JPS63161004A - Prepolymer from aromatic dicarboxylic acid diallyl ester - Google Patents
Prepolymer from aromatic dicarboxylic acid diallyl esterInfo
- Publication number
- JPS63161004A JPS63161004A JP31451786A JP31451786A JPS63161004A JP S63161004 A JPS63161004 A JP S63161004A JP 31451786 A JP31451786 A JP 31451786A JP 31451786 A JP31451786 A JP 31451786A JP S63161004 A JPS63161004 A JP S63161004A
- Authority
- JP
- Japan
- Prior art keywords
- prepolymer
- diallyl
- formula
- compound
- weight
- 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
- -1 aromatic dicarboxylic acid diallyl ester Chemical class 0.000 title claims abstract description 23
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 12
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 8
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 8
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000003776 cleavage reaction Methods 0.000 claims description 2
- 230000007017 scission Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052740 iodine Inorganic materials 0.000 abstract description 15
- 239000011630 iodine Substances 0.000 abstract description 15
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005977 Ethylene Substances 0.000 abstract description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- 229940093470 ethylene Drugs 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000005266 casting Methods 0.000 description 11
- 239000003999 initiator Substances 0.000 description 11
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 10
- 239000004342 Benzoyl peroxide Substances 0.000 description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QNVNLUSHGRBCLO-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- MNUOZFHYBCRUOD-UHFFFAOYSA-N hydroxyphthalic acid Natural products OC(=O)C1=CC=CC(O)=C1C(O)=O MNUOZFHYBCRUOD-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- VJRSWIKVCUMTFK-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC(F)=C(F)C(F)(F)F.FC(F)=C(F)C(F)(F)F.FC(F)=C(F)C(F)(F)F VJRSWIKVCUMTFK-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000005670 ethenylalkyl group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- PJSREVXKVTYFLE-UHFFFAOYSA-N 4-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoronon-1-enoxy)phthalic acid Chemical compound OC(=O)C1=CC=C(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C=C1C(O)=O PJSREVXKVTYFLE-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- MWRVRCAFWBBXTL-UHFFFAOYSA-N 4-hydroxyphthalic acid Chemical compound OC(=O)C1=CC=C(O)C=C1C(O)=O MWRVRCAFWBBXTL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 241000876472 Umma Species 0.000 description 1
- PDAVOLCVHOKLEO-UHFFFAOYSA-N acetyl benzenecarboperoxoate Chemical compound CC(=O)OOC(=O)C1=CC=CC=C1 PDAVOLCVHOKLEO-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は新規な芳香族ジカルボン酸ジアリルのプレポリ
マーに閤する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel diallyl aromatic dicarboxylic acid prepolymer.
(従来の技術)
芳香族ノカルボン酸ジアリル、例えばフタル酸ジアリル
は重合性官能基を2個有する熱硬化性樹脂のモノマーで
ある。一般に、このような2個以上の重合性官能基を有
するモノマーよりポリマーを得て所期の形状に成型する
には、溶剤可溶性或いは熱可塑性を有する程度の重合度
にて一旦重合反応を停止し、溶剤溶液として或いは熱可
塑性樹脂として成型した後、或いは成型すると同時に、
更に重合をすすめて不溶不融の樹脂、すなわち、硬化物
に成型する工程をたどる。この工程における溶剤可溶性
或いは熱可塑性ポリマーは、一般にプレポリマーと称せ
られる。(Prior Art) Diallyl aromatic nocarboxylate, for example diallyl phthalate, is a thermosetting resin monomer having two polymerizable functional groups. Generally, in order to obtain a polymer from a monomer having two or more polymerizable functional groups and mold it into a desired shape, the polymerization reaction must be stopped once at a degree of polymerization that is solvent soluble or thermoplastic. , after or simultaneously with molding as a solvent solution or as a thermoplastic resin,
Further polymerization is carried out to form an insoluble and infusible resin, that is, a cured product. The solvent-soluble or thermoplastic polymer used in this process is generally referred to as a prepolymer.
従来のフタル酸ジアリルなどのプレポリマーの硬化物は
ソケット、コネクター等の電気部品用成形材料、積層板
、化粧板等として有用であるが、耐水性が乏しいという
欠点があった。Conventional cured products of prepolymers such as diallyl phthalate are useful as molding materials for electrical parts such as sockets and connectors, laminates, decorative boards, etc., but they have the drawback of poor water resistance.
(発明が解決しようとする問題点)
本発明の目的は耐水性に優れた硬化物を与える新規な芳
香族ジカルボン酸ジアリルのプレポリマーを提供するこ
とにある。(Problems to be Solved by the Invention) An object of the present invention is to provide a novel diallyl aromatic dicarboxylic acid prepolymer that provides a cured product with excellent water resistance.
(問題点を解決するための手段)
本発明は式
(X11116〜14のパーフルオロアルケニル基を示
す)で表わされる繰返し単位を含有する含フツ素芳香族
ジカルボン酸ジアリルのプレポリマーに係る。(Means for Solving the Problems) The present invention relates to a prepolymer of diallyl fluorine-containing aromatic dicarboxylic acid containing a repeating unit represented by the formula (representing a perfluoroalkenyl group of X11116-14).
Xで表わされる炭素数6〜14のパーフルオロアルケニ
ル基としては例えば式
%式%
(R1,R2及びR3はそれぞれ炭素数1〜6のパーフ
ルオロアルキル基またはいずれかの一つがFi子、その
他は炭素数1〜6のパーフルオロアルキル基を示し、R
4は炭素数1〜5のパーフルオロアルキル基を示す、)
で表わされる基を示すことができ、特に好適なものとし
てはへキサフルオロプロペンの2量体又は3量体、テト
ラブルオロエチレンの4〜7量体からフッ素原子1個が
脱離して形成される基を挙げることができ、構造式で例
示すると下記のとおりである。The perfluoroalkenyl group having 6 to 14 carbon atoms represented by Represents a perfluoroalkyl group having 1 to 6 carbon atoms, R
4 represents a perfluoroalkyl group having 1 to 5 carbon atoms.)
Particularly preferred are groups formed by the elimination of one fluorine atom from a dimer or trimer of hexafluoropropene, or a tetramer to heptamer of tetrafluoroethylene. Examples of the structural formulas are as follows.
(cp、)2c=6c、Fs、 CF。(cp,)2c=6c,Fs, C.F.
本発明において、(1)式で表わされる繰返し単位は、
本発明のプレポリマーの単量体である(Xは前記と同じ
)で表わされる含フツ素ジカルボン酸ジアリルが転化し
たものであるので、(2)式で表わされる化合物は、式
H2
及び/又は
に転化することがあって、本発明のプレポリマーには、
これらの繰返し単位が(1)式の繰返し単位に比べて少
量存在することがある0本発明のプレポリマーでは、こ
れらの繰返し単位の存在は必要ではない。In the present invention, the repeating unit represented by formula (1) is
Since diallyl fluorine-containing dicarboxylate represented by (X is the same as above), which is a monomer of the prepolymer of the present invention, is converted, the compound represented by formula (2) is a compound represented by formula H2 and/or The prepolymers of the present invention include:
Although these repeating units may be present in small amounts compared to the repeating units of formula (1), the presence of these repeating units is not necessary in the prepolymer of the present invention.
本発明においては(1)式の繰り返し単位と(1)式以
外の繰り返し単位を含有する共重合体も包含される。The present invention also includes copolymers containing repeating units of formula (1) and repeating units other than formula (1).
(1)式以外の繰り返し単位としては例えばエチレン、
酢酸ビニル、弗化ビニル、塩化ビニル、アクリルアミド
、メタクリルアミド、スチレン、a−メチルスチレン、
p−メチルスチレン、アクリル酸又はメタクリル酸のフ
ルキルエステル、ベンジル7クリレート又はメタクリレ
ート、ビニルアルキルエーテル、ハロゲン化アルキルビ
ニルエーテル、ビニルアルキルケトン、シクロヘキシル
アクリレート又はメタクリレート、無水マレイン酸、ブ
タジェン、イソプレン、クロロプレン、フタル酸ジアリ
ル、イソフタル酸ジアリル、テレフタル酸ジアリル等の
如き各種の化合物の二重結合が開裂して生成する繰返し
単位を挙げることができる。Examples of repeating units other than formula (1) include ethylene,
Vinyl acetate, vinyl fluoride, vinyl chloride, acrylamide, methacrylamide, styrene, a-methylstyrene,
p-methylstyrene, furkyl ester of acrylic or methacrylic acid, benzyl 7-acrylate or methacrylate, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, cyclohexyl acrylate or methacrylate, maleic anhydride, butadiene, isoprene, chloroprene, phthalic acid Examples include repeating units produced by cleavage of double bonds in various compounds such as diallyl, diallyl isophthalate, diallyl terephthalate, and the like.
本発明のプレポリマーにおいて好ましい分子量は数平均
分子量で約1000〜50000.特に約3000〜1
0000の範囲であり、また好ましいヨウ素価(試料t
OOgに付加するヨウ素のグラム数)は好ましくは約
10〜95、より好ましくは約25〜80の範囲である
。The preferred molecular weight of the prepolymer of the present invention is about 1,000 to 50,000 in number average molecular weight. Especially about 3000~1
0000, and a preferable iodine value (sample t
The number of grams of iodine added to OOg is preferably in the range of about 10-95, more preferably about 25-80.
分子量が余り大であるとデル化した重合体の加工が困難
であり、余り小であると実用的な強度のある硬化体が得
られ難い、またヨウ素価が小さすぎると実用的な強度の
ある硬化体が得られず、大きすぎるものはその硬化物の
耐衝撃性が劣る。If the molecular weight is too high, it will be difficult to process the deltized polymer; if the molecular weight is too small, it will be difficult to obtain a cured product with practical strength; and if the iodine value is too low, it will be difficult to process the polymer. A cured product cannot be obtained, and if the size is too large, the cured product will have poor impact resistance.
本発明のプレポリマーは上記化合物(2)を単独重合又
は共重合させることにより得られる。The prepolymer of the present invention can be obtained by homopolymerizing or copolymerizing the above compound (2).
共重合成分としてはエチレン系化合物例えばエチレン、
酢酸ビニル、弗化ビニル、塩化ビニル、アクリルアミド
、メタクリルアミド、スチレン、a−7チルスチレン、
p−メチルスチレン、アクリル酸又はメタクリル酸のア
ルキルエステル、ベンツルアクリレート又はメタクリレ
ート、ビニルアルキルエーテル、ハロゲン化アルキルビ
ニルエーテル、ビニルアルキルケトン、シクロヘキシル
アクリレート又はメタクリレート、無水マレイン酸、共
役ジエン系化合物例えばブタジェン、イソプレン、クロ
ロブレン、独立ジエン系化合物例えばフタル酸ジアリル
、イソフタル酸ジアリル、テレフタル酸ジアリル等の如
き各種の重合し得る化合物を挙げることができる。プレ
ポリマーにおける繰返し単位(1)の割合は約1%(重
量%、以下同じ)以上、好ましくは約10%以上とする
のがよい。As a copolymerization component, ethylene compounds such as ethylene,
Vinyl acetate, vinyl fluoride, vinyl chloride, acrylamide, methacrylamide, styrene, a-7 tylstyrene,
p-methylstyrene, alkyl esters of acrylic or methacrylic acid, benzyl acrylate or methacrylate, vinyl alkyl ethers, halogenated alkyl vinyl ethers, vinyl alkyl ketones, cyclohexyl acrylate or methacrylate, maleic anhydride, conjugated diene compounds such as butadiene, isoprene , chlorobrene, independent diene compounds such as diallyl phthalate, diallyl isophthalate, diallyl terephthalate and the like. The proportion of the repeating unit (1) in the prepolymer is preferably about 1% (by weight, the same applies hereinafter) or more, preferably about 10% or more.
約1%未満では耐水性は期待されない。Water resistance is not expected below about 1%.
重合反応の方式や条件は、任意に選択でき、例えばラジ
カル重合において塊状重合、溶液重合、懸濁重合、乳化
重合など各種の方式を、イオン重合においてカチオン重
合などの方式を採用することができる。ラジカル重合の
開始剤としては遊離ラジカルを生じる化合物が使用され
る。好ましいラジカル開始剤としてベンゾイルパーオキ
サイド、tert ”fチルパーベンゾエート、アセ
チルベンゾイルパーオキサイド、サクシニルパーオキサ
イド、ジイソプロピルパーオキシノカーボネート、アン
モニウムパーサル7エートなどの過酸化物お上びアゾビ
スイソブチロニトリルなどの7ゾニトリル類などが挙げ
られる。また特公昭35−16035に記載されている
ような式
〔ZはC1、OHあるいはOH基に変換できる任意の基
、Rは低級アルキル(炭素数1〜4)、伯はθ〜4、■
はθ〜(4−m))で表わされる鎖長調整剤を用いるこ
ともできる0分子量の調節及びゲル化の防止は、鎖長調
整剤をモノマーに対して好ましくは約10〜25重量%
の存在下に重合するが、重合開始剤量、重合温度、重合
時間等を調節することにより行うことができる。ラジカ
ル開始剤の使用量は単量体に対し0.1〜10%(重量
)の範囲から選ばれる。しかし使用される開始剤の使用
量の範囲は以上に限定されるものではなく、目的の重合
体の重合度、反応時間、重合温度などの因子に依って適
宜選択される。重合温度は開始剤の分解温度に応じて一
80℃〜+250℃である。一般に一40℃〜+150
℃の範囲が好ましい、溶液重合で使用できる溶媒として
は、ベンゼン、トルエン、キシレン等の芳香族炭化水素
、クロロホルム、塩・化メチレン、塩化エチレンなどの
低塩基性溶媒が使用される。これは1種又は2種以上を
混合して使用することもできる。またカチオン重合の場
合、三7ツ化ホウ素エチルエーテラート、塩化アルミニ
ウムなどの重合可能な開始剤を用い、−30℃から25
0℃の温度でトルエン、ベンゼンなどの溶媒中で重合す
ることができる。The method and conditions of the polymerization reaction can be arbitrarily selected, and for example, various methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used in radical polymerization, and cationic polymerization can be used in ionic polymerization. Compounds that generate free radicals are used as initiators for radical polymerization. Preferred radical initiators include peroxides such as benzoyl peroxide, tert'f-thyl perbenzoate, acetyl benzoyl peroxide, succinyl peroxide, diisopropyl peroxynocarbonate, ammonium persal 7ate, and azobisisobutyronitrile. 7 zonitrile, etc. Also, the formula as described in Japanese Patent Publication No. 35-16035 [Z is C1, OH or any group that can be converted into an OH group, R is lower alkyl (C1 to C4 ), Haku is θ~4, ■
A chain length regulator represented by θ~(4-m)) can also be used.0 To control the molecular weight and prevent gelation, the chain length regulator is preferably used in an amount of about 10 to 25% by weight based on the monomer.
The polymerization can be carried out by adjusting the amount of polymerization initiator, polymerization temperature, polymerization time, etc. The amount of the radical initiator used is selected from the range of 0.1 to 10% (by weight) based on the monomer. However, the range of the amount of the initiator to be used is not limited to the above, and is appropriately selected depending on factors such as the degree of polymerization of the target polymer, reaction time, and polymerization temperature. The polymerization temperature is between -80°C and +250°C, depending on the decomposition temperature of the initiator. Generally -40℃~+150℃
As the solvent that can be used in the solution polymerization, the temperature preferably ranges from 0.degree. These may be used alone or in combination of two or more. In addition, in the case of cationic polymerization, a polymerizable initiator such as boron trisulfide ethyl etherate or aluminum chloride is used to
Polymerization can be carried out in a solvent such as toluene or benzene at a temperature of 0°C.
反応混合物から重合体を回収する場合も通常の方法が採
用されてよく、例えば重合生成物をメタノール、ジイソ
プロピルエーテル、ジメチルエーテル、石油エーテル、
n−ヘキサンの如(重合体が溶解しない貧溶剤に加えて
重合体のみを沈殿させる。重合体の精製には沈殿として
得られた重合体をア七トン、メチルエチルケトン、酢酸
エチル、ノオキサン、テトラヒドロフラン、二塩化エタ
ン、900 ホルム、ffi塩化炭素、トリクロロエチ
レン、ベンゼン、トルエンなどの溶媒に溶解した後、上
記の貧溶媒に加えて重合体を再沈殿させることによって
行うのが好ましい。Conventional methods may be used to recover the polymer from the reaction mixture; for example, the polymerization product may be recovered from methanol, diisopropyl ether, dimethyl ether, petroleum ether,
Only the polymer is precipitated in addition to a poor solvent such as n-hexane (in which the polymer does not dissolve). To purify the polymer, the polymer obtained as a precipitate is mixed with acetone, methyl ethyl ketone, ethyl acetate, nooxane, tetrahydrofuran, It is preferable to dissolve the polymer in a solvent such as ethane dichloride, 900% form, ffi carbon chloride, trichloroethylene, benzene, toluene, or the like, and then reprecipitate the polymer in addition to the above-mentioned poor solvent.
本発明のプレポリマーのモノマーである化合物(2)は
新規化合物であり、例えば式
で示されるヒドロキシ芳香族クヵルボン酸誘導体トX
F (X !1116〜14のパーフルオロアルケニル
基を示す)で表わされるパーフルオロアルケンを反応さ
せることにより得られる。Compound (2), which is a monomer of the prepolymer of the present invention, is a new compound, for example, a hydroxyaromatic carboxylic acid derivative represented by the formula
It is obtained by reacting a perfluoroalkene represented by F (X represents a perfluoroalkenyl group of !1116-14).
上記化合物(3)は新規化合物であり、これを製造する
には例えばヒドロキシフタル酸をアリルアルコールで触
媒の存在下にエステル化する。反応は通常ヒドロキシフ
タル酸1モルに対して、アリルアルコ一ル約2〜40モ
ル使用して行うのが好ましい。触媒には、濃硫酸、パラ
トルエンスルホン酸、三7ツ化ホウ素エチルエーテラー
トなどが例示される。反応温度は好ましくは約50〜2
00℃、反応時間は適宜定めればよ(一般に約30分〜
20時間程度が好ましく、反応圧力は特に制限はない。The above compound (3) is a new compound, and can be produced by, for example, esterifying hydroxyphthalic acid with allyl alcohol in the presence of a catalyst. The reaction is usually preferably carried out using about 2 to 40 moles of allyl alcohol per 1 mole of hydroxyphthalic acid. Examples of the catalyst include concentrated sulfuric acid, para-toluenesulfonic acid, and boron trisulfide ethyl etherate. The reaction temperature is preferably about 50-2
00℃, reaction time can be determined as appropriate (generally about 30 minutes ~
The reaction time is preferably about 20 hours, and the reaction pressure is not particularly limited.
この反応は溶媒中で行うのが好ましい。溶媒には、ベン
ゼン、トルエン、キシレン、ジアリルエーテルなど水と
共沸し、実質的には水と混合して溶液を形成しないもの
が好ましい、生成した化合物(3)は公知の方法、例え
ば濃縮、抽出、蒸留、クロマトグラフィー等で精製可能
であるが、精製を行ゎ1ずに、次工程でXFで表わされ
るパーフルオロアルケンと反応させることもできる。This reaction is preferably carried out in a solvent. The solvent is preferably one that is azeotropic with water and does not substantially form a solution when mixed with water, such as benzene, toluene, xylene, diallyl ether, etc. The produced compound (3) can be processed by known methods such as concentration, It can be purified by extraction, distillation, chromatography, etc., but it can also be reacted with a perfluoroalkene represented by XF in the next step without purification.
式XFで表わされるパーフルオロアルケンとしては例え
ば式
%式%
(R1,R2及びR3はそれぞれ炭素数1〜6のパーフ
ルオロアルキル基またはいずれかの一つがF原子、その
他は炭素数1〜6のパーフルオロアルキル基を示す)で
表わされる化合物を示すことができ、特に好適なものと
してはへキサフルオロプロペンの2fi体及び3量体、
テトラフルオロエチレンの4〜7量体を挙げることがで
き、構造式で例示すると、下記のとおりである。The perfluoroalkene represented by the formula (representing a perfluoroalkyl group); particularly preferred examples include 2fi forms and trimers of hexafluoropropene;
Tetrafluoroethylene tetra- to heptamers can be mentioned, and examples of the structural formulas are as follows.
(CF、)2C=CF(C,F、)、
反応は塩基の存在下、溶媒中で行うのが好ましい。塩基
としては例えばトリエチルアミン、トリメチルアミン、
トリプロピルアミン等のアミン類、アルカリ金属または
その水酸化物等を、溶媒としてはアセトニトリル、ジメ
チルホルムアミド、ツメチルスルホキシドなどの非プロ
トン性極性溶媒が好適に使用できる。化合物(3)とパ
ーフルオロアルケンの割合は通常前者1モルに対して後
者を約1〜10モル用いるのが好ましい1反応温度は適
宜選択できるが約θ〜40℃、特に約θ〜20℃の範囲
が好ましい。塩基は化合物(3)1モルに対して約1〜
20モルの範囲で用いるのが好適である。目的物である
化合物(2)は通常、固体が液体に溶解した有機化合物
混合系の分離について用いられる公知の方法で分離、回
収できるが、例えば大過剰の希塩酸中に反応生成物を加
え生成した沈殿を回収し、これを減圧下で蒸留すること
により回収することができる。(CF,)2C=CF(C,F,), The reaction is preferably carried out in a solvent in the presence of a base. Examples of the base include triethylamine, trimethylamine,
Amines such as tripropylamine, alkali metals or their hydroxides, etc., and aprotic polar solvents such as acetonitrile, dimethylformamide, and trimethylsulfoxide are preferably used as the solvent. The ratio of compound (3) and perfluoroalkene is usually about 1 to 10 moles of the latter per 1 mole of the former.The reaction temperature can be selected as appropriate, but it is preferably about θ to 40°C, especially about θ to 20°C. A range is preferred. The base is used in an amount of about 1 to 1 mole of compound (3).
It is preferable to use it in a range of 20 mol. Compound (2), which is the target product, can usually be separated and recovered by a known method used for the separation of a mixed organic compound system in which a solid is dissolved in a liquid. The precipitate can be collected and recovered by distilling it under reduced pressure.
(4)式のXFで示される化合物の中にはR”
F
及び
で示される化合物が包含される。(4) Among the compounds represented by XF in the formula, R”
Compounds represented by F and are included.
これらからは、それぞれ が生成する。From these, each is generated.
より具体的には例えば が生成する。More specifically, for example is generated.
また化合物(2)は例えば式
(×は前記に同じ)で表わされる公知の芳香族ノカルボ
ン酸とアリルアルコールを反応させることによっても得
られる。化合物(5)は公知の化合物である。反応は溶
媒中で行うのが好ましい、溶媒としては水と共沸し、実
質的には水と混合しなり1ものが好ましく、例えばベン
ゼン、トルエン、キシレン、ジアリルエーテルなどを挙
げることができる。化合物(5)とアリルアルコールの
割合は通常前者1モルに対して後者を約2〜10モル用
いるのが好ましい。反応温度は適宜選択できるが約50
〜200℃、特に約70〜160℃の範囲が好ましい。Compound (2) can also be obtained, for example, by reacting a known aromatic nocarboxylic acid represented by the formula (x is the same as above) with allyl alcohol. Compound (5) is a known compound. The reaction is preferably carried out in a solvent. Preferably, the solvent is one that is azeotropic with water and substantially miscible with water, such as benzene, toluene, xylene, diallyl ether, and the like. The ratio of compound (5) to allyl alcohol is preferably about 2 to 10 moles of the latter per 1 mole of the former. The reaction temperature can be selected as appropriate, but it is approximately 50℃.
A range of -200<0>C, especially about 70-160<0>C is preferred.
目的物である化合物(2)は通常、固体が液体に溶解し
た有機化合物混合系の分離について用いられる公知の方
法で分離、回収でさ、例えば濃縮、蒸留、ガスクロマト
グラフィー等により回収することができる。Compound (2), which is the target product, can be usually separated and recovered by a known method used for separating an organic compound mixture system in which a solid is dissolved in a liquid, such as concentration, distillation, gas chromatography, etc. can.
本発明のプレポリマーは、単独でまたはフタル酸ノアリ
ル、イソフタル酸ジアリル、テレフタル酸ジアリル等の
プレポリマーと混合して、熱重合開始剤、光重合開始剤
等の存在下で熱によりまたは光により、あるいは開始剤
の存在しない系で電子線、〃ンマ線などの活性エネルギ
ー線により硬化することができる。開始剤の存在下では
、その開始剤のキャリアとしてフタル酸ジアリル、イソ
フタル酸ジアリル、テレフタル酸ジアリル等のモノマー
を混合することも可能である。モノマーの使用量は混合
物中90重量%程度までとするのが好ましい。The prepolymer of the present invention can be used alone or in combination with a prepolymer such as noallyl phthalate, diallyl isophthalate, diallyl terephthalate, etc., by heat or light in the presence of a thermal polymerization initiator, a photopolymerization initiator, etc. Alternatively, curing can be carried out using active energy rays such as electron beams and umma rays in the absence of an initiator. In the presence of an initiator, it is also possible to mix monomers such as diallyl phthalate, diallyl isophthalate, diallyl terephthalate, etc. as carriers for the initiator. The amount of monomer used is preferably up to about 90% by weight in the mixture.
熱重合開始剤としては例えばメチルエチルケトンパーオ
キサイド、シクロヘキサノンパーオキサイド等のケトン
パーオキサイド類、t−ブチルパーベンゾエート、t−
ブチルパーオキシ−2−エチルヘキソエートなどのパー
エステル79、L−ブチルハイドロパーオキサイド、ク
メンハイドロパーオキサイドなどのハイドロパーオキサ
イド類、ベンゾイルパーオキサイドなどのノアシルバー
オキサイド類などを、また光重合開始剤としては例えば
2,2−ノエトキシアセトフェノン、2,2−ジメトキ
シ−2−フェニルアセトフェノン等のベンゾインアルキ
ルエーテル類、ノエトキシアセトフエノン等の7セトフ
エノン類、ベンゾ7エ/ン等のケトン類、2−クロロチ
オキサントン等のチオキサントン類などが挙げられる。Examples of thermal polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, t-butyl perbenzoate, and t-butyl perbenzoate.
Perester 79 such as butyl peroxy-2-ethylhexoate, hydroperoxides such as L-butyl hydroperoxide and cumene hydroperoxide, and noarsilver oxides such as benzoyl peroxide, etc., and photopolymerization can be initiated. Examples of the agent include benzoin alkyl ethers such as 2,2-noethoxyacetophenone and 2,2-dimethoxy-2-phenylacetophenone, 7cetophenones such as noethoxyacetophenone, ketones such as benzo7e/one, Examples include thioxanthone such as 2-chlorothioxanthone.
開始剤の使用量はプレポリマー及びキャリアに対して約
o、oot〜20重量%、好ましくは約0.1〜10重
量%とするのが良い。The amount of initiator used is about o, oot to 20% by weight, preferably about 0.1 to 10% by weight, based on the prepolymer and carrier.
熱、光、活性エネルギー線のいずれを問わず、硬化温度
は室温〜250℃、好ましくは室温〜180℃の範囲が
用いられる。Regardless of heat, light, or active energy rays, the curing temperature ranges from room temperature to 250°C, preferably from room temperature to 180°C.
(発明の効果)
本発明のプレポリマーは、炭素−炭素二重結合を末端に
有する側鎖を有するので、架橋性を有して硬化体を与え
るとともに、もう一つの側鎖であるパーフルオロアルケ
ニルオキシ頻を有するので、本発明のプレポリマーが与
える硬化体は、耐水性が優れている。即ち、本発明のプ
レポリマーは、従来のフタル酸ジアリルな・どのプレポ
リマーに比゛べて、耐水性が極めて優れている硬化体を
与え、(1)式で表わされる繰返し単位を約50重量%
含有するプレポリマーでも約1/10の吸水率を示す硬
化体を与える。(Effects of the Invention) Since the prepolymer of the present invention has a side chain having a carbon-carbon double bond at the end, it has crosslinkability and provides a cured product, and also has perfluoroalkenyl as another side chain. Since the prepolymer of the present invention has an oxidized polymer, the cured product provided by the prepolymer of the present invention has excellent water resistance. That is, the prepolymer of the present invention provides a cured product with extremely superior water resistance compared to conventional prepolymers such as diallyl phthalate, and has a repeating unit represented by formula (1) of about 50% by weight. %
Even with the prepolymer contained, a cured product exhibiting a water absorption rate of about 1/10 is obtained.
(実 施 例) 以下に参考例、実施例及び比較例を挙げて説明する。(Example) Reference examples, working examples, and comparative examples will be described below.
参考例1
5−ヒドロキシイソフタル酸0.2モルを攪拌機、冷却
管、温度計を備えた反応容器に入れ、アリルアルコール
0.6モル、トルエン3001、硫酸1.3g。Reference Example 1 0.2 mole of 5-hydroxyisophthalic acid was placed in a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and 0.6 mole of allyl alcohol, 3001 g of toluene, and 1.3 g of sulfuric acid were added.
p−メトキシ7エ/−ル0.2gを加えて加熱下に還流
させた。留出してくる水分は冷却管で凝縮後、トルエン
と分離しトルエンは連続的に反応容器へ返送した。8時
間後に加熱を停止し、放冷した。0.2 g of p-methoxy 7 ether was added and the mixture was heated to reflux. The distilled water was condensed in a cooling tube and separated from toluene, which was continuously returned to the reaction vessel. After 8 hours, heating was stopped and the mixture was allowed to cool.
この時点で留出した水分の合計は7−1であった。The total amount of water distilled out at this point was 7-1.
反応液を飽和食塩水を用いて水層が酸性を示さなくなる
まで洗浄した後、トルエンを減圧下に留去した。この濃
縮液を減圧下に蒸留して5−ヒドロキシインフタル酸ジ
アリル27g([率52%)を得た。After washing the reaction solution with saturated brine until the aqueous layer no longer showed acidity, toluene was distilled off under reduced pressure. This concentrated solution was distilled under reduced pressure to obtain 27 g (yield: 52%) of diallyl 5-hydroxyinphthalate.
b、p、 202〜205℃15mmHgかくして得
られた5−ヒドロキシイソフタル酸ジアリル26gをジ
メチルホルムアミド90m lに溶解し、トリエチルア
ミン31.を加え攪拌しながら室温下にヘキサフルオロ
プロペン3量体45gを10分間で滴下し、撹拌を続け
た。2時間後、反応液を多量の希塩酸中に投入し沈殿し
た油状物を分離、水洗して減圧下に蒸留し5−(パーフ
ルオロノネニルオキシ)イソフタル酸ジアリル(化合物
A) 41g(収率59%)を得た。b, p, 202-205°C, 15 mmHg 26 g of diallyl 5-hydroxyisophthalate thus obtained was dissolved in 90 ml of dimethylformamide, and 31. While stirring, 45 g of hexafluoropropene trimer was added dropwise over 10 minutes at room temperature, and stirring was continued. After 2 hours, the reaction solution was poured into a large amount of diluted hydrochloric acid, and the precipitated oil was separated, washed with water, and distilled under reduced pressure to obtain 41 g of diallyl 5-(perfluorononenyloxy)isophthalate (compound A) (yield 59). %) was obtained.
b@p、 150〜b
参考例2
参考例1における5−ヒドロキシイソフタル酸の代りに
4−ヒドロキシフタル酸を用いた以外は参考例1と同様
にして4−(パーフルオロノネニルオキシ)フタル酸ジ
アリル(化合物B)を得た。b@p, 150-b Reference Example 2 4-(perfluorononenyloxy)phthalic acid was prepared in the same manner as in Reference Example 1 except that 4-hydroxyphthalic acid was used instead of 5-hydroxyisophthalic acid in Reference Example 1. Diallyl (compound B) was obtained.
b、p、 160〜b
参考例3
参考例1におけるヘキサフルオロプロペン3量体の代り
に2量体30.を用い、5−ヒドロキシイソフタル酸ジ
アリルとの反応温度を0〜4℃とする以外は参考例1と
同様にして5−(パーフルオロヘキセニルオキシ)イソ
フタル酸ジアリル(化合物C)39gを得た。b, p, 160-b Reference Example 3 In place of the hexafluoropropene trimer in Reference Example 1, dimer 30. 39 g of diallyl 5-(perfluorohexenyloxy)isophthalate (compound C) was obtained in the same manner as in Reference Example 1 except that the reaction temperature with diallyl 5-hydroxyisophthalate was 0 to 4°C.
b@p、 128〜131℃15−曽Hg参考例4
参考例2におけるヘキサフルオロプロペン3f1体の代
りにテトラフルオロエチレン5量体50gを用いる以外
は参考例2と同様にして4−(パーフルオロデセニルオ
キシ)フタル酸ジアリル(化合+11kD)を得た。b@p, 128-131°C 15-SoHgReference Example 4 4-(Perfluoro Diallyl decenyloxy)phthalate (compound +11 kD) was obtained.
b、9.165〜b
実施例I
C0OCI(zct(”CI(2
化合物A (250g)、テレフタル酸ジアリル250
g。b, 9.165-b Example I C0OCI(zct("CI(2) Compound A (250g), diallyl terephthalate 250
g.
過酸化ベンゾイル7g5ジブチルスズシラツレ−トロ6
1水250gを撹拌機、冷却管を備えた反応容器に入れ
、85℃で5時間反応させた0反応後、室温まで冷却し
アセトン50.を加え静置した。有機層を大量のメタノ
ール中へ滴下しながら攪拌し、生成した沈殿を口過、メ
タノール洗浄した後、減圧下に乾燥、粉砕して白色粉末
120.を得た。このものはヨウ素価66、ゲルパーミ
エイションクロマトグラフイーにより求めたポリスチレ
ン換算の数平均分子量Mnは8,6X103、重量平均
分子1hは5.3X10’であり、フッ素含量は18,
5wt%であった。Benzoyl peroxide 7g 5 Dibutyltin Shirathuro 6
1. 250 g of water was placed in a reaction vessel equipped with a stirrer and a cooling tube and reacted at 85° C. for 5 hours. After the reaction, it was cooled to room temperature and 50 g of acetone was added. was added and left to stand. The organic layer was dropped into a large amount of methanol while stirring, and the resulting precipitate was filtered, washed with methanol, dried under reduced pressure, and ground to a white powder of 120. I got it. This material has an iodine value of 66, a polystyrene equivalent number average molecular weight Mn determined by gel permeation chromatography of 8.6X103, a weight average molecular weight 1h of 5.3X10', and a fluorine content of 18.
It was 5wt%.
従って上記白色粉末は化合物(A)とテレフタル酸ジア
リルのモル比が1 :4.3であるプレポリマーであっ
た。このプレポリマー50重量部をテレフタル酸ジアリ
ルエステル50重量部に溶解し、過酸化ベンゾイル2重
1部を加えて内径50−のシャーレに流延して、90℃
で8時間加熱し直径50曽鰺、厚さ31IIIの注型板
を作製した。Therefore, the white powder was a prepolymer in which the molar ratio of compound (A) and diallyl terephthalate was 1:4.3. 50 parts by weight of this prepolymer was dissolved in 50 parts by weight of diallyl terephthalate, 1 part by weight of benzoyl peroxide was added, and the mixture was cast at 90°C in a Petri dish with an inner diameter of 50°C.
The mixture was heated for 8 hours to produce a casting plate with a diameter of 50 mm and a thickness of 31 mm.
実施例2
含フッ素芳香族ノカルボン酸ジアリルとして化合物B
(250g)を用い、反応時間を4時間とする以外は実
施例1と同様にして白色粉末102gを得た。Example 2 Compound B as diallyl fluorine-containing aromatic nocarboxylic acid
102 g of a white powder was obtained in the same manner as in Example 1, except that (250 g) was used and the reaction time was changed to 4 hours.
このもののヨウ素価は70、Mnは7.3X10’、同
一は4.4X104であり、フッ素含量は18,6wt
%であった。The iodine value of this product is 70, the Mn is 7.3X10', the same is 4.4X104, and the fluorine content is 18.6wt.
%Met.
従って上記白色粉末は化合物(B)とテレフタル酸ジア
リルのモル比が1 :4.3であるプレポリマーであっ
た。さらにこのプレポリマーを用い、実施例1と同様に
して注型板を作製した。Therefore, the white powder was a prepolymer in which the molar ratio of compound (B) and diallyl terephthalate was 1:4.3. Furthermore, using this prepolymer, a casting plate was produced in the same manner as in Example 1.
実施例3
実施例2における化合物(B)を375g、テレフタル
酸ジアリルを125g用いる以外は実施例2と同様にし
て白色粉末148gを得た。このもののヨウ素価は49
、Mnは1.lX10’、習−は4,6X 10%、フ
ッ素含量は31.4wt%であった。従って上記白色粉
末は化合物(B)とテレフタル酸ジアリルのモル比が1
:1.4であるプレポリマーであった。さらにこのプレ
ポリマーを用い、実施例1と同様にして注型板を作製し
た。Example 3 148 g of white powder was obtained in the same manner as in Example 2, except that 375 g of compound (B) and 125 g of diallyl terephthalate were used. The iodine value of this thing is 49
, Mn is 1. lX10', Xi- was 4,6X 10%, and the fluorine content was 31.4 wt%. Therefore, the above white powder has a molar ratio of compound (B) and diallyl terephthalate of 1.
:1.4. Furthermore, using this prepolymer, a casting plate was produced in the same manner as in Example 1.
実施例4
実施例1におけるテレフタル酸ジアリルの代りにフタル
酸ジアリル125gとインフタル酸ジアリル125gを
用いる以外は実施例1と同様にして白色粉末118gを
得た。このもののヨウ素価は65.8nは7.2X10
’、8賀は4,2X10’であり、フッ素含量は18.
7wt%であった。従って上記白色粉末は化合物(A)
とジアリルエステルのモル比が1 :4,3であるプレ
ポリマーであった。さらにこのプレポリマーを用い、実
施例1と同様にして注型板を作製した。Example 4 118 g of white powder was obtained in the same manner as in Example 1, except that 125 g of diallyl phthalate and 125 g of diallyl inphthalate were used instead of diallyl terephthalate in Example 1. The iodine value of this thing is 65.8n, which is 7.2X10
', 8ga is 4,2X10', and the fluorine content is 18.
It was 7wt%. Therefore, the above white powder is compound (A)
The prepolymer had a molar ratio of 1:4.3 and diallyl ester. Furthermore, using this prepolymer, a casting plate was produced in the same manner as in Example 1.
実施例5
実施例1におけるテレフタル酸ジアリルの代りにイソフ
タル酸ジアリルを用いる以外は実施例1と同様にして白
色粉末121gを得た。このもののヨウ素価は72、I
VIIは5,6X 10’、簡−は6.lXl0’であ
り、フッ素含量は18,5wt%であった。従って上記
白色粉末は化合物(A)とイソフタル酸ジアリルのモル
比が1 :4.3であるプレポリマーであった。さらに
このプレポリマーを用い、実施例1と同様にして注型板
を作製した。Example 5 121 g of white powder was obtained in the same manner as in Example 1 except that diallyl isophthalate was used instead of diallyl terephthalate. The iodine value of this substance is 72, I
VII is 5.6X 10', simple is 6. lXl0', and the fluorine content was 18.5 wt%. Therefore, the white powder was a prepolymer in which the molar ratio of compound (A) and diallyl isophthalate was 1:4.3. Furthermore, using this prepolymer, a casting plate was produced in the same manner as in Example 1.
実施例6
実施例2においてテレフタル酸ジアリルは用いず、全量
を化合物(B)とする以外は実施例2と同様にして、化
合物(B)の単独重合プレポリマー87gを得た。この
もののヨウ素価は28、[1は2.4×103.8賃は
4,8X10コであり、フッ素含量は45.9%であっ
た。このプレポリマー50重量部と化合物(B)を加熱
下に均一に混合し、過酸化ベンゾイル2重量部を加えて
90℃で8時間加熱して注型板を作製した。Example 6 87 g of a homopolymerized prepolymer of compound (B) was obtained in the same manner as in Example 2 except that diallyl terephthalate was not used and the entire amount was used as compound (B). The iodine value of this product was 28, the iodine value was 2.4 x 103.8, and the fluorine content was 45.9%. 50 parts by weight of this prepolymer and compound (B) were uniformly mixed under heating, 2 parts by weight of benzoyl peroxide was added, and the mixture was heated at 90° C. for 8 hours to prepare a casting plate.
実施例7
化合物c (300g)、テレフタル酸ジアリル200
g。Example 7 Compound c (300g), diallyl terephthalate 200
g.
過酸化ベンゾイル7g、ジブチルスズシラツレ−)6g
、水250gを用い実施例1と同様にして白色粉末10
8gを得た。このものはヨウ素価71、簡n=9.2X
10コ、簡−=5.9X10’であり、フッ素含量は1
9.8wt%であった。従って上記白色粉末は化合物(
C)とテレフタル酸ジアリルのモル比が1:2.1であ
るプレポリマーであった。このプレポリマー60重量部
をテレフタル酸ジアリル40部を混合し、過酸化ベンゾ
イル2重量部を加えて実施例1と同様にして注型板を作
製した。7 g of benzoyl peroxide, 6 g of dibutyltin silica
, White powder 10 was prepared in the same manner as in Example 1 using 250 g of water.
8g was obtained. This one has an iodine value of 71, simple n=9.2X
10 pieces, simple = 5.9X10', and the fluorine content is 1
It was 9.8 wt%. Therefore, the above white powder is a compound (
The prepolymer had a molar ratio of C) and diallyl terephthalate of 1:2.1. A casting plate was prepared in the same manner as in Example 1 by mixing 60 parts by weight of this prepolymer with 40 parts by weight of diallyl terephthalate and adding 2 parts by weight of benzoyl peroxide.
実施例8
Xがテトラブルオロエチレン5量体である化合物りを5
00g用い、反応時間を6時間とする以外は実施例6と
同様にして単独重合プレポリマー107gを得た。この
もののヨウ素価は26、Mnは3.2×10’、同一は
6,7X 10’であり、フッ素含量は48.5%であ
った。このプレポリマー70重量部と化合物(D)30
重量部を加熱下に均一に混合し、過酸化ベンゾイル2重
量部を加えて実施例1と同様にして注型板を作製した。Example 8 Compound 5 where X is a tetrafluoroethylene pentamer
107 g of a homopolymerized prepolymer was obtained in the same manner as in Example 6, except that 00 g was used and the reaction time was 6 hours. The iodine value of this product was 26, the Mn was 3.2 x 10', the same was 6,7 x 10', and the fluorine content was 48.5%. 70 parts by weight of this prepolymer and 30 parts by weight of compound (D)
Parts by weight were uniformly mixed under heating, 2 parts by weight of benzoyl peroxide was added, and a casting plate was prepared in the same manner as in Example 1.
比較例1
フタル酸ジアリルプレポリマー〔商品名グイソーグツブ
A、大阪曹達(株)製、Mn=6,7X103、g替=
2.6X10’、ヨウ素価61 ) 50重量部をテレ
フタル酸ジアリル50重量部に溶解し、過酸化ベンゾイ
ル2重量部を加えて実施例1と同様にして注型板を作製
した。Comparative Example 1 Diallyl phthalate prepolymer [trade name Guiso Gutsubu A, manufactured by Osaka Soda Co., Ltd., Mn = 6,7X103, g change =
2.6X10', iodine value 61) was dissolved in 50 parts by weight of diallyl terephthalate, 2 parts by weight of benzoyl peroxide was added, and a casting plate was prepared in the same manner as in Example 1.
比較例2
テレフタルF!!ジアリル系ポリマー〔商品名グプレン
、大阪曹達(株)製、簡n=7,3X10コ、閘−=2
.5X 10’、ヨウ素価51〕をグイソーグツプAの
代りに用いる以外は比較例1と同様にして注型板を作製
した。Comparative Example 2 Terephthal F! ! Diallyl-based polymer [trade name: Guprene, manufactured by Osaka Soda Co., Ltd., simple n = 7, 3 x 10, lock = 2
.. A casting plate was prepared in the same manner as in Comparative Example 1, except that 5×10′, iodine value 51] was used instead of Guiso Gup A.
実施例及び比較例で得られた注型板を用い、JIS K
−6911に準じて23℃における吸水率を測定した。Using the casting plates obtained in Examples and Comparative Examples, JIS K
-6911, the water absorption rate at 23°C was measured.
結果を第1表に示す。The results are shown in Table 1.
第 1 表Chapter 1 Table
Claims (3)
す)で表わされる繰返し単位を含有する含フッ素芳香族
ジカルボン酸ジアリルのプレポリマー。(1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) A preform of diallyl fluorine-containing aromatic dicarboxylate containing a repeating unit represented by (X represents a perfluoroalkenyl group having 6 to 14 carbon atoms) polymer.
割合が少なくとも1重量%である特許請求の範囲第1項
記載のプレポリマー。(2) The prepolymer according to claim 1, wherein the proportion of repeating units of formula (1) in the prepolymer is at least 1% by weight.
イソフタル酸ジアリル及びテレフタル酸ジアリルの群か
ら選ばれる少なくとも1種の1個のアリル基の二重結合
が開裂して生成する繰返し単位である特許請求の範囲第
1項記載のプレポリマー。(3) The repeating unit other than formula (1) is diallyl phthalate,
The prepolymer according to claim 1, which is a repeating unit produced by cleavage of the double bond of at least one allyl group selected from the group of diallyl isophthalate and diallyl terephthalate.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31451786A JPS63161004A (en) | 1986-12-24 | 1986-12-24 | Prepolymer from aromatic dicarboxylic acid diallyl ester |
US07/109,413 US4841093A (en) | 1986-10-22 | 1987-10-19 | Aromatic dicarboxylic acid diallyl ester derivative, prepolymer derived from the derivative and curable resin composition containing the derivative |
EP87115518A EP0264948B1 (en) | 1986-10-22 | 1987-10-22 | Aromatic dicarboxylic acid diallyl ester derivative, prepolymer derived from the derivative and curable resin composition containing the derivative |
DE8787115518T DE3775878D1 (en) | 1986-10-22 | 1987-10-22 | DISCONNECTING A DIALLYLESTER OF AN AROMATIC DICARBONIC ACID, PRAEPOLYMER DERIVED FROM THIS AND CURING RESIN COMPOSITION CONTAINING THIS COLLECTING. |
US07/338,835 US5061770A (en) | 1986-10-22 | 1989-04-14 | Aromatic dicarboxylic acid diallyl ester derivative, prepolymer derived from the derivative and curable resin composition containing the derivative |
US07/606,982 US5175207A (en) | 1986-10-22 | 1990-10-31 | Aromatic dicarboxylic acid diallyl ester derivatives, prepolymer derived from the derivative and curable resin composition containing the derivative |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31451786A JPS63161004A (en) | 1986-12-24 | 1986-12-24 | Prepolymer from aromatic dicarboxylic acid diallyl ester |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63161004A true JPS63161004A (en) | 1988-07-04 |
JPH0415245B2 JPH0415245B2 (en) | 1992-03-17 |
Family
ID=18054235
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP31451786A Granted JPS63161004A (en) | 1986-10-22 | 1986-12-24 | Prepolymer from aromatic dicarboxylic acid diallyl ester |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63161004A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016135803A (en) * | 2016-04-05 | 2016-07-28 | 大石 哲也 | Manufacturing method of perfluoroalkenyl oxy group-containing arene compound |
-
1986
- 1986-12-24 JP JP31451786A patent/JPS63161004A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016135803A (en) * | 2016-04-05 | 2016-07-28 | 大石 哲也 | Manufacturing method of perfluoroalkenyl oxy group-containing arene compound |
Also Published As
Publication number | Publication date |
---|---|
JPH0415245B2 (en) | 1992-03-17 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
LAPS | Cancellation because of no payment of annual fees |