JP4698586B2 - Novel phenolic compound and novel epoxy resin derivable from the phenolic compound - Google Patents
Novel phenolic compound and novel epoxy resin derivable from the phenolic compound Download PDFInfo
- Publication number
- JP4698586B2 JP4698586B2 JP2006519423A JP2006519423A JP4698586B2 JP 4698586 B2 JP4698586 B2 JP 4698586B2 JP 2006519423 A JP2006519423 A JP 2006519423A JP 2006519423 A JP2006519423 A JP 2006519423A JP 4698586 B2 JP4698586 B2 JP 4698586B2
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- Prior art keywords
- epoxy resin
- acid
- general formula
- compound
- phenolic compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003822 epoxy resin Substances 0.000 title claims description 40
- 229920000647 polyepoxide Polymers 0.000 title claims description 40
- 150000002989 phenols Chemical class 0.000 title description 8
- -1 phenol compound Chemical class 0.000 claims description 51
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000123 paper Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000417 fungicide Substances 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- RXWDMYWEKIFIFE-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-1-(4-phenylphenyl)ethyl]phenol Chemical group C=1C=C(O)C=CC=1C(C=1C=CC(=CC=1)C=1C=CC=CC=1)(C)C1=CC=C(O)C=C1 RXWDMYWEKIFIFE-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C1C(C(*)C*)C2CC2)=C1N Chemical compound CC(C1C(C(*)C*)C2CC2)=C1N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- XLQQCWFQMJTQTF-UHFFFAOYSA-N 1,1'-biphenyl;dicyclohexylmethanone Chemical compound C1=CC=CC=C1C1=CC=CC=C1.C1CCCCC1C(=O)C1CCCCC1 XLQQCWFQMJTQTF-UHFFFAOYSA-N 0.000 description 1
- ZXPCCXXSNUIVNK-UHFFFAOYSA-N 1,1,1,2,3-pentachloropropane Chemical compound ClCC(Cl)C(Cl)(Cl)Cl ZXPCCXXSNUIVNK-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- HSQOPVUSHBNOOL-UHFFFAOYSA-M 1,1-dimethylpiperidin-1-ium;iodide Chemical compound [I-].C[N+]1(C)CCCCC1 HSQOPVUSHBNOOL-UHFFFAOYSA-M 0.000 description 1
- FJEQTUWHWBFLAK-UHFFFAOYSA-M 1,1-dimethylpyrrolidin-1-ium;chloride Chemical compound [Cl-].C[N+]1(C)CCCC1 FJEQTUWHWBFLAK-UHFFFAOYSA-M 0.000 description 1
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 1
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- GKYHYQLPNLSRKB-UHFFFAOYSA-M 1-benzyl-1-methylpiperidin-1-ium;chloride Chemical compound [Cl-].C=1C=CC=CC=1C[N+]1(C)CCCCC1 GKYHYQLPNLSRKB-UHFFFAOYSA-M 0.000 description 1
- PIQHFQPDLYOGLZ-UHFFFAOYSA-M 1-benzyl-1-methylpyrrolidin-1-ium;chloride Chemical compound [Cl-].C=1C=CC=CC=1C[N+]1(C)CCCC1 PIQHFQPDLYOGLZ-UHFFFAOYSA-M 0.000 description 1
- LCZRPQGSMFXSTC-UHFFFAOYSA-M 1-butyl-1-methylpyrrolidin-1-ium;bromide Chemical compound [Br-].CCCC[N+]1(C)CCCC1 LCZRPQGSMFXSTC-UHFFFAOYSA-M 0.000 description 1
- GDKLIUJRYOQUOF-UHFFFAOYSA-M 1-ethyl-1-methylpiperidin-1-ium;acetate Chemical compound CC([O-])=O.CC[N+]1(C)CCCCC1 GDKLIUJRYOQUOF-UHFFFAOYSA-M 0.000 description 1
- RWPRNPXSHGRVPR-UHFFFAOYSA-M 1-ethyl-1-methylpiperidin-1-ium;iodide Chemical compound [I-].CC[N+]1(C)CCCCC1 RWPRNPXSHGRVPR-UHFFFAOYSA-M 0.000 description 1
- KHJQQUGSPDBDRM-UHFFFAOYSA-M 1-ethyl-1-methylpyrrolidin-1-ium;bromide Chemical compound [Br-].CC[N+]1(C)CCCC1 KHJQQUGSPDBDRM-UHFFFAOYSA-M 0.000 description 1
- CHZLVSBMXZSPNN-UHFFFAOYSA-N 2,4-dimethylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C(C)=C1 CHZLVSBMXZSPNN-UHFFFAOYSA-N 0.000 description 1
- VRRDONHGWVSGFH-UHFFFAOYSA-N 2,5-diethylcyclohexane-1,4-diamine Chemical compound CCC1CC(N)C(CC)CC1N VRRDONHGWVSGFH-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 description 1
- RWKGRPMIVVAART-UHFFFAOYSA-N 2-[(2-hydroxyphenyl)methyl]-4-methyl-3-phenylphenol Chemical compound C=1C=CC=CC=1C=1C(C)=CC=C(O)C=1CC1=CC=CC=C1O RWKGRPMIVVAART-UHFFFAOYSA-N 0.000 description 1
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical compound OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- ZZURXLMHTYYCST-UHFFFAOYSA-N 2-sulfanylacetic acid Chemical compound OC(=O)CS.OC(=O)CS ZZURXLMHTYYCST-UHFFFAOYSA-N 0.000 description 1
- DYAOREPNYXXCOA-UHFFFAOYSA-N 2-sulfanylundecanoic acid Chemical compound CCCCCCCCCC(S)C(O)=O DYAOREPNYXXCOA-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 description 1
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- 239000000314 lubricant Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
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- LIBWSLLLJZULCP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCCNC1=CC=CC=C1 LIBWSLLLJZULCP-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
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- 238000010791 quenching Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
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- 239000003566 sealing material Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
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- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
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- 150000003505 terpenes Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- UMMDBKGUDMBUSR-UHFFFAOYSA-M tris-decyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(CCCCCCCCCC)CCCCCCCCCC UMMDBKGUDMBUSR-UHFFFAOYSA-M 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/28—Ethers with hydroxy compounds containing oxirane rings
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
Description
本発明は新規フェノール化合物及び該フェノール化合物から誘導し得る新規エポキシ樹脂に関し、詳しくは、合成樹脂原料等として好適に用いられるフェノール化合物、及び塗料、接着剤、成型品等に用いる材料として有用で、該フェノール化合物から誘導し得るエポキシ樹脂に関するものである。 The present invention relates to a novel phenol compound and a novel epoxy resin that can be derived from the phenol compound. Specifically, the phenol compound is preferably used as a synthetic resin raw material and the like, and is useful as a material used for paints, adhesives, molded articles, The present invention relates to an epoxy resin that can be derived from the phenol compound.
ポリフェノール化合物は、フェノール樹脂、エポキシ樹脂、ポリカーボネート樹脂、ポリエステル樹脂等の合成樹脂用原料、エポキシ硬化剤、感熱記録に用いられる顕色剤や退色防止剤、電子材料の原料等として有用であり、また、酸化防止剤、殺菌剤、防菌防カビ剤等の添加剤としても有用である。 Polyphenol compounds are useful as raw materials for synthetic resins such as phenol resins, epoxy resins, polycarbonate resins, and polyester resins, epoxy curing agents, developers and anti-fading agents used in thermal recording, and raw materials for electronic materials. It is also useful as an additive for antioxidants, bactericides, fungicides and fungicides.
また、エポキシ樹脂は、接着性、耐熱性、耐薬品性、電気特性、機械特性等に優れるため、塗料、接着剤、成型品等に用いる材料として広く使用されており、IC封止材料、積層材料、電気絶縁材料等の電気電子分野においても広く活用されている。 Epoxy resins are widely used as materials for paints, adhesives, molded products, etc. because of their excellent adhesiveness, heat resistance, chemical resistance, electrical properties, mechanical properties, etc. It is also widely used in electrical and electronic fields such as materials and electrical insulating materials.
近年、特に、電気電子分野において、機器の小型化、高性能化に伴って、用いられる樹脂に対しても、機械的特性や熱的特性の向上のみならず、耐湿性、電気絶縁性、低誘電性等の向上がますます強く要求されるに至っており、それに伴って、かかる要求を満足する樹脂を提供し得る新たなビスフェノール化合物が求められている。 In recent years, especially in the field of electrical and electronic equipment, along with the downsizing and high performance of equipment, not only improved mechanical and thermal properties, but also moisture resistance, electrical insulation, Improvements in dielectric properties and the like have been increasingly demanded, and accordingly, new bisphenol compounds capable of providing a resin that satisfies such requirements have been demanded.
新規のフェノール化合物の開発は多く行われており、例えば、特許文献1には、テルペンジフェノール化合物が提案されており、特許文献2には、4−置換シクロヘキシリデンビスフェノール類が提案されているが、これらの化合物は上記の要求を未だ満足できるものではない。 Many new phenol compounds have been developed. For example, Patent Document 1 proposes terpene diphenol compounds, and Patent Document 2 proposes 4-substituted cyclohexylidene bisphenols. However, these compounds still cannot satisfy the above requirements.
また、例えば、特許文献3には、4−〔1,1−ビス(4−ヒドロキシフェニル)エチル〕ビフェニル等のビスフェノール化合物を電子受容性化合物として使用してなる記録材料が提案されており、特許文献4には、ビフェニルアルキリデン−4,4’−ビスフェノール化合物より誘導されるポリカーボネート系共重合体が提案されており、特許文献5には、メチル−フェニル−メチリデンビスフェノールを顕色剤として使用してなる感熱記録体が提案されており、特許文献6には、シクロヘキシルメチレン−4,4’−ビスフェノール化合物等を電子受容性化合物として使用してなる感熱記録材料が提案されている。しかし、これらも上記の要求を未だ満足できるものではない。 For example, Patent Document 3 proposes a recording material using a bisphenol compound such as 4- [1,1-bis (4-hydroxyphenyl) ethyl] biphenyl as an electron-accepting compound. Document 4 proposes a polycarbonate copolymer derived from a biphenylalkylidene-4,4′-bisphenol compound, and Patent Document 5 uses methyl-phenyl-methylidenebisphenol as a developer. A thermal recording material using a cyclohexylmethylene-4,4′-bisphenol compound or the like as an electron-accepting compound is proposed in Patent Document 6. However, these still cannot satisfy the above requirements.
従って、本発明の目的は、合成樹脂原料等として好適に用いられるフェノール化合物を提供すること、ならびに、塗料、接着剤、成型品等に用いる材料として有用なエポキシ樹脂を提供することにある。 Accordingly, an object of the present invention is to provide a phenol compound that is suitably used as a synthetic resin raw material and the like, and to provide an epoxy resin that is useful as a material for use in paints, adhesives, molded articles, and the like.
本発明者等は、鋭意検討を重ねた結果、新規フェノール化合物及び該フェノール化合物から誘導し得るエポキシ樹脂が、上記目的を満足し得ることを見出し、本発明に到達した。 As a result of intensive studies, the present inventors have found that a novel phenol compound and an epoxy resin that can be derived from the phenol compound can satisfy the above object, and have reached the present invention.
即ち、本発明は、下記一般式(I)で表されるフェノール化合物を提供するものである。 That is, the present invention provides a phenol compound represented by the following general formula (I).
また、本発明は、下記一般式(II)で表されるエポキシ樹脂を提供するものである。 The present invention also provides an epoxy resin represented by the following general formula (II).
以下、本発明のフェノール化合物及びエポキシ樹脂について詳細に説明する。 Hereinafter, the phenolic compound and the epoxy resin of the present invention will be described in detail.
上記一般式(I)中、Cyで表される炭素原子数3〜10のシクロアルキル基としては、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、メチルシクロヘキシル、シクロヘプチル、シクロオクチル、シクロノニル、シクロデシル等の基が挙げられる。また、Y及びZで表される炭素原子数1〜10のアルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、第二ブチル、第三ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、イソオクチル、第三オクチル、2−エチルヘキシル、ノニル、イソノニル、デシル、イソデシル、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル、シクロノニル、シクロデシル等の直鎖、分岐及び環状のアルキル基が挙げられる。また、Xで表わされる炭素原子数3〜10のシクロアルキル基としては、Cyとして例示したものと同様のものが挙げられ、また、Xで表わされるフェニル基を置換し得る炭素原子数1〜10のアルキル基としては、Y及びZとして例示したものと同様のものが挙げられる。 In the above general formula (I), the cycloalkyl group having 3 to 10 carbon atoms represented by Cy is a group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc. Is mentioned. Examples of the alkyl group having 1 to 10 carbon atoms represented by Y and Z include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl and isooctyl. , Tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and the like. Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by X include those exemplified as Cy, and also has 1 to 10 carbon atoms capable of substituting the phenyl group represented by X. Examples of the alkyl group include those similar to those exemplified as Y and Z.
本発明のフェノール化合物としては、例えば、下記の化合物等が挙げられる。 Examples of the phenol compound of the present invention include the following compounds.
本発明のフェノール化合物の製造方法は特に限定されるものではないが、例えば、下記〔化11〕に示すように、ケトン化合物(1)とフェノール化合物(2)の混合物を、酸性触媒の存在下に反応させることによって容易に製造することができる。 The method for producing the phenolic compound of the present invention is not particularly limited. For example, as shown in the following [Chemical Formula 11], a mixture of the ketone compound (1) and the phenolic compound (2) is added in the presence of an acidic catalyst. It can be easily produced by reacting with.
上記反応に使用される酸性触媒としては、例えば、メタンスルホン酸、ベンゼンスルホン酸、m−キシレンスルホン酸、p−トルエンスルホン酸、ヒドロキシメチルスルホン酸、2−ヒドロキシエチルスルホン酸、ヒドロキシプロピルスルホン酸、トリフルオロメタンスルホン酸、スルホサリチル酸、スルホフタル酸等のスルホン酸類;硫酸、無水硫酸、発煙硫酸、クロロ硫酸、フルオロ硫酸、塩酸、塩化水素ガス、シュウ酸、ギ酸、リン酸、トリクロロ酢酸、トリフルオロ酢酸、ケイタングステン酸、リンタングステン酸等のヘテロポリ酸、強酸性のイオン交換樹脂等が挙げられる。 Examples of the acidic catalyst used in the above reaction include methanesulfonic acid, benzenesulfonic acid, m-xylenesulfonic acid, p-toluenesulfonic acid, hydroxymethylsulfonic acid, 2-hydroxyethylsulfonic acid, hydroxypropylsulfonic acid, Sulfonic acids such as trifluoromethanesulfonic acid, sulfosalicylic acid, sulfophthalic acid; sulfuric acid, sulfuric anhydride, fuming sulfuric acid, chlorosulfuric acid, fluorosulfuric acid, hydrochloric acid, hydrogen chloride gas, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid, Examples include heteropolyacids such as silicotungstic acid and phosphotungstic acid, and strongly acidic ion exchange resins.
さらに、上記反応においては、反応を促進するためにメルカプタン触媒を使用することができ、該メルカプタン触媒としては、例えば、メチルメルカプタン、エチルメルカプタン、プロピルメルカプタン、ブチルメルカプタン、オクチルメルカプタン、ドデシルメルカプタン、1,6−ヘキサンジチオール等のアルキルメルカプタン類;チオフェノール、チオクレゾール等の芳香族メルカプタン類;メルカプト酢酸(チオグリコール酸)、3−メルカプトプロピオン酸、メルカプトウンデカン酸、チオ安息香酸等のメルカプト有機酸類;2−メルカプトベンゾチアゾール等の複素環族メルカプタン類;硫化水素等が挙げられる。 Furthermore, in the above reaction, a mercaptan catalyst can be used to promote the reaction. Examples of the mercaptan catalyst include methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, octyl mercaptan, dodecyl mercaptan, 1, Alkyl mercaptans such as 6-hexanedithiol; aromatic mercaptans such as thiophenol and thiocresol; mercapto organic acids such as mercaptoacetic acid (thioglycolic acid), 3-mercaptopropionic acid, mercaptoundecanoic acid, and thiobenzoic acid; 2 -Heterocyclic mercaptans such as mercaptobenzothiazole; hydrogen sulfide and the like.
本反応において、フェノール化合物(2)は、ケトン化合物(1)の1モルに対して、1モル以上、特に2〜10モルの範囲で使用することが好ましく、酸性触媒はケトン化合物(1)1モルに対し、0.001〜2.0モル、特に0.01〜1.5モル使用することが好ましく、メルカプト触媒は、ケトン化合物(1)1モルに対し、特に0.001〜1.0モル使用することが好ましい。 In this reaction, the phenol compound (2) is preferably used in an amount of 1 mol or more, particularly 2 to 10 mol, per 1 mol of the ketone compound (1), and the acidic catalyst is the ketone compound (1) 1 It is preferable to use 0.001 to 2.0 mol, particularly 0.01 to 1.5 mol, based on mol, and the mercapto catalyst is particularly 0.001 to 1.0 mol per mol of the ketone compound (1). It is preferable to use molar.
また、上記反応には、汎用溶媒を使用することができ、該溶媒としては、例えば、トルエン、キシレン、クメン等の芳香族炭化水素系溶媒;テレピン油、D−リモネン、ピネン等のテルペン系炭化水素油;ミネラルスピリット、スワゾール#310(コスモ松山石油(株))、ソルベッソ#100(エクソン化学(株))等のパラフィン系溶剤;メタノール、エタノール等のアルコール系溶媒;酢酸エチル等のエステル溶媒;ジクロロエタン、四塩化炭素、クロロホルム、トリクロロエチレン、塩化メチレン、クロロベンゼン等のハロゲン系溶媒;テトラヒドロフラン、ジオキサン等の環状エーテル系溶媒;アニリン、トリエチルアミン、ピリジン、ジオキサン、酢酸、アセトニトリル、二硫化炭素等が挙げられる。 In addition, a general-purpose solvent can be used for the above reaction, and examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene and cumene; terpene carbonization such as terpine oil, D-limonene and pinene. Hydrogen oil; paraffinic solvents such as mineral spirit, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); alcohol solvents such as methanol and ethanol; ester solvents such as ethyl acetate; Examples include halogen solvents such as dichloroethane, carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and chlorobenzene; cyclic ether solvents such as tetrahydrofuran and dioxane; aniline, triethylamine, pyridine, dioxane, acetic acid, acetonitrile, and carbon disulfide.
本反応は0〜200℃、特に10〜100℃の範囲で行なうのが好ましい。0℃未満であると反応が遅くなり長時間の反応が必要となり、200℃を越えると副反応が多く起こり好ましくない。反応時間は、反応温度が0〜200℃の場合、通常、数分〜数十時間の範囲から選択される。 This reaction is preferably carried out in the range of 0 to 200 ° C, particularly 10 to 100 ° C. If it is less than 0 ° C., the reaction is slow, and a long reaction time is required. When the reaction temperature is 0 to 200 ° C., the reaction time is usually selected from the range of several minutes to several tens of hours.
本発明のフェノール化合物は、フェノール樹脂、エポキシ樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリスルホン樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルイミド樹脂、ポリビスマレイミド樹脂、ポリアリレート樹脂、ポリアセタール樹脂等の合成樹脂用原料;エポキシ硬化剤;顕色剤、退色防止剤等の感熱記録材料;電子材料原料;酸化防止剤、紫外線吸収剤、難燃剤、殺菌剤、防菌防カビ剤等の添加剤、及びそれらの原料としても有用である。 The phenol compound of the present invention is used for synthetic resins such as phenol resin, epoxy resin, polycarbonate resin, polyester resin, polysulfone resin, polyimide resin, polyamideimide resin, polyetherimide resin, polybismaleimide resin, polyarylate resin, polyacetal resin, etc. Raw materials; Epoxy curing agents; Heat sensitive recording materials such as developers and anti-fading agents; Electronic material raw materials; Additives such as antioxidants, ultraviolet absorbers, flame retardants, bactericides, fungicides and fungicides, and their It is also useful as a raw material.
上記一般式(II)で表わされる本発明のエポキシ樹脂としては、例えば、下記の化合物等が挙げられる。 As an epoxy resin of this invention represented by the said general formula (II), the following compound etc. are mentioned, for example.
本発明のエポキシ樹脂の製造方法は特に限定されるものではないが、例えば、上記一般式(II)におけるnが0であるエポキシ樹脂は、下記〔化20〕に示すように、本発明のフェノール化合物(I)とエピクロルヒドリン(3)とを、アルカリ及びルイス酸又は層間移動触媒の存在下に反応させることによって容易に製造することができる。 The method for producing the epoxy resin of the present invention is not particularly limited. For example, the epoxy resin in which n in the general formula (II) is 0 is represented by the following formula [20]. It can be easily produced by reacting compound (I) with epichlorohydrin (3) in the presence of an alkali and a Lewis acid or an intercalation catalyst.
上記反応で使用されるアルカリとしては、例えば、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム等が挙げられる。また、ルイス酸としては、上記で例示した如き酸性触媒、四塩化スズ、三フッ化ホウ素、四塩化チタン、活性白土、塩化アルミニウム、塩化マグネシウム、渦マンガン酸カリウム、クロム酸カリウム等が挙げられる。また、層間移動触媒としては、例えば、テトラメチルアンモニウムクロリド、テトラブチルアンモニウムブロミド、メチルトリオクチルアンモニウムクロリド、メチルトリデシルアンモニウムクロリド、ベンジルトリエチルアンモニウムクロリド、N,N−ジメチルピロリジニウムクロリド、N−エチル−N−メチルピロリジニウムヨージド、N−ブチル−N−メチルピロリジニウムブロミド、N−ベンジル−N−メチルピロリジニウムクロリド、N−エチル−N−メチルピロリジニウムブロミド、N−ブチル−N−メチルモルホリニウムブロミド、N−ブチル−N−メチルモルホリニウムヨージド、N−アリル−N−メチルモルホリニウムブロミド、N−メチル−N−ベンジルピペリジニウムクロリド、N−メチル−N−ベンジルピペリジニウムブロミド、N,N−ジメチルピペリジニウムヨージド、N−メチル−N−エチルピペリジニウムアセテート、N−メチル−N−エチルピペリジニウムヨージド等が挙げられるが、テトラメチルアンモニウムクロリド、ベンジルトリエチルアンモニウムクロリドが好ましい。 Examples of the alkali used in the above reaction include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like. Examples of the Lewis acid include acidic catalysts as exemplified above, tin tetrachloride, boron trifluoride, titanium tetrachloride, activated clay, aluminum chloride, magnesium chloride, potassium vortex manganate, and potassium chromate. Examples of the interlayer transfer catalyst include tetramethylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium chloride, methyltridecylammonium chloride, benzyltriethylammonium chloride, N, N-dimethylpyrrolidinium chloride, N-ethyl. -N-methylpyrrolidinium iodide, N-butyl-N-methylpyrrolidinium bromide, N-benzyl-N-methylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium bromide, N-butyl- N-methylmorpholinium bromide, N-butyl-N-methylmorpholinium iodide, N-allyl-N-methylmorpholinium bromide, N-methyl-N-benzylpiperidinium chloride, N-methyl-N -Benzylpiperidi Umbromide, N, N-dimethylpiperidinium iodide, N-methyl-N-ethylpiperidinium acetate, N-methyl-N-ethylpiperidinium iodide, and the like include tetramethylammonium chloride, benzyltriethyl Ammonium chloride is preferred.
上記反応において、エピクロルヒドリンは、本発明のフェノール化合物(I)の水酸基1当量に対し、1当量以上、特に2〜10当量の範囲で使用することが好ましく、アルカリは、上記水酸基1当量に対し、0.1〜2.0モル、特に0.3〜1.5モル使用するのが好ましく、層間移動触媒は、本発明のフェノール化合物(I)の水酸基1当量に対し、0.01〜10モル%、特に0.2〜5モル%使用するのが好ましい。また、上記一般式(II)におけるnが1〜10のエポキシ樹脂も、nが0の場合の上記反応に準じて製造することができ、その際にはエピクロルヒドリンの使用量を適宜選択すればよい。また、上記一般式(II)におけるnが1〜10のエポキシ樹脂は、上記一般式(II)におけるnが0のエポキシ樹脂及び上記一般式(I)で表わされる本発明のフェノール化合物を反応させることによっても製造することができる。 In the above reaction, epichlorohydrin is preferably used in an amount of 1 equivalent or more, particularly 2 to 10 equivalents, based on 1 equivalent of the hydroxyl group of the phenol compound (I) of the present invention. It is preferable to use 0.1 to 2.0 mol, particularly 0.3 to 1.5 mol, and the interlayer transfer catalyst is 0.01 to 10 mol with respect to 1 equivalent of the hydroxyl group of the phenol compound (I) of the present invention. %, Particularly 0.2 to 5 mol% is preferred. Moreover, the epoxy resin whose n in the said general formula (II) is 1-10 can also be manufactured according to the said reaction in case n is 0, and should just select the usage-amount of epichlorohydrin suitably in that case . The epoxy resin having n of 1 to 10 in the general formula (II) is reacted with the epoxy resin having n of 0 in the general formula (II) and the phenol compound of the present invention represented by the general formula (I). Can also be manufactured.
上記〔化20〕に示す反応においては、本発明のフェノール化合物(I)の製造に用い得る溶媒として例示した如き溶媒を使用することができる。また、過剰のエピクロルヒドリンを溶媒として使用することもできる。 In the reaction shown in the above [Chemical Formula 20], a solvent as exemplified as a solvent that can be used in the production of the phenol compound (I) of the present invention can be used. Excess epichlorohydrin can also be used as a solvent.
本反応は20〜100℃、特に30〜60℃の範囲で行なうのが好ましい。20℃未満であると反応が遅くなり長時間の反応が必要となり、100℃を越えると副反応が多く起こり好ましくない。反応時間は、反応温度が20〜100℃の場合、通常、数分〜数十時間の範囲から選択される。 This reaction is preferably carried out in the range of 20 to 100 ° C, particularly 30 to 60 ° C. If it is less than 20 ° C., the reaction is delayed and a long reaction time is required. When the reaction temperature is 20 to 100 ° C., the reaction time is usually selected from the range of several minutes to several tens of hours.
本発明のエポキシ樹脂は、通常、エポキシ樹脂用の硬化剤と組み合わせて使用され、該硬化剤としては、例えば、ジエチレントリアミン、トリエチレントリアミン、テトラエチレンペンタミン等のポリアルキルポリアミン類;1,2−ジアミノシクロヘキサン、1,4−ジアミノ−3,6−ジエチルシクロヘキサン、イソホロンジアミン等の脂環式ポリアミン類;m−キシリレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン等の芳香族ポリアミン類等のポリアミン類が挙げられる。また、これらのポリアミン類と、フェニルグリシジルエーテル、ブチルグリシジルエーテル、ビスフェノールA−ジグリシジルエーテル、ビスフェノールF−ジグリシジルエーテル等のグリシジルエーテル類又はカルボン酸のグリシジルエステル類等の各種エポキシ樹脂とを常法によって反応させることによって製造されるポリエポキシ付加変性物;これらのポリアミン類と、フタル酸、イソフタル酸、ダイマー酸等のカルボン酸類とを常法によって反応させることによって製造されるアミド化変性物;これらのポリアミン類とホルムアルデヒド等のアルデヒド類及びフェノール、クレゾール、キシレノール、第三ブチルフェノール、レゾルシン等の核に少なくとも一個のアルデヒド化反応性場所を有するフェノール類とを常法によって反応させることによって製造されるマンニッヒ化変性物等が挙げられる。さらに、ジシアンジアミド、酸無水物、イミダゾール類等の潜在性硬化剤も使用できる。 The epoxy resin of the present invention is usually used in combination with a curing agent for epoxy resin. Examples of the curing agent include polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; 1,2- Alicyclic polyamines such as diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophoronediamine; polyamines such as aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone It is done. In addition, these polyamines and glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, or various epoxy resins such as glycidyl esters of carboxylic acid are used in a conventional manner. Polyepoxy addition-modified products produced by reacting them with these; amidation-modified products produced by reacting these polyamines with carboxylic acids such as phthalic acid, isophthalic acid, and dimer acid; Reaction of aldehydes such as formaldehyde with phenols having at least one aldehyde-reactive site in the nucleus such as phenol, cresol, xylenol, tert-butylphenol, resorcin, etc. Mannich-modified products and the like that are prepared by. Furthermore, latent curing agents such as dicyandiamide, acid anhydrides, and imidazoles can also be used.
また、本発明のエポキシ樹脂を使用する際には、必要に応じて、硬化触媒;モノグリシジルエーテル類、ジオクチルフタレート、ジブチルフタレート、ベンジルアルコール、コールタール等の反応性又は非反応性の希釈剤(可塑剤);ガラス繊維、炭素繊維、セルロース、ケイ砂、セメント、カオリン、クレー、水酸化アルミニウム、ベントナイト、タルク、シリカ、微粉末シリカ、二酸化チタン、カーボンブラック、グラファイト、酸化鉄、瀝青物質等の充填剤もしくは顔料;γ−アミノプロピルトリエトキシシラン、N−β−(アミノエチル)−γ−アミノプロピルトリエトキシシラン、N−β−(アミノエチル)−N’−β−(アミノエチル)−γ−アミノプロピルトリエトキシシラン、γ−アニリノプロピルトリエトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、β−(3,4−エポキシシクロヘキシル)エチルトリエトキシシラン、ビニルトリエトキシシラン、N−β−(N−ビニルベンジルアミノエチル)−γ−アミノプロピルトリエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン等のシランカップリング剤;キャンデリラワックス、カルナウバワックス、木ろう、イボタロウ、みつろう、ラノリン、鯨ろう、モンタンワックス、石油ワックス、脂肪酸ワックス、脂肪酸エステル、脂肪酸エーテル、芳香族エステル、芳香族エーテル等の潤滑剤;増粘剤;チキソトロピック剤;酸化防止剤;光安定剤;紫外線吸収剤;難燃剤;消泡剤;防錆剤;コロイダルシリカ、コロイダルアルミナ等の常用の添加物を添加してもよく、さらに、キシレン樹脂、石油樹脂等の粘着性の樹脂類を併用することもできる。 In addition, when using the epoxy resin of the present invention, if necessary, a curing catalyst; a reactive or non-reactive diluent such as monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, coal tar, etc. Plasticizer); glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, fine powder silica, titanium dioxide, carbon black, graphite, iron oxide, bituminous substances, etc. Filler or pigment: γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -N′-β- (aminoethyl) -γ -Aminopropyltriethoxysilane, γ-anilinopropyltriethoxysilane, γ-glycol Sidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane, γ- Silane coupling agents such as methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane; candelilla wax, carnauba wax, wood wax, ibotarou, beeswax, lanolin, spermaceti, montan Lubricants such as waxes, petroleum waxes, fatty acid waxes, fatty acid esters, fatty acid ethers, aromatic esters, aromatic ethers; thickeners; thixotropic agents; antioxidants; light stabilizers; ultraviolet absorbers; Foaming agent; rust preventive; colloidal Ca may be added additives conventional such colloidal alumina, further xylene resins, may be used in combination tacky resin such as petroleum resin.
さらに、本発明のエポキシ樹脂は、ウレタン変性、シリカ変性、リン酸変性、アミン変性、(メタ)アクリル酸変性等の各種の変性品の原料としても使用することができる。 Furthermore, the epoxy resin of the present invention can also be used as a raw material for various modified products such as urethane modification, silica modification, phosphoric acid modification, amine modification, and (meth) acrylic acid modification.
本発明のエポキシ樹脂あるいはその変性品は、例えば、コンクリート、セメントモルタル、各種金属、皮革、ガラス、ゴム、プラスチック、木、布、紙等に対する塗料あるいは接着剤;包装用粘着テープ、粘着ラベル、冷凍食品ラベル、リムーバルラベル、POSラベル、粘着壁紙、粘着床材の粘着剤;アート紙、軽量コート紙、キャストコート紙、塗工板紙、カーボンレス複写機、含浸紙等の加工紙;天然繊維、合成繊維、ガラス繊維、炭素繊維、金属繊維等の収束剤、ほつれ防止剤、加工剤等の繊維処理剤;シーリング材、セメント混和剤、防水材等の建築材料;電子・電気機器用封止剤等の広範な用途に使用することができる。 The epoxy resin of the present invention or a modified product thereof includes, for example, paints or adhesives for concrete, cement mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc .; adhesive tape for packaging, adhesive label, frozen Food labels, removable labels, POS labels, adhesive wallpaper, adhesives for adhesive flooring; art paper, lightweight coated paper, cast coated paper, coated paperboard, carbonless copiers, impregnated paper and other processed paper; natural fiber, synthetic Fiber treatment agents such as fibers, glass fibers, carbon fibers, metal fibers, etc., fiber treatment agents such as fraying prevention agents and processing agents; building materials such as sealing materials, cement admixtures and waterproofing materials; sealants for electronic and electrical equipment, etc. It can be used for a wide range of applications.
以下、実施例等を示して本発明のフェノール化合物及びエポキシ樹脂を更に詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, although an example etc. are shown and a phenol compound and an epoxy resin of the present invention are explained still in detail, the present invention is not limited to these.
〔参考例1〕ビフェニルシクロヘキシルケトン(ケトン化合物K−1)の製造
攪拌装置、冷却管、温度計を付した5L四つ口フラスコに塩化アルミニウム454.7g、クロロベンゼン2630gを仕込み、氷浴下で攪拌しながらビフェニル438.3gを添加し、溶解させた。その後、シクロヘキサンカルボン酸クロライド500.0gを0〜8℃で2.5時間かけて滴下し、その後ゆっくりと20℃まで昇温し、2時間さらに反応させた。
反応液を、氷水4kg中に攪拌下、発熱に注意しながら注ぎ、油水分離して得た有機層を希塩酸3kgで洗浄後、さらに水3kgで3回洗浄した。無水硫酸ナトリウムで脱水後、溶媒を留去し、ヘキサンから再結晶して白色結晶563.5g(収率75%)を得た。
得られた白色結晶は、1H−NMR及びIRによる分析を行なったところ、以下の1H−NMRのケミカルシフト及びIRの吸収を示し、目的物であるケトン化合物K−1であることが確認された。また、該白色結晶は、融点が86.9℃(示差熱ピークトップ)であった。[Reference Example 1] Production of biphenyl cyclohexyl ketone (ketone compound K-1) Into a 5 L four-necked flask equipped with a stirrer, a condenser tube and a thermometer were charged 454.7 g of aluminum chloride and 2630 g of chlorobenzene and stirred in an ice bath. While adding 438.3 g of biphenyl, it was dissolved. Thereafter, 500.0 g of cyclohexanecarboxylic acid chloride was added dropwise at 0-8 ° C. over 2.5 hours, and then the temperature was slowly raised to 20 ° C. and further reacted for 2 hours.
The reaction solution was poured into 4 kg of ice water with stirring while paying attention to heat generation, and the organic layer obtained by oil-water separation was washed with 3 kg of dilute hydrochloric acid and further washed with 3 kg of water three times. After dehydration with anhydrous sodium sulfate, the solvent was distilled off, and recrystallization from hexane gave 563.5 g (yield 75%) of white crystals.
When the obtained white crystals were analyzed by 1 H-NMR and IR, they showed the following 1 H-NMR chemical shift and IR absorption, and were confirmed to be the target ketone compound K-1. It was done. The white crystals had a melting point of 86.9 ° C. (differential heat peak top).
(1H−NMRのケミカルシフト)
(Chemical shift of 1 H-NMR)
(IR absorption)
[実施例1]1,1−ビス(4’−ヒドロキシフェニル)−1−(1”−ビフェニル)−1−シクロヘキシルメタン(化合物P−1)の製造
攪拌装置、冷却管、温度計を付した1L四つ口フラスコに、参考例1で得られたケトン化合物K−1の70.5g、フェノール200.7g、チオ酢酸10.15gを仕込み、水冷下、攪拌しながらトリフルオロメタンスルホン酸40.0gを18℃で20分かけて滴下した。水冷17〜19℃で18時間反応後、水冷したまま水500gを加えて反応をクエンチし、トルエン500gで抽出した。有機層をpH3〜4になるまで水で洗浄し、減圧下でトルエン、水及び過剰のフェノールを留去し、さらにトルエンを加えて析出した結晶をろ取し、トルエンで分散洗浄し、淡黄色結晶59.2g(収率51.2%)を得た。
得られた淡黄色結晶は、1H−NMR及びIRによる分析を行なったところ、以下の1H−NMRのケミカルシフト及びIRの吸収を示し、目的物である化合物P−1であることが確認された。また、該淡黄色結晶は、融点が239.5℃(示差熱ピークトップ)であった。Example 1 Production of 1,1-bis (4′-hydroxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (Compound P-1) A stirrer, a condenser, and a thermometer were attached. A 1 L four-necked flask was charged with 70.5 g of the ketone compound K-1 obtained in Reference Example 1, 200.7 g of phenol, and 10.15 g of thioacetic acid, and 40.0 g of trifluoromethanesulfonic acid with stirring under water cooling. Was added dropwise over 20 minutes at 18 ° C. After reaction for 18 hours at 17 to 19 ° C. with water cooling, 500 g of water was added while cooling with water to quench the reaction, and extraction was performed with 500 g of toluene. After washing with water, toluene, water and excess phenol were distilled off under reduced pressure. Further, toluene was added and the precipitated crystals were collected by filtration, dispersed and washed with toluene, and 59.2 g of light yellow crystals (yield) It was obtained 1.2%).
When the obtained pale yellow crystal was analyzed by 1 H-NMR and IR, it showed the following 1 H-NMR chemical shift and IR absorption, and was confirmed to be the target compound P-1. It was done. The pale yellow crystals had a melting point of 239.5 ° C. (differential heat peak top).
(1H−NMRのケミカルシフト)
(Chemical shift of 1 H-NMR)
(IR absorption)
[実施例2]1,1−ビス(4’−エポキシプロパニルオキシフェニル)−1−(1”−ビフェニル)−1−シクロヘキシルメタン(化合物E−1)の製造
攪拌装置、冷却管、温度計を付した500mL四つ口フラスコに、実施例1で得られたフェノール化合物(化合物P−1)57.5g、エピクロルヒドリン195.8gを仕込み、ベンジルトリエチルアンモニムクロライド0.602gを加え、64℃まで昇温し、18時間攪拌した。その後54℃まで降温し、24質量%水酸化ナトリウム水溶液43.0gを滴下、30分攪拌した。その後、エピクロルヒドリンと水を共沸により留去し、さらに121℃まで昇温してエピクロルヒドリンを完全に留去した。続いてメチルイソブチルケトン216gを加えて3回水洗し、24質量%水酸化ナトリウム2.2gを滴下した。80℃で2時間攪拌、室温に戻し、3質量%モノリン酸ナトリウム水溶液で中和後、3回水洗した。溶媒を減圧留去し、黄色固形エポキシ樹脂57g(収率78.8%)を得た。
得られた黄色固形エポキシ樹脂は、1H−NMR及びIRによる分析を行なったところ、以下の1H−NMRのケミカルシフト及びIRの吸収を示し、目的物である化合物E−1であることが確認された。また、該黄色固形エポキシ樹脂は、融点が64.2℃(示差熱ピークトップ)であった。Example 2 Production of 1,1-bis (4′-epoxypropanyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (Compound E-1) Stirrer, condenser, thermometer Is charged with 57.5 g of the phenolic compound (Compound P-1) obtained in Example 1 and 195.8 g of epichlorohydrin, and 0.602 g of benzyltriethylammonium chloride is added to 64 ° C. The temperature was raised and the mixture was stirred for 18 hours, then the temperature was lowered to 54 ° C., 43.0 g of a 24% by mass aqueous sodium hydroxide solution was added dropwise and stirred for 30 minutes, and then epichlorohydrin and water were distilled off azeotropically, and further 121 ° C. The epichlorohydrin was completely distilled off by heating to 216 g, followed by adding 216 g of methyl isobutyl ketone and washing with water three times. 2.2 g of sodium chloride was added dropwise, and the mixture was stirred at 80 ° C. for 2 hours, returned to room temperature, neutralized with a 3% by mass aqueous sodium monophosphate solution, and washed with water three times. Yield 78.8%) was obtained.
When the obtained yellow solid epoxy resin was analyzed by 1 H-NMR and IR, it showed the following 1 H-NMR chemical shift and IR absorption, and was the target compound E-1. confirmed. The yellow solid epoxy resin had a melting point of 64.2 ° C. (differential heat peak top).
(1H−NMRのケミカルシフト)
(Chemical shift of 1 H-NMR)
(IR absorption)
<使用例1>
化合物E−1の100g、アデカハードナーEH−3326(旭電化工業製;メチルテトラヒドロ無水フタル酸)58.8g、トリフェニルフォスフィン1.59gを混合し、100℃で1時間、130℃で2時間、160℃で2時間ずつ加熱し、硬化物を得た。
この硬化物のガラス転移温度(Tg)を測定したところ、155℃であった。<Use Example 1>
Compound E-1 (100 g), Adeka Hardener EH-3326 (Asahi Denka Kogyo; methyltetrahydrophthalic anhydride) (58.8 g) and triphenylphosphine (1.59 g) were mixed and mixed at 100 ° C. for 1 hour and at 130 ° C. for 2 hours. And heated at 160 ° C. for 2 hours to obtain a cured product.
It was 155 degreeC when the glass transition temperature (Tg) of this hardened | cured material was measured.
<比較使用例1>
エピコート834(ジャパンエポキシレジン製;ビスフェノールA型エポキシ樹脂)100g、アデカハードナーEH−3326の66.4g、トリフェニルフォスフィン1.66gを混合し、100℃で1時間、130℃で2時間、160℃で2時間ずつ加熱し、硬化物を得た。
この硬化物のガラス転移温度(Tg)を測定したところ、130℃であった。<Comparative use example 1>
Epicoat 834 (manufactured by Japan Epoxy Resin; bisphenol A type epoxy resin) 100 g, 66.4 g of Adeka Hardener EH-3326, and 1.66 g of triphenylphosphine were mixed, and 100 ° C. for 1 hour, 130 ° C. for 2 hours, 160 Heated at 2 ° C. for 2 hours to obtain a cured product.
It was 130 degreeC when the glass transition temperature (Tg) of this hardened | cured material was measured.
〔比較例1〕1,1−ビス(4’−エポキシプロパニルオキシフェニル)−1−(1”−ビフェニル)−1−エタン(化合物HE−1)の製造
4−〔1,1−ビス(4−ヒドロキシフェニル)エチル〕ビフェニル21.9g及びエピクロルヒドリン99.7gを仕込み、ベンジルトリエチルアンモニムクロライド0.272gを加え、75℃まで昇温し、15時間反応させた。水とエピクロルヒドリンを共沸して還流脱水させながら48質量%水酸化ナトリウム水溶液10.01gを滴下し、さらに還流脱水を行った後、130℃まで昇温してエピクロルヒドリンを留去した。トルエン59.9gを加えて80℃で1時間攪拌し、水23gを加えて水洗した。
その後、48質量%水酸化ナトリウム水溶液0.72g、水0.29g及びベンジルトリエチルアンモニムクロライド0.273gを加えて、80℃で3時間反応させた後、水洗した。次いで、1質量%モノリン酸ナトリウム水溶液で中和し、さらに3回水洗した後、ろ渦し、130℃減圧下で脱溶媒して、黄色固形エポキシ樹脂23.9g(収率83%)を得た。
得られた黄色固形エポキシ樹脂は、1H−NMR及びIRによる分析を行なったところ、以下の1H−NMRのケミカルシフト及びIRの吸収を示し、目的物である化合物HE−1であることが確認された。Comparative Example 1 Preparation of 1,1-bis (4′-epoxypropanyloxyphenyl) -1- (1 ″ -biphenyl) -1-ethane (Compound HE-1) 4- [1,1-bis ( 4-hydroxyphenyl) ethyl] biphenyl (21.9 g) and epichlorohydrin (99.7 g) were added, benzyltriethylammonium chloride (0.272 g) was added, and the mixture was heated to 75 ° C. and allowed to react for 15 hours. Then, 10.01 g of a 48 mass% sodium hydroxide aqueous solution was added dropwise while refluxing and dehydrating, and then the temperature was raised to 130 ° C. to distill off epichlorohydrin, and 59.9 g of toluene was added at 80 ° C. The mixture was stirred for 1 hour, and 23 g of water was added and washed with water.
Thereafter, 0.72 g of a 48% by mass aqueous sodium hydroxide solution, 0.29 g of water and 0.273 g of benzyltriethylammonium chloride were added and reacted at 80 ° C. for 3 hours, followed by washing with water. Next, the solution was neutralized with a 1% by mass sodium monophosphate aqueous solution, further washed with water three times, filtered and vortexed, and desolvated at 130 ° C. under reduced pressure to obtain 23.9 g of a yellow solid epoxy resin (yield 83%). It was.
When the obtained yellow solid epoxy resin was analyzed by 1 H-NMR and IR, it showed the following 1 H-NMR chemical shift and IR absorption, and was the target compound HE-1. confirmed.
(1H−NMRのケミカルシフト)
(Chemical shift of 1 H-NMR)
(IR absorption)
〔比較例2〕1,1−ビス(4’−エポキシプロパニルオキシフェニル)−1−(1”−ビフェニル)−1−プロパン(化合物HE−2)の製造
4−〔1,1−ビス(4−ヒドロキシフェニル)プロピル〕ビフェニル13.5g及びエピクロルヒドリン59.7gを仕込み、ベンジルトリエチルアンモニムクロライド0.163gを加え、75℃まで昇温し、14時間攪拌した。水とエピクロルヒドリンを共沸して還流脱水させながら48質量%水酸化ナトリウム水溶液5.43gを滴下し、さらに還流脱水を行った後、130℃まで昇温してエピクロルヒドリンを留去した。トルエン32.6gを加えて80℃で1時間攪拌し、水12.4gを加えて水洗した。
その後、48質量%水酸化ナトリウム水溶液0.72g、水0.29g及びベンジルトリエチルアンモニムクロライド0.152gを加えて、80℃で3時間反応させた後、水洗した。次いで、1質量%モノリン酸ナトリウム水溶液を加えて中和し、さらに3回水洗した後、ろ過し、130℃減圧下で脱溶媒して、橙色固形エポキシ樹脂13.8g(収率79%)を得た。
得られた橙色固形エポキシ樹脂は、1H−NMR及びIRによる分析を行なったところ、以下の1H−NMRのケミカルシフト及びIRの吸収を示し、目的物である化合物HE−2であることが確認された。Comparative Example 2 Production of 1,1-bis (4′-epoxypropanyloxyphenyl) -1- (1 ″ -biphenyl) -1-propane (Compound HE-2) 4- [1,1-bis ( 4-hydroxyphenyl) propyl] biphenyl 13.5 g and epichlorohydrin 59.7 g were added, 0.163 g of benzyltriethylammonium chloride was added, the temperature was raised to 75 ° C., and the mixture was stirred for 14 hours. While refluxing dehydration, 5.43 g of a 48% by mass aqueous sodium hydroxide solution was added dropwise, followed by further refluxing and dehydration, and then the temperature was raised to 130 ° C. to distill off epichlorohydrin. The mixture was stirred for an hour, and 12.4 g of water was added and washed with water.
Thereafter, 0.72 g of a 48% by mass aqueous sodium hydroxide solution, 0.29 g of water and 0.152 g of benzyltriethylammonium chloride were added and reacted at 80 ° C. for 3 hours, followed by washing with water. Next, the mixture was neutralized by adding a 1% by mass sodium monophosphate aqueous solution, further washed with water three times, filtered, and desolvated under reduced pressure at 130 ° C. to obtain 13.8 g of an orange solid epoxy resin (yield 79%). Obtained.
When the obtained orange solid epoxy resin was analyzed by 1 H-NMR and IR, it showed the following 1 H-NMR chemical shift and IR absorption, indicating that it was the target compound HE-2. confirmed.
(1H−NMRのケミカルシフト)
(Chemical shift of 1 H-NMR)
(IR absorption)
<使用例2及び比較使用例2〜4>
エポキシ樹脂(〔表1〕に記載)3.5g、プロピレングリコールモノメチルエーテルアセテート(PGM−Ac)1.5g、アデカハードナーEH−3326(配合量は〔表1〕に記載)及びキュアゾール2E4MZ(四国化成工業(株)製;2−エチル−4−メチルイミダゾール)の0.06gを混合し、硬化性組成物を作成した。該硬化性組成物3gをガラス板上に直径7cmに均一に塗布し、80℃で60分、さらに150℃で120分加熱して硬化させて硬化物を得た。得られた硬化物を80℃の湯浴中に60分浸漬し、質量増加率(%)を求めた〔吸水率〕。それらの結果を表1に示す。<Use Example 2 and Comparative Use Examples 2-4>
Epoxy resin (described in [Table 1]) 3.5 g, propylene glycol monomethyl ether acetate (PGM-Ac) 1.5 g, Adeka Hardener EH-3326 (the amount is described in [Table 1]) and Curesol 2E4MZ (Shikoku Chemicals) 0.06 g of Kogyo Co., Ltd .; 2-ethyl-4-methylimidazole) was mixed to prepare a curable composition. 3 g of the curable composition was uniformly applied to a diameter of 7 cm on a glass plate and cured by heating at 80 ° C. for 60 minutes and further at 150 ° C. for 120 minutes to obtain a cured product. The obtained cured product was immersed in a hot water bath at 80 ° C. for 60 minutes, and the mass increase rate (%) was determined [water absorption rate]. The results are shown in Table 1.
本発明によるフェノール化合物は、エポキシ樹脂用の原料等として有用である。また、該フェノール化合物より誘導し得るエポキシ樹脂は、硬化物性及び耐水性に優れた硬化物を提供し得るものである。 The phenol compound according to the present invention is useful as a raw material for epoxy resins. Moreover, the epoxy resin which can be induced | guided | derived from this phenol compound can provide the hardened | cured material excellent in hardened | cured material property and water resistance.
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JP4738190B2 (en) * | 2006-02-01 | 2011-08-03 | 株式会社Adeka | Epoxy resin, alkali-developable resin composition, and alkali-developable photosensitive resin composition |
JP4878876B2 (en) * | 2006-03-15 | 2012-02-15 | 株式会社Adeka | Epoxy resin, alkali-developable resin composition, and alkali-developable photosensitive resin composition |
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JP5311750B2 (en) * | 2007-02-28 | 2013-10-09 | 株式会社Adeka | Phenol resin, epoxy resin, alkali-developable resin composition, and alkali-developable photosensitive resin composition |
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JP2000239206A (en) * | 1998-12-25 | 2000-09-05 | Honshu Chem Ind Co Ltd | Asymmetric alkylidene polyhydric phenols and production thereof |
JP2002316963A (en) * | 2001-02-15 | 2002-10-31 | Osaka Gas Co Ltd | Bisphenol with low activity as endocrine disruptor |
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JP2003306461A (en) * | 2002-02-15 | 2003-10-28 | Honshu Chem Ind Co Ltd | 1,3,5-tris(4-hydroxyphenyl)adamantane and method for producing the same |
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JP2003064121A (en) * | 2001-08-23 | 2003-03-05 | Tosoh Corp | Method of producing polyolefin |
JP2003306461A (en) * | 2002-02-15 | 2003-10-28 | Honshu Chem Ind Co Ltd | 1,3,5-tris(4-hydroxyphenyl)adamantane and method for producing the same |
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