JPH0457694B2 - - Google Patents
Info
- Publication number
- JPH0457694B2 JPH0457694B2 JP62288476A JP28847687A JPH0457694B2 JP H0457694 B2 JPH0457694 B2 JP H0457694B2 JP 62288476 A JP62288476 A JP 62288476A JP 28847687 A JP28847687 A JP 28847687A JP H0457694 B2 JPH0457694 B2 JP H0457694B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- reaction
- ester
- synthesis
- yield
- 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.)
- Expired - Lifetime
Links
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 130
- 238000006243 chemical reaction Methods 0.000 description 96
- 230000015572 biosynthetic process Effects 0.000 description 64
- 238000003786 synthesis reaction Methods 0.000 description 60
- 229920000642 polymer Polymers 0.000 description 43
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 42
- 239000000178 monomer Substances 0.000 description 39
- 150000002148 esters Chemical class 0.000 description 37
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 32
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 31
- 239000000203 mixture Substances 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 22
- 230000004044 response Effects 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- 238000004440 column chromatography Methods 0.000 description 19
- -1 alkene halide Chemical class 0.000 description 18
- 230000005684 electric field Effects 0.000 description 18
- 230000010287 polarization Effects 0.000 description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 18
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 18
- 230000002269 spontaneous effect Effects 0.000 description 17
- 230000007704 transition Effects 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 15
- 230000006399 behavior Effects 0.000 description 15
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 14
- 235000019341 magnesium sulphate Nutrition 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000004973 liquid crystal related substance Substances 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 6
- QGFSQVPRCWJZQK-UHFFFAOYSA-N 9-Decen-1-ol Chemical compound OCCCCCCCCC=C QGFSQVPRCWJZQK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- LAEZQMVVQHICOO-UHFFFAOYSA-N 2-chloro-3-methylpentan-1-ol Chemical compound CCC(C)C(Cl)CO LAEZQMVVQHICOO-UHFFFAOYSA-N 0.000 description 5
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 5
- WYUVZDIOIFXZSJ-UHFFFAOYSA-N 2-methylbutyl 4-(4-hydroxyphenyl)benzoate Chemical compound C1=CC(C(=O)OCC(C)CC)=CC=C1C1=CC=C(O)C=C1 WYUVZDIOIFXZSJ-UHFFFAOYSA-N 0.000 description 5
- GDBUZIKSJGRBJP-UHFFFAOYSA-N 4-acetoxy benzoic acid Chemical compound CC(=O)OC1=CC=C(C(O)=O)C=C1 GDBUZIKSJGRBJP-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 125000001033 ether group Chemical group 0.000 description 5
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 5
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- QOCVTOZYTRKRHI-UHFFFAOYSA-N 10-chlorodec-1-ene Chemical compound ClCCCCCCCCC=C QOCVTOZYTRKRHI-UHFFFAOYSA-N 0.000 description 4
- PXUHUAWWMDRECM-UHFFFAOYSA-N 2-fluorooctan-1-ol Chemical compound CCCCCCC(F)CO PXUHUAWWMDRECM-UHFFFAOYSA-N 0.000 description 4
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 4
- JTGCXYYDAVPSFD-UHFFFAOYSA-N 4-(4-hydroxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(O)C=C1 JTGCXYYDAVPSFD-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- QNXYZQSFDTZEBK-UHFFFAOYSA-N dodec-11-en-1-ol Chemical compound OCCCCCCCCCCC=C QNXYZQSFDTZEBK-UHFFFAOYSA-N 0.000 description 4
- 230000005621 ferroelectricity Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- SJWFXCIHNDVPSH-MRVPVSSYSA-N (2R)-octan-2-ol Chemical compound CCCCCC[C@@H](C)O SJWFXCIHNDVPSH-MRVPVSSYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-BYPYZUCNSA-N (2S)-butan-2-ol Chemical compound CC[C@H](C)O BTANRVKWQNVYAZ-BYPYZUCNSA-N 0.000 description 3
- QPKMYSABIIWIIS-UHFFFAOYSA-N 12-chlorododec-1-ene Chemical compound ClCCCCCCCCCCC=C QPKMYSABIIWIIS-UHFFFAOYSA-N 0.000 description 3
- YCVMFKRVGOAHAA-UHFFFAOYSA-N 2-methylbutyl 4-hydroxybenzoate Chemical compound CCC(C)COC(=O)C1=CC=C(O)C=C1 YCVMFKRVGOAHAA-UHFFFAOYSA-N 0.000 description 3
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004990 Smectic liquid crystal Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- FYXQIMAAEMCZLV-UHFFFAOYSA-N ethyl 4-(4-hydroxyphenyl)benzoate Chemical compound C1=CC(C(=O)OCC)=CC=C1C1=CC=C(O)C=C1 FYXQIMAAEMCZLV-UHFFFAOYSA-N 0.000 description 3
- GPOPHQSTNHUENT-UHFFFAOYSA-N methyl ethyl caproic acid Natural products CCC(C)CCCCC(O)=O GPOPHQSTNHUENT-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- NBUCOPILRSUCHR-UHFFFAOYSA-N 2-(hydroxymethyl)butanenitrile Chemical compound CCC(CO)C#N NBUCOPILRSUCHR-UHFFFAOYSA-N 0.000 description 2
- VZIQXGLTRZLBEX-UHFFFAOYSA-N 2-chloro-1-propanol Chemical compound CC(Cl)CO VZIQXGLTRZLBEX-UHFFFAOYSA-N 0.000 description 2
- QMYSXXQDOZTXAE-UHFFFAOYSA-N 2-chloro-3-methylpentanoic acid Chemical compound CCC(C)C(Cl)C(O)=O QMYSXXQDOZTXAE-UHFFFAOYSA-N 0.000 description 2
- FTOKYBLHOYVORA-UHFFFAOYSA-N 2-chlorobutan-1-ol Chemical compound CCC(Cl)CO FTOKYBLHOYVORA-UHFFFAOYSA-N 0.000 description 2
- RVBUZBPJAGZHSQ-UHFFFAOYSA-N 2-chlorobutanoic acid Chemical compound CCC(Cl)C(O)=O RVBUZBPJAGZHSQ-UHFFFAOYSA-N 0.000 description 2
- XNINAOUGJUYOQX-UHFFFAOYSA-N 2-cyanobutanoic acid Chemical compound CCC(C#N)C(O)=O XNINAOUGJUYOQX-UHFFFAOYSA-N 0.000 description 2
- NVIVQGNQOLBSLT-UHFFFAOYSA-N 2-fluorohexan-1-ol Chemical compound CCCCC(F)CO NVIVQGNQOLBSLT-UHFFFAOYSA-N 0.000 description 2
- LRKCNYYCJZXSHR-UHFFFAOYSA-N 2-fluorononan-1-ol Chemical compound CCCCCCCC(F)CO LRKCNYYCJZXSHR-UHFFFAOYSA-N 0.000 description 2
- SASJUHYALINSSV-UHFFFAOYSA-N 2-fluorooctanoic acid Chemical compound CCCCCCC(F)C(O)=O SASJUHYALINSSV-UHFFFAOYSA-N 0.000 description 2
- BGSOIHDNGJTTCV-UHFFFAOYSA-N 2-fluorooctyl 4-hydroxybenzoate Chemical compound CCCCCCC(F)COC(=O)C1=CC=C(O)C=C1 BGSOIHDNGJTTCV-UHFFFAOYSA-N 0.000 description 2
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 2
- OVBFMEVBMNZIBR-UHFFFAOYSA-N 2-methylvaleric acid Chemical compound CCCC(C)C(O)=O OVBFMEVBMNZIBR-UHFFFAOYSA-N 0.000 description 2
- IWTBVKIGCDZRPL-UHFFFAOYSA-N 3-methylpentanol Chemical compound CCC(C)CCO IWTBVKIGCDZRPL-UHFFFAOYSA-N 0.000 description 2
- IGIDLTISMCAULB-UHFFFAOYSA-N 3-methylvaleric acid Chemical compound CCC(C)CC(O)=O IGIDLTISMCAULB-UHFFFAOYSA-N 0.000 description 2
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 2
- DQHUGAIXHZQNOJ-UHFFFAOYSA-N 4-dec-1-enoxybenzoyl chloride Chemical compound CCCCCCCCC=COC1=CC=C(C(Cl)=O)C=C1 DQHUGAIXHZQNOJ-UHFFFAOYSA-N 0.000 description 2
- YNPVNLWKVZZBTM-UHFFFAOYSA-N 4-methylhexan-1-ol Chemical compound CCC(C)CCCO YNPVNLWKVZZBTM-UHFFFAOYSA-N 0.000 description 2
- KFARNLMRENFOHE-UHFFFAOYSA-N 5-methylheptan-1-ol Chemical compound CCC(C)CCCCO KFARNLMRENFOHE-UHFFFAOYSA-N 0.000 description 2
- WWRGKAMABZHMCN-UHFFFAOYSA-N 6-methyloctan-1-ol Chemical compound CCC(C)CCCCCO WWRGKAMABZHMCN-UHFFFAOYSA-N 0.000 description 2
- SNMOMUYLFLGQQS-UHFFFAOYSA-N 8-bromooct-1-ene Chemical compound BrCCCCCCC=C SNMOMUYLFLGQQS-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000002140 halogenating effect Effects 0.000 description 2
- UIZVMOZAXAMASY-UHFFFAOYSA-N hex-5-en-1-ol Chemical compound OCCCCC=C UIZVMOZAXAMASY-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 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
- URSAOWKEGRPVPC-UHFFFAOYSA-N (2-chloro-3-methylpentyl) 4-hydroxybenzoate Chemical compound CCC(C)C(Cl)COC(=O)C1=CC=C(O)C=C1 URSAOWKEGRPVPC-UHFFFAOYSA-N 0.000 description 1
- BTANRVKWQNVYAZ-SCSAIBSYSA-N (2R)-butan-2-ol Chemical compound CC[C@@H](C)O BTANRVKWQNVYAZ-SCSAIBSYSA-N 0.000 description 1
- SJWFXCIHNDVPSH-QMMMGPOBSA-N (2S)-octan-2-ol Chemical compound CCCCCC[C@H](C)O SJWFXCIHNDVPSH-QMMMGPOBSA-N 0.000 description 1
- GAWAYYRQGQZKCR-UWTATZPHSA-N (2r)-2-chloropropanoic acid Chemical compound C[C@@H](Cl)C(O)=O GAWAYYRQGQZKCR-UWTATZPHSA-N 0.000 description 1
- JYVLIDXNZAXMDK-YFKPBYRVSA-N (2s)-pentan-2-ol Chemical compound CCC[C@H](C)O JYVLIDXNZAXMDK-YFKPBYRVSA-N 0.000 description 1
- VTMXYYQJEPXEIM-UHFFFAOYSA-N (4-butan-2-yloxycarbonylphenyl) 4-dec-9-enoxybenzoate Chemical compound C1=CC(C(=O)OC(C)CC)=CC=C1OC(=O)C1=CC=C(OCCCCCCCCC=C)C=C1 VTMXYYQJEPXEIM-UHFFFAOYSA-N 0.000 description 1
- NNPICKDDMMMVQW-UHFFFAOYSA-N (4-pentan-2-yloxycarbonylphenyl) 4-dec-9-enoxybenzoate Chemical compound C1=CC(C(=O)OC(C)CCC)=CC=C1OC(=O)C1=CC=C(OCCCCCCCCC=C)C=C1 NNPICKDDMMMVQW-UHFFFAOYSA-N 0.000 description 1
- DIVCBWJKVSFZKJ-ZCFIWIBFSA-N (4r)-4-methylhexanoic acid Chemical compound CC[C@@H](C)CCC(O)=O DIVCBWJKVSFZKJ-ZCFIWIBFSA-N 0.000 description 1
- DIVCBWJKVSFZKJ-LURJTMIESA-N (4s)-4-methylhexanoic acid Chemical compound CC[C@H](C)CCC(O)=O DIVCBWJKVSFZKJ-LURJTMIESA-N 0.000 description 1
- GAWAYYRQGQZKCR-REOHCLBHSA-N (S)-2-chloropropanoic acid Chemical compound C[C@H](Cl)C(O)=O GAWAYYRQGQZKCR-REOHCLBHSA-N 0.000 description 1
- WLAMNBDJUVNPJU-BYPYZUCNSA-N (S)-2-methylbutyric acid Chemical compound CC[C@H](C)C(O)=O WLAMNBDJUVNPJU-BYPYZUCNSA-N 0.000 description 1
- AWRUMPCQJSCWRV-UHFFFAOYSA-N 2-methylbutyl 4-[4-(4-dec-9-enoxybenzoyl)oxyphenyl]benzoate Chemical compound C1=CC(C(=O)OCC(C)CC)=CC=C1C(C=C1)=CC=C1OC(=O)C1=CC=C(OCCCCCCCCC=C)C=C1 AWRUMPCQJSCWRV-UHFFFAOYSA-N 0.000 description 1
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 1
- DIVCBWJKVSFZKJ-UHFFFAOYSA-N 4-methylhexanoic acid Natural products CCC(C)CCC(O)=O DIVCBWJKVSFZKJ-UHFFFAOYSA-N 0.000 description 1
- LZIFXXVPLXFRNI-UHFFFAOYSA-N 4-oct-7-enoxybenzoic acid Chemical compound OC(=O)C1=CC=C(OCCCCCCC=C)C=C1 LZIFXXVPLXFRNI-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- RIMXEJYJXDBLIE-UHFFFAOYSA-N 6-bromohex-1-ene Chemical compound BrCCCCC=C RIMXEJYJXDBLIE-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- UNLWKCQMJLSQSS-UHFFFAOYSA-N [4-(2-chloro-3-methylpentoxy)carbonylphenyl] 4-dec-9-enoxybenzoate Chemical compound C1=CC(C(=O)OCC(Cl)C(C)CC)=CC=C1OC(=O)C1=CC=C(OCCCCCCCCC=C)C=C1 UNLWKCQMJLSQSS-UHFFFAOYSA-N 0.000 description 1
- IGXFONJVKZEWBP-UHFFFAOYSA-N [4-(2-fluorooctoxycarbonyl)phenyl] 4-dec-9-enoxybenzoate Chemical compound C1=CC(C(=O)OCC(F)CCCCCC)=CC=C1OC(=O)C1=CC=C(OCCCCCCCCC=C)C=C1 IGXFONJVKZEWBP-UHFFFAOYSA-N 0.000 description 1
- UIEWETXPGFWKAS-UHFFFAOYSA-N [4-(2-methylbutoxycarbonyl)phenyl] 4-(4-dec-9-enoxyphenyl)benzoate Chemical compound C1=CC(C(=O)OCC(C)CC)=CC=C1OC(=O)C1=CC=C(C=2C=CC(OCCCCCCCCC=C)=CC=2)C=C1 UIEWETXPGFWKAS-UHFFFAOYSA-N 0.000 description 1
- MUTQJZXDJHIEHQ-UHFFFAOYSA-N [4-(2-methylbutoxycarbonyl)phenyl] 4-dec-9-enoxybenzoate Chemical compound C1=CC(C(=O)OCC(C)CC)=CC=C1OC(=O)C1=CC=C(OCCCCCCCCC=C)C=C1 MUTQJZXDJHIEHQ-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- ZUOTXZHOGPQFIU-UHFFFAOYSA-N butan-2-yl 4-hydroxybenzoate Chemical compound CCC(C)OC(=O)C1=CC=C(O)C=C1 ZUOTXZHOGPQFIU-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004403 ethyl p-hydroxybenzoate Substances 0.000 description 1
- 229940043351 ethyl-p-hydroxybenzoate Drugs 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RBBOWEDMXHTEPA-UHFFFAOYSA-N hexane;toluene Chemical compound CCCCCC.CC1=CC=CC=C1 RBBOWEDMXHTEPA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- WXPWPYISTQCNDP-UHFFFAOYSA-N oct-7-en-1-ol Chemical compound OCCCCCCC=C WXPWPYISTQCNDP-UHFFFAOYSA-N 0.000 description 1
- JNXAOLWWDAIBSE-UHFFFAOYSA-N octan-2-yl 4-hydroxybenzoate Chemical compound CCCCCCC(C)OC(=O)C1=CC=C(O)C=C1 JNXAOLWWDAIBSE-UHFFFAOYSA-N 0.000 description 1
- ZSSKNOXKMJCTRN-UHFFFAOYSA-N octan-2-yl 4-hydroxybenzoate;thionyl dichloride Chemical compound ClS(Cl)=O.CCCCCCC(C)OC(=O)C1=CC=C(O)C=C1 ZSSKNOXKMJCTRN-UHFFFAOYSA-N 0.000 description 1
- VIZHEHGQHCKXBS-UHFFFAOYSA-N pentan-2-yl 4-hydroxybenzoate Chemical compound CCCC(C)OC(=O)C1=CC=C(O)C=C1 VIZHEHGQHCKXBS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
- Polyethers (AREA)
Description
〔産業上の利用分野〕
本発明は新規なポリマーに関するものである。
さらに詳しくいえば、本発明はオプトエレクトロ
ニクス分野、特に電卓、時計などの表示素子、電
子光学シヤツター、電子光学絞り、光変調器、光
通信光路切換スイツチ、メモリー、液晶プリンタ
ーヘツド、焦点距離可変レンズなどの種々の電子
光学デバイスとして有用な、常温付近でも強誘電
性を示す上に、外的因子に対する応答速度が速く
て動画表示が可能であり、かつ大画面や屈曲画面
の表示素子として有利に使用しうる液晶性を有す
るポリマーに関するものである。
〔従来の技術〕
従来、低分子液晶を用いた表示素子は電卓、時
計などのデジタル表示に広く使用されている。こ
れらの利用分野では、通常、従来の低分子液晶は
間隔をミクロンオーダーで制御した２枚のガラス
基板の間にはさんで使用されている。しかしなが
ら、このような間〓の調整は大型画面および曲面
画面では実現が不可能であつた。この難点を解決
する１つの手段として、液晶を高分子化し、それ
自体を成形可能ならしめることが試みられている
（J.Polym.Sci、Polym.Lett.、Ed.13、243（1975）、
Polym.Bull.６、309（1982）、特開昭55−21479号
公報など）。
しかしながら、これらの液晶ポリマーにおいて
は、電界など外的因子の変化に対するその透過光
量変化等の応答速度が一般に遅く、未だ満足しう
るものは得られていない。
また、前記公開公報に示されている液晶ポリマ
ーは、ポリマー自体は常温では液晶としての性質
を示さず、ガラス転移温度以上で透明化温度未満
の温度範囲で加熱して液晶化しなければならない
という欠点を有している。
〔発明が解決しようとする問題点〕
本発明は、常温付近でも強誘電性を示す上に、
外的因子に対する応答が速く動画表示が可能であ
り、かつ大画面、屈曲画面の表示素子として有利
に使用できるポリマーを提供しようとするもので
ある。
〔問題点を解決するための手段〕
本発明者らは、鋭意検討を重ねた結果、特定の
構造を有するポリエーテル型ポリマーが常温付近
で強誘電性を示すことを見い出し、本発明を完成
するに至つた。
すなわち、本発明は、下記一般式からなる繰り
返し単位を有するポリマーを提供するものであ
る。
（式中、ｋは１〜30の整数であり、
R1は
[Industrial Application Field] The present invention relates to a novel polymer.
More specifically, the present invention is applicable to the field of optoelectronics, particularly display elements for calculators and watches, electro-optical shutters, electro-optical apertures, optical modulators, optical communication optical path switching switches, memories, liquid crystal printer heads, variable focal length lenses, etc. It is useful as a variety of electro-optical devices.It shows ferroelectricity even at room temperature, has a fast response speed to external factors, and can display moving images, and can be advantageously used as a display element for large screens and curved screens. This invention relates to polymers with liquid crystal properties that can be used. [Prior Art] Conventionally, display elements using low-molecular liquid crystals have been widely used for digital displays in calculators, watches, and the like. In these fields of application, conventional low-molecular liquid crystals are usually used by sandwiching them between two glass substrates whose spacing is controlled on the order of microns. However, such time adjustment has not been possible with large screens and curved screens. As a means to solve this difficulty, attempts have been made to polymerize liquid crystals and make them moldable (J. Polym. Sci, Polym. Lett., Ed. 13 , 243 (1975),
Polym. Bull. 6 , 309 (1982), Japanese Unexamined Patent Publication No. 55-21479, etc.). However, in these liquid crystal polymers, the response speed of changes in the amount of transmitted light, etc. to changes in external factors such as electric field is generally slow, and a satisfactory product has not yet been obtained. Furthermore, the liquid crystal polymer disclosed in the above-mentioned publication has the disadvantage that the polymer itself does not exhibit liquid crystal properties at room temperature, and must be heated in a temperature range above the glass transition temperature and below the transparency temperature to become liquid crystal. have. [Problems to be solved by the invention] The present invention exhibits ferroelectricity even at room temperature, and
The present invention aims to provide a polymer that has a quick response to external factors, is capable of displaying moving images, and can be advantageously used as a display element for large screens and curved screens. [Means for Solving the Problems] As a result of extensive studies, the present inventors discovered that a polyether type polymer having a specific structure exhibits ferroelectricity at around room temperature, and completed the present invention. It came to this. That is, the present invention provides a polymer having a repeating unit represented by the following general formula. (In the formula, k is an integer from 1 to 30, and R 1 is
【式】【formula】
【式】【formula】
【式】または[expression] or
【式】であり、
Ｘは−COO−または−OCO−であり、
R2は−COOR3、−OCOR3、または−OR3であ
り、
R3は[Formula], X is -COO- or -OCO-, R 2 is -COOR 3 , -OCOR 3 or -OR 3 , and R 3 is
【式】
であり、
R4およびR5はそれぞれ−CH3、ハロゲン原子、
または−CNであり、
ｍおよびｎはそれぞれ０〜10の整数であり、た
だしR4が−CH3である場合にはｎは０ではなく、
ｐは０または１であり、
＊のついたＣは不斉炭素原子である。）
本発明のポリマーの数平均分子量は、200を越
え、400000以下である。2000以下であるとである
と該ポリマーのフイルム、塗膜としての成形性に
支障を生じる場合があり、一方、400000を越える
と応答速度が小さいなどの好ましくない効果の現
れることがある。そして、数平均分子量の特に好
ましい範囲はR1の種類、ｋの値、R3の光学純度
などに依存するので一概に規定できないが、3000
〜200000である。
以下に、本発明のポリマーの一般的な合成方法
を示す。
本発明のポリマーは、下記一般式
（ここで、ｋ、Ｘ、R1、R2、R3、R4、ｍ、およ
びｎは先に規定したと同じ意味を有する。）
で示されるモノマーを公知の方法で重合すること
により得ることができる。
これらのモノマーは例えば次のようにして得る
ことができる。
(1) R1が[Formula], R 4 and R 5 are respectively -CH 3 , halogen atom,
or -CN, m and n are each integers from 0 to 10, provided that when R4 is -CH3 , n is not 0, p is 0 or 1, and C is an asymmetric carbon atom. ) The number average molecular weight of the polymer of the present invention is more than 200 and less than 400,000. If it is less than 2,000, the moldability of the polymer as a film or coating may be impaired, while if it exceeds 400,000, undesirable effects such as low response speed may occur. A particularly preferable range of the number average molecular weight cannot be unconditionally defined because it depends on the type of R 1 , the value of k, the optical purity of R 3 , etc.
~200000. A general method for synthesizing the polymer of the present invention is shown below. The polymer of the present invention has the following general formula: (Here, k, X, R 1 , R 2 , R 3 , R 4 , m, and n have the same meanings as defined above.) be able to. These monomers can be obtained, for example, as follows. (1) R 1 is
【式】である場合
下記の反応式で示されるように、アルケノー
ル（）をピリジンの存在下、塩化チオニル等
のハロゲン化剤でハロゲン化し、アルケンハラ
イド（）を得る。アルケンハライド（）と
化合物（）とを、炭酸カリウム等のアルカリ
の存在下、２−ブタノン等の適当な溶媒中で反
応させてエーテル体（）を得る。次いで、こ
のエーテル体（）をジクロロメタン等の適当
な溶媒中で、ｍ−クロロ過安息香酸等の過酸で
オキシラン化することにより、目的とするモノ
マー（）を得る。
（式中、Ｙはハロゲンである。）
アルケノール（）としては、例えば、９−
デセン−１−オール、11−ドデセン−１−オー
ル、７−オクテン−１−オール、５−ヘキセン
−１−オールなどが好ましい。
ここで、上記化合物（）
[Formula] As shown in the reaction formula below, an alkenol () is halogenated with a halogenating agent such as thionyl chloride in the presence of pyridine to obtain an alkene halide (). An alkene halide () and a compound () are reacted in a suitable solvent such as 2-butanone in the presence of an alkali such as potassium carbonate to obtain an ether (). Next, the desired monomer (2) is obtained by oxiranizing this ether (2) with a peracid such as m-chloroperbenzoic acid in a suitable solvent such as dichloromethane. (In the formula, Y is a halogen.) As the alkenol (), for example, 9-
Decen-1-ol, 11-dodecen-1-ol, 7-octen-1-ol, 5-hexen-1-ol and the like are preferred. Here, the above compound ()
【式】 は、下記の如くして合成される。 〔【formula】 is synthesized as follows. [
【式】の合成〕
下記反応式に示す如く、4′−ヒドロキシビフ
エニル−４−カルボン酸と光学活性アルコール
（）とを、適当な溶媒、例えばベンゼンなど
の溶媒中において、エステル化触媒、例えば濃
硫酸やｐ−トルエンスルホン酸などの存在下
に、所望の温度で反応させることにより、この
エステル化合物（）を得る。
光学活性アルコール（）としては、例えば
（＋）−２−メチルブタノール、（−）−２−メチ
ルブタノール、（＋）−２−クロロブタノール、
（−）−２−クロルブタノール、（＋）−２−メチ
ルペンタノール、（−）−２−メチルペンタノー
ル、（＋）−３−メチルペンタノール、（−）−３
−メチルペンタノール、（＋）−４−メチルヘキ
サノール、（−）−４−メチルヘキサノール、
（＋）−２−クロルプロパノール、（−）−２−ク
ロルプロパノール、（＋）−５−メチルヘプタノ
ール、（−）−５−メチルヘプタノール、（＋）−
６−メチルオクタノール、（−）−６−メチルオ
クタノール、（＋）−２−シアノブタノール、
（−）−２−シアノブタノール、（＋）−２−ブタ
ノール、（−）−２−ブタノール、（＋）−２−ペ
ンタノール、（−）−２−ペンタノール、（＋）−
２−オクタノール、（−）−２−オクタノール、
（＋）−２−フルオロオクタノール、（−）−２−
フルオロオクタノール、（＋）−２−フルオロヘ
キサノール、（−）−２−フルオロヘキサノー
ル、（＋）−２−フルオロノナノール、（−）−２
−フルオロノナノール、（＋）−２−クロロ−３
−メチルペンタノール、（−）−２−クロロ−３
−メチルペンタノールなどが用いられる。
好ましくは（−）−２−メチルブタノール、
（＋）−２−ブタノール、（−）−２−ペンタノー
ル、（−）−２−オクタノール、（−）−２−フル
オロオクタノール、および（−）−２−クロロ
−３−メチルペンタノールが用いられる。
〔Synthesis of [Formula]] As shown in the reaction formula below, 4'-hydroxybiphenyl-4-carboxylic acid and an optically active alcohol () are mixed in a suitable solvent such as benzene, and an esterification catalyst, e.g. This ester compound () is obtained by reacting at a desired temperature in the presence of concentrated sulfuric acid, p-toluenesulfonic acid, or the like. Examples of the optically active alcohol () include (+)-2-methylbutanol, (-)-2-methylbutanol, (+)-2-chlorobutanol,
(-)-2-chlorobutanol, (+)-2-methylpentanol, (-)-2-methylpentanol, (+)-3-methylpentanol, (-)-3
-methylpentanol, (+)-4-methylhexanol, (-)-4-methylhexanol,
(+)-2-chloropropanol, (-)-2-chloropropanol, (+)-5-methylheptanol, (-)-5-methylheptanol, (+)-
6-methyloctanol, (-)-6-methyloctanol, (+)-2-cyanobutanol,
(-)-2-cyanobutanol, (+)-2-butanol, (-)-2-butanol, (+)-2-pentanol, (-)-2-pentanol, (+)-
2-octanol, (-)-2-octanol,
(+)-2-fluorooctanol, (-)-2-
Fluorooctanol, (+)-2-fluorohexanol, (-)-2-fluorohexanol, (+)-2-fluorononanol, (-)-2
-Fluorononanol, (+)-2-chloro-3
-methylpentanol, (-)-2-chloro-3
-Methylpentanol etc. are used. Preferably (-)-2-methylbutanol,
(+)-2-butanol, (-)-2-pentanol, (-)-2-octanol, (-)-2-fluorooctanol, and (-)-2-chloro-3-methylpentanol were used. It will be done. [
【式】の合成〕
下記反応式に示す如く、ビフエニル−４，
4′−ジオールと光学活性カルボン酸（）を反
応させることにより、このエステル化合物
（）が得られる。
光学活性カルボン酸（）としては、例え
ば、（＋）−２−メチルブタン酸、（−）−２−メ
チルブタン酸、（＋）−２−クロルブタン酸、
（−）−２−クロルブタン酸、（＋）−２−メチル
ペンタン酸、（−）−２−メチルペンタン酸、
（＋）−３−メチルペンタン酸、（−）−３−メチ
ルペンタン酸、（＋）−４−メチルヘキサン酸、
（−）−４−メチルヘキサン酸、（＋）−２−クロ
ルプロパン酸、（−）−２−クロルプロパン酸、
（＋）−６−メチルオクタン酸、（−）−６−メチ
ルオクタン酸、（＋）−２−シアノブタン酸、
（−）−２−シアノブタン酸、（＋）−２−フルオ
ロオクタン酸、（−）−２−フルオロオクタン
酸、（＋）−２−クロロ−３−メチルペンタン
酸、（−）−２−クロロ−３−メチルペンタン酸
などが挙げられる。
〔Synthesis of [Formula]] As shown in the reaction formula below, biphenyl-4,
This ester compound () is obtained by reacting 4'-diol with an optically active carboxylic acid (). Examples of the optically active carboxylic acid () include (+)-2-methylbutanoic acid, (-)-2-methylbutanoic acid, (+)-2-chlorobutanoic acid,
(-)-2-chlorobutanoic acid, (+)-2-methylpentanoic acid, (-)-2-methylpentanoic acid,
(+)-3-methylpentanoic acid, (-)-3-methylpentanoic acid, (+)-4-methylhexanoic acid,
(-)-4-methylhexanoic acid, (+)-2-chloropropanoic acid, (-)-2-chloropropanoic acid,
(+)-6-methyloctanoic acid, (-)-6-methyloctanoic acid, (+)-2-cyanobutanoic acid,
(-)-2-cyanobutanoic acid, (+)-2-fluorooctanoic acid, (-)-2-fluorooctanoic acid, (+)-2-chloro-3-methylpentanoic acid, (-)-2-chloro -3-methylpentanoic acid and the like. [
【式】の合成〕
下記の反応式で示されるように、前記光学活
性アルコール〔〕をトシル化し、これにビフ
エニル−４，4′−ジオールを反応させてこのエ
ーテル体（）を得る。
(2) R1が
である場合
下記反応式で示す如く、アルケンハライド
（）とｐ−ヒドロキシ安息香酸エチルエステ
ルとを、アセトン等の適当な溶媒中で炭酸カリ
ウム等のアルカリの存在下で反応させ、エーテ
ル体を得る。次いで、このエーテル体における
カルボキシル基の保護基を水酸化カリウム水溶
液、塩酸等により脱離させ、カルボン酸体とす
る。このカルボン酸体に塩化チオニル等のハロ
ゲン化剤を加え、トルエン等の溶媒中で加熱
し、酸ハライドとする。次いで、この酸ハライ
ドと前記化合物（）とをトルエン等の溶媒中
でピリジンの存在下に反応させ、エステル体
（XI）を得た後、ジクロロメタン等の適当な溶
媒中でｍ−クロロ過安息香酸等の過酸を用いて
オキシラン化することにより、目的とするモノ
マー（XII）を得る。
(3) R1が
である場合
下記反応式で示す如く、アルケンハライド
（）とハイドロキノンとを炭酸カリウム等のア
ルカリの存在下で反応させ、エーテル体（）
を得る。
下記化合物（）を塩化チオニル等により酸
クロリド化する。得られた酸クロリドとエーテル
体（）とをピリジンの存在下反応させ、エス
テル体（）を得る。以後は(1)と同様にオキシ
ラン化を行い、目的とするモノマー（）を得
る。
ここで、上記化合物（）
Synthesis of [Formula]] As shown in the reaction formula below, the optically active alcohol [ ] is tosylated, and this is reacted with biphenyl-4,4'-diol to obtain the ether form ( ). (2) R 1 is As shown in the reaction formula below, an alkene halide () and p-hydroxybenzoic acid ethyl ester are reacted in a suitable solvent such as acetone in the presence of an alkali such as potassium carbonate to obtain an ether. Next, the protecting group of the carboxyl group in this ether form is removed with an aqueous potassium hydroxide solution, hydrochloric acid, etc. to obtain a carboxylic acid form. A halogenating agent such as thionyl chloride is added to this carboxylic acid, and the mixture is heated in a solvent such as toluene to form an acid halide. Next, this acid halide and the above compound () are reacted in the presence of pyridine in a solvent such as toluene to obtain ester compound (XI), and then m-chloroperbenzoic acid is reacted in a suitable solvent such as dichloromethane. The desired monomer (XII) is obtained by oxirane conversion using a peracid such as . (3) R 1 is As shown in the reaction formula below, an alkene halide () and hydroquinone are reacted in the presence of an alkali such as potassium carbonate to form an ether form ().
get. The following compound () is converted into acid chloride using thionyl chloride or the like. The obtained acid chloride and the ether () are reacted in the presence of pyridine to obtain the ester (). Thereafter, oxirane conversion is performed in the same manner as in (1) to obtain the desired monomer (). Here, the above compound ()
【式】 は下記の如くして得られる。 〔【formula】 is obtained as follows. [
【式】の合
成〕
光学活性アルコール（）とビフエニル−
４，4′−ジカルボン酸をトルエン等の溶媒中で
エステル化触媒の存在下反応させ、上記エステ
ル体（）を得る。
〔Synthesis of [Formula]] Optically active alcohol () and biphenyl-
4,4'-dicarboxylic acid is reacted in a solvent such as toluene in the presence of an esterification catalyst to obtain the above ester (2). [
【式】の合
成〕
光学活性カルボン酸（）を塩化チオニル等
により酸クロリド化した後、4′−ヒドロキシビ
フエニル−４−カルボン酸とピリジンの存在下
反応させ、上記エステル体（）を得る。
〔Synthesis of [Formula]] The optically active carboxylic acid () is converted into acid chloride using thionyl chloride or the like, and then reacted with 4'-hydroxybiphenyl-4-carboxylic acid in the presence of pyridine to obtain the above ester (). [
【式】の合成〕
4′−ヒドロキシビフエニル−４−カルボン酸
エチルエステルと光学活性アルコール（）を
トシル化して得たSynthesis of [Formula]] Obtained by tosylating 4'-hydroxybiphenyl-4-carboxylic acid ethyl ester and optically active alcohol ()
【式】
とを炭酸カリウム等の存在下反応させ、エーテ
ル体を得る。このエーテル体をアルカリ水溶液
等と反応させ、保護基のエステルを加水分解
し、上記化合物（）を得る。
(4) R1が[Formula] is reacted in the presence of potassium carbonate, etc. to obtain an ether form. This ether form is reacted with an aqueous alkaline solution or the like to hydrolyze the ester of the protective group to obtain the above compound (). (4) R 1 is
【式】であ
る場合
前記(2)のR1が
であるモノマーの合成法において、化合物
（）[Formula] If R 1 in (2) above is In the method of synthesizing a monomer, the compound ()
【式】 の代わりに化合物（）【formula】 compound () instead of
【式】
を用い、その他は同様にして反応させ、下記の
目的とするモノマー（XI）を得る。
ここで、上記化合物（）は下記の如くし
て得られる。
〔Using [Formula] and reacting in the same manner as above, the following desired monomer (XI) is obtained. Here, the above compound () can be obtained as follows. [
【式】の合成〕
上記(1)における化合物（）の合成におい
て、4′−ヒドロキシビフエニル−４−カルボン
酸の代わりにｐ−ヒドロキシ安息香酸を用い
て、同様の反応を行い、上記エステル体（
XII）を得る。
〔Synthesis of [Formula]] In the synthesis of compound () in (1) above, p-hydroxybenzoic acid was used instead of 4'-hydroxybiphenyl-4-carboxylic acid, and the same reaction was carried out to obtain the above ester form. (
XII). [
【式】の合成〕
上記(1)における化合物（）の合成におい
て、ビフエニル−４，4′−ジオールの代わりに
ハイドロキノンを用いて、同様の反応を行い、
上記エステル体（）を得る。
〔Synthesis of [Formula]] In the synthesis of compound () in (1) above, hydroquinone was used instead of biphenyl-4,4'-diol, and the same reaction was carried out,
The above ester compound () is obtained. [
【式】の合成〕
上記(1)における化合物（）の合成におい
て、ビフエニル−４，4′−ジオールの代わりに
ハイドロキノンを用いて、同様の反応を行い、
上記エーテル体（）を得る。
(5) R1がSynthesis of [Formula]] In the synthesis of compound () in (1) above, hydroquinone was used instead of biphenyl-4,4'-diol, and the same reaction was carried out,
The above ether form () is obtained. (5) R 1 is
【式】であ
る場合
下記反応式で示す如く、上記(3)のR1が
であるモノマーの合成において、化合物（
）[Formula] As shown in the reaction formula below, R 1 in (3) above is In the synthesis of a monomer, the compound (
)
【式】
の代わりに化合物（）
compound () instead of [formula]
【式】
を用いて同様の反応を行い、目的とする下記一
般式のモノマー（）を得る。
ここで、上記化合物（）は下記の如く
して得られる。
〔A similar reaction is carried out using [Formula] to obtain the desired monomer () of the following general formula. Here, the above compound () can be obtained as follows. [
【式】の合成〕
上記(3)における化合物（）の合成におい
て、ビフエニル−４，4′−ジカルボン酸の代わ
りにテレフタル酸を用いて同様の反応を行い、
上記エステル体（）を得る。
〔Synthesis of [Formula]] In the synthesis of compound () in (3) above, a similar reaction is carried out using terephthalic acid instead of biphenyl-4,4'-dicarboxylic acid,
The above ester compound () is obtained. [
【式】の合成〕
上記(3)における化合物（）の合成におい
て、4′−ヒドロキシビフエニル−４−カルボン
酸の代わりにｐ−ヒドロキシ安息香酸を用いて
同様の反応を行い、上記エステル体（）
を得る。
R3COOH
（）→R3COC1
〔Synthesis of [Formula]] In the synthesis of compound () in (3) above, p-hydroxybenzoic acid was used instead of 4'-hydroxybiphenyl-4-carboxylic acid to carry out the same reaction, and the above ester form ( )
get. R 3 COOH () → R 3 COC1 [
【式】の合成〕
上記(3)における化合物（）の合成におい
て、4′−ヒドロキシビフエニル−４−カルボン
酸エチルエステルの代わりにｐ−ヒドロキシ安
息香酸エチルエステルを用いて同様の反応を行
い、上記エーテル体（）を得る。
(6) R1が
である場合
上記(2)のR1が
であるモノマーの合成において、ｐ−ヒドロキ
シ安息香酸エチルエステルの代わりに4′−ヒド
ロキシビフエニル−４−カルボン酸エチルエス
テルを用い、化合物（）
Synthesis of [Formula]] In the synthesis of compound () in (3) above, a similar reaction is carried out using p-hydroxybenzoic acid ethyl ester instead of 4'-hydroxybiphenyl-4-carboxylic acid ethyl ester, The above ether form () is obtained. (6) R 1 is If R 1 in (2) above is In the synthesis of the monomer, 4'-hydroxybiphenyl-4-carboxylic acid ethyl ester was used instead of p-hydroxybenzoic acid ethyl ester, and the compound ()
【式】
の代わりに前記化合物（）
The above compound () in place of [Formula]
【式】
を用いて、同様の反応を行い、目的とする下記
一般式のモノマー（）を得る。
(7) R1が
である場合
上記(3)のR1が
であるモノマーの合成において、ハイドロキノ
ンの代わりにビフエニル−４，4′−１ジオール
を用い、化合物（）
A similar reaction is carried out using [Formula] to obtain the desired monomer () of the following general formula. (7) R 1 is If R 1 in (3) above is In the synthesis of the monomer, biphenyl-4,4'-1 diol is used instead of hydroquinone, and the compound ()
【式】
の代わりに前記化合物（）
The above compound () in place of [Formula]
以下、本発明を実施例により説明するが、本発
明の範囲はこれら実施例によりなんら限定される
ものではない。
なお、得られたポリマーの構造は、NMR、
IR、元素分析により確認し、また相転移温度の
測定および相の確認は、それぞれDSCおよび偏
光顕微鏡により行つた。（glass：ガラス状態、
Cry：結晶状態、S1：未同定のスメクチツク相
（液晶相であるが電解に応答しない相）、SmC*：
カイラルスメクチツクＣ相、SmA：スメチクツ
クＡ相、Ｎ：ネマチツク相、N*：カイラルネマ
チツク相、Iso：等方相、相転移挙動の数字は相
変化温度を℃で表したものである。）
電界応答速度および自発分極値は次のようにし
て測定した。
電界応答速度の測定
20×10mmのITO基板２枚の間にポリマーをはさ
み、スペーサーで厚さを25μｍに調整し、交流電
場Ｅ＝２×106V／ｍをかけ、その際の透過光量
の変化（０→90％）の応答時間を測定した。
自発分極値の測定
面積0.2cm2のITO円形透明電極付ガラス基板で
ポリマーを挟持し、スペーサーで厚さを10μｍに
調整した。波高値200Vの三角波状に変化する電
圧を印加し、この時観測される分極反転電流の信
号から、自発分極値を求めた。
実施例 １
(1) 4′−ヒドロキシビフエニル−４−カルボン酸
２−メチルブチルエステルの合成
4′−ヒドロキシビフエニル−４−カルボン酸
93ミリモル（20ｇ）および（Ｓ）−（−）−２−
メチルブタノール467ミリモル（41ｇ）を濃硫
酸２mlの存在下、ベンゼン150ml中で、水を除
去しながら25時間還流した。反応液を濃縮後、
トルエン−ヘキサン混合溶媒より再結晶し、目
的とするエステル26.0ｇ〔m.p.116〜117.8、
〔α〕23 D＝＋4.35°（CHCl3）〕を得た。（収率98％）
(2) 10−クロロ−１−デセンの合成
９−デセン−１−オール26.0ｇにピリジン10
滴を加え、ナスフラスコに入れた。氷冷下、塩
化チオニル24.0ｇを滴下した。滴下後、70℃で
8.5時間反応を行つた。反応後、ジクロロメタ
ンで希釈し、炭酸カリウム水溶液で洗浄した。
硫酸マグネシウム上で乾燥した後、減圧濃縮し
た。残渣をカラムクロマトグラフイーにより精
製し、10−クロロ−１−デセン27.7ｇを得た。
（収率95％）
(3) 4′−（９−デセニルオキシ）ビフエニル−４
−カルボン酸２−メチルブチルエステルの合成
(2)で得た10−クロロ−１−デセン2.5ｇ、ヨ
ウ化ナトリウム6.5ｇを２−ブタノンに溶解さ
せ、80℃で17時間撹拌した。反応後、ジクロロ
メタンで希釈し、水洗した。硫酸マグネシウム
上で乾燥した後、溶媒を減圧留去した。残渣に
(1)で得た4′−ヒドロキシビフエニル−４−カル
ボン酸２−メチルブチルエステル4.8ｇ、炭酸
カリウム2.4ｇを加え、２−ブタノン中で80℃
にて20時間反応を行つた。反応後、無機物をろ
過により除き、減圧濃縮した後、カラムクロマ
トグラフイーにより精製し、目的とするビフエ
ニル誘導体4.6ｇを得た。（収率76％）
(4) オキシラン化
(3)で得たビフエニル誘導体3.0ｇ、ｍ−クロ
ロ過安息香酸1.5ｇをジクロロメタンに溶解さ
せ、系をアルゴン置換し、次いで室温で１日撹
拌した。反応後、炭酸カリウム水溶液で洗浄
し、さらに水洗した。硫酸マグネシウム上で乾
燥した後、溶媒を減圧留去し、目的とする下式
で表されるモノマー3.0ｇを得た。（収率97％）
(5) ポリマーの合成
(4)で得たモノマー0.5ｇをジクロロメタン５
mlに溶解し、系をアルゴン置換した。塩化第二
スズ0.015ｇを加え、室温で６日間重合反応を
行つた。反応後、反応溶液をメタノールへ注い
だ。生じた沈殿を再沈殿を繰り返して精製し、
目的とする下式で表される繰り返し単位を有す
るポリオキシラン（Mn＝2800）0.4ｇを得た。
（収率80％）
得られたポリマーの相転移挙動、電界応答速
度、自発分極値を表に示し、1H−NMR分析のチ
ヤートを第１図に示した。
実施例 ２
(1) 12−クロロ−１−ドデセンの合成
９−デセン−１−オールの代わりに11−ドデ
セン−１−オール6.0ｇを用いたことを除いて
実施例１の(2)と同様の操作を行つて、12−クロ
ロ−１−ドデセン5.2ｇを得た。（収率79％）
(2) 4′−（11−ドデセニルオキシ）ビフエニル−
４−カルボン酸２−メチルブチルエステルの合
成
10−クロロ−１−デセンの代わりに(1)で得た
12−クロロ−１−ドデセン5.2ｇを用いたこと
を除いて実施例１の(3)と同様の操作を行つて、
目的とするビフエニル誘導体8.8ｇを得た。（収
率76％）
(3) オキシラン化
(2)で得たビフエニル誘導体8.8ｇに対し、実
施例１の(4)と同様の操作を行い、下式で表され
るモノマー8.8ｇを得た。（収率95％）
(4) ポリマーの合成
(3)で得たモノマー2.3ｇに、実施例１の(5)と
同様の操作を行つて重合させ、目的とする下式
で表される繰り返し単位を有するポリオキシラ
ン（Mn＝3200）1.5ｇを得た。（収率65％）
得られたポリマーの相転移挙動、電界応答速
度、自発分極値を表に示し、1H−NMR分析のチ
ヤートを第２図に示した。
実施例 ３
(1) 4′−（７−オクテニルオキシ）ビフエニル−
４−カルボン酸２−メチルブチルエステルの合
成
８−ブロモ−１−オクテン5.0ｇ、実施例１
の(1)で得た4′−ヒドロキシビフエニル−４−カ
ルボン酸２−メチルブチルエステル8.2ｇ、炭
酸カリウム4.0ｇをアセトン中で20時間還流し
た。反応後、ジクロロメタンを加えて希釈し、
無機物をろ過により除いた。溶媒を減圧留去
し、残渣をカラムクロマトグラフイーにより精
製し、目的とするビフエニル誘導体7.5ｇを得
た。（収率73％）
(2) オキシラン化
(1)で得たビフエニル誘導体7.4ｇに対し、実
施例１の(4)と同様の操作を行い、下式で表され
るモノマー7.6ｇを得た。（収率99％）
(3) ポリマーの合成
(2)で得たモノマー2.05ｇに、実施例１の(5)と
同様の操作を行つて重合させ、目的とする下式
で表される繰り返し単位を有するポリオキシラ
ン（Mn＝3300）1.4ｇを得た。（収率68％）
得られたポリマーの相転移挙動、電界応答速
度、自発分極値を表に示し、1H−NMR分析のチ
ヤートを第３図に示した。
実施例 ４
(1) ｐ−（９−デセニルオキシ）安息香酸の合成
実施例１で得た10−クロロ−１−デセン10.0
ｇとヨウ化ナトリウム25ｇとを２−ブタノン中
で80℃で10時間反応させ、ヨード化した。水
洗、乾燥、溶媒除去を行つた後、ｐ−ヒドロキ
シ安息香酸エチルエステル11.5ｇ、炭酸カリウ
ム9.6ｇを加え、無水エタトール中で15時間還
流した。水酸化カリウム水溶液（水酸化カリウ
ム4.0ｇを含む）を加え、さらに５時間80℃で
加熱した。反応後、塩酸酸性としてから、減圧
濃縮した。残渣に水を加えて懸濁させ、不溶物
を集めて絵乾燥し、ｐ−（９−デセニルオキシ）
安息香酸9.5ｇを得た。（収率60％）
(2) 4′−〔ｐ−（９−デセニルオキシ）ベンゾイル
オキシ〕ビフエニル−４−カルボン酸２−メチ
ルブチルエステルの合成
(1)で得たｐ−（９−デセニルオキシ）安息香
酸にトルエンを加え、氷冷した。塩化チオニル
5.0ｇを滴下した。80℃にて７時間反応を行つ
た。反応後、減圧濃縮し、粗製ｐ−デセニルオ
キシ安息香酸クロリドを得た。実施例１の(1)で
得た4′−ヒドロキシビフエニル−４−カルボン
酸２−メチルブチルエステル12.0ｇおよびピリ
ジン3.3ｇをトルエンに溶解させ、氷冷した。
そこへ上記の粗製ｐ−デセニルオキシ安息香酸
クロリドのトルエン溶液を滴下した。50℃にて
５時間反応を行つた。反応後、水洗し、硫酸マ
グネシウム上で乾燥した後、溶媒を減圧留去し
た。残渣をカラムクロマトグラフイーにより精
製し、目的とする上記エステル体9.3ｇを得た。
（収率50％）
(3) オキシラン化
(2)で得たエステル体9.0ｇに対し、実施例１
の(4)と同様の操作を行い、下式で表されるモノ
マー8.5ｇを得た。（収率92％）
(4) ポリマーの合成
(3)で得たモノマー5.6ｇに、実施例１の(5)と
同様の操作を行つて重合させ、目的とする下式
で表される繰り返し単位を有するポリオキシラ
ン（Mn＝4100）3.1ｇを得た。（収率55％）
得られたポリマーの相転移挙動、電界応答速
度、自発分極値を表に示し、1H−NMR分析のチ
ヤートを第４図に示した。
実施例 ５
(1) ｐ−ヒドロキシ安息香酸２−メチルブチルエ
ステルの合成
ｐ−ヒドロキシ安息香酸4.0ｇおよび（−）−
２−メチルブタノール12.5ｇを硫酸の存在下、
トルエン中で、水を除去しながら６時間還流し
た。次に、反応液を水洗し、硫酸を除いた。そ
の後、乾燥、濃縮、およびカラムクロマトグラ
フイーによる精製を行い、目的とするエステル
5.0ｇ〔室温で液体、〔α〕23 D＝＋4.9°（CHCl3）〕
を得た。（収率83％）
(2) ４−〔4′−（９−デセニルオキシ）ベンゾイル
オキシ〕安息香酸２−メチルブチルエステルの
合成
実施例４の(1)と同様にして得たｐ−（９−デ
セニルオキシ）安息香酸4.5ｇにトルエンを加
え、氷冷した。さらに、氷冷下にて塩化チオニ
ル3.5ｇを滴下した。滴下後、80℃にて７時間
反応を行つた。反応後、反応液を濃縮し、酸ク
ロリド体を得た。一方、(1)で得た４−ヒドロキ
シ安息香酸２−メチルブチルエステル4.5ｇお
よびピリジン1.8ｇをトルエンに溶解させ、氷
冷した。そこへ、上記の酸クロリド体のトルエ
ン溶液を滴下した。滴下後、50℃にて５時間反
応を行つた。反応後、生成物を水洗し、硫酸マ
グネシウム上で乾燥した後、カラムクロマトグ
ラフイーにより精製し、目的とする上記エステ
ル体5.5ｇを得た。（収率72％）
(3) オキシラン化
(2)で得たエステル体5.5ｇに対し、実施例１
の(4)と同様の操作を行い、下式で表されるモノ
マー5.2ｇを得た。（収率92％）
(4) ポリマーの合成
(3)で得たモノマー5.0ｇに、実施例１の(5)と
同様の操作を行つて重合させ、目的とする下式
で表される繰り返し単位を有するポリオキシラ
ン（Mn＝3600）3.5ｇを得た。（収率70％）
得られたポリマーの相転移挙動、電界応答速
度、自発分極値を表に示し、1H−NMR分析のチ
ヤートを第５図に示した。
実施例 ６
(1) ｐ−ヒドロキシ安息香酸１−メチルプロピル
エステルの合成
ｐ−アセトキシ安息香酸23ｇに塩化チオニル
20ｇを滴下した。混合物を80℃に加熱して３時
間反応させた。反応後、過剰の塩化チオニルを
減圧留去し、酸クロリド体を得た。この酸クロ
リドをトルエンに溶解させ、氷冷した。そこ
へ、（＋）−２−ブタノール10ｇ、ピリジン11ｇ
を含むトルエン溶液を滴下し、次いで室温で１
晩撹拌した。反応後、溶液を水洗、乾燥、およ
び減圧濃縮した。残渣をエーテルに溶解させ
た。そこへベンジルアミン９ｇを滴下した。混
合物を１時間室温で撹拌した。反応後、反応液
を水洗、乾燥、および減圧濃縮した。残渣をカ
ラムクロマトグラフイーによつて精製し、目的
とするエステル19.1ｇ（室温で液体、〔α〕23 D＝
＋29.6°（CHCl3）〕を得た。（収率77％）
(2) ４−〔4′−（９−デセニルオキシ）ベンゾイル
オキシ〕安息香酸１−メチルプロピルエステル
の合成
実施例４の(1)と同様にして得たｐ−（９−デ
セニルオキシ）安息香酸13.5ｇにトルエンを加
え、氷冷した。そこへ、塩化チオニル９ｇを滴
下した。80℃にて３時間反応を行つた。反応
後、反応液を濃縮し、酸クロリド体を得た。一
方、(1)で得た４−ヒドロキシ安息香酸１−メチ
ルプロピルエステル10ｇおよびピリジン４ｇを
トルエンに溶解させ、氷冷した。そこへ、上記
の酸クロリド体のトルエン溶液を滴下した。次
いで、50℃にて５時間反応を行つた。反応後、
生成物を水洗し、硫酸マグネシウム上で乾燥し
た後、溶媒を減圧留去した。残渣をカラムクロ
マトグラフイーにより精製し、目的とする上記
エステル体12.6ｇを得た。（収率57％）
(3) オキシラン化
(2)で得たエステル体12.5ｇに対し、実施例１
の(4)と同様の操作を行い、下式で表されるモノ
マー11.6ｇを得た。（収率90％）
(4) ポリマーの合成
(3)で得たモノマー11.5ｇに、実施例１の(5)と
同様の操作を行つて重合させ、目的とする下式
で表される繰り返し単位を有するポリオキシラ
ン（Mn＝3300）7.1ｇを得た。（収率62％）
得られたポリマーの相転移挙動、電界応答速
度、自発分極値を表に示し、1H−NMR分析のチ
ヤートを第６図に示した。
実施例 ７
(1) ｐ−ヒドロキシ安息香酸１−メチルブチルエ
ステルの合成
ｐ−アセトキシ安息香酸25ｇに塩化チオニル
25ｇを滴下した。混合物を80℃に加熱して３時
間反応させた。反応後、過剰の塩化チオニルを
減圧留去し、酸クロリド体を得た。この酸クロ
リドをトルエンに溶解させ、氷冷した。そこ
へ、（−）−２−ペンタノール10.2ｇ、ピリジン
11ｇを含むトルエン溶液を滴下した。次いで、
室温で１晩撹拌した。反応後、溶液を水洗、乾
燥、減圧濃縮し、残渣をエーテルに溶解させ
た。そこへ、ベンジルアミン18ｇを滴下した。
混合物を１時間室温で撹拌した。反応後、生成
物を水洗、乾燥、および減圧濃縮した。残渣を
カラムクロマトグラフイーによつて精製し、目
的とするエステル〔室温で液体、〔α〕23 D＝−
27.3°（CHCl3）〕20.3ｇを得た。（収率86％）
(2) ４−〔4′−（９−デセニルオキシ）ベンゾイル
オキシ〕安息香酸１−メチルブチルエステルの
合成
実施例４の(1)と同様にして得たｐ−（９−デ
セニルオキシ）安息香酸12.7ｇにトルエンを加
え、氷冷した。そこへ塩化チオニル8.2ｇを滴
下した。80℃にて７時間反応を行つた。反応
後、反応液を濃縮し、酸クロリド体を得た。一
方、(1)で得た４−ヒドロキシ安息香酸１−メチ
ルブチルエステル10.0ｇおよびピリジン3.8ｇ
をトルエンに溶解させ、氷冷した。そこへ、上
記の酸クロリド体のトルエン溶液を滴下した。
50℃にて５時間反応を行つた。反応後、生成物
を水洗し、硫酸マグネシウム上で乾燥した後、
溶媒を減圧留去した。残渣をカラムクロマトグ
ラフイーにより精製し、目的とする上記エステ
ル体15.1ｇを得た。（収率71％）
(3) オキシラン化
(2)で得たエステル体15.1ｇに対し、実施例１
の(4)と同様の操作を行い、下式で表されるモノ
マー14.7ｇを得た。（収率94％）
(4) ポリマーの合成
(3)で得たモノマー14.7ｇに、実施例１の(5)と
同様の操作を行つて重合させ、目的とする下式
で表される繰り返し単位を有するポリオキシラ
ン（Mn＝3600）8.8ｇを得た。（収率60％）
得られたポリマーの相転移挙動、電界応答速
度、自発分極値を表に示し、1H−NMR分析のチ
ヤートを第７図に示した。
実施例 ８
(1) ｐ−ヒドロキシ安息香酸１−メチルヘプチル
エステルの合成
ｐ−アセトキシ安息香酸32ｇに塩化チオニル
32ｇを滴下した。混合物を80°に加熱して３時
間反応させた。反応後、過剰の塩化チオニルを
減圧留去し、酸クロリド体を得た。この酸クロ
リドをトルエンに溶解させ、氷冷した。そこ
へ、（−）−２−オクタノール25ｇ、ピリジン16
ｇを含むトルエン溶液を滴下した。混合物を室
温で１晩撹拌した。反応後、溶液を水洗、乾
燥、および減圧濃縮した。残渣をエーテルに溶
解させた。そこへ、ベンジルアミン21ｇを滴下
した。混合物を１時間室温で撹拌した。反応
後、生成物を水洗、乾燥、および減圧濃縮し
た。残渣をカラムクロマトグラフイーによつて
精製し、目的とするエステル39.9ｇ〔室温で液
体、〔α〕23 D＝−33.8°（CHCl3）〕を得た。（収率
83％）
(2) ４−〔4′−（９−デセニルオキシ）ベンゾイル
オキシ〕安息香酸１−メチルヘプチルエステル
の合成
実施例４の(1)と同様にして得たｐ−（９−デ
セニルオキシ）安息香酸9.4ｇにトルエンを加
え、氷冷した。混合物に塩化チオニル6.0ｇを
滴下した。次いで、80℃にて７時間反応を行つ
た。反応後、生成物を濃縮し、酸クロリド体を
得た。一方、(1)で得た４−ヒドロキシ安息香酸
１−メチルヘプチルエステル7.7ｇおよびピリ
ジン2.7ｇをトルエンに溶解させ、氷冷した。
そこへ、上記の酸クロリド体のトルエン溶液を
滴下した。次いで、50℃にて５時間反応を行つ
た。反応後、生成物を水洗し、硫酸マグネシウ
ム上で乾燥した後、溶媒を減圧留去した。残渣
をカラムクロマトグラフイーにより精製し、目
的とする上記エステル体9.4ｇを得た。（収率60
％）
(3) オキシラン化
(2)で得たエステル体9.4ｇに対し、実施例１
の(4)と同様の操作を行い、下式で表されるモノ
マー9.1ｇを得た。（収率60％）
(4) ポリマーの合成
(3)で得たモノマー9.1ｇに、実施例１の(5)と
同様の操作を行つて重合させ、目的とする下式
で表される繰り返し単位を有するポリオキシラ
ン（Mn＝3800）6.1ｇを得た。（収率60％）
得られたポリマーの相転移挙動、電界応答速
度、自発分極値を表に示し、1H−NMR分析のチ
ヤートを第８図に示した。
実施例 ９
(1) ４−〔4′−（９−デセニルオキシ）ビフエニル
−４−カルボニルオキシ〕安息香酸２−メチル
ブチルエステルの合成
4′−（９−デセニルオキシ）ビフエニル−４
−カルボン酸5.0ｇにトルエンを加え、氷冷し
た。混合物に塩化チオニル2.6ｇを滴下した。
次いで、80℃にて７時間反応を行つた。反応
後、生成物を濃縮し、酸クロリド体を得た。実
施例５の(1)と同様にして得た４−ヒドロキシ安
息香酸２−メチルブチルエステル3.1ｇおよび
ピリジン1.5ｇをトルエンに溶解させ、氷冷し
た。そこへ、上記の酸クロリド体のトルエン溶
液を滴下した。次いで、50℃にて５時間反応を
行つた。反応後、生成物を水洗し、硫酸マグネ
シウム上で乾燥した後、溶媒を減圧留去した。
残渣をカラムクロマトグラフイーにより精製
し、目的とする上記エステル体5.2ｇを得た。
（収率68％）
(2) オキシラン化
(1)で得たエステル体5.2ｇに対し、実施例１
の(4)と同様の操作を行い、下式で表されるモノ
マー4.9ｇを得た。（収率92％）
(3) ポリマーの合成
(2)で得たモノマー4.9ｇに、実施例１の(5)と
同様の操作を行つて重合させ、目的とする下式
で表される繰り返し単位を有するポリオキシラ
ン（Mn＝3400）4.3ｇを得た。（収率88％）
得られたポリマーの相転移挙動、電界応答速
度、自発分極値を表に示し、1H−NMR分析のチ
ヤートを第９図に示した。
実施例 10
(1) ｐ−ヒドロキシ安息香酸２−フルオロオクチ
ルエステルの合成
ｐ−アセトキシ安息香酸5.4ｇに塩化チオニ
ル11ｇを滴下した。混合物を80℃に加熱して３
時間反応させた。反応後、過剰の塩化チオニル
を減圧留去し、酸クロリド体を得た。この酸ク
ロリドをトルエンに溶解させ、氷冷した。そこ
へ、（−）−２−フルオロオクタノール4.4ｇ、
ピリジン３ｇを含むトルエン溶液を滴下した。
混合物を室温で１晩撹拌した。反応後、溶液を
水洗、乾燥、および減圧濃縮した。残渣をエー
テルに溶解させた。そこへ、ベンジルアミン10
ｇを滴下した。混合物を５時間室温で撹拌し
た。反応後、生成物を水洗、乾燥、および減圧
濃縮した。残渣をカラムクロマトグラフイーに
よつて精製し、目的とするエステル4.9ｇを得
た。（収率73％）
(2) ４−〔4′−（９−デセニルオキシ）ベンゾイル
オキシ〕安息香酸２−フルオロオクチルエステ
ルの合成
実施例４の(1)と同様にして得たｐ−（９−デ
セニルオキシ）安息香酸3.0ｇにトルエンを加
え、氷冷した。混合物に塩化チオニル2.0ｇを
滴下した。次いで、80℃にて３時間反応を行つ
た。反応後、生成物を濃縮し、酸クロリド体を
得た。一方、(1)で得た４−ヒドロキシ安息香酸
２−フルオロオクチルエステル1.7ｇおよびピ
リジン0.9ｇをトルエンに溶解させ、氷冷した。
そこへ、上記の酸クロリド体のトルエン溶液を
滴下した。次いで、室温にて15時間反応を行つ
た。反応後、生成物を水洗し、硫酸マグネシウ
ム上で乾燥した後、溶媒を減圧留去した。残渣
をカラムクロマトグラフイーにより精製し、目
的とする上記エステル体2.8ｇを得た。（収率85
％）
(3) オキシラン化
(2)で得たエステル体2.8ｇに対し、実施例１
の(4)と同様の操作を行い、下式で表されるモノ
マー2.6ｇを得た。（収率91％）
(4) ポリマーの合成
(3)で得たモノマー2.6ｇに、実施例１の(5)と
同様の操作を行つて重合させ、目的とする下式
で表される繰り返し単位を有するポリオキシラ
ン（Mn＝3000）2.2ｇを得た。（収率84％）
得られたポリマーの相転移挙動、電界応答速
度、自発分極値を表に示し、1H−NMR分析のチ
ヤートを第１０図に示した。
実施例 11
(1) 4′−（５−ヘキセニルオキシ）ビフエニル−
４−カルボン酸２−メチルブチルエステルの合
成
６−ブロモ−１−ヘキセン4.7ｇ、4′−ヒド
ロキシビフエニル−４−カルボン酸２−メチル
ブチルエステル6.3ｇ、および炭酸カリウム3.1
ｇを２−ブタノン中で20時間還流した。反応
後、水洗により無機塩を除いた。硫酸マグネシ
ウム上で乾燥した後、溶媒を減圧留去し、残渣
をカラムクロマトグラフイーにより精製し、目
的とするエステル体6.4ｇを得た。（収率79％）
(2) オキシラン化
(1)で得たエステル体1.7ｇに対し、実施例１
の(4)と同様の操作を行い、下式で表されるモノ
マー1.6ｇを得た。（収率89％）
(3) ポリマーの合成
(2)で得たモノマー1.6ｇに、実施例１の(5)と
同様の操作を行つて重合させ、目的とする下式
で表される繰り返し単位を有するポリオキシラ
ン（Mn＝3000）1.0ｇを得た。（収率63％）
得られたポリマーの相転移挙動、電界応答速
度、自発分極値を表に示し、1H−NMR分析のチ
ヤートを第１１図に示した。
実施例 12
(1) ｐ−（７−オクテニルオキシ）安息香酸の合
成
８−ブロモ−１−オクテン9.4ｇ、ｐ−ヒド
ロキシ安息香酸エチル9.0ｇ、および炭酸カリ
ウム7.6ｇをエタノール中で10時間還流した。
そこへ水酸化ナトリウム2.4ｇを含む水溶液を
加え、さらに10時間還流した。反応後、水で希
釈し、そこへ塩酸を滴下してPHを２とした。生
じた沈殿を集め、十分に水洗してから乾燥し、
目的とするエーテル体10.8ｇを得た。（収率89
％）
(2) ４−〔ｐ−（７−オクテニルオキシ）ベンゾイ
ルオキシ〕ビフエニル−４−カルボン酸２−メ
チルブチルエステルの合成
(1)で得たｐ−（７−オクテニルオキシ）安息
香酸９ｇをトルエンに懸濁させ、氷冷した。そ
こへ塩化チオニル６ｇを滴下した。滴下後、昇
温し、80℃にて６時間反応させた。反応後、減
圧濃縮して酸クロリド体を得た。そこへ、トル
エンを加えてトルエン溶液とし、氷冷した。
4′−ヒドロキシビフエニル−４−カルボン酸
２−メチルブチルエステル10ｇおよびピリジン
３ｇを含むトルエン溶液を、上記の酸クロリド
のトルエン溶液に滴下した。滴下後、昇温し、
50℃にて８時間反応させた。反応後、生成物を
水洗し、硫酸マグネシウム上で乾燥した後、減
圧濃縮を行つた。残渣をエタノールから再結晶
し、目的とする上記エステル体8.2ｇを得た。
（収率45％）
(3) オキシラン化
(2)で得たエステル体7.2ｇをｍ−クロロ過安
息香酸３ｇにより酸化し、下式で表されるモノ
マー6.3ｇを得た。（収率85％）
(4) ポリマーの合成
(3)で得たモノマー1.8ｇに、実施例１の(5)と
同様の操作を行つて重合させ、目的とする下式
で表される繰り返し単位を有するポリオキシラ
ン（Mn＝5100）1.5ｇを得た。（収率83％）
得られたポリマーの相転移挙動、電界応答速
度、自発分極値を表に示し、1H−NMR分析のチ
ヤートを第１２図に示した。
実施例 13
(1) ｐ−ヒドロキシ安息香酸２−クロロ−３−メ
チルペンチルエステルの合成
ｐ−アセトキシ安息香酸24ｇに塩化チオニル
32ｇを滴下した。混合物を80℃に加熱して３時
間反応させた。反応後、過剰の塩化チオニルを
減圧留去し、酸クロリド体を得た。この酸クロ
リドをトルエンに溶解させ、氷冷した。そこ
へ、（−）−２−クロロ−３−メチルペンタノー
ル13.7ｇ、トリエチルアミン14ｇを含むトルエ
ン溶液を滴下した。混合物を室温で１晩撹拌し
た。反応後、溶液を水洗、乾燥、および減圧濃
縮した。残渣をエーテルに溶解させた。そこ
へ、ベンジルアミン17ｇを滴下した。混合物を
１時間室温で撹拌した。反応後、水洗、乾燥、
および減圧濃縮を行つた。残渣をカラムクロマ
トグラフイーによつて精製し、目的とするエス
テル20.3ｇ〔〔α〕23 D＝＋11.6°（CHCl3）〕を得た。
（収率79％）
(2) ４−〔4′−（９−デセニルオキシ）ベンゾイル
オキシ〕安息香酸２−クロロ−３−メチルペン
チルエステルの合成
実施例４の(1)と同様にして得たｐ−デセニル
オキシ安息香酸0.82ｇにトルエンを加え、氷冷
した。そこへ塩化チオニル1.1ｇを滴下し、80
℃にて７時間反応を行つた。反応後、反応液を
濃縮し、酸クロリド体を得た。(1)で得たｐ−ヒ
ドロキシ安息香酸２−クロロ−３−メチルペン
チルエステル0.76ｇおよびピリジン0.5ｇをト
ルエンに溶解させ、氷冷した。そこへ、上記の
酸クロリド体のトルエン溶液を滴下した。室温
にて15時間反応を行つた。反応後、水洗し、硫
酸マグネシウム上で乾燥した後、溶媒を減圧留
去した。残渣をカラムクロマトグラフイーによ
り精製し、目的とする上記エステル体1.14ｇを
得た。（収率74％）
(3) オキシラン化
(2)で得たエステル体0.52ｇに対し、実施例１
の(4)と同様の操作を行い、下式で表されるモノ
マー0.48ｇを得た。（収率90％）
(4) ポリマーの合成
(3)で得たモノマー0.48ｇに、実施例１の(5)と
同様の操作を行つて重合させ、目的とする下式
で表される繰り返し単位を有するポリオキシラ
ン（Mn＝2800）0.44ｇを得た。（収率92％）
得られたポリマーの相転移挙動、電界応答速
度、自発分極値を表に示し、1H−NMR分析のチ
ヤートを第１３図に示した。
実施例 14
(1) 4′−（９−デセニルオキシ）ビフエニル−４
−カルボン酸２−クロロ−３−メチルペンチル
エステルの合成
4′−（９−デセニルオキシ）ビフエニル−４
−カルボン酸4.0ｇにトルエンを加え、氷冷し
た。そこへ、塩化チオニル2.0ｇを滴下した。
800℃にて７時間反応を行つた。反応後、反応
液を濃縮し、酸クロリド体を得た。２−クロロ
−３−メチルペンタノール1.7ｇおよびピリジ
ン1.0ｇをトルエンに溶解させ、氷冷した。そ
こへ、上記の酸クロリド体のトルエン溶液を滴
下した。室温にて15時間反応を行つた。反応
後、反応液を水洗し、硫酸マグネシウム上で乾
燥した後、溶媒を減圧留去した。残渣をカラム
クロマトグラフイーにより精製し、目的とする
上記エステル体4.3ｇを得た。（収率80％）
(2) オキシラン化
(1)で得たエステル体4.3ｇに対し、実施例１
の(4)と同様の操作を行い、下式で表されるモノ
マー4.2ｇを得た。（収率95％）
(3) ポリマーの合成
(2)で得たモノマー4.2ｇに、実施例１の(5)と
同様の操作を行つて重合させ、目的とする下式
で表される繰り返し単位を有するポリオキシラ
ン（Mn＝3300）3.2ｇを得た。（収率76％）
得られたポリマーの相転移挙動、電界応答速
度、自発分極値を表に示し、1H−NMR分析のチ
ヤートを第１４図に示した。
EXAMPLES The present invention will be explained below with reference to Examples, but the scope of the present invention is not limited in any way by these Examples. The structure of the obtained polymer was determined by NMR,
This was confirmed by IR and elemental analysis, and the phase transition temperature was measured and the phase was confirmed by DSC and polarizing microscope, respectively. (glass: glass state,
Cry: crystalline state, S 1 : unidentified smectic phase (liquid crystal phase but does not respond to electrolysis), SmC * :
Chiral smectic C phase, SmA: Smectic A phase, N: Nematic phase, N * : Chiral nematic phase, Iso: Isotropic phase. The number of phase transition behavior is the phase change temperature expressed in °C. ) The electric field response speed and spontaneous polarization value were measured as follows. Measurement of electric field response speed A polymer was sandwiched between two 20 x 10 mm ITO substrates, the thickness was adjusted to 25 μm with a spacer, and an alternating current electric field E = 2 x 10 6 V/m was applied, and the amount of transmitted light at that time was measured. The response time of the change (0→90%) was measured. Measurement of spontaneous polarization value The polymer was sandwiched between ITO circular transparent electrode-attached glass substrates with an area of 0.2 cm 2 and the thickness was adjusted to 10 μm using spacers. A voltage varying in the shape of a triangular wave with a peak value of 200 V was applied, and the spontaneous polarization value was determined from the polarization inversion current signal observed at this time. Example 1 (1) Synthesis of 4'-hydroxybiphenyl-4-carboxylic acid 2-methylbutyl ester 4'-hydroxybiphenyl-4-carboxylic acid
93 mmol (20 g) and (S)-(-)-2-
467 mmol (41 g) of methylbutanol was refluxed in 150 ml of benzene in the presence of 2 ml of concentrated sulfuric acid for 25 hours while removing water. After concentrating the reaction solution,
Recrystallized from a toluene-hexane mixed solvent to obtain 26.0 g of the desired ester [mp116-117.8,
[α] 23 D = +4.35° (CHCl 3 )] was obtained. (Yield 98%) (2) Synthesis of 10-chloro-1-decene Add 10 pyridine to 26.0 g of 9-decen-1-ol.
Added drops and placed in an eggplant flask. 24.0 g of thionyl chloride was added dropwise under ice cooling. After dropping, at 70℃
The reaction was carried out for 8.5 hours. After the reaction, the mixture was diluted with dichloromethane and washed with an aqueous potassium carbonate solution.
After drying over magnesium sulfate, it was concentrated under reduced pressure. The residue was purified by column chromatography to obtain 27.7 g of 10-chloro-1-decene.
(Yield 95%) (3) 4'-(9-decenyloxy)biphenyl-4
-Synthesis of carboxylic acid 2-methylbutyl ester 2.5 g of 10-chloro-1-decene obtained in (2) and 6.5 g of sodium iodide were dissolved in 2-butanone and stirred at 80°C for 17 hours. After the reaction, it was diluted with dichloromethane and washed with water. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure. to the residue
Add 4.8 g of 4'-hydroxybiphenyl-4-carboxylic acid 2-methylbutyl ester obtained in (1) and 2.4 g of potassium carbonate, and add the mixture to 80°C in 2-butanone.
The reaction was carried out for 20 hours. After the reaction, inorganic substances were removed by filtration, concentrated under reduced pressure, and purified by column chromatography to obtain 4.6 g of the desired biphenyl derivative. (Yield 76%) (4) Oxiranization 3.0 g of the biphenyl derivative obtained in (3) and 1.5 g of m-chloroperbenzoic acid were dissolved in dichloromethane, the system was purged with argon, and then stirred at room temperature for 1 day. After the reaction, the mixture was washed with an aqueous potassium carbonate solution and further washed with water. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 3.0 g of the desired monomer represented by the following formula. (Yield 97%) (5) Synthesis of polymer 0.5 g of the monomer obtained in (4) was mixed with 5 g of dichloromethane.
ml and the system was purged with argon. 0.015 g of stannic chloride was added, and a polymerization reaction was carried out at room temperature for 6 days. After the reaction, the reaction solution was poured into methanol. The resulting precipitate is purified by repeating reprecipitation,
0.4 g of the desired polyoxirane (Mn=2800) having a repeating unit represented by the following formula was obtained.
(yield 80%) The phase transition behavior, electric field response speed, and spontaneous polarization value of the obtained polymer are shown in the table, and the chart of 1 H-NMR analysis is shown in FIG. Example 2 (1) Synthesis of 12-chloro-1-dodecene Same as Example 1 (2) except that 6.0 g of 11-dodecen-1-ol was used instead of 9-decen-1-ol. By performing the above operation, 5.2 g of 12-chloro-1-dodecene was obtained. (Yield 79%) (2) 4′-(11-dodecenyloxy)biphenyl-
Synthesis of 4-carboxylic acid 2-methylbutyl ester Obtained in (1) instead of 10-chloro-1-decene
The same operation as in Example 1 (3) was performed except that 5.2 g of 12-chloro-1-dodecene was used.
8.8 g of the desired biphenyl derivative was obtained. (Yield 76%) (3) Oxiranization 8.8 g of the biphenyl derivative obtained in (2) was subjected to the same operation as in (4) of Example 1 to obtain 8.8 g of a monomer represented by the following formula. . (yield 95%) (4) Synthesis of polymer 2.3 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane ( Mn=3200) 1.5g was obtained. (yield 65%) The phase transition behavior, electric field response speed, and spontaneous polarization value of the obtained polymer are shown in the table, and the chart of 1 H-NMR analysis is shown in Figure 2. Example 3 (1) 4'-(7-octenyloxy)biphenyl-
Synthesis of 4-carboxylic acid 2-methylbutyl ester 8-bromo-1-octene 5.0 g, Example 1
8.2 g of 4'-hydroxybiphenyl-4-carboxylic acid 2-methylbutyl ester obtained in (1) and 4.0 g of potassium carbonate were refluxed in acetone for 20 hours. After the reaction, add dichloromethane to dilute,
Inorganics were removed by filtration. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 7.5 g of the desired biphenyl derivative. (Yield 73%) (2) Oxiranization 7.4 g of the biphenyl derivative obtained in (1) was subjected to the same operation as in (4) of Example 1 to obtain 7.6 g of a monomer represented by the following formula. . (Yield 99%) (3) Synthesis of polymer 2.05 g of the monomer obtained in (2) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane ( Mn=3300) 1.4g was obtained. (yield 68%) The phase transition behavior, electric field response speed, and spontaneous polarization value of the obtained polymer are shown in the table, and the chart of 1 H-NMR analysis is shown in Figure 3. Example 4 (1) Synthesis of p-(9-decenyloxy)benzoic acid 10-chloro-1-decene obtained in Example 1 10.0
g and 25 g of sodium iodide in 2-butanone at 80° C. for 10 hours to iodize. After washing with water, drying, and removing the solvent, 11.5 g of p-hydroxybenzoic acid ethyl ester and 9.6 g of potassium carbonate were added, and the mixture was refluxed in anhydrous ethanol for 15 hours. An aqueous potassium hydroxide solution (containing 4.0 g of potassium hydroxide) was added, and the mixture was further heated at 80° C. for 5 hours. After the reaction, the mixture was acidified with hydrochloric acid and concentrated under reduced pressure. Add water to the residue to suspend it, collect the insoluble matter and dry it to obtain p-(9-decenyloxy).
9.5 g of benzoic acid was obtained. (Yield 60%) (2) Synthesis of 4'-[p-(9-decenyloxy)benzoyloxy]biphenyl-4-carboxylic acid 2-methylbutyl ester p-(9-decenyloxy)benzoin obtained in (1) Toluene was added to the acid and cooled on ice. Thionyl chloride
5.0g was dropped. The reaction was carried out at 80°C for 7 hours. After the reaction, the reaction mixture was concentrated under reduced pressure to obtain crude p-decenyloxybenzoic acid chloride. 12.0 g of 4'-hydroxybiphenyl-4-carboxylic acid 2-methylbutyl ester obtained in (1) of Example 1 and 3.3 g of pyridine were dissolved in toluene and cooled on ice.
The above toluene solution of crude p-decenyloxybenzoic acid chloride was added dropwise thereto. The reaction was carried out at 50°C for 5 hours. After the reaction, the mixture was washed with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 9.3 g of the desired ester.
(Yield 50%) (3) Example 1 was added to 9.0 g of the ester obtained in oxirane formation (2).
The same operation as in (4) was performed to obtain 8.5 g of a monomer represented by the following formula. (Yield 92%) (4) Polymer synthesis 5.6 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane ( Mn=4100) 3.1g was obtained. (yield 55%) The phase transition behavior, electric field response speed, and spontaneous polarization value of the obtained polymer are shown in the table, and the chart of 1 H-NMR analysis is shown in FIG. Example 5 (1) Synthesis of p-hydroxybenzoic acid 2-methylbutyl ester 4.0 g of p-hydroxybenzoic acid and (-)-
12.5 g of 2-methylbutanol in the presence of sulfuric acid,
It was refluxed in toluene for 6 hours while removing water. Next, the reaction solution was washed with water to remove sulfuric acid. After that, drying, concentration, and purification by column chromatography are performed to obtain the desired ester.
5.0g [Liquid at room temperature, [α] 23 D = +4.9° (CHCl 3 )]
I got it. (Yield 83%) (2) Synthesis of 4-[4'-(9-decenyloxy)benzoyloxy]benzoic acid 2-methylbutyl ester p-(9- Toluene was added to 4.5 g of decenyloxybenzoic acid and cooled on ice. Furthermore, 3.5 g of thionyl chloride was added dropwise under ice cooling. After the dropwise addition, the reaction was carried out at 80°C for 7 hours. After the reaction, the reaction solution was concentrated to obtain an acid chloride. On the other hand, 4.5 g of 4-hydroxybenzoic acid 2-methylbutyl ester obtained in (1) and 1.8 g of pyridine were dissolved in toluene and cooled on ice. A toluene solution of the above acid chloride was added dropwise thereto. After the dropwise addition, the reaction was carried out at 50°C for 5 hours. After the reaction, the product was washed with water, dried over magnesium sulfate, and purified by column chromatography to obtain 5.5 g of the desired ester. (Yield 72%) (3) Example 1 was added to 5.5 g of the ester obtained in oxirane formation (2).
The same operation as in (4) was performed to obtain 5.2 g of a monomer represented by the following formula. (Yield 92%) (4) Polymer synthesis 5.0 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane ( Mn=3600) 3.5g was obtained. (yield 70%) The phase transition behavior, electric field response speed, and spontaneous polarization value of the obtained polymer are shown in the table, and the chart of 1 H-NMR analysis is shown in FIG. Example 6 (1) Synthesis of p-hydroxybenzoic acid 1-methylpropyl ester Thionyl chloride was added to 23 g of p-acetoxybenzoic acid.
20g was dropped. The mixture was heated to 80°C and reacted for 3 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride. This acid chloride was dissolved in toluene and cooled on ice. There, (+)-2-butanol 10g, pyridine 11g
dropwise toluene solution containing
Stirred overnight. After the reaction, the solution was washed with water, dried, and concentrated under reduced pressure. The residue was dissolved in ether. 9 g of benzylamine was added dropwise thereto. The mixture was stirred for 1 hour at room temperature. After the reaction, the reaction solution was washed with water, dried, and concentrated under reduced pressure. The residue was purified by column chromatography to obtain 19.1 g of the desired ester (liquid at room temperature, [α] 23 D =
+29.6° (CHCl 3 )] was obtained. (Yield 77%) (2) Synthesis of 4-[4'-(9-decenyloxy)benzoyloxy]benzoic acid 1-methylpropyl ester p-(9- Toluene was added to 13.5 g of decenyloxybenzoic acid and cooled on ice. 9 g of thionyl chloride was added dropwise thereto. The reaction was carried out at 80°C for 3 hours. After the reaction, the reaction solution was concentrated to obtain an acid chloride. On the other hand, 10 g of 4-hydroxybenzoic acid 1-methylpropyl ester obtained in (1) and 4 g of pyridine were dissolved in toluene and cooled on ice. A toluene solution of the above acid chloride was added dropwise thereto. Next, the reaction was carried out at 50°C for 5 hours. After the reaction,
After washing the product with water and drying over magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 12.6 g of the desired ester. (Yield 57%) (3) Example 1 was added to 12.5 g of the ester obtained in oxirane formation (2).
The same operation as in (4) was performed to obtain 11.6 g of a monomer represented by the following formula. (yield 90%) (4) Synthesis of polymer 11.5 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane ( Mn=3300) 7.1g was obtained. (yield 62%) The phase transition behavior, electric field response speed, and spontaneous polarization value of the obtained polymer are shown in the table, and the chart of 1 H-NMR analysis is shown in FIG. Example 7 (1) Synthesis of p-hydroxybenzoic acid 1-methylbutyl ester Thionyl chloride was added to 25 g of p-acetoxybenzoic acid.
25g was dropped. The mixture was heated to 80°C and reacted for 3 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride. This acid chloride was dissolved in toluene and cooled on ice. There, (-)-2-pentanol 10.2g, pyridine
A toluene solution containing 11 g was added dropwise. Then,
Stir overnight at room temperature. After the reaction, the solution was washed with water, dried, and concentrated under reduced pressure, and the residue was dissolved in ether. 18 g of benzylamine was added dropwise thereto.
The mixture was stirred for 1 hour at room temperature. After the reaction, the product was washed with water, dried, and concentrated under reduced pressure. The residue was purified by column chromatography to obtain the desired ester [liquid at room temperature, [α] 23 D = −
20.3 g of 27.3° (CHCl 3 ) was obtained. (Yield 86%) (2) Synthesis of 4-[4'-(9-decenyloxy)benzoyloxy]benzoic acid 1-methylbutyl ester p-(9- Toluene was added to 12.7 g of decenyloxybenzoic acid and cooled on ice. 8.2 g of thionyl chloride was added dropwise thereto. The reaction was carried out at 80°C for 7 hours. After the reaction, the reaction solution was concentrated to obtain an acid chloride. On the other hand, 10.0 g of 4-hydroxybenzoic acid 1-methylbutyl ester obtained in (1) and 3.8 g of pyridine
was dissolved in toluene and cooled on ice. A toluene solution of the above acid chloride was added dropwise thereto.
The reaction was carried out at 50°C for 5 hours. After the reaction, the product was washed with water and dried over magnesium sulfate.
The solvent was removed under reduced pressure. The residue was purified by column chromatography to obtain 15.1 g of the desired ester. (Yield 71%) (3) Example 1 was added to 15.1 g of the ester obtained in oxirane formation (2).
The same operation as in (4) was performed to obtain 14.7 g of a monomer represented by the following formula. (Yield 94%) (4) Polymer synthesis 14.7 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane ( Mn=3600) 8.8g was obtained. (yield 60%) The phase transition behavior, electric field response speed, and spontaneous polarization value of the obtained polymer are shown in the table, and the chart of 1 H-NMR analysis is shown in FIG. Example 8 (1) Synthesis of p-hydroxybenzoic acid 1-methylheptyl ester Thionyl chloride was added to 32 g of p-acetoxybenzoic acid.
32g was dropped. The mixture was heated to 80° and reacted for 3 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride. This acid chloride was dissolved in toluene and cooled on ice. There, 25 g of (-)-2-octanol, 16 g of pyridine
A toluene solution containing g was added dropwise. The mixture was stirred at room temperature overnight. After the reaction, the solution was washed with water, dried, and concentrated under reduced pressure. The residue was dissolved in ether. 21 g of benzylamine was added dropwise thereto. The mixture was stirred for 1 hour at room temperature. After the reaction, the product was washed with water, dried, and concentrated under reduced pressure. The residue was purified by column chromatography to obtain 39.9 g of the desired ester [liquid at room temperature, [α] 23 D = -33.8° (CHCl 3 )]. (yield
(83%) (2) Synthesis of 4-[4'-(9-decenyloxy)benzoyloxy]benzoic acid 1-methylheptyl ester p-(9-decenyloxy)benzoic acid obtained in the same manner as in Example 4 (1) Toluene was added to 9.4 g of acid and cooled on ice. 6.0 g of thionyl chloride was added dropwise to the mixture. Next, the reaction was carried out at 80°C for 7 hours. After the reaction, the product was concentrated to obtain an acid chloride. On the other hand, 7.7 g of 4-hydroxybenzoic acid 1-methylheptyl ester obtained in (1) and 2.7 g of pyridine were dissolved in toluene and cooled on ice.
A toluene solution of the above acid chloride was added dropwise thereto. Next, the reaction was carried out at 50°C for 5 hours. After the reaction, the product was washed with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 9.4 g of the desired ester. (yield 60
%) (3) Example 1 was added to 9.4 g of the ester obtained in oxirane conversion (2).
The same operation as in (4) was performed to obtain 9.1 g of a monomer represented by the following formula. (yield 60%) (4) Synthesis of polymer 9.1 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane ( Mn=3800) 6.1g was obtained. (yield 60%) The phase transition behavior, electric field response speed, and spontaneous polarization value of the obtained polymer are shown in the table, and the chart of 1 H-NMR analysis is shown in FIG. Example 9 (1) Synthesis of 4-[4'-(9-decenyloxy)biphenyl-4-carbonyloxy]benzoic acid 2-methylbutyl ester 4'-(9-decenyloxy)biphenyl-4
-Toluene was added to 5.0 g of carboxylic acid and cooled on ice. 2.6 g of thionyl chloride was added dropwise to the mixture.
Next, the reaction was carried out at 80°C for 7 hours. After the reaction, the product was concentrated to obtain an acid chloride. 3.1 g of 4-hydroxybenzoic acid 2-methylbutyl ester obtained in the same manner as in Example 5 (1) and 1.5 g of pyridine were dissolved in toluene and cooled on ice. A toluene solution of the above acid chloride was added dropwise thereto. Next, the reaction was carried out at 50°C for 5 hours. After the reaction, the product was washed with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure.
The residue was purified by column chromatography to obtain 5.2 g of the desired ester.
(Yield 68%) (2) Oxirane conversion Example 1 was added to 5.2 g of the ester obtained in (1).
The same operation as in (4) was performed to obtain 4.9 g of a monomer represented by the following formula. (Yield 92%) (3) Polymer synthesis 4.9 g of the monomer obtained in (2) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane ( Mn=3400) 4.3g was obtained. (yield 88%) The phase transition behavior, electric field response speed, and spontaneous polarization value of the obtained polymer are shown in the table, and the chart of 1 H-NMR analysis is shown in FIG. 9. Example 10 (1) Synthesis of p-hydroxybenzoic acid 2-fluorooctyl ester 11 g of thionyl chloride was added dropwise to 5.4 g of p-acetoxybenzoic acid. Heat the mixture to 80℃ and
Allowed time to react. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride. This acid chloride was dissolved in toluene and cooled on ice. There, 4.4 g of (-)-2-fluorooctanol,
A toluene solution containing 3 g of pyridine was added dropwise.
The mixture was stirred at room temperature overnight. After the reaction, the solution was washed with water, dried, and concentrated under reduced pressure. The residue was dissolved in ether. There, benzylamine 10
g was added dropwise. The mixture was stirred for 5 hours at room temperature. After the reaction, the product was washed with water, dried, and concentrated under reduced pressure. The residue was purified by column chromatography to obtain 4.9 g of the desired ester. (Yield 73%) (2) Synthesis of 4-[4'-(9-decenyloxy)benzoyloxy]benzoic acid 2-fluorooctyl ester p-(9- Toluene was added to 3.0 g of decenyloxybenzoic acid and cooled on ice. 2.0 g of thionyl chloride was added dropwise to the mixture. Next, a reaction was carried out at 80°C for 3 hours. After the reaction, the product was concentrated to obtain an acid chloride. On the other hand, 1.7 g of 4-hydroxybenzoic acid 2-fluorooctyl ester obtained in (1) and 0.9 g of pyridine were dissolved in toluene and cooled on ice.
A toluene solution of the above acid chloride was added dropwise thereto. Next, the reaction was carried out at room temperature for 15 hours. After the reaction, the product was washed with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 2.8 g of the desired ester. (yield 85
%) (3) Example 1 was added to 2.8 g of the ester obtained in oxirane conversion (2).
The same operation as in (4) was performed to obtain 2.6 g of a monomer represented by the following formula. (Yield 91%) (4) Synthesis of polymer 2.6 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane ( Mn=3000) 2.2g was obtained. (yield 84%) The phase transition behavior, electric field response speed, and spontaneous polarization value of the obtained polymer are shown in the table, and the chart of 1 H-NMR analysis is shown in FIG. Example 11 (1) 4'-(5-hexenyloxy)biphenyl-
Synthesis of 4-carboxylic acid 2-methylbutyl ester 6-bromo-1-hexene 4.7 g, 4'-hydroxybiphenyl-4-carboxylic acid 2-methylbutyl ester 6.3 g, and potassium carbonate 3.1
g was refluxed in 2-butanone for 20 hours. After the reaction, inorganic salts were removed by washing with water. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 6.4 g of the desired ester. (Yield 79%) (2) Oxirane formation Example 1 was added to 1.7 g of the ester obtained in (1).
The same operation as in (4) was performed to obtain 1.6 g of a monomer represented by the following formula. (yield 89%) (3) Polymer synthesis 1.6 g of the monomer obtained in (2) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane ( Mn=3000) 1.0g was obtained. (yield 63%) The phase transition behavior, electric field response speed, and spontaneous polarization value of the obtained polymer are shown in the table, and the chart of 1 H-NMR analysis is shown in FIG. 11. Example 12 (1) Synthesis of p-(7-octenyloxy)benzoic acid 9.4 g of 8-bromo-1-octene, 9.0 g of ethyl p-hydroxybenzoate, and 7.6 g of potassium carbonate were refluxed in ethanol for 10 hours. did.
An aqueous solution containing 2.4 g of sodium hydroxide was added thereto, and the mixture was further refluxed for 10 hours. After the reaction, the mixture was diluted with water, and hydrochloric acid was added dropwise thereto to adjust the pH to 2. Collect the resulting precipitate, wash thoroughly with water, and dry.
10.8 g of the desired ether body was obtained. (yield 89
%) (2) Synthesis of 4-[p-(7-octenyloxy)benzoyloxy]biphenyl-4-carboxylic acid 2-methylbutyl ester p-(7-octenyloxy)benzoic acid obtained in (1) 9 g was suspended in toluene and cooled on ice. 6 g of thionyl chloride was added dropwise thereto. After the dropwise addition, the temperature was raised and the mixture was reacted at 80°C for 6 hours. After the reaction, the mixture was concentrated under reduced pressure to obtain an acid chloride. Toluene was added thereto to obtain a toluene solution, which was cooled on ice. A toluene solution containing 10 g of 4'-hydroxybiphenyl-4-carboxylic acid 2-methylbutyl ester and 3 g of pyridine was added dropwise to the above toluene solution of acid chloride. After dropping, the temperature is raised,
The reaction was carried out at 50°C for 8 hours. After the reaction, the product was washed with water, dried over magnesium sulfate, and then concentrated under reduced pressure. The residue was recrystallized from ethanol to obtain 8.2 g of the desired ester.
(Yield 45%) (3) Oxiranization 7.2 g of the ester obtained in (2) was oxidized with 3 g of m-chloroperbenzoic acid to obtain 6.3 g of a monomer represented by the following formula. (yield 85%) (4) Polymer synthesis 1.8 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane ( Mn=5100) 1.5g was obtained. (yield 83%) The phase transition behavior, electric field response speed, and spontaneous polarization value of the obtained polymer are shown in the table, and the chart of 1 H-NMR analysis is shown in FIG. 12. Example 13 (1) Synthesis of p-hydroxybenzoic acid 2-chloro-3-methylpentyl ester Thionyl chloride was added to 24 g of p-acetoxybenzoic acid.
32g was dropped. The mixture was heated to 80°C and reacted for 3 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain an acid chloride. This acid chloride was dissolved in toluene and cooled on ice. A toluene solution containing 13.7 g of (-)-2-chloro-3-methylpentanol and 14 g of triethylamine was added dropwise thereto. The mixture was stirred at room temperature overnight. After the reaction, the solution was washed with water, dried, and concentrated under reduced pressure. The residue was dissolved in ether. 17 g of benzylamine was added dropwise thereto. The mixture was stirred for 1 hour at room temperature. After reaction, washing with water, drying,
and concentrated under reduced pressure. The residue was purified by column chromatography to obtain 20.3 g of the desired ester [[α] 23 D =+11.6° (CHCl 3 )].
(Yield 79%) (2) Synthesis of 4-[4'-(9-decenyloxy)benzoyloxy]benzoic acid 2-chloro-3-methylpentyl ester p obtained in the same manner as in Example 4 (1) Toluene was added to 0.82 g of -decenyloxybenzoic acid, and the mixture was cooled on ice. Drop 1.1g of thionyl chloride there,
The reaction was carried out at ℃ for 7 hours. After the reaction, the reaction solution was concentrated to obtain an acid chloride. 0.76 g of p-hydroxybenzoic acid 2-chloro-3-methylpentyl ester obtained in (1) and 0.5 g of pyridine were dissolved in toluene and cooled on ice. A toluene solution of the above acid chloride was added dropwise thereto. The reaction was carried out at room temperature for 15 hours. After the reaction, the mixture was washed with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 1.14 g of the desired ester. (Yield 74%) (3) Example 1 was added to 0.52 g of the ester obtained in oxirane formation (2).
The same operation as in (4) was performed to obtain 0.48 g of a monomer represented by the following formula. (yield 90%) (4) Synthesis of polymer 0.48 g of the monomer obtained in (3) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane ( Mn=2800) 0.44g was obtained. (Yield 92%) The phase transition behavior, electric field response speed, and spontaneous polarization value of the obtained polymer are shown in the table, and the chart of 1 H-NMR analysis is shown in FIG. 13. Example 14 (1) 4'-(9-decenyloxy)biphenyl-4
-Synthesis of carboxylic acid 2-chloro-3-methylpentyl ester 4'-(9-decenyloxy)biphenyl-4
-Toluene was added to 4.0 g of carboxylic acid and cooled on ice. Thereto, 2.0 g of thionyl chloride was added dropwise.
The reaction was carried out at 800°C for 7 hours. After the reaction, the reaction solution was concentrated to obtain an acid chloride. 1.7 g of 2-chloro-3-methylpentanol and 1.0 g of pyridine were dissolved in toluene and cooled on ice. A toluene solution of the above acid chloride was added dropwise thereto. The reaction was carried out at room temperature for 15 hours. After the reaction, the reaction solution was washed with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 4.3 g of the desired ester. (Yield 80%) (2) Oxirane conversion Example 1 was added to 4.3 g of the ester obtained in (1).
The same operation as in (4) was performed to obtain 4.2 g of a monomer represented by the following formula. (yield 95%) (3) Polymer synthesis 4.2 g of the monomer obtained in (2) was polymerized in the same manner as in (5) of Example 1 to obtain the desired polyoxirane ( Mn=3300) 3.2g was obtained. (yield 76%) The phase transition behavior, electric field response speed, and spontaneous polarization value of the obtained polymer are shown in the table, and the chart of 1 H-NMR analysis is shown in FIG. 14.
【表】【table】
【表】【table】
【表】【table】
本発明のポリマーは、常温付近でも強誘電性を
示す上に、外的因子に対する応答速度が速くて動
画表示が可能であり、かつ大画面や屈曲画面の表
示素子としても有利に使用することができ、オプ
トエレクトロニクス分野における種々の電子光学
デバイスとして有用であり、その工業的価値は大
である。
The polymer of the present invention not only exhibits ferroelectricity even at room temperature, but also has a fast response speed to external factors, making it possible to display moving images, and it can also be advantageously used as a display element for large screens and curved screens. It is useful as various electro-optical devices in the optoelectronics field, and its industrial value is great.
第１図〜第１４図は、それぞれ実施例１〜実施
例14で得られたポリマーの1H−NMR分析のチヤ
ートを表す。
Figures 1 to 14 represent charts of 1 H-NMR analysis of the polymers obtained in Examples 1 to 14, respectively.
１ 一般式；
（式中、R1、R2、R3およびR4は２価の炭化水素
基、R5は１価の炭化水素基、R6は炭素数１〜６
のアルキル基、Ａはフエノール性水酸基を有する
１価の芳香族基、ａは１〜３の数を示し、ｍは10
〜500の数、ｎは１以上の数を示す。）で表わさ
れ、分子量が500〜50000である、加水分解性シリ
ル基で分子鎖末端が閉塞されたポリエーテル。
２ R1がエチレン基および／またはプロピレン
基である、特許請求の範囲第１項記載のポリエー
テル。
３ R1がプロピレン基である、特許請求の範囲
第２項記載のポリエーテル。
４ R2がメチレン基である、特許請求の範囲第
１項記載のポリエーテル。
５ R6がメチル基またはエチル基である、特許
1 General formula; (In the formula, R 1 , R 2 , R 3 and R 4 are divalent hydrocarbon groups, R 5 is a monovalent hydrocarbon group, and R 6 has 1 to 6 carbon atoms.
alkyl group, A is a monovalent aromatic group having a phenolic hydroxyl group, a is a number from 1 to 3, m is 10
~500, n represents a number of 1 or more. ) and has a molecular weight of 500 to 50,000, a polyether whose molecular chain ends are blocked with a hydrolyzable silyl group. 2. The polyether according to claim 1, wherein R 1 is an ethylene group and/or a propylene group. 3. The polyether according to claim 2, wherein R 1 is a propylene group. 4. The polyether according to claim 1, wherein R 2 is a methylene group. 5 Patent where R 6 is a methyl group or an ethyl group
Claims (1)
子、 または、−CNであり、 ｍおよびｎはそれぞれ０〜10の整数であり、
ただしR4が−CH3である場合はｎは０ではな
く、 ｐは０または１であり、 ＊のついたＣは不斉炭素原子である。）, R 3 is [Formula], R 4 and R 5 are each -CH 3 , a halogen atom, or -CN, m and n are each an integer from 0 to 10,
However, when R 4 is -CH 3 , n is not 0, p is 0 or 1, and C with * is an asymmetric carbon atom. )
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28847687A JPS63264629A (en) | 1986-12-29 | 1987-11-17 | Polymer |
| DE3752264T DE3752264T2 (en) | 1986-12-29 | 1987-12-29 | Liquid crystalline polymer |
| EP87119309A EP0274128B1 (en) | 1986-12-29 | 1987-12-29 | Liquid-crystalline polymer |
| US07/272,010 US4877858A (en) | 1986-12-29 | 1988-11-16 | Liquid-crystalline polymer |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61-309466 | 1986-12-29 | ||
| JP30946686 | 1986-12-29 | ||
| JP28847687A JPS63264629A (en) | 1986-12-29 | 1987-11-17 | Polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63264629A JPS63264629A (en) | 1988-11-01 |
| JPH0457694B2 true JPH0457694B2 (en) | 1992-09-14 |
Family
ID=26557197
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28847687A Granted JPS63264629A (en) | 1986-12-29 | 1987-11-17 | Polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63264629A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0768337B2 (en) * | 1988-05-11 | 1995-07-26 | ポリプラスチックス株式会社 | Method for producing resin that exhibits anisotropy when melted |
| US4954600A (en) * | 1988-06-27 | 1990-09-04 | Idemitsu Kosan Co., Ltd. | Ferroelectric liquid-crystalline polymer and epoxide usable to preparation of the ferroelectric liquid-crystalline polymer |
| JPH0757845B2 (en) * | 1989-02-22 | 1995-06-21 | 出光興産株式会社 | Ferroelectric liquid crystal composition |
| US5190686A (en) * | 1988-08-26 | 1993-03-02 | Idemitsu Kosan Co., Ltd. | Liquid-crystalline copolymer |
| JPH02101049A (en) * | 1988-10-05 | 1990-04-12 | Idemitsu Kosan Co Ltd | Liquid crystal compound and liquid crystal polymer |
| JP2832864B2 (en) * | 1989-08-08 | 1998-12-09 | キヤノン株式会社 | Polymer liquid crystal composition and polymer liquid crystal device |
| JP2806590B2 (en) * | 1990-01-25 | 1998-09-30 | 出光興産株式会社 | Polymer liquid crystal compound and its intermediate epoxy compound |
| JP2933805B2 (en) * | 1992-09-30 | 1999-08-16 | シャープ株式会社 | Polymer-dispersed liquid crystal composite film, liquid crystal display device, and method of manufacturing the same |
| JP2831521B2 (en) * | 1992-12-17 | 1998-12-02 | シャープ株式会社 | Ferroelectric liquid crystal display device and method of manufacturing the same |
| US6277503B1 (en) | 1998-03-03 | 2001-08-21 | Matsushita Electric Idustrial Co., Ltd | Organic electroluminescent component |
| KR100461474B1 (en) | 1998-12-28 | 2004-12-16 | 이데미쓰 고산 가부시키가이샤 | Organic electroluminescence device |
| JP4609032B2 (en) * | 2004-10-20 | 2011-01-12 | チッソ株式会社 | Photopolymerizable compound and composition containing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62201419A (en) * | 1986-01-24 | 1987-09-05 | ヘキスト・セラニーズ・コーポレーション | Side chain type liquid crystal oriented polymer showing non-linear optical response |
-
1987
- 1987-11-17 JP JP28847687A patent/JPS63264629A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62201419A (en) * | 1986-01-24 | 1987-09-05 | ヘキスト・セラニーズ・コーポレーション | Side chain type liquid crystal oriented polymer showing non-linear optical response |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63264629A (en) | 1988-11-01 |
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