrogen gas, and compound (1) can be easily produced by reacting compound (2) using an additive and a solvent.

[0028] The metal catalyst used in the hydrogenation reaction of this embodiment is not particularly limited, but is preferably nickel, palladium, iron, copper, rhodium, ruthenium, platinum, cobalt, or manganese, and more preferably nickel, palladium, lithium, or rhodium.

[0029] The nickel catalyst used in the hydrogenation reaction of this embodiment is not particularly limited, but sponge nickel is particularly preferred. The palladium catalyst used in the hydrogenation reaction of this embodiment is not particularly limited, but is particularly preferably palladium supported on carbon or palladium supported on alumina.

[0030] The catalyst used in the hydrogenation reaction of this embodiment is preferably used in an amount of 0.01 to 100 mol % relative to compound (2).

[0031] In order to efficiently proceed with the hydrogenation reaction of this embodiment, the reaction temperature is preferably between room temperature and 200° C., and particularly preferably between room temperature and 120° C. Furthermore, hydrocarbons, alcohols, esters, and halogenated hydrocarbons can be used as the solvent, and in order to efficiently proceed with the reaction, alcohols or toluene are preferred.

[0032] In the hydrogenation reaction of this embodiment, when a hydrogenation reagent is used, a boron hydride reagent, an aluminum hydride reagent, or a lithium hydride reagent is preferred.

[0033] As the reaction system for the hydrogenation reaction of this embodiment, various reaction systems can be used, such as a batch system using a tank reactor or the like, a semi-batch system, or a continuous flow system in which the reaction mixture flows through a column reactor.

[0034] As a reaction method for the hydrogenation reaction of this embodiment, it is also possible to carry out the hydrogenation reaction without isolating and purifying the compound (2) obtained by the oxo reaction of the compound (3). TIFF0007823429000012.tif3862

[0035] <Polymer> The present invention encompasses polymers obtained by polymerization using a diol compound represented by formula (1). Specific examples of such polymers include various polymers such as epoxy resins obtained by copolymerization of a diol compound represented by formula (1) with an epoxy compound such as epichlorohydrin, polyester resins obtained by polycondensation with a dicarboxylic acid such as terephthalic acid, and polycarbonates obtained by polycondensation with phosgene or transesterification with diphenyl carbonate.

[0036] (polyester) The polyester obtained by polymerization using the diol compound represented by formula (1) of the present invention is not particularly limited, but is preferably a polyester composed of terephthalic acid or its ester-forming derivative as a dicarboxylic acid and the diol compound represented by formula (1).

[0037] In addition to terephthalic acid, the dicarboxylic acid may be, for example, an aromatic dicarboxylic acid such as isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, or diphenoxyethanedicarboxylic acid; an aliphatic carboxylic acid such as dodecanedioic acid, adipic acid, sebacic acid, azelaic acid, or decanedicarboxylic acid; an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid; or a hydroxycarboxylic acid such as hydroxybenzoic acid, glycolic acid, or hydroxyethoxybenzoic acid. Commercially available polyesters may also be used.

[0038] The dicarboxylic acids including terephthalic acid may be derived from fossil fuels, or may be derived from plants and obtained through fermentation, etc. Terephthalic acid is known as a plant-derived raw material.

[0039] The polyester resin composition of the present invention may be produced by either a continuous method or a batch method.

[0040] In the method for producing the polyester resin composition of the present invention, the transesterification step, the esterification step, and the polycondensation step may be carried out by conventionally known methods.

[0041] In polycondensation, a polycondensation catalyst is usually used to increase reactivity. Known catalysts for the polycondensation reaction include those containing antimony, germanium, titanium, and aluminum.

[0042] (Polycarbonate) Polycarbonates are polymers that may be linear or branched and contain a carbonyl group and monomer units derived from the diol compound represented by formula (1). Polycarbonates are generally produced by the polymerization reaction of a dihydroxy compound with carbonyl chloride (phosgene), a carbonic acid diester (e.g., dimethyl carbonate, diphenyl carbonate), or carbon monoxide or carbon dioxide.

[0043] The polycarbonate derived from the diol compound represented by formula (1) can be synthesized by a conventional method such as interfacial polymerization, pyridine method, transesterification method, etc. Commercially available polycarbonates can also be used. (Compound represented by formula (6))

[0044] The polymerization moieties represented by formulae (P1) to (P4) can be introduced using known organic synthetic chemistry techniques, see, for example, Japanese Patent Application Nos. 2001-378508, 2002-115270, 2002-335266, and 2002-300068, respectively.

[0045] (Polymer obtained by polymerizing the compound represented by formula (6)) The polymer of the present invention is obtained by polymerizing a polymerizable composition containing at least one compound (6), optionally adding a catalyst or solvent. The copolymer may be a random copolymer, an alternating copolymer, a block copolymer, a graft copolymer, or the like. The repeating unit structure may be isotactic, syndiotactic, or atactic.

[0046] Various polymerization reaction methods can be used to obtain the polymer of the present invention from compound (6). Usable polymerization reaction methods include free radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization. To produce the polymer of the present invention, it is preferable to select a polymerization method suitable for the intended use.

[0047] Examples of initiators for photoradical polymerization include 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocure 1173), 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Irgacure 651), Irgacure 500 (trade name), Irgacure 2959 (trade name), Irgacure 907 (trade name), Irgacure 369 (trade name), Irgacure 1300 (trade name), Irgacure 819 (trade name), Irgacure 1700 (trade name), and Irgacure 1800. (trade name), Irgacure 1850 (trade name), Darocur 4265 (trade name), Irgacure 784 (trade name), p-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(p-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzyl dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate mixture, etc.

[0048] A photocationic polymerization initiator may be added to the composition of the present invention. Examples of photocationic polymerization initiators include diaryliodonium salts (hereinafter abbreviated as DAS) and triarylsulfonium salts (hereinafter abbreviated as TAS). Examples of DAS include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium tetra(pentafluorophenyl)borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, and 4-methoxyphenylphenyliodonium tetrafluoroborate. phenylphenyliodonium-p-toluenesulfonate, 4-methoxyphenylphenyliodonium diphenyliodonium tetra(pentafluorophenyl)borate, bis(4-tert-butylphenyl)iodonium diphenyliodonium tetrafluoroborate, bis(4-tert-butylphenyl)iodonium diphenyliodonium hexafluoroarsenate, bis(4-tert-butylphenyl)iodonium diphenyliodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium trifluoroacetate, bis(4-tert-butylphenyl)iodonium p-toluenesulfonate, bis(4-tert-butylphenyl)iodonium diphenyliodonium tetra(pentafluorophenyl)borate, and the like.

[0049] The sensitivity of DAS can be increased by adding a photosensitizer such as thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene, or rubrene.

[0050] TAS includes triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfonium tetra(pentafluorophenyl)borate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, and 4-methoxyphenyldiphenylsulfonium tetrafluoroborate. Examples of the sulfonium fluoride include phenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium triphenylsulfonium tetra(pentafluorophenyl)borate, 4-phenylthiophenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroarsenate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium-p-toluenesulfonate, and 4-phenylthiophenyldiphenylsulfonium tetra(pentafluorophenyl)borate.

[0051] Specific trade names of photocationic polymerization initiators include UCC's Cyracure UVI-6990, Cyracure UVI-6974, and Cyracure UVI-6992, Asahi Denka Kogyo Co., Ltd.'s Adeka Optomer SP-150, SP-152, SP-170, and SP-172, Rhodia Co., Ltd.'s PHOTOINITIATOR 2074, Chiba Specialty Chemicals Co., Ltd.'s Irgacure 250, GE Silicones' UV-9380C, San-Apro Co., Ltd.'s HS series and CPI series, as well as Midori Chemical Co., Ltd.'s TPS series, TAZ series, DPI series, BPI series, MDS series, DTS series, SI series, PI series, NDI series, PAI series, NAI series, NI series, DAM series, MBZ series, PYR series, DNB series, NB series, and the like.

[0052] The composition of the present invention can be combined with a cationic photoinitiator and a radical photoinitiator can be added to achieve hybrid curing. Examples of radical photoinitiators include Darocure 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one), Irgacure 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure 651 (2,2-dimethoxy-1,2-diphenylethan-1-one), Irgacure 500, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 1300, Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850, Darocure 4265, and Irgacure 784, all of which are manufactured by Chiba Specialty Chemicals.

[0053] Other examples of the photoradical polymerization initiator include p-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(p-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzil dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate mixture, and benzophenone / methyltriethanolamine mixture.

[0054] In the present invention, a thermal polymerization initiator may be added. Specific examples of product names include San-Aid (main agent) SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-160, SI-180, and San-Aid (auxiliary agent) SI, manufactured by Sanshin Chemical Industry Co., Ltd. These may be used together with a photoradical initiator and a photocationic polymerization initiator, or may be used together with a photoradical initiator.

[0055] The polymerizable compound of the present invention may contain a heat curing agent. Examples of the heat curing agent include acidic or basic compounds having an amino group, a carboxyl group, a mercapto group, etc., compounds having a phenol moiety, and compounds having an acid anhydride moiety. Basic compounds having an amino group, compounds having a phenol, and compounds having an acid anhydride moiety are more preferred. These may be used together with a photocationic polymerization initiator or a photoradical initiator.

[0056] Examples of the thermal curing agent having an amino group include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, laromine, diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylsulfone, polyoxypropylenediamine, polyoxypropylenetriamine, polycyclohexylpolyamine mixtures, and N-aminoethylpiperazine.

[0057] Examples of the phenolic hardener are phenol novolac, xylylene novolac, bisphenol A novolac, triphenylmethane novolac, biphenyl novolac, dicyclopentadiene phenol novolac, and terpene phenol novolac.

[0058] Examples of the heat curing agent having an acid anhydride include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenetetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, ethylene glycol bisanhydrotrimellitate, glycerin bis(anhydrotrimellitate) monoacetate, dodecenyl succinic anhydride, aliphatic dibasic acid polyanhydrides, and chlorendic anhydride.

[0059] The compound of formula (6) can be produced from the compound of formula (1) of the present invention as a starting material. Because the compound of formula (6) has polymerizable moieties at both ends, it is easy to prepare a polymer with a high degree of polymerization and a high molecular weight. In a composition of a compound of formula (6) and a compound other than formula (6), if the compound other than formula (1) contains a large proportion of compounds with one polymerizable moiety, the resulting polymer has a low molecular weight, a low glass transition point and melting point, and excellent processability. For applications requiring such properties, a weight-average molecular weight range of 500 to 500,000 is preferred. If the compound other than formula (1) is polyfunctional, the resulting polymer has a high molecular weight and excellent chemical and heat resistance. For applications requiring such properties, a weight-average molecular weight range of 500,000 or more is preferred. When the composition of the present invention is applied to a substrate and polymerized to fix the molecular orientation and obtain optical anisotropy, no further processing is required, so the molecular weight is not an issue. It is sufficient to satisfy the conditions of the usage environment.

[0060] To further increase the molecular weight, a crosslinking agent can be added. This makes it possible to obtain a polymer with infinite molecular weight and excellent chemical and heat resistance. Any crosslinking agent known to those skilled in the art can be used.

[0061] The compounds and compositions of the present invention have high polymerizability. A stabilizer may be added to facilitate handling. Any stabilizer known to those skilled in the art may be used, including, for example, hydroquinone, 4-ethoxyphenol, and 3,5-di-t-butyl-4-hydroxytoluene (BHT).

[0062] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples.

[0063] [ 1 H-NMR analysis] The compounds obtained in the examples were dissolved in DMSO-d6 or CDCl3, and the 1H-NMR analysis was performed at room temperature using a nuclear magnetic resonance spectrometer (Agilent Technologies, Inc.) Tetramethylsilane (TMS) was used as the zero-point reference substance for the δ value.

[0064] [ 13 C-NMR analysis] The compounds obtained in the examples were dissolved in DMSO-d6, and the 13 C-NMR analysis was performed at room temperature using a nuclear magnetic resonance spectrometer (Agilent Technologies, Inc.). Tetramethylsilane (TMS) was used as the zero-point reference substance for the δ value.

[0065] [GC-MS analysis] The compounds obtained in the examples were dissolved in chloroform and measured using a gas chromatograph mass spectrometer (GC / MS-TQ8040 manufactured by Shimadzu Corporation).

[0066] <Weight average molecular weight (Mw) and number average molecular weight (Mn)> The weight-average molecular weight (Mw), number-average molecular weight (Mn), and partial acidity (Mw / Mn) were analyzed by gel permeation chromatography (GPC) using polystyrene equivalents. A polystyrene standard sample was used as the standard. 2 mg of the sample was dissolved in 2 mL of eluent, and the resulting solution was used as the analytical sample. A Shimadzu LC-9A gel permeation chromatograph manufactured by Shimadzu Corporation and a Shodex GF-7M HQ column manufactured by Showa Denko (DMF used as the developing solvent) were used. [Example]

[0067] Synthesis of compound (4), compound (5), or a mixture thereof from 9,10-dioxotetradecahydro-1,4:5,8-dimethanoanthracene-2,7-dicarbaldehyde, 9,10-dioxotetradecahydro-1,4:5,8-dimethanoanthracene-2,6-dicarbaldehyde, or a mixture thereof (compound (2)) TIFF0007823429000013.tif31167

[0068] A mixture of 9,10-dioxotetradecahydro-1,4:5,8-dimethanoanthracene-2,7-dicarboxaldehyde and 9,10-dioxotetradecahydro-1,4:5,8-dimethanoanthracene-2,6-dicarboxaldehyde (compound (2)) (37.5 g), sponge nickel (0.50 g), and 2-ethylhexanol (150 mL) as a solvent were added to a 500 mL autoclave (manufactured by Nitto Koatsu Corporation). The autoclave was equipped with a nitrogen line, a hydrogen gas line, a pressure gauge, a mantle heater, and a thermometer. After the system was purged with nitrogen three times, the system was pressurized to 2.6 MPa with hydrogen gas and reacted at 120 °C for 4 hours. After the reaction was completed, the system was cooled to room temperature, the pressure was reduced to atmospheric pressure, and the reaction liquid was recovered. After filtering off the catalyst, the recovered reaction solution was concentrated under reduced pressure using an evaporator, and the resulting solid was recrystallized. The resulting crystals were then dried under reduced pressure to obtain 20 g (yield 53%) of a mixture of compound (4) and compound (5). [Example]

[0069] Synthesis of Compound (4) or Compound (5) from 1,4:5,8-dimethano-1,4,4a,5,8,8a,9a,10a-octahydroanthracene-9,10-dione (Compound (3)) TIFF0007823429000014.tif35169

[0070] 1,4:5,8-Dimethano-1,4,4a,5,8,8a,9a,10a-octahydroanthracene-9,10-dione (compound (3)) (30 g), triphenylphosphine (0.32 g), [Rh(acac)(CO)] (64 mg), and dichloromethane (120 mL) were added to a 500 mL autoclave (manufactured by Nitto Koatsu Co., Ltd.). The autoclave was equipped with a nitrogen line, an oxo gas (CO / H) line, a pressure gauge, a mantle heater, and a thermometer. After the system was purged with nitrogen three times, the system was pressurized to 2 MPa with oxo gas and reacted at 80 °C for 3 hours. After the reaction was completed, the system was cooled to room temperature and then depressurized to atmospheric pressure. Sponge nickel (0.5 g) was added, and the system was pressurized to 2.6 MPa with hydrogen gas and reacted at 120 °C for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, and the pressure was reduced to atmospheric pressure to recover the reaction solution. The recovered reaction solution was concentrated under reduced pressure using an evaporator, and the resulting solid was recrystallized. The crystals were dried under reduced pressure to obtain 18.8 g (yield 50%) of a mixture of compound (4) and compound (5).

[0071] The mixture of the obtained compound (4) and compound (5) 1 The H-NMR values ​​are as follows: 1 H―NMR (DMSO-d6) δ = 0.94(d,J=13.1Hz,2H), 1.24(d,J=9.7Hz,2H), 1.30-1.34(m,2H), 1.38(d,J=9.9Hz,2H), 1.50-1.58(m,2H), 2.62(dd,J=3.7, 17.0Hz,4H), 2.83(dq,J=4.2, 13.2Hz,4H), 3.03 - 3.13(m,4H), 4.50(t,J=5.4,2H).

[0072] The mixture of the obtained compound (4) and compound (5) 13 The C-NMR values ​​are as follows: 13 C―NMR(DMSO-d6) δ = 29.10, 35.00, 39.36, 42.82, 45.10, 52.56, 52.94, 64.40, 213.57. [Example]

[0073] Synthesis of 1,4:5,8-dimethano-1,4,4a,5,8,8a,9a,10a-octahydroanthracene-9,10-dione diacrylate (compound (8)) TIFF0007823429000015.tif34168

[0074] A mixture of compound (7) (3.35 g), acrylic acid (2.10 g), 4-dimethylaminopyridine (3.37 g), and THF (70 mL) was cooled in an ice bath. 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide (7.73 g) was added and stirred overnight. Distilled water was added, and the reaction mixture was extracted twice with methylene chloride. The organic layers were combined, washed with 2 M hydrochloric acid and saturated aqueous sodium bicarbonate, and dried over anhydrous sodium sulfate. The solvent was evaporated, and the residue was purified by column chromatography (silica gel) to obtain 3.52 g (75.3% yield) of the desired product.

[0075] The obtained compound (8) 1 The H-NMR values ​​are as follows: 1 H―NMR (CDCl3;δ ppm) δ = 0.94(d,J=13.1Hz,2H), 1.24(d,J=9.7Hz,2H), 1.30-1.34(m,2H), 1.38(d,J=9.9Hz,2H), 1.50-1.58(m,2H), 2.62(dd,J=3.7, 17.0Hz,4H), 2.83(dq,J=4.2, 13.2Hz,4H), 3.03 - 3.13(m,4H), 4.50(t,J=5.4,2H),5.83(dd,2H),6.13(dd,2H),6.41(dd,2H). [Example]

[0076] Compound (8) (10 mg) prepared in Example 3, azobiscyclohexanecarbonitrile (0.1 mg), and benzene (100 μL) were placed in a glass ampoule. The ampoule was cooled to −60°C, thoroughly degassed using a vacuum pump, and then sealed. The ampoule was heated at 110°C for 24 hours. The resulting reaction mixture was reprecipitated three times from methanol (15 mL) to obtain a polymer (7.5 mg). The weight-average molecular weight (Mw) measured by GPC was 31,000. The polydispersity (Mw / Mn) was 2.11.

[0077] Compound (6) is synthesized according to the aforementioned synthesis literature and synthesis examples. Examples of such compounds are as follows: TIFF0007823429000016.tif235167

[0078] TIFF0007823429000017.tif243165

[0079] TIFF0007823429000018.tif238160

[0080] TIFF0007823429000019.tif239164 [Industrial Applicability]

[0081] The compound of the present invention has hydroxyl groups at both ends and is very useful as a synthetic intermediate for various compounds. By using a novel diol that serves as a raw material for various polymers, it is possible to provide polymers with excellent heat resistance and transparency. Furthermore, the production method of the present invention uses easily available compounds as raw materials, allowing the corresponding diol to be easily produced, making it industrially useful.

Claims

1. A compound according to formula (1). [In formula (1), at least one hydrogen atom in the norbornane skeleton may be independently replaced with one kind of substituent selected from the group consisting of halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 1 to 20 carbon atoms, alkynyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, saturated or unsaturated cyclic hydrocarbon group having 3 to 20 carbon atoms, saturated or unsaturated heterocyclic group having 3 to 20 carbon atoms, and groups in which at least one hydrogen atom in these groups is replaced with halogen.] In addition, when there are a plurality of the same symbols in the formula, they may have the same structure or each may independently have a different structure. P is independently any of the polymerizable groups of formula (P1), (P2), (P3) or (P4); R d is hydrogen, halogen, methyl, ethyl or trifluoromethyl.

2. In formula (P1), (P2) or (P4), R d The compound of claim 1, wherein is hydrogen.

3. A polymer obtained from the compound according to claim 1 or 2, wherein P has at least one structural unit represented by group (PM1), (PM2), (PM3), or (PM4) in formula (1) according to claim 1. In the formula, when there are a plurality of the same symbols, they may have the same structure, or each may independently have a different structure. d is hydrogen, halogen, methyl, ethyl or trifluoromethyl.

Images