JP6691660B2 - Method for producing polyarylene sulfide resin - Google Patents
Method for producing polyarylene sulfide resin Download PDFInfo
- Publication number
- JP6691660B2 JP6691660B2 JP2015227757A JP2015227757A JP6691660B2 JP 6691660 B2 JP6691660 B2 JP 6691660B2 JP 2015227757 A JP2015227757 A JP 2015227757A JP 2015227757 A JP2015227757 A JP 2015227757A JP 6691660 B2 JP6691660 B2 JP 6691660B2
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- JP
- Japan
- Prior art keywords
- alkali metal
- mol
- water
- reaction
- hydrosulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims description 43
- 229920005989 resin Polymers 0.000 title claims description 42
- 239000011347 resin Substances 0.000 title claims description 42
- 229920000412 polyarylene Polymers 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- -1 aliphatic cyclic compound Chemical class 0.000 claims description 108
- 238000006243 chemical reaction Methods 0.000 claims description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- 229910052783 alkali metal Inorganic materials 0.000 claims description 65
- 150000001875 compounds Chemical class 0.000 claims description 29
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 25
- 125000004434 sulfur atom Chemical group 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 150000003951 lactams Chemical class 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 238000000034 method Methods 0.000 description 24
- 239000000203 mixture Substances 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- 230000009257 reactivity Effects 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 150000004677 hydrates Chemical class 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000011088 calibration curve Methods 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012765 fibrous filler Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- WIAVVDGWLCNNGT-UHFFFAOYSA-M lithium;butanoate Chemical compound [Li+].CCCC([O-])=O WIAVVDGWLCNNGT-UHFFFAOYSA-M 0.000 description 2
- HXQGSILMFTUKHI-UHFFFAOYSA-M lithium;sulfanide Chemical compound S[Li] HXQGSILMFTUKHI-UHFFFAOYSA-M 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 1
- CDPKJZJVTHSESZ-UHFFFAOYSA-N 4-chlorophenylacetic acid Chemical compound OC(=O)CC1=CC=C(Cl)C=C1 CDPKJZJVTHSESZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- IBSGAWQJFSDRBJ-UHFFFAOYSA-M cesium sulfanide Chemical compound [SH-].[Cs+] IBSGAWQJFSDRBJ-UHFFFAOYSA-M 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QTNDMWXOEPGHBT-UHFFFAOYSA-N dicesium;sulfide Chemical compound [S-2].[Cs+].[Cs+] QTNDMWXOEPGHBT-UHFFFAOYSA-N 0.000 description 1
- PMUKAEUGVCXPDF-SEPHDYHBSA-L dilithium;(e)-but-2-enedioate Chemical compound [Li+].[Li+].[O-]C(=O)\C=C\C([O-])=O PMUKAEUGVCXPDF-SEPHDYHBSA-L 0.000 description 1
- PMUKAEUGVCXPDF-UAIGNFCESA-L dilithium;(z)-but-2-enedioate Chemical compound [Li+].[Li+].[O-]C(=O)\C=C/C([O-])=O PMUKAEUGVCXPDF-UAIGNFCESA-L 0.000 description 1
- JQVALDCWTQRVQE-UHFFFAOYSA-N dilithium;dioxido(dioxo)chromium Chemical compound [Li+].[Li+].[O-][Cr]([O-])(=O)=O JQVALDCWTQRVQE-UHFFFAOYSA-N 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- VNSVQJIXVXZDJF-UHFFFAOYSA-L dilithium;phthalate Chemical compound [Li+].[Li+].[O-]C(=O)C1=CC=CC=C1C([O-])=O VNSVQJIXVXZDJF-UHFFFAOYSA-L 0.000 description 1
- QTTDHHKBHTUYCK-UHFFFAOYSA-L dilithium;propanedioate Chemical compound [Li+].[Li+].[O-]C(=O)CC([O-])=O QTTDHHKBHTUYCK-UHFFFAOYSA-L 0.000 description 1
- BBLSYMNDKUHQAG-UHFFFAOYSA-L dilithium;sulfite Chemical compound [Li+].[Li+].[O-]S([O-])=O BBLSYMNDKUHQAG-UHFFFAOYSA-L 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940031993 lithium benzoate Drugs 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- XQHAGELNRSUUGU-UHFFFAOYSA-M lithium chlorate Chemical compound [Li+].[O-]Cl(=O)=O XQHAGELNRSUUGU-UHFFFAOYSA-M 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 description 1
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- WAHQBNXSPALNEA-UHFFFAOYSA-L lithium succinate Chemical compound [Li+].[Li+].[O-]C(=O)CCC([O-])=O WAHQBNXSPALNEA-UHFFFAOYSA-L 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- AVOVSJYQRZMDQJ-KVVVOXFISA-M lithium;(z)-octadec-9-enoate Chemical compound [Li+].CCCCCCCC\C=C/CCCCCCCC([O-])=O AVOVSJYQRZMDQJ-KVVVOXFISA-M 0.000 description 1
- IOEDDFFKYCBADJ-UHFFFAOYSA-M lithium;4-methylbenzenesulfonate Chemical compound [Li+].CC1=CC=C(S([O-])(=O)=O)C=C1 IOEDDFFKYCBADJ-UHFFFAOYSA-M 0.000 description 1
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 description 1
- LTRVAZKHJRYLRJ-UHFFFAOYSA-N lithium;butan-1-olate Chemical compound [Li+].CCCC[O-] LTRVAZKHJRYLRJ-UHFFFAOYSA-N 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- PNDUWCHQCLZPAH-UHFFFAOYSA-M lithium;hexanoate Chemical compound [Li+].CCCCCC([O-])=O PNDUWCHQCLZPAH-UHFFFAOYSA-M 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- HPCCWDVOHHFCKM-UHFFFAOYSA-M lithium;hydrogen sulfate Chemical compound [Li+].OS([O-])(=O)=O HPCCWDVOHHFCKM-UHFFFAOYSA-M 0.000 description 1
- BTAUEIDLAAYHSL-UHFFFAOYSA-M lithium;octanoate Chemical compound [Li+].CCCCCCCC([O-])=O BTAUEIDLAAYHSL-UHFFFAOYSA-M 0.000 description 1
- KDDRURKXNGXKGE-UHFFFAOYSA-M lithium;pentanoate Chemical compound [Li+].CCCCC([O-])=O KDDRURKXNGXKGE-UHFFFAOYSA-M 0.000 description 1
- HAUKUGBTJXWQMF-UHFFFAOYSA-N lithium;propan-2-olate Chemical compound [Li+].CC(C)[O-] HAUKUGBTJXWQMF-UHFFFAOYSA-N 0.000 description 1
- AXMOZGKEVIBBCF-UHFFFAOYSA-M lithium;propanoate Chemical compound [Li+].CCC([O-])=O AXMOZGKEVIBBCF-UHFFFAOYSA-M 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- LXOXXUIVMOYGST-UHFFFAOYSA-M rubidium(1+);sulfanide Chemical compound [SH-].[Rb+] LXOXXUIVMOYGST-UHFFFAOYSA-M 0.000 description 1
- AHKSSQDILPRNLA-UHFFFAOYSA-N rubidium(1+);sulfide Chemical compound [S-2].[Rb+].[Rb+] AHKSSQDILPRNLA-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- OMHSPROLCMCXLS-UHFFFAOYSA-M sodium;2-(methylamino)butanoate Chemical compound [Na+].CCC(NC)C([O-])=O OMHSPROLCMCXLS-UHFFFAOYSA-M 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Description
本発明はポリアリーレンスルフィド樹脂の製造方法に関する。 The present invention relates to a method for producing a polyarylene sulfide resin.
ポリアリーレンスルフィド樹脂（以下、ＰＰＳと言うことがある。）に代表されるポリアリーレンスルフィド樹脂（以下、ＰＡＳと言うことがある。）は、耐熱性、耐薬品性に優れ、電気電子部品、自動車部品、給湯器部品、繊維、フィルム用途等に幅広く用いられている。 Polyarylene sulfide resins (hereinafter sometimes referred to as PAS) represented by polyarylene sulfide resins (hereinafter sometimes referred to as PPS) are excellent in heat resistance and chemical resistance, and are excellent in electric and electronic parts and automobiles. Widely used for parts, water heater parts, textiles, film applications, etc.
高分子量ポリアリーレンスルフィド樹脂の製造方法として、ポリハロ芳香族化合物および有機極性溶媒の存在下に、アルカリ金属硫化物を滴下して重合反応させる、いわゆる「Ｓ滴下法」と呼ばれる方法が知られている。 As a method for producing a high-molecular-weight polyarylene sulfide resin, a so-called “S dropping method” is known, in which an alkali metal sulfide is added dropwise to cause a polymerization reaction in the presence of a polyhaloaromatic compound and an organic polar solvent. ..
例えば、有機極性溶媒及びポリハロ芳香族化合物を含む混合物中にアルカリ金属水硫化物及び／またはアルカリ金属硫化物からなる含水スルフィド化剤を反応混合物から水が除去され得る速度で導入して反応を行うことによって、高分子量かつ直鎖状のポリアリーレンスルフィドを製造し、ポリアリーレンスルフィドの靱性を改善する技術が開示されている。しかし、前記方法によって得られるポリアリーレンスルフィドは、分子量が高く靱性が多少改善されるものの、未だ十分なものではなかった。また、ポリアリーレンスルフィドの靱性を改善する為に、シランカップリング剤で変成する方法も知られているが、この方法によって得られるポリアリーレンスルフィドは、分子量は高められるものの、酸又はアルカリとの反応活性点が少ないためシランカップリング剤等のカップリング剤で変性することが困難であり、結局、実用的な靱性が得られないものであった。 For example, the reaction is carried out by introducing an alkali metal hydrosulfide and / or a hydrous sulfidizing agent comprising an alkali metal sulfide into a mixture containing an organic polar solvent and a polyhaloaromatic compound at a rate at which water can be removed from the reaction mixture. Thus, a technique for producing a high molecular weight and linear polyarylene sulfide and improving the toughness of the polyarylene sulfide is disclosed. However, although the polyarylene sulfide obtained by the above method has a high molecular weight and a toughness is improved to some extent, it is still not sufficient. Further, in order to improve the toughness of the polyarylene sulfide, a method of modifying with a silane coupling agent is also known, but the polyarylene sulfide obtained by this method has a higher molecular weight, but a reaction with an acid or an alkali. Since the number of active sites is small, it is difficult to modify with a coupling agent such as a silane coupling agent, and eventually, practical toughness cannot be obtained.
そこで、ポリハロ芳香族化合物、脂肪族系環状化合物、アルカリ金属水酸化物及び水の存在下、前記脂肪族系環状化合物を加水分解させ（工程１）、次いで、アルカリ金属硫化物またはアルカリ金属水硫化物を系内に滴下して順次加えながら重合反応（工程２）を行う方法が提案されている（特許文献２参照）。 Therefore, the aliphatic cyclic compound is hydrolyzed in the presence of a polyhaloaromatic compound, an aliphatic cyclic compound, an alkali metal hydroxide and water (step 1), and then an alkali metal sulfide or an alkali metal hydrosulfide is added. A method has been proposed in which a polymerization reaction (step 2) is carried out while dropping substances into the system and sequentially adding them (see Patent Document 2).
この方法は、脂肪族系環状化合物の加水分解物とポリハロ芳香族化合物（ＤＣＢ）の存在下で、アルカリ金属硫化物またはアルカリ金属水硫化物およびアルカリ金属水酸化物を系内に順次加えるため、該脂肪族系環状化合物の加水分解物がアルカリ金属塩（ＳＭＡＢ）を生成し、さらに該ＳＭＡＢと該ポリハロ芳香族化合物とが副反応を起こして、下記構
造式（１）
In this method, an alkali metal sulfide or an alkali metal hydrosulfide and an alkali metal hydroxide are sequentially added to the system in the presence of a hydrolyzate of an aliphatic cyclic compound and a polyhaloaromatic compound (DCB). The hydrolyzate of the aliphatic cyclic compound forms an alkali metal salt (SMAB), and further, the SMAB and the polyhaloaromatic compound undergo a side reaction to give the following structural formula (1).
また、この方法は、反応系にスルフィド化剤を順次加えるため、原料中に占める硫黄源の存在割合が低く、該脂肪族系環状化合物の加水分解物のアルカリ金属塩の割合も低くなることから、ポリマーの成長末端が副反応を起こす確率も低くなる。その結果、反応活性点となるポリマー末端のカルボキシ基量を充分増加させることができていなかった。このため、ＣＰ−ＭＡＢＡを精製工程で除去した後に得られるＰＡＳ樹脂は、シランカップリング剤や官能基含有熱可塑性エラストマー等で変性しても、靱性や耐衝撃性等の機械的強度の向上が充分なものとは言えなかった。また、ポリマーの成長末端が副反応を起こす確率が低くなるとはいえ、やはりＣＰ−ＭＡＢＡの存在により、さらにポリマーの高分子量化を図る際には、阻害要因となっており、この方法によって得られるポリアリーレンスルフィドも、分子量の高いポリマーが得られるものの、未だ十分なものではなかった。
Further, in this method, since the sulfidizing agent is sequentially added to the reaction system, the proportion of the sulfur source in the raw material is low, and the proportion of the alkali metal salt of the hydrolyzate of the aliphatic cyclic compound is also low. Also, the probability that the growing end of the polymer will cause a side reaction is reduced. As a result, it was not possible to sufficiently increase the amount of the carboxy group at the polymer terminal, which becomes the reaction active point. Therefore, the PAS resin obtained after removing CP-MABA in the purification step is improved in mechanical strength such as toughness and impact resistance even when modified with a silane coupling agent or a functional group-containing thermoplastic elastomer. It wasn't enough. Further, although the probability of causing a side reaction at the growth end of the polymer is low, the presence of CP-MABA is also an inhibitory factor in further increasing the polymer molecular weight, and is obtained by this method. Polyarylene sulfide was also not sufficient, although a polymer having a high molecular weight could be obtained.
そこで本発明が解決しようとする課題は、ポリマー末端のカルボキシ基量が多く、かつ、高分子量のポリアリーレンスルフィド樹脂を生産性良く製造する方法を提供することにある。 Therefore, an object of the present invention is to provide a method for producing a high-molecular weight polyarylene sulfide resin having a large amount of carboxy groups at the polymer terminal with high productivity.
本願発明者らは種々の検討を行った結果、特許文献１に記載の方法は、滴下する硫化ナトリウムが反応装置の接液部の金属原子を溶出し、これが重合反応を阻害する要因となっていること、また、特許文献２に記載の方法では、スルフィド化剤滴下の前段階で、すでに多量のＣＰ−ＭＡＢＡが反応系内にあることが、ＰＡＳ重合反応の阻害要因となっていることを見出し、上記課題を解決するに至った。 As a result of various investigations by the inventors of the present application, in the method described in Patent Document 1, sodium sulfide to be dropped elutes metal atoms in the wetted portion of the reaction device, which becomes a factor that inhibits the polymerization reaction. In addition, in the method described in Patent Document 2, a large amount of CP-MABA is already present in the reaction system before the dropping of the sulfidizing agent is a factor that inhibits the PAS polymerization reaction. Heading, it came to solve the above-mentioned subject.
すなわち本発明は、脂肪族系環状化合物とポリハロ芳香族化合物を含む反応容器中に、
（ａ）水と、アルカリ金属水硫化物と、脂肪族系環状化合物の加水分解物のアルカリ金属塩と、アルカリ金属水酸化物とを供給しながら、または、（ｂ）水と、アルカリ金属水硫化物と、前記アルカリ金属塩と、アルカリ金属硫化物とを供給しながら、重合反応させることを特徴とするポリアリーレンスルフィド樹脂の製造方法、に関する。
That is, the present invention, in a reaction vessel containing an aliphatic cyclic compound and a polyhalo aromatic compound,
While supplying (a) water, an alkali metal hydrosulfide, an alkali metal salt of a hydrolyzate of an aliphatic cyclic compound, and an alkali metal hydroxide, or (b) water and an alkali metal water. The present invention relates to a method for producing a polyarylene sulfide resin, which comprises performing a polymerization reaction while supplying a sulfide, the alkali metal salt, and an alkali metal sulfide.
本発明により、ポリマー末端のカルボキシ基量が多く、かつ、高分子量のポリアリーレンスルフィド樹脂を生産性良く製造する方法を提供することができる。 According to the present invention, it is possible to provide a method for producing a high-molecular weight polyarylene sulfide resin having a large amount of carboxy groups at the polymer terminal with high productivity.
本発明のポリアリーレンスルフィドの製造方法は、脂肪族系環状化合物とポリハロ芳香族化合物を含む反応容器中に、（ａ）水と、アルカリ金属水硫化物と、脂肪族系環状化合物の加水分解物のアルカリ金属塩（以下、脂肪族系環状化合物の加水分解物のアルカリ金属塩を「ＳＭＡＢ」と言うことがある）と、アルカリ金属水酸化物とを供給しながら、または、（ｂ）水と、アルカリ金属水硫化物と、前記アルカリ金属塩と、アルカリ金属硫化物とを供給しながら、重合反応させることを特徴とする。以下、具体的に詳述する。 The method for producing a polyarylene sulfide of the present invention comprises: (a) water, an alkali metal hydrosulfide, and a hydrolyzate of an aliphatic cyclic compound in a reaction vessel containing an aliphatic cyclic compound and a polyhaloaromatic compound. While supplying the alkali metal salt (hereinafter, the alkali metal salt of the hydrolyzate of the aliphatic cyclic compound may be referred to as "SMAB") and the alkali metal hydroxide, or (b) water. The polymerization reaction is performed while supplying the alkali metal hydrosulfide, the alkali metal salt, and the alkali metal sulfide. The details will be described below.
本発明は、まず始めに、反応容器内に、脂肪族系環状化合物とポリハロ芳香族化合物を供給し、脂肪族系環状化合物とポリハロ芳香族化合物を含む重合反応に供する溶液を得る（以下、工程（１）と記す）。 The present invention, first, in the reaction vessel, to supply an aliphatic cyclic compound and a polyhaloaromatic compound, to obtain a solution to be subjected to a polymerization reaction containing an aliphatic cyclic compound and a polyhaloaromatic compound (hereinafter, step (1)).
本発明で用いる脂肪族系環状化合物としては、加水分解によって開環し得るものであれば公知のものを特に限定されることなく用いることができるが、このような脂肪族系環状化合物の具体例としてはＮ−メチル−２−ピロリドン（以下、ＮＭＰと略記する。）、Ｎ−シクロヘキシル−２−ピロリドン、Ｎ−メチル−ε−カプロラクタム、ホルムアミド、アセトアミド、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、２−ピロリドン、ε−カプロラクタム、ヘキサメチルホスホルアミド、テトラメチル尿素、Ｎ−ジメチルプロピレン尿素、１，３−ジメチル−２−イミダゾリジノン酸などの脂肪族環状アミド化合物、アミド尿素、及びラクタム類が挙げられる。これらの中でも反応性が良好である点から脂肪族環状アミド化合物、特にＮＭＰが好ましい。 As the aliphatic cyclic compound used in the present invention, known compounds can be used without particular limitation as long as they can be opened by hydrolysis, and specific examples of such aliphatic cyclic compounds As N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N-cyclohexyl-2-pyrrolidone, N-methyl-ε-caprolactam, formamide, acetamide, N-methylformamide, N, N-dimethylacetamide. , 2-pyrrolidone, ε-caprolactam, hexamethylphosphoramide, tetramethylurea, N-dimethylpropyleneurea, aliphatic cyclic amide compounds such as 1,3-dimethyl-2-imidazolidinone acid, amideurea, and lactam The kind is mentioned. Of these, aliphatic cyclic amide compounds, particularly NMP, are preferable because of their good reactivity.
本発明で用いるポリハロ芳香族化合物としては、例えば、ｐ−ジハロベンゼン、ｍ−ジハロベンゼン、ｏ−ジハロベンゼン、１，２，３−トリハロベンゼン、１，２，４−トリハロベンゼン、１，３，５−トリハロベンゼン、１，２，３，５−テトラハロベンゼン、１，２，４，５−テトラハロベンゼン、１，４，６−トリハロナフタレン、２，５−ジハロトルエン、１，４−ジハロナフタレン、１−メトキシ−２，５−ジハロベンゼン、４，４’−ジハロビフェニル、３，５−ジハロ安息香酸、２，４−ジハロ安息香酸、２，５−ジハロニトロベンゼン、２，４−ジハロニトロベンゼン、２，４−ジハロアニソール、ｐ，ｐ’−ジハロジフェニルエーテル、４，４’−ジハロベンゾフェノン、４，４’−ジハロジフェニルスルホン、４，４’−ジハロジフェニルスルホキシド、４，４’−ジハロジフェニルスルフィド、及び、上記各化合物の芳香環に炭素原子数１〜１８のアルキル基を核置換基として有する化合物が挙げられる。また、上記各化合物中に含まれるハロゲン原子は、塩素原子、臭素原子であることが望ましい。 Examples of the polyhalo aromatic compound used in the present invention include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalo. Benzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene, 1,4,6-trihalonaphthalene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1 -Methoxy-2,5-dihalobenzene, 4,4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p, p'-dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenyl sulfone, 4,4 - dihalodiphenyl sulfoxide, 4,4'-dihalodiphenyl sulfide, and a compound having an aromatic ring in the alkyl group having 1 to 18 carbon atoms of each of the above compounds as nuclear substituents. Further, the halogen atom contained in each of the above compounds is preferably a chlorine atom or a bromine atom.
前記ポリハロ芳香族化合物の中でも、本発明では線状高分子量ＰＡＳ樹脂を効率的に製造できる点から、２官能性のジハロ芳香族化合物が好ましく、とりわけ最終的に得られるＰＡＳ樹脂の機械的強度や成形性が良好となる点からｐ−ジクロロベンゼン、ｍ−ジクロロベンゼン、４，４’−ジクロロベンゾフェノン及び４，４’−ジクロロジフェニルスルホンが好ましく、特にｐ−ジクロロベンゼンが好ましい。また、線状ＰＡＳ樹脂のポリマー構造の一部に分岐構造を持たせたい場合には、上記ジハロ芳香族化合物と共に、１，２，３−トリハロベンゼン、１，２，４−トリハロベンゼン、又は１，３，５−トリハロベンゼンを一部併用することが好ましい。 Among the polyhaloaromatic compounds, a bifunctional dihaloaromatic compound is preferable in the present invention because a linear high molecular weight PAS resin can be efficiently produced, and particularly, the mechanical strength of the finally obtained PAS resin and From the viewpoint of good moldability, p-dichlorobenzene, m-dichlorobenzene, 4,4′-dichlorobenzophenone and 4,4′-dichlorodiphenyl sulfone are preferable, and p-dichlorobenzene is particularly preferable. Moreover, when it is desired to have a branched structure in a part of the polymer structure of the linear PAS resin, 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, or 1 may be used together with the above dihaloaromatic compound. It is preferable to partially use 3,3,5-trihalobenzene together.
その他、ポリハロ芳香族化合物の適当な選択組合せによって２種以上の異なる反応単位を含む共重合体を得ることもでき、例えば、ｐ−ジクロルベンゼンと、４，４’−ジクロルベンゾフェノン又は４，４’−ジクロルジフェニルスルホンとを組み合わせて使用することで耐熱性に優れたポリアリーレンスルフィドを得ることもでき、好ましい。 In addition, a copolymer containing two or more different reaction units can be obtained by an appropriate selected combination of polyhaloaromatic compounds. For example, p-dichlorobenzene and 4,4′-dichlorobenzophenone or 4, It is preferable to use in combination with 4′-dichlorodiphenyl sulfone, because a polyarylene sulfide having excellent heat resistance can be obtained.
ポリハロ芳香族化合物の仕込み量は、特に限定されないが、仕込み量がそのまま重合反応に供されるため、生産性ないし経済性から、後述する工程（２）で仕込む、（ａ）アルカリ金属水硫化物に由来する硫黄原子１モルに対して、または、（ｂ）アルカリ金属水硫化物およびアルカリ金属硫化物に由来する硫黄原子１モルに対して、０．７モル〜１．２モルの範囲が好ましく、さらに０．８〜１．１モルの範囲がより好ましく、等モルの割合で用いることが特に好ましい。 The charging amount of the polyhaloaromatic compound is not particularly limited, but since the charging amount is directly used for the polymerization reaction, (a) an alkali metal hydrosulfide charged in the step (2) described later from the viewpoint of productivity or economy. It is preferably in the range of 0.7 mol to 1.2 mol with respect to 1 mol of the sulfur atom derived from, or with respect to 1 mol of the sulfur atom derived from (b) the alkali metal hydrosulfide and the alkali metal sulfide. Further, the range of 0.8 to 1.1 moles is more preferable, and it is particularly preferable to use them in an equimolar ratio.
脂肪族系環状化合物とポリハロ芳香族化合物を含む反応容器は、温度や圧力等の条件を適宜調整することにより、脂肪族系環状化合物とポリハロ芳香族化合物を含む重合反応用溶液を得る。反応容器内の条件としては、開放系又は密閉系の何れでもよいが、不活性ガス存在下に、密閉系で反応させことが生産性を向上させる観点から好ましい。温度条件としては、特に制限されないが、１２０〜２８０℃、好ましくは１８０〜２５０℃の範囲であることが好ましい。 In the reaction vessel containing the aliphatic cyclic compound and the polyhaloaromatic compound, a solution for polymerization reaction containing the aliphatic cyclic compound and the polyhaloaromatic compound is obtained by appropriately adjusting the conditions such as temperature and pressure. The conditions in the reaction vessel may be either an open system or a closed system, but it is preferable to carry out the reaction in a closed system in the presence of an inert gas, from the viewpoint of improving productivity. The temperature condition is not particularly limited, but it is preferably in the range of 120 to 280 ° C, preferably 180 to 250 ° C.
本発明は、次に、（ａ）水と、アルカリ金属水硫化物と、ＳＭＡＢと、アルカリ金属水酸化物とを、または、（ｂ）水と、アルカリ金属水硫化物と、ＳＭＡＢと、アルカリ金属硫化物とを、前記工程（１）で仕込んだ脂肪族系環状化合物とポリハロ芳香族化合物とを含む反応容器中に供給しながら、これら各成分を用いて重合反応させる（以下、工程（２）と記す）。水は、単独で反応容器中に供給しても良いし、水以外の任意の一成分以上、好ましくは水以外の全ての成分を水溶液とすることで反応容器中に供給しても良い。 The present invention then comprises (a) water, alkali metal hydrosulfide, SMAB, and alkali metal hydroxide, or (b) water, alkali metal hydrosulfide, SMAB, and alkali. While supplying the metal sulfide to the reaction vessel containing the aliphatic cyclic compound and the polyhaloaromatic compound charged in the step (1), a polymerization reaction is performed using these components (hereinafter, referred to as step (2 ))). Water may be supplied to the reaction container alone, or may be supplied to the reaction container by forming an arbitrary aqueous solution of one or more components other than water, preferably all components other than water into an aqueous solution.
前記ＳＭＡＢは、（ａ）水と、アルカリ金属水硫化物と、ＳＭＡＢと、アルカリ金属水酸化物とを供給する場合、または、（ｂ）水と、アルカリ金属水硫化物と、ＳＭＡＢと、アルカリ金属硫化物とを供給する場合、いずれの場合においても（ｉ）アルカリ金属水酸化物および脂肪族系環状化合物を水の存在下で反応させることにより得たものを用いるか、または、（ｉｉ）アルカリ金属硫化物と脂肪族系環状化合物を水の存在下で反応させることにより、ＳＭＡＢとアルカリ金属水硫化物の混合物として得たものを用いることができる。 The SMAB is (a) in the case of supplying water, an alkali metal hydrosulfide, SMAB, and an alkali metal hydroxide, or (b) water, an alkali metal hydrosulfide, SMAB, and an alkali. In the case of supplying the metal sulfide, in any case, (i) the one obtained by reacting the alkali metal hydroxide and the aliphatic cyclic compound in the presence of water is used, or (ii) A mixture obtained by reacting an alkali metal sulfide and an aliphatic cyclic compound in the presence of water as a mixture of SMAB and an alkali metal hydrosulfide can be used.
前記ＳＭＡＢを、（ｉ）アルカリ金属水酸化物および脂肪族系環状化合物を水の存在下で反応させることにより得る場合、それぞれの仕込み量は特に限定する必要はないが、収率や反応性の観点から、（アルカリ金属水酸化物）／（脂肪族系環状化合物）がモル比で１／１以下の範囲であることが好ましく、１／１〜１／１０の範囲であることがより好ましい。同じく、（アルカリ金属水酸化物）／（水）がモル比で１／１以下の範囲であることが好ましく、１／１〜１／１０の範囲であることがより好ましい。 When the SMAB is obtained by reacting (i) an alkali metal hydroxide and an aliphatic cyclic compound in the presence of water, the charged amounts of each do not have to be particularly limited, but the yield and the reactivity are not limited. From the viewpoint, the molar ratio of (alkali metal hydroxide) / (aliphatic cyclic compound) is preferably 1/1 or less, and more preferably 1/1 to 1/10. Similarly, the molar ratio of (alkali metal hydroxide) / (water) is preferably 1/1 or less, more preferably 1/1 to 1/10.
一方、前記ＳＭＡＢを、（ｉｉ）アルカリ硫化物および脂肪族系環状化合物を水の存在下で反応させることにより、ＳＭＡＢとアルカリ金属水硫化物の混合物として得る場合、それぞれの仕込み量は特に限定する必要はないが、収率や反応性の観点から、（アルカリ金属硫化物）／（脂肪族系環状化合物）がモル比で１／１以下の範囲であることが好ましく、１／１〜１／１０の範囲であることがより好ましい。同じく、（アルカリ金属硫化物）／（水）がモル比で１／１以下の範囲であることが好ましく、１／１〜１／３０の範囲であることがより好ましい。 On the other hand, when the above-mentioned SMAB is obtained as a mixture of (ii) an alkali sulfide and an aliphatic cyclic compound in the presence of water, as a mixture of SMAB and an alkali metal hydrosulfide, the respective charged amounts are particularly limited. Although not necessary, from the viewpoint of yield and reactivity, it is preferable that the molar ratio of (alkali metal sulfide) / (aliphatic cyclic compound) is 1/1 or less, and 1/1 to 1 / The range of 10 is more preferable. Similarly, the molar ratio of (alkali metal sulfide) / (water) is preferably 1/1 or less, and more preferably 1/1 to 1/30.
前記ＳＭＡＢを得る、（ｉ）および（ｉｉ）いずれの方法においても反応させる際の条件はＳＭＡＢを得る公知の範囲で特に制限されないが、反応温度１５０〜２５０の範囲で、不活性ガス存在下に、密閉系で反応させことが生産性を向上させる観点から好ましい。 The conditions for reacting in any of the methods (i) and (ii) for obtaining the SMAB are not particularly limited within the known range for obtaining the SMAB, but at a reaction temperature of 150 to 250 in the presence of an inert gas. From the viewpoint of improving productivity, it is preferable to carry out the reaction in a closed system.
このようにして得られたＳＭＡＢまたはＳＭＡＢとアルカリ金属水硫化物の混合物は、適宜、水と、アルカリ金属水硫化物と、アルカリ金属水酸化物またはアルカリ金属硫化物と伴に、前記工程（１）を経て得られた反応容器中に供給し、これら各成分を重合反応させればよい。 The SMAB or the mixture of SMAB and alkali metal hydrosulfide thus obtained may be appropriately mixed with water, an alkali metal hydrosulfide, an alkali metal hydroxide or an alkali metal sulfide and the above-mentioned step (1). ), And then supply each of these components to a polymerization reaction.
反応容器に供給するＳＭＡＢとアルカリ金属水硫化物とアルカリ金属水酸化物またはアルカリ金属硫化物とのそれぞれの仕込み量は特に限定する必要はないが、収率や反応性の観点から、以下の範囲とすることが好ましい。 The amounts of SMAB, alkali metal hydrosulfide, and alkali metal hydroxide or alkali metal sulfide to be fed to the reaction vessel are not particularly limited, but from the viewpoint of yield and reactivity, It is preferable that
すなわち、（ａ）水と、アルカリ金属水硫化物と、ＳＭＡＢと、アルカリ金属水酸化物とを、反応容器中に供給する場合は、アルカリ金属水硫化物に由来する硫黄原子の合計１モルに対して、ＳＭＡＢとアルカリ金属水酸化物の合計が０．０１〜２．０モルの範囲であることが好ましく、０．１〜１．５モルの範囲であることがより好ましく、０．４〜１．２モルの範囲がさらに好ましい。また、アルカリ金属水酸化物とＳＭＡＢの合計１モルに対して、ＳＭＡＢが０．０１〜１．０モルの範囲であることが好ましく、０．０５〜０．５モルの範囲であることがより好ましく、０．１〜０．２モルの範囲であることがさらに好ましい。さらに反応容器に供給されるアルカリ金属水硫化物１モルに対して、反応容器に供給されるＳＭＡＢと、工程（１）で仕込んだ反応容器中に含まれる脂肪族系環状化合物との合計が１〜６モルの範囲となるよう調整することが好ましい。さらに、反応容器に供給する水の仕込み量はアルカリ金属水硫化物に由来する硫黄原子の合計１モルに対して、１〜５０モルの範囲であることが好ましく、さらに２〜２０モルの範囲であることがより好ましい。 That is, when (a) water, alkali metal hydrosulfide, SMAB, and alkali metal hydroxide are supplied into the reaction vessel, the total amount of sulfur atoms derived from the alkali metal hydrosulfide is 1 mol. On the other hand, the sum of SMAB and alkali metal hydroxide is preferably in the range of 0.01 to 2.0 mol, more preferably 0.1 to 1.5 mol, and 0.4 to The range of 1.2 mol is more preferable. Further, SMAB is preferably in the range of 0.01 to 1.0 mol, and more preferably in the range of 0.05 to 0.5 mol, based on 1 mol of the total of alkali metal hydroxide and SMAB. It is preferably in the range of 0.1 to 0.2 mol and more preferably in the range of 0.1 to 0.2 mol. Furthermore, for 1 mol of the alkali metal hydrosulfide supplied to the reaction vessel, the sum of the SMAB supplied to the reaction vessel and the aliphatic cyclic compound contained in the reaction vessel prepared in step (1) is 1 It is preferable to adjust the amount to be in the range of 6 mol. Further, the amount of water supplied to the reaction vessel is preferably in the range of 1 to 50 mol, and more preferably in the range of 2 to 20 mol, based on 1 mol of the total amount of sulfur atoms derived from the alkali metal hydrosulfide. More preferably.
また、（ｂ）水と、アルカリ金属水硫化物と、ＳＭＡＢと、アルカリ金属硫化物とを、反応容器中に供給する場合は、アルカリ金属水硫化物およびアルカリ金属硫化物に由来する硫黄原子の合計１モルに対して、ＳＭＡＢとアルカリ金属硫化物の合計が０．０１〜２．０モルの範囲であることが好ましく、０．１〜１．５モルの範囲であることがより好ましく、０．４〜１．２モルの範囲がさらに好ましい。また、アルカリ金属硫化物１モルに対して、ＳＭＡＢが０．０１〜１．０モルの範囲であることが好ましく、０．０５〜０．５モルの範囲であることがより好ましく、０．１〜０．２モルの範囲であることがさらに好ましい。さらに反応容器に供給されるアルカリ金属水硫化物とＳＭＡＢの合計１モルに対して、反応容器に供給されるＳＭＡＢと、工程（１）で仕込んだ反応容器中に含まれる脂肪族系環状化合物との合計が１〜６モルの範囲となるよう調整することが好ましい。さらに、反応容器に供給する水の仕込み量はアルカリ金属水硫化物およびアルカリ金属硫化物に由来する硫黄原子の合計１モルに対して、１〜５０モルの範囲であることが好ましく、さらに２〜２０モルの範囲であることがより好ましい。 When (b) water, alkali metal hydrosulfide, SMAB, and alkali metal sulfide are supplied into the reaction vessel, the alkali metal hydrosulfide and the sulfur atom derived from the alkali metal sulfide are added. The total amount of SMAB and alkali metal sulfide is preferably in the range of 0.01 to 2.0 mol, more preferably 0.1 to 1.5 mol, and more preferably 0 to 1 mol in total. The range of 0.4 to 1.2 mol is more preferable. Further, SMAB is preferably in the range of 0.01 to 1.0 mol, more preferably in the range of 0.05 to 0.5 mol, and more preferably 0.1 to 1 mol of the alkali metal sulfide. It is more preferably in the range of to 0.2 mol. Further, with respect to a total of 1 mol of alkali metal hydrosulfide and SMAB supplied to the reaction vessel, SMAB supplied to the reaction vessel and an aliphatic cyclic compound contained in the reaction vessel prepared in step (1) It is preferable to adjust such that the total of is in the range of 1 to 6 mol. Furthermore, the charged amount of water supplied to the reaction vessel is preferably in the range of 1 to 50 mol, and further 2 to 2 mol per 1 mol of the total amount of the alkali metal hydrosulfide and the sulfur atom derived from the alkali metal sulfide. It is more preferably in the range of 20 mol.
アルカリ金属水硫化物と、ＳＭＡＢと、アルカリ金属水酸化物またはアルカリ金属硫化物の各成分は、貯留漕（タンク）に貯留され、貯留漕から反応容器へ、配管を通じて供給され、反応容器中で、重合反応が行われる。アルカリ金属水硫化物、ＳＭＡＢと、アルカリ金属水酸化物またはアルカリ金属硫化物の各成分は、それぞれ独立に貯留漕に貯留されていてもよいし、任意の２成分以上の成分を同じ貯留漕に貯留していても良い。特に、上記（ｉｉ）の方法ではＳＭＡＢとアルカリ金属水硫化物の混合物として得られるので、両成分を同じ貯留漕に貯留しておくことが望ましい。また、各配管は、各貯留漕から反応容器へそれぞれ合流することなく連通していてもよいし、任意の配管同士が途中で合流されていてもよい。 The alkali metal hydrosulfide, SMAB, and each component of the alkali metal hydroxide or the alkali metal sulfide are stored in a storage tank (tank), and are supplied from the storage tank to the reaction container through a pipe, in the reaction container. , A polymerization reaction is carried out. The alkali metal hydrosulfide, SMAB, and each component of the alkali metal hydroxide or the alkali metal sulfide may be stored independently in a storage tank, or any two or more components may be stored in the same storage tank. It may be stored. In particular, since the method (ii) gives a mixture of SMAB and alkali metal hydrosulfide, it is desirable to store both components in the same storage tank. Further, the respective pipes may be communicated with each other from the respective storage tanks to the reaction container without being joined, or arbitrary pipes may be joined together on the way.
貯留漕（タンク）、配管およびポンプが前記各成分と接する部分（以下、接液部）は、ステンレス鋼にチタンやジルコニウム等の耐腐食性に優れた素材を用いて耐腐食加工を施した材料を用いることもできるが、上記（ａ）の方法、すなわち、各貯留漕から反応容器へ供給される各成分がアルカリ金属水硫化物と、脂肪族系環状化合物の加水分解物のアルカリ金属塩と、アルカリ金属水酸化物であり、かつ、それぞれ別々に供給する場合にあっては、ステンレス鋼をそのまま用いてもステンレス鋼を構成する金属原子の溶出を抑えることができるため、特殊な加工処理が不要となり、製造設備の簡素化の観点から好ましい。 The parts where the storage tank (tank), pipes and pumps come into contact with the above components (hereinafter referred to as the liquid contact parts) are made of stainless steel that has been subjected to corrosion resistance processing using materials with excellent corrosion resistance such as titanium and zirconium. However, the above-mentioned method (a), that is, each component supplied from each storage tank to the reaction vessel is an alkali metal hydrosulfide and an alkali metal salt of a hydrolyzate of an aliphatic cyclic compound. , If they are alkali metal hydroxides and are supplied separately, the elution of the metal atoms constituting the stainless steel can be suppressed even if the stainless steel is used as it is. It is not necessary and is preferable from the viewpoint of simplifying manufacturing equipment.
ここで、本発明で用いるアルカリ金属水硫化物としては、アルカリ金属水硫化物の水和物等が挙げられ、該アルカリ金属水硫化物としては、例えば水硫化リチウム、水硫化ナトリウム、水硫化カリウム、水硫化ルビジウムまたは水硫化セシウム等が挙げられる。これらはそれぞれ単独で用いてもよいし、２種以上を混合して用いてもよい。これらアルカリ金属水硫化物の中では水硫化ナトリウムと水硫化カリウムが好ましく、特に水硫化ナトリウムが好ましい。これらアルカリ金属水硫化物は無水物または水和物等として使用することができ、入手の容易さから、化合物内に結晶水を有する、液状又は固体状の水和物として用いることもできる。これらアルカリ金属水硫化物は、反応系内に仕込む際の取扱い性に優れることから水溶液として用いることが好ましく、その濃度は１質量％から水溶液の取扱い時の温度における飽和濃度までの範囲であることが好ましく、さらに５〜５０質量％となる範囲がより好ましい。 Here, examples of the alkali metal hydrosulfide used in the present invention include hydrates of alkali metal hydrosulfide, and examples of the alkali metal hydrosulfide include lithium hydrosulfide, sodium hydrosulfide, and potassium hydrosulfide. , Rubidium hydrosulfide, cesium hydrosulfide, and the like. These may be used alone or in combination of two or more. Among these alkali metal hydrosulfides, sodium hydrosulfide and potassium hydrosulfide are preferable, and sodium hydrosulfide is particularly preferable. These alkali metal hydrosulfides can be used as anhydrides or hydrates, etc., and due to their easy availability, they can also be used as liquid or solid hydrates having water of crystallization in the compound. These alkali metal hydrosulfides are preferably used as an aqueous solution because they are easy to handle when charged into the reaction system, and the concentration thereof is in the range from 1% by mass to the saturated concentration at the temperature at which the aqueous solution is handled. Is preferable, and the range of 5 to 50 mass% is more preferable.
また、本発明で用いるアルカリ金属水酸化物としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウムが挙げられる。これらの中でも特に水酸化リチウムと水酸化ナトリウム及び水酸化カリウムが好ましく、特に水酸化ナトリウムが好ましい。アルカリ金属水酸化物は、水溶液として用いることが好ましく、その濃度は１質量％から水溶液の取扱い時の温度における飽和濃度までの範囲であることが好ましく、さらに５〜５０質量％となる範囲がより好ましい。 Examples of the alkali metal hydroxide used in the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide. Among these, lithium hydroxide, sodium hydroxide and potassium hydroxide are particularly preferable, and sodium hydroxide is particularly preferable. The alkali metal hydroxide is preferably used as an aqueous solution, and the concentration thereof is preferably in the range of 1% by mass to the saturated concentration at the temperature at which the aqueous solution is handled, and more preferably in the range of 5 to 50% by mass. preferable.
さらに、本発明で用いるアルカリ金属硫化物としては、例えば、硫化リチウム、硫化ナトリウム、硫化カリウム、硫化ルビジウムおよび硫化セシウムが挙げられ、これらアルカリ金属硫化物の中では硫化ナトリウムと水硫化カリウムが好ましく、特に硫化ナトリウムがより好ましい。これらはそれぞれ単独で用いてもよいし、２種以上を混合して用いてもよい。また、これらアルカリ金属硫化物は無水物または水和物等として使用することができ、入手の容易さから、化合物内に結晶水を有する、液状又は固体状の水和物として用いることもできる。これらアルカリ金属硫化物は、反応系内に仕込む際の取扱い性に優れることから水溶液として用いることが好ましく、その濃度は１質量％から水溶液の取扱い時の温度における飽和濃度までの範囲であることが好ましく、さらに５〜２５質量％となる範囲がより好ましい。 Further, examples of the alkali metal sulfide used in the present invention include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide and cesium sulfide. Among these alkali metal sulfides, sodium sulfide and potassium hydrosulfide are preferable, Particularly, sodium sulfide is more preferable. These may be used alone or in combination of two or more. Further, these alkali metal sulfides can be used as anhydrides or hydrates, etc., and due to their easy availability, they can also be used as liquid or solid hydrates having water of crystallization in the compound. These alkali metal sulfides are preferably used as an aqueous solution because they are easy to handle when charged into the reaction system, and the concentration thereof ranges from 1% by mass to a saturated concentration at the temperature at which the aqueous solution is handled. The range of 5 to 25% by mass is more preferable.
工程（２）では、リチウム塩化合物を反応系内に加え、リチウムイオンの存在下で反応を行ってもよい。ここで使用できるリチウム塩化合物の具体例としては、例えば、フッ化リチウム、塩化リチウム、臭化リチウム、ヨウ化リチウム、炭酸リチウム、炭酸水素リチウム、硫酸リチウム、硫酸水素リチウム、リン酸リチウム、リン酸水素リチウム、リン酸二水素リチウム、亜硝酸リチウム、亜硫酸リチウム、塩素酸リチウム、クロム酸リチウム、モリブデン酸リチウム、ギ酸リチウム、酢酸リチウム、シュウ酸リチウム、マロン酸リチウム、プロピオン酸リチウム、酪酸リチウム、イソ酪酸リチウム、マレイン酸リチウム、フマル酸リチウム、ブタン二酸リチウム、吉草酸リチウム、ヘキサン酸リチウム、オクタン酸リチウム、酒石酸リチウム、ステアリン酸リチウム、オレイン酸リチウム、安息香酸リチウム、フタル酸リチウム、ベンゼンスルホン酸リチウム、ｐ−トルエンスルホン酸リチウム、硫化リチウム、水硫化リチウム、水酸化リチウム等の無機リチウム塩化合物；リチウムメトキシド、リチウムエトキシド、リチウムポロポキシド、リチウムイソプロポキシド、リチウムブトキシド、リチウムフェノキシド等の有機リチウム塩化合物が挙げられる。これらの中でも塩化リチウムと酢酸リチウムが好ましく、特に塩化リチウムが好ましい。また、上記リチウム塩化合物は無水物又は含水物又は水溶液として用いることができる。リチウム塩化合物を反応系内に加え、リチウムイオンの存在下で反応を行う場合、その使用量は、アルカリ金属水硫化物の硫黄原子１モルに対し、好ましくは０．０１モル以上０．９モル未満の範囲となる割合で用いることがポリアリーレンスルフィド樹脂をより高分子量化できるため好ましい。 In the step (2), a lithium salt compound may be added to the reaction system to carry out the reaction in the presence of lithium ions. Specific examples of the lithium salt compound that can be used here include lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium carbonate, lithium hydrogen carbonate, lithium sulfate, lithium hydrogen sulfate, lithium phosphate, and phosphoric acid. Lithium hydrogen, lithium dihydrogen phosphate, lithium nitrite, lithium sulfite, lithium chlorate, lithium chromate, lithium molybdate, lithium formate, lithium acetate, lithium oxalate, lithium malonate, lithium propionate, lithium butyrate, iso Lithium butyrate, lithium maleate, lithium fumarate, lithium butanedioate, lithium valerate, lithium hexanoate, lithium octanoate, lithium tartarate, lithium stearate, lithium oleate, lithium benzoate, lithium phthalate, benzenesul Inorganic lithium salt compounds such as lithium acid oxide, lithium p-toluenesulfonate, lithium sulfide, lithium hydrosulfide, lithium hydroxide; lithium methoxide, lithium ethoxide, lithium poropoxide, lithium isopropoxide, lithium butoxide, lithium Examples thereof include organic lithium salt compounds such as phenoxide. Among these, lithium chloride and lithium acetate are preferable, and lithium chloride is particularly preferable. The lithium salt compound can be used as an anhydride, a hydrate, or an aqueous solution. When the lithium salt compound is added to the reaction system and the reaction is carried out in the presence of lithium ions, the amount used is preferably 0.01 mol or more and 0.9 mol or less per 1 mol of the sulfur atom of the alkali metal hydrosulfide. It is preferable to use the polyarylene sulfide resin in a ratio within the range below because the polyarylene sulfide resin can have a higher molecular weight.
工程（２）の反応条件は特に制限されるものではないが、重合反応が容易に進行し得る温度、すなわち２００〜３００℃、好ましくは２１０〜２８０℃、更に好ましくは２１５〜２６０℃の範囲にて、脱水を行いながら反応させることが好ましい。 The reaction conditions of step (2) are not particularly limited, but are within a temperature range where the polymerization reaction can easily proceed, that is, 200 to 300 ° C, preferably 210 to 280 ° C, more preferably 215 to 260 ° C. Then, it is preferable to carry out the reaction while dehydrating.
本発明のポリアリーレンスルフィド樹脂の製造方法の重合反応に存在させる水分は、加水分解反応などの併発を回避させるために、なるべく少ない方が良い傾向にあるものの、他方、重合反応が全く無水の状態である場合は、反応速度が著しく遅くなるといった問題がある。従って、本発明の重合反応において反応系内に存在すべき水分量は、重合に使用したアルカリ金属水硫化物またはアルカリ金属水硫化物およびアルカリ金属硫化物に由来する硫黄原子の合計１モルに対して、重合反応終了時１モル未満であることが好ましく、反応が円滑に進行する点から、０．０２モル以上存在させることがより好ましく、さらに０．０３〜０．６０モルの範囲が特に好ましく、０．０５〜０．５０の範囲が最も好ましい。上記の範囲を満たす場合には、反応速度の制御性と高分子量化との両立がより容易に行えるため好ましい。 The water present in the polymerization reaction of the method for producing a polyarylene sulfide resin of the present invention tends to be as small as possible in order to avoid concurrent occurrence of a hydrolysis reaction and the like, while the polymerization reaction is in a completely anhydrous state. When it is, there is a problem that the reaction rate becomes remarkably slow. Therefore, the amount of water that should be present in the reaction system in the polymerization reaction of the present invention is 1 mol based on the total amount of the alkali metal hydrosulfide used for the polymerization or the alkali metal hydrosulfide and the sulfur atom derived from the alkali metal sulfide. At the end of the polymerization reaction, the amount is preferably less than 1 mol, more preferably 0.02 mol or more, and particularly preferably 0.03 to 0.60 mol, from the viewpoint that the reaction proceeds smoothly. , 0.05 to 0.50 is most preferable. When the above range is satisfied, both controllability of reaction rate and high molecular weight can be more easily achieved, which is preferable.
なお、本発明の製造方法では、上記水分量を重合終了時に満たしていることが好ましいが、ポリハロ芳香族化合物の転化率が８０モル％を越えた時点以降、より好ましくは６０モル％を越えた時点以降、さらに好ましくは重合開始直後から上記範囲を満たしていることが好ましい。 In the production method of the present invention, the above water content is preferably satisfied at the end of the polymerization, but after the conversion of the polyhaloaromatic compound exceeds 80 mol%, more preferably it exceeds 60 mol%. It is preferable that the above range is satisfied after the time point, more preferably immediately after the initiation of the polymerization.
ここで、ポリハロ芳香族化合物の転化率とは、次の式で表されるものである。
転化率（％）＝（仕込み量−残存量）／仕込み量×１００
ただし、「仕込み量」は反応系内に仕込んだポリハロ芳香族化合物の質量を表し、また「残存量」は反応系内に残存するポリハロ芳香族化合物の質量を表すものとする。
Here, the conversion rate of the polyhalo aromatic compound is represented by the following formula.
Conversion rate (%) = (charged amount-residual amount) / charged amount x 100
However, the "charged amount" represents the mass of the polyhaloaromatic compound charged in the reaction system, and the "residual amount" represents the mass of the polyhaloaromatic compound remaining in the reaction system.
また、工程（２）において、系内の前記水分量を維持するための脱水方法としては、特に制限されるものでなく、ＳＭＡＢの導入速度の他、反応系の温度、圧力のコントロールによって行うこともできるが、具体的には、水、溶媒、ポリハロ芳香族化合物の各蒸気圧曲線によりコントロールすべき温度、圧力を類推し、その圧力、温度条件に設定することによって所望の系内水分量に調節すればよい。 Further, in the step (2), the dehydration method for maintaining the water content in the system is not particularly limited, and may be performed by controlling the temperature and pressure of the reaction system in addition to the introduction rate of SMAB. However, specifically, the temperature and pressure to be controlled by each vapor pressure curve of water, solvent, and polyhaloaromatic compound are analogized, and the desired amount of water in the system is set by setting the pressure and temperature conditions. Adjust it.
重合反応により得られたポリアリーレンスルフィド樹脂を含む反応混合物は後処理工程を施すことができる。後処理工程としては、公知の方法であればよく、特に制限されるものではないが、例えば、重合反応終了後、先ず反応混合物をそのまま、あるいは酸または塩基を加えた後、減圧下または常圧下で溶媒を留去し、次いで溶媒留去後の固形物を水、アセトン、メチルエチルケトン、アルコール類などの溶媒で１回または２回以上洗浄し、更に中和、水洗、濾過および乾燥する方法、或いは、重合反応終了後、反応混合物に水、アセトン、メチルエチルケトン、アルコール類、エーテル類、ハロゲン化炭化水素、芳香族炭化水素、脂肪族炭化水素などの溶媒（使用した重合溶媒に可溶であり、且つ少なくともポリアリーレンスルフィド樹脂に対しては貧溶媒である溶媒）を沈降剤として添加して、ポリアリーレンスルフィド樹脂や無機塩等の固体状生成物を沈降させ、これらを濾別、洗浄、乾燥する方法、或いは、重合反応終了後、反応混合物に反応溶媒（又は低分子ポリマーに対して同等の溶解度を有する有機溶媒）を加えて撹拌した後、濾過して低分子量重合体を除いた後、水、アセトン、メチルエチルケトン、アルコール類などの溶媒で１回または２回以上洗浄し、その後中和、水洗、濾過および乾燥をする方法等が挙げられる。 The reaction mixture containing the polyarylene sulfide resin obtained by the polymerization reaction can be subjected to a post-treatment step. The post-treatment step may be any known method and is not particularly limited. For example, after the completion of the polymerization reaction, the reaction mixture is first left as it is, or after adding an acid or a base, under reduced pressure or under normal pressure. The solvent is distilled off with, then the solid matter after the solvent is distilled off is washed once or twice or more with a solvent such as water, acetone, methyl ethyl ketone, alcohols, and further neutralized, washed with water, filtered and dried, or After completion of the polymerization reaction, the reaction mixture contains water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons and other solvents (soluble in the polymerization solvent used, and At least a solvent that is a poor solvent for the polyarylene sulfide resin) is added as a precipitating agent to obtain a solid such as a polyarylene sulfide resin or an inorganic salt. The products are allowed to settle, and these are separated by filtration, washed and dried, or after the completion of the polymerization reaction, a reaction solvent (or an organic solvent having an equivalent solubility to the low molecular weight polymer) is added to the reaction mixture and stirred. Then, the low molecular weight polymer is removed by filtration, followed by washing once or twice or more with a solvent such as water, acetone, methyl ethyl ketone, or alcohol, and then neutralizing, washing with water, filtering and drying. Be done.
なお、上記に例示したような後処理方法において、ポリアリーレンスルフィド樹脂の乾燥は真空中で行なってもよいし、空気中あるいは窒素のような不活性ガス雰囲気中で行なってもよい。 In the post-treatment method as exemplified above, the polyarylene sulfide resin may be dried in vacuum or in air or in an inert gas atmosphere such as nitrogen.
この様にして得られたポリアリーレンスルフィド樹脂は、そのまま各種成形材料等に利用可能であるが、空気あるいは酸素富化空気中あるいは減圧条件下で熱処理を行い、酸化架橋させてもよい。この熱処理の温度は、目標とする架橋処理時間や処理する雰囲気によっても異なるものの、１８０℃〜２７０℃の範囲であることが好ましい。また、前記熱処理は押出機等を用いてポリアリーレンスルフィド樹脂の融点以上で、ポリアリーレンスルフィド樹脂を溶融した状態で行ってもよいが、ポリアリーレンスルフィド樹脂の熱劣化の可能性が高まるため、融点プラス１００℃以下で行うことが好ましい。 The polyarylene sulfide resin thus obtained can be directly used for various molding materials and the like, but may be heat-treated in air or oxygen-enriched air or under reduced pressure to be oxidatively crosslinked. The temperature of this heat treatment is preferably in the range of 180 ° C to 270 ° C, although it varies depending on the target crosslinking treatment time and the treatment atmosphere. Further, the heat treatment may be carried out in a molten state of the polyarylene sulfide resin by using an extruder or the like at a melting point of the polyarylene sulfide resin or more, but since the possibility of heat deterioration of the polyarylene sulfide resin increases, the melting point It is preferable to carry out at plus 100 ° C. or lower.
以上詳述した本発明の製造方法によって得られたポリアリーレンスルフィド樹脂は、射出成形、押出成形、圧縮成形、ブロー成形の如き各種溶融加工法により、耐熱性、成形加工性、寸法安定性等に優れた成形物に加工することが出来る。 The polyarylene sulfide resin obtained by the production method of the present invention described above in detail has heat resistance, molding processability, dimensional stability, etc. by various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding. It can be processed into excellent molded products.
また、本発明により得られたポリアリーレンスルフィド樹脂は、更に強度、耐熱性、寸法安定性等の性能を改善するために、各種充填材と組み合わせたポリアリーレンスルフィド樹脂組成物として使用することが出来る。充填材としては、特に制限されるものではないが、例えば、繊維状充填材、無機充填材等が挙げられる。繊維状充填材としては、ガラス繊維、炭素繊維、シランガラス繊維、セラミック繊維、アラミド繊維、金属繊維、チタン酸カリウム、炭化珪素、硫酸カルシウム、珪酸カルシウム等の繊維、ウォラストナイト等の天然繊維等が使用出来る。また無機充填材としては、硫酸バリウム、硫酸カルシウム、クレー、バイロフェライト、ベントナイト、セリサイト、ゼオライト、マイカ、雲母、タルク、アタルパルジャイト、フェライト、珪酸カルシウム、炭酸カルシウム、炭酸マグネシウム、ガラスビーズ等が使用出来る。また、成形加工の際に添加剤として離型剤、着色剤、耐熱安定剤、紫外線安定剤、発泡剤、防錆剤、難燃剤、滑剤等の各種添加剤を含有せしめることが出来る。 Further, the polyarylene sulfide resin obtained by the present invention can be used as a polyarylene sulfide resin composition in combination with various fillers in order to further improve performances such as strength, heat resistance and dimensional stability. .. The filler is not particularly limited, but examples thereof include a fibrous filler and an inorganic filler. Examples of the fibrous filler include glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, fibers such as potassium titanate, silicon carbide, calcium sulfate, calcium silicate, and natural fibers such as wollastonite. Can be used. Further, as the inorganic filler, barium sulfate, calcium sulfate, clay, biloferrite, bentonite, sericite, zeolite, mica, mica, talc, atarupulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads and the like. Can be used. Further, various additives such as a release agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, an anticorrosive agent, a flame retardant, and a lubricant can be added as additives during molding.
更に、本発明により得られたポリアリーレンスルフィド樹脂は、用途に応じて、適宜、ポリエステル、ポリアミド、ポリイミド、ポリエーテルイミド、ポリカーボネート、ポリフェニレンエーテル、ポリスルフォン、ポリエーテルスルフォン、ポリエーテルエーテルケトン、ポリエーテルケトン、ポリアリーレン、ポリエチレン、ポリプロピレン、ポリ四弗化エチレン、ポリ二弗化エチレン、ポリスチレン、ＡＢＳ樹脂、エポキシ樹脂、シリコーン樹脂、フェノール樹脂、ウレタン樹脂、液晶ポリマー等の合成樹脂、或いは、ポリオレフィン系ゴム、弗素ゴム、シリコーンゴム等のエラストマーを配合したポリアリーレンスルフィド樹脂組成物として使用してもよい。 Furthermore, the polyarylene sulfide resin obtained by the present invention is, depending on the application, polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyether sulfone, polyether ether ketone, polyether. Synthetic resin such as ketone, polyarylene, polyethylene, polypropylene, polytetrafluoride ethylene, polydifluoride ethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, liquid crystal polymer, or polyolefin rubber. Alternatively, it may be used as a polyarylene sulfide resin composition containing an elastomer such as fluororubber or silicone rubber.
本発明の製造方法で得られるポリアリーレンスルフィド樹脂は、ポリアリーレンスルフィド樹脂の本来有する耐熱性、寸法安定性等の諸性能も具備しているので、例えば、コネクタ、プリント基板及び封止成形品等の電気・電子部品、ランプリフレクター及び各種電装品部品などの自動車部品、各種建築物、航空機及び自動車などの内装用材料、あるいはＯＡ機器部品、カメラ部品及び時計部品などの精密部品等の射出成形若しくは圧縮成形、若しくはコンポジット、シート、パイプなどの押出成形、又は引抜成形などの各種成形加工用の材料として、或いは繊維若しくはフィルム用の材料として幅広く有用である。 Since the polyarylene sulfide resin obtained by the production method of the present invention has various properties such as heat resistance and dimensional stability originally possessed by the polyarylene sulfide resin, for example, a connector, a printed circuit board, a molded encapsulation product, etc. Electrical / electronic parts, automotive parts such as lamp reflectors and various electrical component parts, interior materials for various buildings, aircraft and automobiles, or injection molding of precision parts such as OA equipment parts, camera parts and watch parts. It is widely useful as a material for various molding processes such as compression molding, extrusion molding of composites, sheets and pipes, or pultrusion molding, or as a material for fibers or films.
以下に実施例を挙げて本発明を具体的に説明する。これら例は例示的なものであって限定的なものではない。 The present invention will be specifically described below with reference to examples. These examples are illustrative and not limiting.
（ＰＰＳ樹脂の溶融粘度の測定）
製造したＰＰＳ樹脂を島津製作所製の高化式フローテスター（ＣＦＴ−５００Ｄ）を用い、３００℃、荷重：１．９６×１０６Ｐａ、Ｌ／Ｄ＝１０ｍｍ／１ｍｍなる条件にて、６分間保持した後に測定した値を溶融粘度（Ｖ６）とし、同条件にて、１５分間保持した後に測定した値を溶融粘度（Ｖ１５）とした。
(Measurement of melt viscosity of PPS resin)
The manufactured PPS resin is held for 6 minutes under the conditions of 300 ° C., load: 1.96 × 10 6 Pa, L / D = 10 mm / 1 mm using a Shimadzu Koka type flow tester (CFT-500D). After that, the value measured was defined as melt viscosity (V6), and the value measured after holding for 15 minutes under the same conditions was defined as melt viscosity (V15).
（ＰＰＳ樹脂のカルボキシ基の定量）
ＰＰＳ樹脂のカルボキシ基の定量を３５０℃でプレスしたのち、急冷することによって非晶性を示すフィルムを作成し、フーリエ変換赤外分光装置(以下「ＦＴ−ＩＲ装置」と略記する。)で測定した。赤外吸収スペクトルのうち６３０．６ｃｍ−１の吸収に対する１７０５ｃｍ−１の吸収の相対強度を求め、別途後述する方法により作成した検量線を用いて測定サンプル中のカルボキシ基の含有量（以下「カルボキシ基の全含有量」と略記する。）を求めた。カルボキシ基の含有量は樹脂組成物１ｇ中のモル数で示され、その単位はμｍｏｌ／ｇで表される。検量線の作成方法は酸処理を行わずにカルボン酸塩を分子末端に含有するＰＰＳ樹脂３ｇに所定量の４−クロロフェニル酢酸を加え良く混合したのち、前記と同じようにしてフィルムを作成し、ＦＴ−ＩＲ装置で測定を行い、カルボキシ基含有量に対する、前記吸収の相対強度比をプロットした検量線を作成した。ＰＰＳ樹脂中のカルボキシ基の含有量が多いほど、エポキシシランカップリング剤や官能基含有熱可塑性エラストマーなどの耐衝撃性改質剤との反応性が向上することから、耐衝撃性に優れる組成物が得られることを示す。
(Quantification of carboxy group of PPS resin)
After quantifying the carboxy group of the PPS resin at 350 ° C., it is rapidly cooled to form an amorphous film, which is measured by a Fourier transform infrared spectroscopic device (hereinafter abbreviated as “FT-IR device”). did. It determined the relative intensity of the absorption of 1705 cm -1 for absorption of 630.6Cm -1 of infrared absorption spectrum, additional content of carboxyl group in the measurement sample using a calibration curve prepared by the method described later (hereinafter "carboxy It is abbreviated as "total content of groups"). The content of the carboxy group is represented by the number of moles in 1 g of the resin composition, and the unit thereof is represented by μmol / g. The method for preparing the calibration curve is to add a predetermined amount of 4-chlorophenylacetic acid to 3 g of a PPS resin containing a carboxylate at the molecular end without acid treatment and mix well, to prepare a film in the same manner as above. The measurement was carried out with an FT-IR apparatus, and a calibration curve was prepared by plotting the relative intensity ratio of the absorption with respect to the carboxy group content. As the content of the carboxy group in the PPS resin increases, the reactivity with the impact modifier such as the epoxysilane coupling agent and the thermoplastic elastomer containing the functional group improves, and thus the composition having excellent impact resistance Is obtained.
（ＣＰ−ＭＡＢＡの定量方法）
ＰＰＳ樹脂を含んだ重合混合物のスラリー５０ｇに７０℃のイオン交換水１００ｇと１ｗｔ％の水酸化ナトリウム水溶液を加えてｐＨを１０．０以上に調整して１０分間撹拌した後に、ろ過し、ろ過後のケーキに７０℃のイオン交換水１００ｇを加えケーキ洗浄を行った。この操作を３回繰り返し、ろ液を全量集めてＨＰＬＣを用いて抽出されたＣＰ−ＭＡＢＡ量を測定した。標準サンプルと同じ保持時間のピーク面積と検量線とから抽出液中の濃度を求め、ＰＰＳ樹脂１ｇ当たりのＣＰ−ＭＡＢＡ含有量を算出した。
(Method for quantifying CP-MABA)
To 50 g of the slurry of the polymerization mixture containing the PPS resin, 100 g of ion-exchanged water at 70 ° C. and a 1 wt% sodium hydroxide aqueous solution were added to adjust the pH to 10.0 or more and the mixture was stirred for 10 minutes, filtered, and then filtered. The cake was washed with 100 g of ion-exchanged water at 70 ° C. to wash the cake. This operation was repeated 3 times, the whole amount of the filtrate was collected, and the amount of CP-MABA extracted was measured using HPLC. The concentration in the extract was determined from the peak area of the same retention time as the standard sample and the calibration curve, and the CP-MABA content per 1 g of PPS resin was calculated.
（反応性評価方法）
ＰＰＳ樹脂を小型粉砕機で粉砕した後、日本工業規格Ｚ８８０１の目開き０．５ｍｍの試験用篩いを用いて篩った。篩いを通過したＰＰＳ樹脂１００質量部に対し、３−グリシドキシプロピルトリメトキシシラン０．５質量部を配合し、均一に混合した後に溶融粘度Ｖ１５を測定した。添加後の溶融粘度Ｖ１５／添加前の溶融粘度Ｖ６の比から粘度上昇度を倍率として算出した。粘度上昇度が大きいほど反応性が高く、優れていることを示す。
(Reactivity evaluation method)
The PPS resin was pulverized with a small pulverizer and then sieved using a Japanese Industrial Standard Z8801 test sieve having an opening of 0.5 mm. 0.5 parts by mass of 3-glycidoxypropyltrimethoxysilane was added to 100 parts by mass of the PPS resin that passed through the sieve, and after uniformly mixing, the melt viscosity V15 was measured. From the ratio of melt viscosity V15 after addition / melt viscosity V6 before addition, the degree of viscosity increase was calculated as a magnification. The greater the degree of increase in viscosity, the higher the reactivity and the better.
（飛散Ｓの定量方法）
ビーカーにサンプル０．５ｇを精秤し、次いで純水を７０ｍｌ、１％水酸化ナトリウム水溶液４ｍｌを加え、撹拌しながら、電位差自動滴定装置を用いて、０．０２ｍｏｌ／Ｌ硝酸銀で滴定する。
(Quantification method of scattered S)
0.5 g of a sample is precisely weighed in a beaker, 70 ml of pure water is added, and 4 ml of a 1% sodium hydroxide aqueous solution is added, and the mixture is titrated with 0.02 mol / L silver nitrate using an automatic potentiometric titrator while stirring.
[実施例１]
温度計、圧力計、攪拌翼付チタンライニングの２リットルオートクレーブに、ＮＭＰ１１８９．６６ｇ（１２モル）、４８質量％ＮａＯＨ水溶液３２８８４ｇ（４モル）を仕込み、密閉し、攪拌しながら窒素雰囲気下で２３０℃まで１時間かけて昇温した。次いで、２３０℃で３時間反応させた後、室温まで冷却し、白色ゲル状液を得た。
[Example 1]
A 2 liter autoclave equipped with a thermometer, a pressure gauge, and a titanium lining with stirring blades was charged with NMP1189.66 g (12 mol) and 48 mass% NaOH aqueous solution 32884 g (4 mol), sealed, and stirred at 230 ° C. under a nitrogen atmosphere. Up to 1 hour. Then, the mixture was reacted at 230 ° C. for 3 hours and then cooled to room temperature to obtain a white gel-like liquid.
得られたゲル状液にアセトン２Ｌを加えて攪拌し、ろ過し、アセトン１Ｌでケーキ洗浄した。この操作を３回繰り返し、白色固体を得た。得られた白色固体を１５０℃で３時間真空乾燥することで目的のｓｏｄｉｕｍ Ｎ−ｍｅｔｈｙｌ−ａｍｉｎｏｂｕｔｙｌａｔｅ（ＳＭＡＢ）を得た。ＳＭＡＢを３６．５２ｇ（０．２６モル）と４８．８０質量％ＮａＯＨ水溶液１２１．５２ｇ（１．４８モル）と水１３１．７５ｇを溶解させたＳＭＡＢ溶液を調整した。 2 L of acetone was added to the obtained gel-like liquid, and the mixture was stirred, filtered, and washed with 1 L of acetone to wash the cake. This operation was repeated 3 times to obtain a white solid. The obtained white solid was vacuum-dried at 150 ° C. for 3 hours to obtain a desired sodium N-methyl-aminobutyrate (SMAB). A SMAB solution was prepared by dissolving 36.52 g (0.26 mol) of SMAB, 121.52 g (1.48 mol) of 48.80 mass% NaOH aqueous solution and 131.75 g of water.
ＳＵＳ製の滴下槽、滴下ポンプ、コンデンサー、デカンターを連結した上記２リットルオートクレーブに、ＮＭＰ６２３ｇ、ＤＣＢ２９９．８６ｇを仕込み、密閉し、攪拌しながら窒素雰囲気下で内温２２０℃まで２時間かけて昇温した。２２０℃到達後、コンデンサーを連結したバルブを開放し、釜内圧力を０．２０ＭＰａに調整した。次いで、内温を２２０℃に、釜内圧力を０．２０ＭＰａに保持しながら、４８．２３質量％ＮａＳＨ水溶液２６０．３６ｇ（２．２４モル）と上記で調整したＳＭＡＢ溶液を滴下槽に仕込み、滴下ポンプを用いてそれぞれ４時間かけて滴下した。滴下中は同時に脱水操作を行い、留出したｐ−ＤＣＢと水の混合蒸気はコンデンサーで凝縮し、デカンターで分離して、ｐ−ＤＣＢはオートクレーブへ戻した。滴下終了後、バルブを閉止し、オートクレーブを密閉し、１時間保持した。１時間保持後、再度コンデンサーを連結したバルブを開放し、釜内圧力が０．１０ＭＰａになるまで１０分間で残水を除去した。留出水量は３７２ｇ、系外に飛散した硫化水素量（飛散Ｓ）は７ｇであった。次いで、内温２３０℃まで２０分掛けて昇温し、２３０℃で３時間保持した。最終釜内圧力は０．１４ＭＰａであった。反応終了後、室温まで冷却した。反応終了時の反応系内の水分量はオートクレーブ中に存在する硫黄原子１モル当たり０．７６モルであった。４時間滴下終了後、ＤＣＢ消費率は７９％であった。 NMP623g and DCB299.86g were charged into the above-mentioned 2 liter autoclave in which a SUS-made dropping tank, a dropping pump, a condenser, and a decanter were connected. did. After reaching 220 ° C, the valve connected to the condenser was opened, and the pressure inside the kettle was adjusted to 0.20 MPa. Next, while maintaining the inner temperature at 220 ° C. and the pressure inside the kettle at 0.20 MPa, 260.36 g (2.24 mol) of a 48.23 mass% NaSH aqueous solution and the SMAB solution adjusted above were charged into the dropping tank. It dripped over 4 hours using the dropping pump, respectively. During the dropping, dehydration operation was performed at the same time, and the distilled vapor of p-DCB and water was condensed with a condenser and separated with a decanter, and p-DCB was returned to the autoclave. After the dropping was completed, the valve was closed, the autoclave was sealed, and the autoclave was kept for 1 hour. After holding for 1 hour, the valve to which the condenser was connected was opened again, and residual water was removed in 10 minutes until the pressure inside the kettle reached 0.10 MPa. The amount of distilled water was 372 g, and the amount of hydrogen sulfide scattered outside the system (scattering S) was 7 g. Then, the internal temperature was raised to 230 ° C. over 20 minutes and the temperature was maintained at 230 ° C. for 3 hours. The final pot pressure was 0.14 MPa. After the reaction was completed, it was cooled to room temperature. The water content in the reaction system at the end of the reaction was 0.76 mol per mol of the sulfur atom present in the autoclave. After the completion of dropping for 4 hours, the DCB consumption rate was 79%.
得られた重合スラリー１００ｇに７０℃のイオン交換水４００ｇを加えて１０分間撹拌した後に、ろ過し、ろ過後のケーキに７０℃のイオン交換水６００ｇを加えケーキ洗浄を行った。得られた含水ケーキに７０℃のイオン交換水４００ｇを加えて１０分間撹拌した後に、ろ過し、ろ過後のケーキに７０℃のイオン交換水６００ｇを加えケーキ洗浄を行った。この操作を２回繰り返した。得られた含水ケーキに７０℃のイオン交換水４００ｇと酢酸を加えてｐＨを４．０に調整して１０分間撹拌した後に、ろ過し、ろ過後のケーキに７０℃のイオン交換水６００ｇを加えケーキ洗浄を行った。得られた含水ケーキに７０℃のイオン交換水４００ｇを加えて１０分間撹拌した後に、ろ過し、ろ過後のケーキに７０℃のイオン交換水６００ｇを加えケーキ洗浄を行った。得られた含水ケーキを熱風乾燥機を用いて１２０℃で４時間乾燥して白色粉末状のポリマーを得た。得られたポリマーの溶融粘度は１３５Ｐａ・ｓ、カルボキシ基含有量は３５μｍｏｌ／ｇ、ＣＰ−ＭＡＢＡ生成量は３２μｍｏｌ／ｇ、および反応性は１４倍、であった。 400 g of ion-exchanged water at 70 ° C. was added to 100 g of the obtained polymerized slurry, stirred for 10 minutes and then filtered, and 600 g of ion-exchanged water at 70 ° C. was added to the filtered cake to wash the cake. 400 g of ion-exchanged water at 70 ° C. was added to the obtained water-containing cake, the mixture was stirred for 10 minutes and then filtered, and 600 g of ion-exchanged water at 70 ° C. was added to the filtered cake to wash the cake. This operation was repeated twice. To the obtained water-containing cake, 400 g of ion-exchanged water at 70 ° C. and acetic acid were added to adjust pH to 4.0 and stirred for 10 minutes, then filtered, and 600 g of ion-exchanged water at 70 ° C. was added to the filtered cake. The cake was washed. 400 g of ion-exchanged water at 70 ° C. was added to the obtained water-containing cake, the mixture was stirred for 10 minutes and then filtered, and 600 g of ion-exchanged water at 70 ° C. was added to the filtered cake to wash the cake. The obtained water-containing cake was dried at 120 ° C. for 4 hours using a hot air dryer to obtain a white powdery polymer. The obtained polymer had a melt viscosity of 135 Pa · s, a carboxy group content of 35 μmol / g, a CP-MABA production amount of 32 μmol / g, and a reactivity of 14 times.
（比較例１）
滴下する溶液を３８．４１質量％Ｎａ２Ｓ水溶液６０９．５０ｇ（Ｎａ２Ｓ３．００モル）に変更した以外は実施例１と同じ操作を行った。留出水量は３５６ｇ、系外に飛散した硫化水素量（飛散Ｓ）は１５ｇであった。最終釜内圧力は０．１０ＭＰａであった。４時間滴下終了後、ＤＣＢ消費率は６０％であった。反応終了時の反応系内の水分量はオートクレーブ中に存在する硫黄原子１モル当たり０．４９モルであった。得られたポリマーの溶融粘度は２１Ｐａ・ｓ、カルボキシ基含有量は１０μｍｏｌ／ｇ、ＣＰ−ＭＡＢＡ生成量は１６μｍｏｌ／ｇ、および反応性は１．０倍であった。
(Comparative Example 1)
Except for changing the solution added dropwise to 38.41 wt% Na 2 S aqueous solution 609.50g (Na 2 S3.00 mol) was subjected to the same procedure as in Example 1. The amount of distilled water was 356 g, and the amount of hydrogen sulfide scattered outside the system (scattering S) was 15 g. The final pot pressure was 0.10 MPa. After the completion of dropping for 4 hours, the DCB consumption rate was 60%. The water content in the reaction system at the end of the reaction was 0.49 mol per mol of the sulfur atom present in the autoclave. The obtained polymer had a melt viscosity of 21 Pa · s, a carboxy group content of 10 μmol / g, a CP-MABA production amount of 16 μmol / g, and a reactivity of 1.0 times.
（比較例２）
実施例１と同じ反応装置を用い、オートクレーブにＮＭＰ４８７ｇ、４９．２１質量％ＮａＯＨ 水溶液１８．２９ｇ（０．２２５モル）を仕込み、撹拌しながら窒素雰囲気下で内温１００℃まで２０分掛けて昇温し、系を閉じ、更に内温２２０℃ まで４０分かけて昇温し、２２０℃で２時間保持した。最終ゲージ圧力は０．２７ＭＰａであった。４時間滴下終了後、ＤＣＢ消費率は７１％であった。
(Comparative example 2)
Using the same reactor as in Example 1, an autoclave was charged with 487 g of NMP and 18.29 g (0.225 mol) of a 49.21 mass% aqueous NaOH solution, and the mixture was heated to an internal temperature of 100 ° C. over 20 minutes while stirring under a nitrogen atmosphere. The system was heated, the system was closed, the internal temperature was further raised to 220 ° C. over 40 minutes, and the temperature was maintained at 220 ° C. for 2 hours. The final gauge pressure was 0.27 MPa. After the completion of dropping for 4 hours, the DCB consumption rate was 71%.
次に、コンデンサを連結したバルブを開放し、ゲージ圧力を０．２０ＭＰａに調整した。次いで、内温を２２０℃に、ゲージ圧力を０．２０ＭＰａに保持しながら、４７．２３質量％ＮａＳＨ 水溶液１７８．０４ｇ（１．５００モル）、４９．２１質量％ＮａＯＨ 水溶液９８．７６ｇ（１．２１５モル）、及びｐ−ＤＣＢ２２０．５ｇ（１．５モル）を３時間かけて滴下した。滴下中は同時に脱水操作を行い、留出したｐ−ＤＣＢと水の混合蒸気はコンデンサで凝縮し、デカンタで分離して、ｐ−ＤＣＢはオートクレーブへ戻した。滴下終了後、バルブを閉止し、オートクレーブを密閉した。留出水量は１７４ｇ、系外に飛散した硫化水素量は１ｇであった。次いで、内温２３０℃まで１０分掛けて昇温し、２３０℃で３時間保持した。最終ゲージ圧力は０．２８ＭＰａであった。４時間滴下終了後、ＤＣＢ消費率は６７％であった。反応終了後、室温まで冷却し、重合スラリーを得た。反応終了時の反応系内の水分量はオートクレーブ中に存在する硫黄原子１モル当たり０．２０モルであった。得られた重合スラリーを実施例１と同様の操作を行いポリマーを得た。得られたポリマーの溶融粘度は４３Ｐａ・ｓ、末端カルボキシ基含有量は８μｍｏｌ／ｇ、ＣＰ−ＭＡＢＡ生成量は６２μｍｏｌ／ｇ、および反応性は１．１倍であった。 Next, the valve connected to the condenser was opened and the gauge pressure was adjusted to 0.20 MPa. Next, while maintaining the internal temperature at 220 ° C. and the gauge pressure at 0.20 MPa, 178.04 g (1.500 mol) of a 47.23% by mass NaSH aqueous solution and 98.76 g (1. 215 mol) and 220.5 g (1.5 mol) of p-DCB were added dropwise over 3 hours. During the dropping, a dehydration operation was performed at the same time, and the mixed vapor of p-DCB and water that had distilled off was condensed by a condenser and separated by a decanter, and p-DCB was returned to the autoclave. After the dropping was completed, the valve was closed and the autoclave was closed. The amount of distilled water was 174 g, and the amount of hydrogen sulfide scattered outside the system was 1 g. Next, the internal temperature was raised to 230 ° C. over 10 minutes and the temperature was maintained at 230 ° C. for 3 hours. The final gauge pressure was 0.28 MPa. After the completion of dropping for 4 hours, the DCB consumption rate was 67%. After completion of the reaction, the mixture was cooled to room temperature to obtain a polymerized slurry. The water content in the reaction system at the end of the reaction was 0.20 mol per mol of the sulfur atom present in the autoclave. The obtained polymerized slurry was treated in the same manner as in Example 1 to obtain a polymer. The obtained polymer had a melt viscosity of 43 Pa · s, a terminal carboxy group content of 8 μmol / g, a CP-MABA production amount of 62 μmol / g, and a reactivity of 1.1 times.
１ 反応容器
２ 撹拌翼
３ 精留塔
４ コンデンサ（凝縮器）
５ 凝縮器からの液体成分を静置分離するためのデカンタ
６ デカンタ下層部の液体を精留塔に戻す還流ポンプ
７ 精留塔及びコンデンサ内部のガス成分の圧力を調製する圧力制御弁
８ 飛散した硫化水素の回収装置
９ アルカリ金属水硫化物（水硫化ナトリウム）を反応容器へ供給するための配管
１０ アルカリ金属水硫化物（水硫化ナトリウム）を反応容器へ供給するためのポンプ
１１ アルカリ金属水硫化物（水硫化ナトリウム）の貯留漕
１２ ＳＭＡＢとアルカリ金属水酸化物（水酸化ナトリウム）を反応容器へ供給するための配管
１３ ＳＭＡＢとアルカリ金属水酸化物（水酸化ナトリウム）を反応容器へ供給するためのポンプ
１４ ＳＭＡＢとアルカリ金属水酸化物（水酸化ナトリウム）の貯留漕
1 Reaction Container 2
5 Decanter for statically separating the liquid component from the
Claims (3)
（ａ）水と、アルカリ金属水硫化物と、脂肪族系環状化合物の加水分解物のアルカリ金属塩と、アルカリ金属水酸化物とを供給しながら、または、（ｂ）水と、アルカリ金属水硫化物と、前記アルカリ金属塩と、アルカリ金属硫化物とを供給しながら、重合反応させるポリアリーレンスルフィド樹脂の製造方法であって、
前記脂肪族系環状化合物は、ラクタムまたは環状アミド化合物であり、
前記脂肪族系環状化合物および前記アルカリ金属塩の仕込み量の合計が、（ａ）アルカリ金属水硫化物に由来する硫黄原子１モルに対して、または、（ｂ）アルカリ金属水硫化物およびアルカリ金属硫化物に由来する硫黄原子１モルに対して、１．０〜６．０モルとなる範囲である、ことを特徴とするポリアリーレンスルフィド樹脂の製造方法。 In a reaction vessel containing an aliphatic cyclic compound and a polyhaloaromatic compound,
While supplying (a) water, an alkali metal hydrosulfide, an alkali metal salt of a hydrolyzate of an aliphatic cyclic compound, and an alkali metal hydroxide, or (b) water and an alkali metal water. A method for producing a polyarylene sulfide resin in which sulfide, the alkali metal salt, and an alkali metal sulfide are supplied and a polymerization reaction is carried out,
The aliphatic cyclic compound is a lactam or a cyclic amide compound,
The total amount of the aliphatic cyclic compound and the alkali metal salt charged is (a) with respect to 1 mol of a sulfur atom derived from an alkali metal hydrosulfide, or (b) an alkali metal hydrosulfide and an alkali metal. A method for producing a polyarylene sulfide resin , which is in a range of 1.0 to 6.0 mol with respect to 1 mol of a sulfur atom derived from a sulfide.
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