JPH01168634A - Production of bis(4-hydroxyphenyl)-cyclohexane - Google Patents
Production of bis(4-hydroxyphenyl)-cyclohexaneInfo
- Publication number
- JPH01168634A JPH01168634A JP32720287A JP32720287A JPH01168634A JP H01168634 A JPH01168634 A JP H01168634A JP 32720287 A JP32720287 A JP 32720287A JP 32720287 A JP32720287 A JP 32720287A JP H01168634 A JPH01168634 A JP H01168634A
- Authority
- JP
- Japan
- Prior art keywords
- cyclohexane
- hydroxyphenyl
- catalyst
- formula
- catalysts
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 title description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- JTJBAXVMAPZCOD-UHFFFAOYSA-N 4-[4-hydroxy-1-(4-hydroxyphenyl)cyclohexyl]phenol Chemical compound C1CC(O)CCC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 JTJBAXVMAPZCOD-UHFFFAOYSA-N 0.000 claims 1
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 150000002431 hydrogen Chemical class 0.000 abstract description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- ISSDNFHHVPONBG-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)cyclohexyl]phenol Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C(C=2C=CC(O)=CC=2)(C=2C=CC(O)=CC=2)CCCC1 ISSDNFHHVPONBG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003377 acid catalyst Substances 0.000 abstract description 3
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical compound O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000370 acceptor Substances 0.000 description 5
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- -1 4- Hydroxyphenylene Chemical group 0.000 description 2
- WVLAOPOBZRLBFP-UHFFFAOYSA-N 4-(4-hydroxyphenyl)-3-phenylphenol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1C1=CC=CC=C1 WVLAOPOBZRLBFP-UHFFFAOYSA-N 0.000 description 2
- QDWPNFNKNZPTTC-UHFFFAOYSA-N 4-[1,4,4-tris(4-hydroxyphenyl)cyclohexyl]phenol Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCC(C=2C=CC(O)=CC=2)(C=2C=CC(O)=CC=2)CC1 QDWPNFNKNZPTTC-UHFFFAOYSA-N 0.000 description 2
- WZCQOMUGRAWORP-UHFFFAOYSA-N 4-[4-(4-hydroxyphenyl)cyclohexyl]phenol Chemical compound C1=CC(O)=CC=C1C1CCC(C=2C=CC(O)=CC=2)CC1 WZCQOMUGRAWORP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- FVIAPUZAEIMEEW-UHFFFAOYSA-N 4-[4-(4-hydroxyphenyl)phenyl]phenol Chemical group C1=CC(O)=CC=C1C1=CC=C(C=2C=CC(O)=CC=2)C=C1 FVIAPUZAEIMEEW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- XCVKVYNICFBSJQ-UHFFFAOYSA-N [Re].[C] Chemical compound [Re].[C] XCVKVYNICFBSJQ-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 1
- DCZFGQYXRKMVFG-UHFFFAOYSA-N cyclohexane-1,4-dione Chemical compound O=C1CCC(=O)CC1 DCZFGQYXRKMVFG-UHFFFAOYSA-N 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical class O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-VENIDDJXSA-N palladium-100 Chemical compound [100Pd] KDLHZDBZIXYQEI-VENIDDJXSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- JOKPITBUODAHEN-UHFFFAOYSA-N sulfanylideneplatinum Chemical compound [Pt]=S JOKPITBUODAHEN-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ビス（４−ヒドロキシフェニル）−シクロヘ
キサンの製造方法に関する。さらに詳細には式（１）
（式中、２つのベンゼン環（ａ）は、同一のシクロヘキ
サン環炭素と結合、）で示されるテトラキス（４〜ヒド
ロキシフエニル）−シクロヘキサンを水素受容体を使用
せずに分解反応させることを特徴とする式（ｆｆ）
で示されるビス（４−ヒドロキシフェニル）−シクロヘ
キサンの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing bis(4-hydroxyphenyl)-cyclohexane. More specifically, tetrakis(4-hydroxyphenyl)-cyclohexane represented by formula (1) (wherein, two benzene rings (a) are bonded to the same cyclohexane ring carbon) using a hydrogen acceptor. The present invention relates to a method for producing bis(4-hydroxyphenyl)-cyclohexane represented by formula (ff), which is characterized in that the decomposition reaction is carried out without decomposition reaction.
ビス（４−ヒドロキシフェニル）−シクロヘキサンはポ
リマー原料あるいは医薬中間体等として有用な化合物で
ある。Bis(4-hydroxyphenyl)-cyclohexane is a compound useful as a polymer raw material or a pharmaceutical intermediate.
フェノールと１．３−シクロヘキサジエンを触媒存在下
に反応させて、１．４−ビス（４−ヒドロキシフェニル
）−シクロヘキサンを得ることは知られている（英国特
許１１２２３７２（’６８）等）。It is known to react phenol and 1,3-cyclohexadiene in the presence of a catalyst to obtain 1,4-bis(4-hydroxyphenyl)-cyclohexane (UK Patent No. 1,122,372 ('68), etc.).
しかし上記従来法においては原料として用いる１、３−
シクロヘキサジエンが高価であり、工業的に入手も困難
であり、有利な方法とは言い難い。However, in the above conventional method, the 1,3-
Cyclohexadiene is expensive and difficult to obtain industrially, so it cannot be called an advantageous method.
本発明者等は、安価な工業的に入手可能な原料を用いた
ビス（４−ヒドロキシフェニル）−シクロヘキサンの製
造方法につき鋭意検討し本発明に到達した。The present inventors have conducted extensive studies on a method for producing bis(4-hydroxyphenyl)-cyclohexane using inexpensive industrially available raw materials, and have arrived at the present invention.
即ち、本発明は式（Ｉ）
（式中、２つのベンゼン環（ａ）は、同一のシクロヘキ
サン環炭素に結合。）で示されるテトラキス（４−ヒド
ロキシフェニル）−シクロヘキサンを水素受容体を使用
せずに分解反応させることを特徴とする式（ｎ）
で示されるビス（４−ヒドロキシフェニル）−シクロヘ
キサンの製造方法である。That is, the present invention provides tetrakis(4-hydroxyphenyl)-cyclohexane represented by formula (I) (wherein, two benzene rings (a) are bonded to the same cyclohexane ring carbon) using a hydrogen acceptor. This is a method for producing bis(4-hydroxyphenyl)-cyclohexane represented by formula (n), which is characterized in that the decomposition reaction is carried out without decomposition reaction.
本発明に於いて原料として使用されるテトラキス（４−
ヒドロキシフェニ）−シクロヘキサンは、例えば特開昭
５６−５５３２８に記載されているようなシクロヘキサ
ンジオンとフェノールを触媒存在下に反応させることに
より得ることができる。Tetrakis (4-
Hydroxyphenylene)-cyclohexane can be obtained, for example, by reacting cyclohexanedione and phenol in the presence of a catalyst as described in JP-A-56-55328.
また、シクロヘキサジオンは対応するジヒドロキシベン
ゼン、卯ちカテコール、レゾルシン、ハイドロキノンの
還元、あるいはシクロヘキサンジオールの酸化等により
得ることができる。Further, cyclohexadione can be obtained by reduction of the corresponding dihydroxybenzene, unicatechol, resorcinol, hydroquinone, or oxidation of cyclohexanediol.
本発明は、このようにして得られる弐（１）のテトラキ
ス（４−ヒドロキシフェニル）−シクロヘキサンを水素
受容体を使用せずに分解反応させることにより、式（Ｉ
Ｉ）のビス（４−ヒドロキシフェニル）−シクロヘキサ
ンを得るものであり、安価で工業的に入手が容易なジヒ
ドロキシベンゼン（カテコール、レゾルシン、ハイドロ
キノン）とフェノールより効率的に目的生成物を得るこ
とができる。In the present invention, the formula (I
I) Bis(4-hydroxyphenyl)-cyclohexane is obtained, and the desired product can be obtained more efficiently than dihydroxybenzene (catechol, resorcinol, hydroquinone) and phenol, which are inexpensive and easily available industrially. .
この分解反応は次の様に進行する。１．１，４．４−テ
トラキス（４−ヒドロキシフェニル）−シクロヘキサン
（■°）を例に挙げて説明すると以下のようになる。This decomposition reaction proceeds as follows. The following is an explanation using 1.1,4.4-tetrakis(4-hydroxyphenyl)-cyclohexane (■°) as an example.
（Ｂ） （ｎ’）即ち、式（ビ）
化合物が分解されて弐（Ａ）で示される中間体となり、
この化合物（Ａ）が不均化反応を起こして、通常約２＝
１で目的の（■”）と副生物（Ｂ）となる。この不均化
反応は、水素移動反応であるので、水素移動触媒の使用
により、温和な条件で反応を進めることが好ましい。(B) (n'), that is, formula (Bi)
The compound is decomposed to become the intermediate shown by (A),
This compound (A) causes a disproportionation reaction, usually about 2=
In step 1, the target (■'') and by-product (B) are obtained. Since this disproportionation reaction is a hydrogen transfer reaction, it is preferable to proceed with the reaction under mild conditions by using a hydrogen transfer catalyst.
また、反応系に水素移動触媒と水素受容体を加えること
により、（Ｂ）の４．４’−ジヒドロキシターフェニル
のみを効率よく製造できることを本発明者らは別に提案
したが、本発明方法においては、水素受容体を使用しな
い。水素受容体の使用は（Ｂ）のみへの反応を増し、目
的の（■゛）の収率が低下する。In addition, the present inventors have separately proposed that only 4,4'-dihydroxyterphenyl (B) can be efficiently produced by adding a hydrogen transfer catalyst and a hydrogen acceptor to the reaction system, but in the method of the present invention, does not use hydrogen acceptors. The use of a hydrogen acceptor increases the reaction to only (B) and reduces the yield of the desired (■゛).
分解反応においては塩基又は酸触媒が使用される。効率
的な分解用触媒は、水酸化ナトリウム、水酸化カリウム
、水酸化リチウム等の如きアルカリ金属水酸化物、水酸
化マグネシウム、水酸化バリウム等の如きアルカリ土類
金属水酸化物、炭酸塩、酢酸塩、フェノキシト、有機弱
酸の塩を包含する。Base or acid catalysts are used in the decomposition reaction. Efficient decomposition catalysts include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, etc., alkaline earth metal hydroxides such as magnesium hydroxide, barium hydroxide, etc., carbonates, acetic acid, etc. salts, phenoxides, and salts of weak organic acids.
また酸類としては、Ｐ−トルエンスルホン酸の如き、酸
、亜硫酸水素カリウムの如き弱酸性の酸塩、塩化アルミ
ニウム、塩化第一すず及びその他の酸性金属塩化物が包
含される。Examples of acids include acids such as P-toluenesulfonic acid, weakly acidic acid salts such as potassium bisulfite, aluminum chloride, stannous chloride, and other acidic metal chlorides.
特に好ましい触媒は、水酸化ナトリウム等の強塩基性触
媒である。その使用量は通常、式（１）のテトラキス（
４−ヒドロキシフェニル）−シクロヘキサンに対し通常
０．１〜４０重量％、好ましくは１〜２０重量％の範囲
である。Particularly preferred catalysts are strongly basic catalysts such as sodium hydroxide. The amount used is usually tetrakis (
The amount is usually 0.1 to 40% by weight, preferably 1 to 20% by weight based on 4-hydroxyphenyl)-cyclohexane.
本発明方法は水素移動触媒なしでも実施できるが、水素
移動触媒を共存させることにより、より高収率で、また
より温和な条件で実施できる。The method of the present invention can be carried out without a hydrogen transfer catalyst, but by coexisting with a hydrogen transfer catalyst, it can be carried out in higher yields and under milder conditions.
水素移動触媒は公知のものなら特に限定されないが、例
えば、ラネーニッケル、還元ニッケル、ニッケルを珪藻
土、アルミナ、軽石、シリカゲル、酸性白土などの種々
の担体に担持したニッケル担体触媒、ラネーコバルト、
還元コバルト、コバルト−担体触媒などのコバルト触媒
、ラネー銅、還元銅、銅−担体触媒などの銅触媒、パラ
ジウム黒、酸化パラジウム、コロイドパラジウム、パラ
ジウム−炭素、パラジウム−硫酸バリウム、パラジウム
−酸化マグネシウム、パラジウム−酸化カルシウム、パ
ラジウム−アルミナなどのパラジウム触媒、白金黒、コ
ロイド白金、酸化白金、硫化白金、白金−炭素のどの白
金−担体触媒等の白金触媒、コロイドロジウム、ロジウ
ム−炭素、酸化ロジウムなどのロジウム触媒、ルテニウ
ム触媒などの白金族触媒、七酸化ニレニウム、レニウム
−炭素などのレニウム触媒、銅クロム酸化物触媒、酸化
モリブデン触媒、酸化バナジウム触媒、酸化タングステ
ン触媒、銀触媒などが挙げられる。Hydrogen transfer catalysts are not particularly limited as long as they are known, but examples include Raney nickel, reduced nickel, nickel supported catalysts in which nickel is supported on various carriers such as diatomaceous earth, alumina, pumice, silica gel, and acid clay, Raney cobalt,
Cobalt catalysts such as reduced cobalt, cobalt-supported catalysts, copper catalysts such as Raney copper, reduced copper, copper-supported catalysts, palladium black, palladium oxide, colloidal palladium, palladium-carbon, palladium-barium sulfate, palladium-magnesium oxide, Palladium catalysts such as palladium-calcium oxide, palladium-alumina, platinum catalysts such as platinum black, colloidal platinum, platinum oxide, platinum sulfide, platinum-carbon supported platinum catalysts, colloidal rhodium, rhodium-carbon, rhodium oxide, etc. Examples include platinum group catalysts such as rhodium catalysts and ruthenium catalysts, rhenium catalysts such as nyrenium heptoxide and rhenium-carbon, copper chromium oxide catalysts, molybdenum oxide catalysts, vanadium oxide catalysts, tungsten oxide catalysts, and silver catalysts.
これらの触媒の内ではパラジウム触媒等白金族触媒が好
ましい、これらの水素移動触媒の使用割合は、前記−最
大（１）で表されるテトラキス（４−ヒドロキシフェニ
ル）−シクロヘキサン１モルに対し前記触媒の金属原子
として通常０．００１〜０．２グラム原子、好ましくは
０．００２〜０．０１グラム原子の範囲である。Among these catalysts, platinum group catalysts such as palladium catalysts are preferable.The usage ratio of these hydrogen transfer catalysts is as follows: - Maximum ratio of the above catalyst to 1 mole of tetrakis(4-hydroxyphenyl)-cyclohexane represented by (1). The metal atom is usually in the range of 0.001 to 0.2 gram atom, preferably 0.002 to 0.01 gram atom.
反応温度は１００〜４００℃、好ましくは１５０〜３０
０℃の範囲で実施するのが良い０反応温度が低い場合は
反応速度が小さく、高い場合は副反応が起こり得策では
ない。The reaction temperature is 100-400°C, preferably 150-30°C.
It is preferable to carry out the reaction in the range of 0°C. If the reaction temperature is low, the reaction rate is low, and if it is high, side reactions may occur.
本発明方法は気相でも実施することができるが、原料や
生成物の融点が高いので、気相反応の場合は３００℃以
上の高温を必要とし、収率、操作性、エネルギー等の面
から液相で実施するのが好ましい、その際、溶媒の存在
下に実施するのが良く、具体的には水のほかエチレング
リコールモノメチルエーテル、エチレングリコールジメ
チルエーテル、ジエチレングリコールモノメチルエーテ
ル、テトラヒドロフラン、ジオキサン、ジプロピルエー
テル、ジフェニルエーテル等のエーテル、エタノール、
イソプロパツール、エチレングリコール、ジエチレング
リコール、トリエチレングリコール、プロピレングリコ
ール等のアルコール、アセトニトリル、プロピオニトリ
ル、ベンゾニトリル等のニトリル、ベンゼン、トルエン
、キシレン、メシチレン、エチルベンゼン、クメン等の
芳香族炭化水素などが挙げられる。The method of the present invention can be carried out in the gas phase, but since the melting points of the raw materials and products are high, a high temperature of 300°C or higher is required in the case of a gas phase reaction, which is disadvantageous in terms of yield, operability, energy, etc. It is preferable to carry out the process in a liquid phase. In this case, it is preferable to carry out the process in the presence of a solvent. Specifically, in addition to water, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, tetrahydrofuran, dioxane, and dipropyl ether are used. , ethers such as diphenyl ether, ethanol,
Alcohols such as isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, nitriles such as acetonitrile, propionitrile, benzonitrile, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, ethylbenzene, cumene, etc. Can be mentioned.
また、スチレン類、フェノール類、ニトロベンゼン、ア
セトンの如き水素受容性の溶媒の使眉は副生の４，４＃
−ジヒドロキシクーフェニル類の生成量を高め、その分
ビス（４−ヒドロキシフェニル）−シクロヘキサンの収
率が低下するので好ましくない。In addition, the use of hydrogen-accepting solvents such as styrenes, phenols, nitrobenzene, and acetone can cause the by-product 4,4#.
This is not preferable because it increases the amount of -dihydroxycuphenyls produced and reduces the yield of bis(4-hydroxyphenyl)-cyclohexane accordingly.
このようにして生成したビス（４−ヒドロキシフェニル
）−シクロへ′キサンは、反応終了後の混合物より水素
移動触媒を分離したのち、酸析や再結晶等の方法で取り
出すことができる。The bis(4-hydroxyphenyl)-cyclohexane thus produced can be recovered by methods such as acid precipitation and recrystallization after separating the hydrogen transfer catalyst from the mixture after the reaction is completed.
また、本発明方法に於いて、必ず副生ずる４、４”−ジ
ヒドロキシターフェニル類は、式（ＩＩ）のビス（４−
ヒドロキシフェニル）−シクロヘキサンと、酸性度、溶
解度等が異なるので、ｐｌ＋を調整して酸析を行うこと
により、あるいは抽出、再結晶を行うことにより分Ｌ！
することができ、高純度のビス（４−ヒドロキシフェニ
ル）−シクロヘキサン及び４，４′−ジヒドロキシター
フェニルを得ることができる。Furthermore, in the method of the present invention, 4,4''-dihydroxyterphenyls, which are always produced as by-products, are bis(4-
Since the acidity, solubility, etc. are different from that of hydroxyphenyl)-cyclohexane, the amount of L!
High purity bis(4-hydroxyphenyl)-cyclohexane and 4,4'-dihydroxyterphenyl can be obtained.
以下、実施例によい本発明を具体的に説明する。Hereinafter, the present invention will be specifically explained with reference to Examples.
〔実施例−１〕
１．４−シクロヘキサンジオンとフェノールを酸触媒下
に反応させて１，１，４．４−テトラキス（４−ヒドロ
キシフェニル）−シクロヘキサンを得た。[Example-1] 1,1,4,4-tetrakis(4-hydroxyphenyl)-cyclohexane was obtained by reacting 1,4-cyclohexanedione and phenol under an acid catalyst.
このようにして得られた１、１，４．４−テトラキス（
４−ヒドロキシフェニル）−シクロヘキサン４５．３ｇ
（０，１０モル）、苛性ソーダ２．３ｇ、 ５％パラジ
ウム炭素２．３ｇ、水１００ ｄを３００ ｄステンレ
ス製オートクレイプに仕込み、内部を窒素ガスで置換し
たのち１９０°Ｃで６時間反応させた。反応終了後、塩
酸水でｐＨ＝４とし、結晶を分離した。ついでこの結晶
をメタノールに加熱溶解し、不溶のパラジウム炭素を分
離回収した。メタノールを留去して白色結晶２０．４ｇ
を得た。ＨＰＬＣによる１、４−ビス（４−ヒドロキシ
フェニル）−シクロヘキサンの純度６５．１％で不純物
の大部分は４，４“−ジヒドロキシ−ｐ−ターフェニル
であった。純度換算収率４９．５％であった。1,1,4,4-tetrakis (
4-hydroxyphenyl)-cyclohexane 45.3g
(0.10 mol), 2.3 g of caustic soda, 2.3 g of 5% palladium on carbon, and 100 d of water were placed in a 300 d stainless steel autoclave, and after purging the inside with nitrogen gas, they were reacted at 190°C for 6 hours. . After the reaction was completed, the pH was adjusted to 4 with hydrochloric acid and the crystals were separated. The crystals were then heated and dissolved in methanol, and insoluble palladium on carbon was separated and recovered. After distilling off methanol, 20.4g of white crystals were obtained.
I got it. The purity of 1,4-bis(4-hydroxyphenyl)-cyclohexane by HPLC was 65.1%, and most of the impurities were 4,4"-dihydroxy-p-terphenyl. Yield in terms of purity was 49.5%. Met.
〔実施例−２〕
１．３−シクロヘキサンジオンとフェノールから１、Ｌ
３，３−テトラキス（４−ヒドロキシフェニル）−シク
ロヘキサンを同様に合成した。次に１．１゜４．４体に
替え、この１．１，３．３体を用いて実施例−１と同様
に反応、処理して１．３−ビス（４−ヒドロキシフェニ
ル）−シクロヘキサン１９．９ｇを得た。[Example-2] 1, L from 1.3-cyclohexanedione and phenol
3,3-tetrakis(4-hydroxyphenyl)-cyclohexane was similarly synthesized. Next, the 1.1゜4.4 body was replaced with 1.1゜4.4 body, and the 1.1,3.3 body was reacted and treated in the same manner as in Example 1 to produce 1.3-bis(4-hydroxyphenyl)-cyclohexane. 19.9g was obtained.
ＨＰＬＣによる純度６３．９％であり、不純物の大部分
は４．４１−ジヒドロキシ−ｍ−ターフェニルであった
。The purity was 63.9% by HPLC, and most of the impurities were 4.41-dihydroxy-m-terphenyl.
純度換算収率４７．４％であった。The yield in terms of purity was 47.4%.
特許出願人 三井東圧化学株式会社Patent applicant Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
サン環炭素と結合。） で示されるテトラキス（４−ヒドロキシフェニル）−シ
クロヘキサンを水素受容体を使用せずに分解反応させる
ことを特徴とする式（II） ▲数式、化学式、表等があります▼（II） で示されるビス（４−ヒドロキシフェニル）−シクロヘ
キサンの製造方法。(1) Formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, two benzene rings (a) are bonded to the same cyclohexane ring carbon.) Tetrakis (4-hydroxy Bis(4-hydroxyphenyl)-cyclohexane represented by formula (II), which is characterized by decomposition reaction of (phenyl)-cyclohexane without using a hydrogen acceptor. manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62327202A JP2516233B2 (en) | 1987-12-25 | 1987-12-25 | Process for producing bis (4-hydroxyphenyl) -cyclohexane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62327202A JP2516233B2 (en) | 1987-12-25 | 1987-12-25 | Process for producing bis (4-hydroxyphenyl) -cyclohexane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01168634A true JPH01168634A (en) | 1989-07-04 |
| JP2516233B2 JP2516233B2 (en) | 1996-07-24 |
Family
ID=18196455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62327202A Expired - Fee Related JP2516233B2 (en) | 1987-12-25 | 1987-12-25 | Process for producing bis (4-hydroxyphenyl) -cyclohexane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2516233B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002062736A1 (en) * | 2001-02-08 | 2002-08-15 | Honshu Chemical Industry Co., Ltd. | Diphenol and process for producing the same |
| WO2005061473A1 (en) | 2003-12-24 | 2005-07-07 | Sumitomo Chemical Company, Limited | Epoxy compounds and cured epoxy resins obtained by curing the compounds |
| WO2007105809A1 (en) | 2006-03-16 | 2007-09-20 | Sumitomo Chemical Company, Limited | Method for producing epoxy compound |
| WO2008130028A1 (en) | 2007-04-19 | 2008-10-30 | Sumitomo Chemical Company, Limited | Epoxy composition |
| JP2013256494A (en) * | 2012-05-14 | 2013-12-26 | Honshu Chem Ind Co Ltd | Process for production of 1,3-bis(4-hydroxyphenyl)cyclohexane |
-
1987
- 1987-12-25 JP JP62327202A patent/JP2516233B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002062736A1 (en) * | 2001-02-08 | 2002-08-15 | Honshu Chemical Industry Co., Ltd. | Diphenol and process for producing the same |
| WO2005061473A1 (en) | 2003-12-24 | 2005-07-07 | Sumitomo Chemical Company, Limited | Epoxy compounds and cured epoxy resins obtained by curing the compounds |
| US7538166B2 (en) | 2003-12-24 | 2009-05-26 | Sumitomo Chemical Company, Limited | Epoxy compounds and cured epoxy resins obtained by curing the compounds |
| WO2007105809A1 (en) | 2006-03-16 | 2007-09-20 | Sumitomo Chemical Company, Limited | Method for producing epoxy compound |
| WO2008130028A1 (en) | 2007-04-19 | 2008-10-30 | Sumitomo Chemical Company, Limited | Epoxy composition |
| JP2013256494A (en) * | 2012-05-14 | 2013-12-26 | Honshu Chem Ind Co Ltd | Process for production of 1,3-bis(4-hydroxyphenyl)cyclohexane |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2516233B2 (en) | 1996-07-24 |
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