CN115427468A - Maleimide copolymer, and chlorine-containing polymer resin composition containing maleimide copolymer and chlorine-containing polymer - Google Patents
Maleimide copolymer, and chlorine-containing polymer resin composition containing maleimide copolymer and chlorine-containing polymer Download PDFInfo
- Publication number
- CN115427468A CN115427468A CN202180029357.0A CN202180029357A CN115427468A CN 115427468 A CN115427468 A CN 115427468A CN 202180029357 A CN202180029357 A CN 202180029357A CN 115427468 A CN115427468 A CN 115427468A
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- China
- Prior art keywords
- mass
- maleimide
- chlorine
- containing polymer
- parts
- Prior art date
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- Pending
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 154
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000000460 chlorine Substances 0.000 title claims abstract description 109
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 109
- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 229920000642 polymer Polymers 0.000 title claims abstract description 62
- 239000002952 polymeric resin Substances 0.000 title claims abstract description 53
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 53
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 146
- 239000000178 monomer Substances 0.000 claims abstract description 119
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 25
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 19
- 239000000155 melt Substances 0.000 claims abstract description 11
- 239000011342 resin composition Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 abstract description 12
- 238000004040 coloring Methods 0.000 abstract description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 123
- 239000000243 solution Substances 0.000 description 59
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 51
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 51
- 238000006116 polymerization reaction Methods 0.000 description 47
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 41
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical class NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 36
- 238000000034 method Methods 0.000 description 34
- 238000004898 kneading Methods 0.000 description 27
- 238000004458 analytical method Methods 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 14
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 13
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 12
- -1 lactone compounds Chemical class 0.000 description 9
- LRRBANSQUYNJTH-UHFFFAOYSA-N 2-tert-butylperoxy-2-methylpropane;2-ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O.CC(C)(C)OOC(C)(C)C LRRBANSQUYNJTH-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 150000008064 anhydrides Chemical class 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 150000003141 primary amines Chemical class 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- UWNNZXDNLPNGQJ-UHFFFAOYSA-N tert-butyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC(C)(C)C UWNNZXDNLPNGQJ-UHFFFAOYSA-N 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 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
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- SXTILEHINBCKSS-UHFFFAOYSA-N 1-chloro-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(Cl)C(=O)C=C1C1=CC=CC=C1 SXTILEHINBCKSS-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- QCOLXFOZKYRROA-UHFFFAOYSA-N 1-methoxy-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(OC)C(=O)C=C1C1=CC=CC=C1 QCOLXFOZKYRROA-UHFFFAOYSA-N 0.000 description 1
- IYBPIDAYDPNCTP-UHFFFAOYSA-N 1-methyl-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(C)C(=O)C=C1C1=CC=CC=C1 IYBPIDAYDPNCTP-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical class C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- GVJRTUUUJYMTNQ-UHFFFAOYSA-N 2-(2,5-dioxofuran-3-yl)acetic acid Chemical compound OC(=O)CC1=CC(=O)OC1=O GVJRTUUUJYMTNQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- JCJIZBQZPSZIBI-UHFFFAOYSA-N 2-[2,6-di(propan-2-yl)phenyl]benzo[de]isoquinoline-1,3-dione Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N(C1=O)C(=O)C2=C3C1=CC=CC3=CC=C2 JCJIZBQZPSZIBI-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
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- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- 238000000071 blow moulding Methods 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- VKNUORWMCINMRB-UHFFFAOYSA-N diethyl malate Chemical compound CCOC(=O)CC(O)C(=O)OCC VKNUORWMCINMRB-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical compound CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229930006978 terpinene Natural products 0.000 description 1
- 150000003507 terpinene derivatives Chemical class 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
The invention provides a maleimide copolymer capable of obtaining a chlorine-containing polymer resin composition which can improve the heat resistance of a chlorine-containing polymer and inhibit coloring, a chlorine-containing polymer resin composition containing the maleimide copolymer and the chlorine-containing polymer, and a formed body thereof. Further, a chlorine-containing polymer resin composition having excellent extrusion moldability can be provided. The present invention provides a maleimide-based copolymer for chlorine-containing polymers, which comprises 50 to 90 mass% of an aromatic vinyl monomer unit, 0.5 to 25 mass% of a vinyl cyanide monomer unit, 0 to 10 mass% of an unsaturated acid anhydride monomer unit, and 5 to 25 mass% of a maleimide-based monomer unit, wherein the melt viscosity measured at 190 ℃ and a shear rate of 100/sec is 200 to 100000Pa sec, and the weight-average molecular weight is 2.5 to 12 ten thousand, based on 100 mass% of the total amount of the aromatic vinyl monomer unit, the vinyl cyanide monomer unit, the unsaturated acid anhydride monomer unit, and the maleimide-based monomer unit.
Description
Technical Field
The present invention relates to a maleimide copolymer and a chlorine-containing polymer resin composition containing the maleimide copolymer and a chlorine-containing polymer.
Background
Chlorine-containing polymer resins are inexpensive and have excellent chemical, physical and mechanical properties, and are used in large quantities for various applications.
However, chlorine-containing polymers have the disadvantage of lacking heat resistance (heat softening temperature), for example when measured by JIS K7206: the Vicat softening temperature measured by the 50 method (load 50N, temperature rise rate 50 ℃/hr) in 1999 is about 82 ℃, and when a stabilizer and a plasticizer are incorporated in usual molding, the softening temperature is further lowered.
As a method for improving heat resistance of chlorine-containing polymer resins, a method of mixing a heat-resistant resin with a chlorine-containing polymer is known (for example, patent documents 1 and 2).
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 06475501
Patent document 2: japanese patent laid-open No. 2006-265373
Disclosure of Invention
Problems to be solved by the invention
The invention provides a maleimide copolymer which can obtain a chlorine-containing polymer resin composition with improved heat resistance of a chlorine-containing polymer and inhibited coloring, a chlorine-containing polymer resin composition containing the maleimide copolymer and the chlorine-containing polymer, and a formed body thereof. Further, a chlorine-containing polymer resin composition having excellent extrusion moldability is provided.
Means for solving the problems
The inventors of the present invention have found, based on the results of their studies, that a maleimide-based copolymer having a specific monomer unit composition, a specific range of melt viscosity and a specific range of weight average molecular weight and having a low level of yellowness can impart heat resistance to a chlorine-containing polymer and at the same time can suppress the occurrence of coloration in a resin composition and a molded article thereof. Further, it was found that the resin composition was excellent in extrusion moldability.
The invention is as follows:
(1): a maleimide-based copolymer for chlorine-containing polymers, which contains 50 to 90 mass% of an aromatic vinyl monomer unit, 0.5 to 25 mass% of a vinyl cyanide monomer unit, 0 to 10 mass% of an unsaturated acid anhydride monomer unit, and 5 to 25 mass% of a maleimide monomer unit, wherein the maleimide-based copolymer has a melt viscosity of 200 to 100000 Pa.sec as measured at 190 ℃ and a shear rate of 100/sec, and a weight-average molecular weight of 2.5 to 12 ten thousand, when the total amount of the aromatic vinyl monomer unit, the vinyl cyanide monomer unit, the unsaturated acid anhydride monomer unit, and the maleimide monomer unit is 100 mass%.
(2): a chlorine-containing polymer resin composition comprising 5 to 50% by mass of the maleimide copolymer of (1) and 50 to 95% by mass of a chlorine-containing polymer.
(3): (2) The chlorine-containing polymer resin composition as described in (1), wherein the melt viscosity is 200 to 70000Pa sec.
(4): (2) The chlorine-containing polymer resin composition according to (3), wherein the maleimide copolymer has a weight-average molecular weight of 5 to 10 ten thousand.
(5): (2) The chlorine-containing polymer resin composition according to any one of (1) to (4), wherein the maleimide-based copolymer contains 50 to 80% by mass of an aromatic vinyl monomer unit.
(6): (2) The chlorine-containing polymer resin composition according to any one of (1) to (5), wherein the maleimide-based copolymer contains 5 to 20% by mass of vinyl cyanide monomer units.
(7): (2) The chlorine-containing polymer resin composition according to any one of (1) to (6), wherein the maleimide-based copolymer contains an unsaturated acid anhydride monomer unit in an amount of 0.3 to 5% by mass.
(8): (2) The chlorine-containing polymer resin composition according to any one of (1) to (7), wherein the maleimide-based copolymer contains 5 to 24% by mass of maleimide-based monomer units.
(9): (2) The chlorine-containing polymer resin composition according to any one of (1) to (8), wherein the maleimide monomer unit is N-arylmaleimide.
(10): a molded article obtained by molding the chlorine-containing polymer resin composition according to any one of (2) to (9).
ADVANTAGEOUS EFFECTS OF INVENTION
The maleimide-based copolymer of the present invention can impart heat resistance to a chlorine-containing polymer and can suppress coloration of a resin composition and a molded article thereof. Therefore, the present invention is applicable to applications requiring heat resistance and good appearance. The present invention is also applicable to extrusion molding because of its excellent kneadability.
Detailed Description
< description of wording >
The meaning of "a to B" described in the specification of the present application means: a is not less than A and not more than B.
The following description will explain embodiments of the present invention in detail. The embodiments may be combined with each other.
(1. Monomer units contained in the maleimide-based copolymer)
The maleimide-based copolymer of the present invention comprises: an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, an unsaturated acid anhydride monomer unit, and a maleimide monomer unit. The monomer units contained in the maleimide-based copolymer will be described below.
(1-1. Aromatic vinyl monomer unit)
Examples of the aromatic vinyl monomer that can be used in the maleimide-based copolymer according to the present invention include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2, 4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α -methylstyrene, α -methyl-p-methylstyrene, and the like. Among them, styrene having a good effect of improving the hue is preferable. The styrene-based monomers may be used alone or in combination of 2 or more.
The maleimide-based copolymer according to the present invention contains 50 to 90% by mass of the aromatic vinyl monomer unit, preferably 50 to 80% by mass, more preferably 60 to 70% by mass, based on 100% by mass of the total amount of the aromatic vinyl monomer unit, the vinyl cyanide monomer unit, the unsaturated acid anhydride monomer unit and the maleimide-based monomer unit. The content thereof may specifically be 50, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 mass%, and may be within a range of 2 arbitrary out of the numerical values exemplified herein. When the amount of the aromatic vinyl monomer unit is less than 50% by mass, the other monomer components contained in the maleimide-based copolymer are relatively increased, and as a result, the maleimide-based copolymer and the chlorine-containing polymer may not be kneaded without melting, or the Yellowing Index (YI) of the maleimide-based copolymer may become high, whereby the chlorine-containing polymer resin composition and the molded article thereof may be colored, and when it exceeds 90% by mass, the heat resistance of the chlorine-containing polymer resin composition may not be sufficiently improved.
(1-2. Vinyl cyanide monomer units)
Examples of the vinyl cyanide monomer unit that can be used in the maleimide-based copolymer according to the present invention include acrylonitrile, methacrylonitrile, ethacrylonitrile, and fumaronitrile. Among them, acrylonitrile is preferable from the viewpoint of hue and heat resistance to the chlorine-containing polymer resin composition. The vinyl cyanide monomer may be used alone or in combination of 2 or more.
The maleimide-based copolymer according to the present invention contains the vinyl cyanide-based monomer unit in an amount of 0.5 to 25% by mass, preferably 5 to 20% by mass, more preferably 1 to 20% by mass, based on 100% by mass of the total of the aromatic vinyl-based monomer unit, vinyl cyanide-based monomer unit, unsaturated acid anhydride monomer unit and maleimide-based monomer unit. The content thereof may be specifically 0.5, 1, 5, 10, 15, 20, or 25% by mass, or may be within a range of any 2 of the numerical values exemplified herein. When the amount of the vinyl cyanide monomer units is less than 0.5% by mass, the heat resistance of the chlorine-containing polymer resin composition may not be sufficiently improved, and when it exceeds 25% by mass, the Yellowness (YI) of the maleimide-based copolymer may become high.
(1-3. Unsaturated acid anhydride monomer Unit)
Examples of the unsaturated acid anhydride monomer unit usable in the maleimide-based copolymer according to the present invention include maleic anhydride, itaconic anhydride, citraconic anhydride, and aconitic anhydride. Among these, maleic anhydride is preferable from the viewpoint of imparting heat resistance to the chlorine-containing polymer resin composition. The unsaturated acid anhydride monomer units may be used alone, or 2 or more kinds may be used in combination.
The maleimide-based copolymer according to the present invention contains the unsaturated acid anhydride monomer unit in an amount of 0 to 10% by mass, preferably 0.3 to 5% by mass, more preferably 0.5 to 5% by mass, based on 100% by mass of the total amount of the aromatic vinyl monomer unit, the vinyl cyanide monomer unit, the unsaturated acid anhydride monomer unit and the maleimide-based monomer unit. The content thereof may specifically be 0, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10% by mass, and may be within a range of any 2 of the numerical values exemplified herein. When the amount of the unsaturated acid anhydride monomer unit exceeds 10% by mass, the flowability may be lowered and the kneadability with the chlorine-containing polymer may be lowered.
(1-4. Maleimide monomer units)
Examples of the maleimide monomer unit that can be used in the maleimide copolymer of the present invention include N-alkylmaleimides such as N-methylmaleimide, N-butylmaleimide and N-cyclohexylmaleimide, and N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide and N-tribromophenylmaleimide. Among these, from the viewpoint of imparting heat resistance to the chlorine-containing polymer resin composition, N-arylmaleimide is preferable, and N-phenylmaleimide is more preferable. The maleimide monomer may be used alone or in combination of 2 or more.
In order to incorporate the maleimide-based copolymer with the maleimide-based monomer unit, for example, a copolymer obtained by copolymerizing a raw material comprising an unsaturated dicarboxylic acid monomer unit with another monomer with ammonia or a primary amine may be imidized, or a raw material comprising a maleimide-based monomer may be copolymerized with another monomer.
The maleimide-based copolymer according to the present invention contains 5 to 25% by mass of maleimide-based monomer units, preferably 5% by mass or more and less than 25% by mass, more preferably 5 to 24% by mass, and still more preferably 10 to 24% by mass, based on 100% by mass of the total amount of aromatic vinyl-based monomer units, vinyl cyanide-based monomer units, unsaturated acid anhydride monomer units, and maleimide-based monomer units. Specifically, the content may be 5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 mass%, or may be within a range between any 2 of the numerical values exemplified herein. When the amount of the maleimide-based monomer unit is less than 5% by mass, the heat resistance of the chlorine-containing polymer resin composition may not be sufficiently improved, and when it exceeds 25% by mass, the maleimide-based copolymer and the chlorine-containing polymer may not be melted and kneaded.
(1-5. Copolymerizable monomer)
The maleimide-based copolymer of the present invention may be obtained by copolymerizing a copolymerizable monomer other than the aromatic vinyl monomer, the vinyl cyanide monomer, the unsaturated acid anhydride monomer unit and the maleimide monomer, within a range not to impair the effects of the present invention. Examples of the monomer copolymerizable with the maleimide-based copolymer include acrylic acid ester monomers such as methyl acrylate, ethyl acrylate and butyl acrylate, methacrylic acid ester monomers such as methyl methacrylate and ethyl methacrylate, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amide and methacrylic acid amide. The monomer copolymerizable with the maleimide-based copolymer may be used alone or in combination of 2 or more.
The content of the monomer is preferably 20% by mass or less, more preferably 10% by mass or less, from the viewpoint of imparting heat resistance to the chlorine-containing polymer resin composition, although the monomer is copolymerizable within a range not to impair the effects of the present invention.
(1-6. Additives)
After completion of the polymerization, additives such as heat-resistant stabilizers including hindered phenol compounds, lactone compounds, phosphorus compounds, and sulfur compounds, light-resistant stabilizers including hindered amine compounds and benzotriazole compounds, lubricants, plasticizers, colorants, antistatic agents, and mineral oils may be added to the polymerization solution as necessary. The amount added is preferably less than 0.2 part by mass relative to 100 parts by mass of the whole monomer units. The additives may be used alone or in combination of 2 or more.
(2. Properties of maleimide copolymer)
(2-1. Melt viscosity of Maleimide copolymer)
The melt viscosity of the maleimide-based copolymer of the present invention is 200 to 100000 Pa.sec, preferably 200 to 70000 Pa.sec, and more preferably 500 to 70000 Pa.sec. Specifically, it may be 200, 500, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 20000, 30000, 40000, 50000, or 100000Pa · sec, or may be within a range of 2 of any of the numerical values exemplified here. When the pressure is less than 200Pa sec, the heat resistance of the chlorine-containing polymer resin composition may not be sufficiently improved, and when the pressure exceeds 100000Pa sec, the maleimide-based copolymer and the chlorine-containing polymer of the mixed resin may not be melt-kneaded.
The melt viscosity was measured by using a capillary rheometer 1D manufactured by toyoyo seiko corporation and a capillary die with L =40mm and D =1 mm.
The melt viscosity of the maleimide-based copolymer can be adjusted by adjusting the mixing ratio of the monomer units constituting the maleimide-based copolymer. For example, the melt viscosity can be increased by increasing the content of the vinyl cyanide monomer unit in the maleimide-based copolymer or increasing the content of the maleimide-based monomer unit in the maleimide-based copolymer. Further, the melt viscosity can be increased by increasing the weight average molecular weight of the maleimide-based copolymer. These adjustment methods may be used in combination. (2-2. Weight-average molecular weight of maleimide copolymer)
The weight average molecular weight of the maleimide-based copolymer of the present invention is 2.5 to 12 ten thousand, preferably 5 to 10 ten thousand. Specifically, it may be 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, or 12 ten thousand, and may be within a range between any 2 of the numerical values exemplified herein. When the weight average molecular weight is less than 2.5 ten thousand, the heat resistance of the chlorine-containing polymer resin composition may not be sufficiently improved, and when it exceeds 12 ten thousand, the torque may be increased during kneading of the chlorine-containing polymer resin composition.
The weight average molecular weight is a value in terms of polystyrene measured by Gel Permeation Chromatography (GPC), and can be measured under the following conditions.
Measurement name: SYSTEM-21Shodex (manufactured by Showa Denko K.K.)
A chromatographic column: 3 PL gel MIXED-B (manufactured by Polymer Laboratories) were used in series
Temperature: 40 deg.C
The detection mode is as follows: differential refractive index
Solvent: tetrahydrofuran (THF)
Temperature: 2% by mass
And (3) correcting a curve: drawn using a standard Polystyrene (PS) (manufactured by Polymer Laboratories, inc.)
As a method for obtaining a maleimide-based copolymer having a preferred weight average molecular weight (Mw) in the range of 2.5 to 12 ten thousand, there can be mentioned a method of adjusting the polymerization temperature, polymerization time and amount of a polymerization initiator to be added, and a method of adjusting the amount of a solvent to be added and the amount of a chain transfer agent to be added. In addition, a method of reducing the molecular weight of the resulting copolymer by decomposing it is also known.
(3. Preparation of Maleimide copolymer)
The polymerization method of the maleimide-based copolymer is, for example, solution polymerization, bulk polymerization or the like. Solution polymerization is preferable from the viewpoint that the maleimide-based copolymer having a uniform copolymerization component can be obtained by polymerizing the maleimide-based copolymer while adding the maleimide-based copolymer in portions. The solvent for solution polymerization is preferably a non-copolymerizable solvent from the viewpoint of less generation of by-products and less adverse effects. Examples thereof include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetophenone, ethers such as tetrahydrofuran and 1, 4-dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, and N, N-dimethylformamide, dimethyl acetone and N-methyl-2-pyrrolidone, among which methyl ethyl ketone and methyl isobutyl ketone are preferable from the viewpoint of easiness of removing the solvent at the time of recovering the maleimide-based copolymer by devolatilization. The polymerization process may be arbitrarily selected from a continuous polymerization type, a batch type (batch type), and a semi-batch type.
The method for producing the maleimide copolymer is not particularly limited, but it is preferably a method capable of radical polymerization, and the polymerization temperature is preferably in the range of 80 to 150 ℃. The polymerization initiator is not particularly limited, and for example, known azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile and azobismethylbutyronitrile, and known organic peroxides such as benzoyl peroxide, t-butyl peroxybenzoate, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane, t-butyl peroxymonocarboxypropyl ester, t-butyl peroxy2-ethylhexanoate, di-t-butyl peroxide, dicumyl peroxide and ethyl-3, 3-bis- (t-butylperoxy) butyrate may be used, and 1 kind or 2 or more kinds of these may be used in combination. From the viewpoint of the reaction rate of polymerization or the control of the rate of polymerization, it is preferable to use an azo compound or an organic peroxide having a half-life of 10 hours at 70 to 120 ℃. The amount of the polymerization initiator used is not particularly limited, but is preferably 0.1 to 1.5% by mass, more preferably 0.1 to 1.0% by mass, based on 100% by mass of the whole monomer units. The amount of the polymerization initiator used is preferably 0.1% by mass or more because a sufficient polymerization rate can be obtained. If the amount of the polymerization initiator used is 1.5% by mass or less, the reaction can be easily controlled by suppressing the polymerization rate, and the target molecular weight can be easily obtained.
A chain transfer agent may be used in the production of the maleimide-based copolymer. The chain transfer agent to be used is not particularly limited, and examples thereof include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, α -methylstyrene dimer, ethyl thioglycolate, limonene, terpinene and the like. The amount of the chain transfer agent to be used is not particularly limited as long as it is within a range in which the target molecular weight can be obtained, but is preferably 0.01 to 0.8% by mass, more preferably 0.1 to 0.5% by mass, based on 100% by mass of the whole monomer units. When the amount of the chain transfer agent used is 0.01 to 0.8% by mass, the target molecular weight can be easily obtained.
As a method for introducing the maleimide monomer unit of the maleimide-based copolymer, there can be used a method of copolymerizing a maleimide monomer, an aromatic vinyl monomer and a vinyl cyanide monomer (direct method), or a method of copolymerizing an unsaturated dicarboxylic anhydride, an aromatic vinyl monomer and a vinyl cyanide monomer in advance and then reacting the unsaturated dicarboxylic anhydride group with ammonia or a primary amine to convert the unsaturated dicarboxylic anhydride group into a maleimide monomer unit (post-imidization method). The post-imidization method is preferred because the amount of the maleimide monomer remaining in the copolymer is small.
Examples of the primary amine used in the post-imidization method include alkylamines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, cyclohexylamine, and decylamine, and aromatic amines such as chlorine-or bromine-substituted alkylamine, aniline, toluidine, and naphthylamine, and among them, aniline and cyclohexylamine are preferable. These primary amines may be used alone, or 2 or more kinds thereof may be used in combination. The amount of the primary amine to be added is not particularly limited, but is preferably 0.7 to 1.1 molar equivalents, and more preferably 0.85 to 1.05 molar equivalents, relative to the unsaturated dicarboxylic anhydride group. It is preferable that the molar equivalent of the monomer unit is 0.7 or more relative to the unsaturated dicarboxylic anhydride monomer unit in the maleimide copolymer, because the thermal stability is good. When the amount is 1.1 molar equivalent or less, the amount of the primary amine remaining in the maleimide-based copolymer is reduced, and therefore, it is preferable.
When a post-imidization method is used to introduce the maleimide monomer units, a catalyst may be used. The catalyst can improve the dehydration ring-closing reaction in the reaction of ammonia or primary amine with unsaturated dicarboxylic anhydride group, especially in the reaction of converting unsaturated dicarboxylic anhydride group into maleimide group. The kind of the catalyst is not particularly limited, but tertiary amines can be used. Examples of the tertiary amine include, but are not particularly limited to, trimethylamine, triethylamine, tripropylamine, tributylamine, N-dimethylaniline and N, N-diethylaniline. The amount of the tertiary amine added is preferably not less than 0.01 molar equivalent to the unsaturated dicarboxylic anhydride group, although not particularly limited. The temperature of the imidization reaction in the present invention is preferably 100 to 250 ℃. More preferably 120 to 200 ℃. When the temperature of the imidization reaction is 100 ℃ or higher, the reaction rate is sufficiently high, and it is preferable from the viewpoint of productivity. It is preferable that the temperature of the imidization reaction is 250 ℃ or lower because the deterioration of the physical properties due to the thermal deterioration of the maleimide-based copolymer can be suppressed.
As a method for removing volatile components such as a solvent used in the solution polymerization and unreacted monomers from the solution after the completion of the solution polymerization or the solution after the completion of the post-imidization of the maleimide-based copolymer (devolatilization method), a known method can be used. For example, a vacuum devolatilization tank with a heater or a devolatilization extruder with an exhaust port may be used. The devolatilized maleimide-based copolymer in a molten state may be transferred to a pelletizing step, extruded into strands from a porous die, and then processed into pellets by a cold cutting method, an in-air hot cutting method, an underwater hot cutting method, or the like.
When the chlorine-containing polymer is in the form of a powder, the maleimide-based copolymer of the present invention is preferably also pulverized into a powder before use. The pulverization method is not particularly limited, and a known pulverization technique can be used. Suitable crushing devices include turbine mill crushers, turbine disc mill crushers, turbine cutter crushers, jet mill crushers, impact crushers, hammer crushers, vibratory crushers, and the like.
(4. Chlorine-containing Polymer)
The chlorine-containing polymer in the present invention is a polymer obtained by polymerizing vinyl chloride alone or a mixture of vinyl chloride and 1 or more monomers copolymerizable therewith, and a chlorine addition polymer obtained by further adding chlorine element to the polymer thus obtained. The chlorine-containing polymer may further contain a compound of the polymer thus obtained and a chlorine addition polymer. Examples of the copolymerizable monomer include vinyl esters such as vinyl acetate and vinyl propionate, acrylates such as methyl acrylate and butyl acrylate, methacrylates such as methyl methacrylate and ethyl methacrylate, fumarates such as butyl malate and diethyl malate, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, cyanides such as acrylonitrile and methacrylonitrile, α -olefins such as ethylene and propylene, styrenes such as styrene, α -methylstyrene, vinyl toluene, t-butyl styrene and chlorostyrene and their substitutes, vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, and phthalates such as vinyl dihalides or vinyl halides and diallyl phthalate.
The chlorine-containing polymer is preferably polyvinyl chloride obtained by polymerizing vinyl chloride, from the viewpoint of affinity with the maleimide-based copolymer.
The average polymerization degree of the chlorine-containing polymer is 680 to 1900, preferably 700 to 1700. When the average polymerization degree is 680 or more, the maleimide-based copolymer is uniformly dispersed, and when it is 1900 or less, the kneading property with the maleimide-based copolymer is excellent.
(4-1. Production of chlorine-containing Polymer)
The method of polymerization of the chlorine-containing polymer is not particularly limited, and may be conventionally known bulk polymerization, solution polymerization, emulsion polymerization, or the like.
(5. Chlorine-containing polymer resin composition comprising maleimide copolymer and chlorine-containing polymer)
The blending ratio of the maleimide-based copolymer and the chlorine-containing polymer in the present invention is preferably 5 to 50% by mass of the maleimide-based copolymer and 50 to 95% by mass of the chlorine-containing polymer, more preferably 5 to 30% by mass of the maleimide-based copolymer and 70 to 95% by mass of the chlorine-containing polymer. When the blending ratio of the maleimide copolymer is adjusted to 5% by mass or more, a sufficient heat resistance-imparting effect can be obtained, and when the blending ratio is adjusted to 50% by mass or less, the deterioration of releasability at the time of kneading can be suppressed.
(5-1. Additive for chlorine-containing Polymer resin composition)
The chlorine-containing polymer resin composition of the present invention may contain an additive as described below, and may actually be an additive composed of a maleimide-based copolymer and a chlorine-containing polymer, within a range not affecting the effect of the present invention.
If necessary, a reinforcing agent, a processability improver, a heat stabilizer, a lubricant, a plasticizer, or the like may be further added singly or in combination to the chlorine-containing polymer resin composition of the present invention.
As other additives, light-resistant stabilizers, ultraviolet absorbers, antioxidants, pigments, dyes, and the like may be optionally added.
(5-2. Production of chlorine-containing Polymer resin composition)
The method for obtaining the chlorine-containing polymer resin composition of the present invention by kneading and mixing the maleimide copolymer and the chlorine-containing polymer is not particularly limited, and a known melt kneading technique can be used. Suitable melt kneading apparatuses include screw extruders such as single-screw extruders, intermeshing-type co-rotating or intermeshing-type counter-rotating twin-screw extruders, non-intermeshing or incomplete intermeshing twin-screw extruders, banbury mixers, ram extruders, and mixing rolls. Further, a plurality of these extruders may be used in combination.
The extruder is composed of a kneading section for melt-kneading the maleimide-based copolymer and the chlorine-containing polymer and at least 1 devolatilization section. The maleimide-based copolymer and the chlorine-containing polymer supplied to the extruder were first melted in the kneading section and kneaded to form a uniform composition. The kneading section may be composed of a known kneading element such as a kneading disk. In the downstream of the kneading section, an element having a push-back action of pushing back the molten resin to the upstream side is used, and from the viewpoint of kneading property, it is preferable to fill the kneading section with the molten resin. Examples of such elements include a reverse lead full-screw type, a reverse shift type, and a seal ring.
The chlorine-containing polymer resin composition can be molded by a known method. Examples thereof include injection molding, sheet extrusion molding, vacuum molding, blow molding, foam molding, profile extrusion molding, and the like. In molding, the chlorine-containing polymer resin composition is usually heated to 170 to 200 ℃ and then processed, and 190 to 200 ℃ is preferred. The formed product can be used for gutters, air-conditioning pipeline covers, factory pipelines, pipes, joints, sprinkler pipelines, window frames, industrial products and the like.
(5-3. Maximum Torque at the time of melt kneading of the chlorine-containing polymer resin composition)
When extrusion molding of the chlorine-containing polymer resin composition is performed, it is advantageous in melt kneading to keep the maximum torque of the chlorine-containing polymer resin composition low during melt kneading. As an index, for example, the maximum torque at the time of adding 20 parts by mass of the maleimide-based copolymer to 100 parts by mass of the chlorine-containing polymer and melt-kneading the mixture can be used. The preferable range of the maximum torque at the time of melt kneading varies depending on the actual conditions and extrusion molding conditions, and for example, a laboratory plastic mill (4C 150, mixer model R60) manufactured by Toyo Seiki Seisaku-Sho K.K. is used, and the value of the maximum torque measured at 190 ℃ under the conditions of a filling amount of 60.0g and 60rpm is preferably 50 N.m or less.
Examples
The details are described below using examples, but the present invention is not limited to the following examples.
< preparation example of Maleimide-based copolymer (A-1) >
73 parts by mass of styrene, 18 parts by mass of acrylonitrile, 1 part by mass of maleic anhydride, 0.22 part by mass of alpha-methylstyrene dimer, and 26 parts by mass of methyl ethyl ketone were charged into an autoclave having a capacity of about 120 liters equipped with a stirrer, and after the gas phase portion was replaced with nitrogen, the temperature was raised to 92 ℃ over 40 minutes while stirring. After the temperature was raised, the mixture was kept at 92 ℃ and a solution prepared by dissolving 7 parts by mass of maleic anhydride and 1.0 part by mass of t-butyl peroxide-2-ethylhexanoate in 35 parts by mass of methyl ethyl ketone was continuously added over 4.5 hours. After the addition, the temperature was raised to 120 ℃ to complete the polymerization within 1 hour. Subsequently, 6 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ℃ for 7 hours. The imidization reaction solution after the completion of the reaction was fed into a vented screw extruder, and volatile components were removed to obtain a granular maleimide-based copolymer A-1. The analysis results of the obtained maleimide-based copolymer are shown in Table 1. In tables 1 and 2, sty is a styrene monomer unit, AN is AN acrylonitrile monomer unit, MAH is a maleic anhydride monomer unit, NPMI is AN N-phenylmaleimide monomer unit, and PVC is polyvinyl chloride.
< preparation example of Maleimide-based copolymer (A-2) >
64 parts by mass of styrene, 20 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.5 part by mass of alpha-methylstyrene dimer, and 31 parts by mass of methyl ethyl ketone were charged in an autoclave having a capacity of about 120 liters equipped with a stirrer, and after the gas phase portion was replaced with nitrogen, the temperature was raised to 92 ℃ over 40 minutes under stirring. After the temperature was raised, the mixture was kept at 92 ℃ for 5.5 hours, and a solution prepared by dissolving 14 parts by mass of maleic anhydride and 0.60 part by mass of t-butyl peroxy-2-ethylhexanoate in 69 parts by mass of methyl ethyl ketone was continuously added. After the addition, the temperature was raised to 120 ℃ to complete the polymerization within 1 hour. Subsequently, 12 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ℃ for 7 hours. The imidization reaction solution after the completion of the reaction was fed into a vented screw extruder, and volatile components were removed to obtain a granular maleimide-based copolymer A-2. The analysis results of the obtained maleimide-based copolymer are shown in Table 1.
< preparation example of Maleimide-based copolymer (A-3) >
79 parts by mass of styrene, 9 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.52 parts by mass of alpha-methylstyrene dimer, and 33 parts by mass of methyl ethyl ketone were charged into an autoclave having a capacity of about 120 liters equipped with a stirrer, and after the gas phase portion was replaced with nitrogen, the temperature was raised to 92 ℃ over 40 minutes under stirring. After the temperature was raised, the mixture was kept at 92 ℃ and a solution prepared by dissolving 9 parts by mass of maleic anhydride and 0.60 part by mass of t-butyl peroxy-2-ethylhexanoate in 47 parts by mass of methyl ethyl ketone was continuously added over 5 hours. After the addition, the temperature was raised to 120 ℃ and the reaction was carried out for 1.5 hours to complete the polymerization. Subsequently, 9 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ℃ for 7 hours. The imidization reaction solution after the completion of the reaction was fed into a vented screw extruder, and volatile components were removed to obtain a granular maleimide-based copolymer A-3. The analysis results of the obtained maleimide-based copolymer are shown in Table 1.
< preparation example of Maleimide-based copolymer (A-4) >
85 parts by mass of styrene, 7 parts by mass of acrylonitrile, 1 part by mass of maleic anhydride, 0.72 part by mass of α -methylstyrene dimer, and 30 parts by mass of methyl ethyl ketone were charged into an autoclave having a capacity of about 120 liters equipped with a stirrer, and after the gas phase portion was replaced with nitrogen, the temperature was raised to 92 ℃ over 40 minutes under stirring. After the temperature was raised, the mixture was kept at 92 ℃ and a solution prepared by dissolving 7 parts by mass of maleic anhydride and 0.80 part by mass of t-butyl peroxy-2-ethylhexanoate in 33 parts by mass of methyl ethyl ketone was continuously added over 6 hours. After the addition, the temperature was raised to 120 ℃ to complete the polymerization within 1 hour. Subsequently, 5 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ℃ for 7 hours. The imidization reaction solution after the completion of the reaction was fed into a vented screw extruder, and volatile components were removed to obtain a granular maleimide-based copolymer A-4. The analysis results of the obtained maleimide-based copolymer are shown in Table 1.
< preparation example of Maleimide-based copolymer (A-5) >
25 parts by mass of styrene, 26 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.53 part by mass of alpha-methylstyrene dimer, and 30 parts by mass of methyl ethyl ketone were charged into an autoclave having a capacity of about 120 liters equipped with a stirrer, and after the gas phase portion was replaced with nitrogen, the temperature was raised to 92 ℃ over 40 minutes while stirring. After the temperature rise, the temperature was maintained at 92 ℃ for 3 hours, and a solution prepared by dissolving 34 parts by mass of styrene, 13 parts by mass of maleic anhydride, and 0.22 part by mass of t-butyl-2-ethylhexanoate in 67 parts by mass of methyl ethyl ketone was continuously added. After the end of the addition of maleic anhydride, a solution of 0.18 parts by mass of t-butyl peroxide-2-ethylhexanoate dissolved in 1 part by mass of methyl ethyl ketone was continuously added over 2.5 hours. After the addition, the temperature was raised to 120 ℃ to complete the polymerization within 1 hour. Subsequently, 12 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ℃ for 7 hours. The imidization reaction solution after the completion of the reaction was fed into a vented screw extruder, and volatile components were removed to obtain a granular maleimide-based copolymer A-5. The analysis results of the obtained maleimide-based copolymer are shown in Table 1.
< preparation example of Maleimide-based copolymer (A-6) >
Styrene 23 parts by mass, acrylonitrile 26 parts by mass, maleic anhydride 2 parts by mass, alpha-methylstyrene dimer 0.32 parts by mass, and methyl ethyl ketone 32 parts by mass were charged into an autoclave having a capacity of about 120 liters equipped with a stirrer, and after the gas phase portion was replaced with nitrogen, the temperature was raised to 92 ℃ over 40 minutes under stirring. After the temperature rise, the mixture was maintained at 92 ℃ for 3 hours, and a solution of 33 parts by mass of styrene, 16 parts by mass of maleic anhydride, and 0.22 part by mass of t-butyl peroxy-2-ethylhexanoate dissolved in 81 parts by mass of methyl ethyl ketone was continuously added. After the end of the addition of maleic anhydride, a solution of 0.18 parts by mass of t-butyl peroxide-2-ethylhexanoate dissolved in 1 part by mass of methyl ethyl ketone was continuously added over 2.5 hours. After the addition, the temperature was raised to 120 ℃ to complete the polymerization within 1 hour. Subsequently, 14 parts by mass of aniline and 0.3 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ℃ for 7 hours. The imidization reaction solution after the completion of the reaction was fed into a vented screw extruder, and volatile components were removed to obtain a granular maleimide-based copolymer A-6. The analysis results of the obtained maleimide-based copolymer are shown in Table 1.
< preparation example of Maleimide-based copolymer (B-1) >
94 parts by mass of styrene, 2 parts by mass of acrylonitrile, 0.4 part by mass of maleic anhydride, 0.58 part by mass of α -methylstyrene dimer, and 28 parts by mass of methyl ethyl ketone were charged into an autoclave having a capacity of about 120 liters equipped with a stirrer, and after the gas phase portion was replaced with nitrogen, the temperature was raised to 92 ℃ over 40 minutes while stirring. After the temperature rise, the mixture was maintained at 92 ℃ for 7.5 hours, and a solution prepared by dissolving 4 parts by mass of maleic anhydride and 1.0 part by mass of t-butyl-2-ethylhexanoate in 18 parts by mass of methyl ethyl ketone was continuously added. After the addition, the temperature was raised to 120 ℃ to complete the polymerization within 1 hour. Subsequently, 3 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ℃ for 7 hours. The imidized reaction solution after the completion of the reaction was fed into a vented screw extruder, and volatile components were removed to obtain a granular maleimide-based copolymer B-1. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
< preparation example of Maleimide-based copolymer (B-2) >
88 parts by mass of styrene, 1 part by mass of maleic anhydride, 0.48 part by mass of α -methylstyrene dimer, and 29 parts by mass of methyl ethyl ketone were charged in an autoclave having a capacity of about 120 liters equipped with a stirrer, and after the gas phase portion was replaced with nitrogen, the temperature was raised to 92 ℃ over 40 minutes under stirring. After the temperature was raised, the mixture was kept at 92 ℃ for 8.5 hours, and a solution prepared by dissolving 11 parts by mass of maleic anhydride and 1.20 parts by mass of t-butyl peroxide-2-ethylhexanoate in 56 parts by mass of methyl ethyl ketone was continuously added. After the addition, the temperature was raised to 120 ℃ to complete the polymerization within 1 hour. Subsequently, 9 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ℃ for 7 hours. The imidization reaction solution after the completion of the reaction was fed into a vented screw extruder, and volatile components were removed to obtain a granular maleimide-based copolymer B-2. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
< preparation example of Maleimide-based copolymer (B-3) >
27 parts by mass of styrene, 33 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.11 part by mass of alpha-methylstyrene dimer, and 24 parts by mass of methyl ethyl ketone were charged into an autoclave having a capacity of about 120 liters equipped with a stirrer, the gas phase part was replaced with nitrogen, and then the temperature was raised to 92 ℃ over 40 minutes under stirring. After the temperature was raised, the mixture was kept at 92 ℃ and a solution of 31 parts by mass of styrene, 7 parts by mass of maleic anhydride and 0.38 part by mass of t-butyl peroxy-2-ethylhexanoate dissolved in 37 parts by mass of methyl ethyl ketone was continuously added over 3.5 hours. After the end of the addition of maleic anhydride, a solution of 0.22 parts by mass of t-butyl peroxy-2-ethylhexanoate dissolved in 2 parts by mass of methyl ethyl ketone was continuously added over 2 hours. After the addition, the temperature was raised to 120 ℃ to complete the polymerization within 1 hour. Subsequently, 6 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ℃ for 7 hours. The imidization reaction solution after the completion of the reaction was fed into a vented screw extruder, and volatile components were removed to obtain a granular maleimide-based copolymer B-3. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
< preparation example of Maleimide-based copolymer (B-4) >
63 parts by mass of styrene, 22 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.59 part by mass of α -methylstyrene dimer, and 30 parts by mass of methyl ethyl ketone were placed in an autoclave having a capacity of about 120 liters equipped with a stirrer, the gas phase part was replaced with nitrogen, and then the temperature was raised to 92 ℃ over 40 minutes while stirring. After the temperature was raised, the mixture was kept at 92 ℃ and a solution of 13 parts by mass of maleic anhydride and 0.44 part by mass of t-butyl peroxy-2-ethylhexanoate dissolved in 69 parts by mass of methyl ethyl ketone was continuously added over 4 hours. After the end of the addition of maleic anhydride, a solution of 0.16 parts by mass of t-butyl peroxide-2-ethylhexanoate dissolved in 1 part by mass of methyl ethyl ketone was continuously added over 1.5 hours. After the addition, the temperature was raised to 120 ℃ to complete the polymerization within 1 hour. Subsequently, 3 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ℃ for 7 hours. The imidization reaction solution after the completion of the reaction was fed into a vented screw extruder, and volatile components were removed to obtain a granular maleimide-based copolymer B-4. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
< preparation example of Maleimide-based copolymer (B-5) >
77 parts by mass of styrene, 19 parts by mass of acrylonitrile, 1 part by mass of maleic anhydride and 25 parts by mass of methyl ethyl ketone were charged into an autoclave having a capacity of about 120 liters equipped with a stirrer, the gas phase part was replaced with nitrogen gas, and then the temperature was raised to 92 ℃ over 40 minutes under stirring. After the temperature was raised, the mixture was kept at 92 ℃ and a solution prepared by dissolving 3 parts by mass of maleic anhydride and 0.82 part by mass of t-butyl peroxy-2-ethylhexanoate in 23 parts by mass of methyl ethyl ketone was continuously added over 4.5 hours. After the end of the addition of maleic anhydride, a solution of 0.18 parts by mass of t-butyl peroxide-2-ethylhexanoate dissolved in 1 part by mass of methyl ethyl ketone was continuously added over 1 hour. After the addition, the temperature was raised to 120 ℃ to complete the polymerization within 1 hour. Subsequently, 2 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ℃ for 7 hours. The imidized reaction solution after the completion of the reaction was fed into a vented screw extruder, and volatile components were removed to obtain a granular maleimide-based copolymer B-5. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
< preparation example of Maleimide-based copolymer (B-6) >
24 parts by mass of styrene, 24 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 0.53 parts by mass of alpha-methylstyrene dimer, and 33 parts by mass of methyl ethyl ketone were charged into an autoclave having a capacity of about 120 liters equipped with a stirrer, and after the gas phase portion was replaced with nitrogen, the temperature was raised to 92 ℃ over 40 minutes under stirring. After the temperature rise, the mixture was maintained at 92 ℃ for 3 hours, and a solution prepared by dissolving 33 parts by mass of styrene, 17 parts by mass of maleic anhydride, and 0.22 part by mass of t-butyl peroxy-2-ethylhexanoate in 85 parts by mass of methyl ethyl ketone was continuously added. After the end of the addition of maleic anhydride, a solution of 0.18 parts by mass of t-butyl peroxide-2-ethylhexanoate dissolved in 1 part by mass of methyl ethyl ketone was continuously added over 2.5 hours. After the addition, the temperature was raised to 120 ℃ to complete the polymerization within 1 hour. Subsequently, 16 parts by mass of aniline and 0.3 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ℃ for 7 hours. The imidization reaction solution after the completion of the reaction was fed into a vented screw extruder, and volatile components were removed to obtain a granular maleimide-based copolymer B-6. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
< preparation example of Maleimide-based copolymer (B-7) >
22 parts by mass of styrene, 10 parts by mass of acrylonitrile, 3 parts by mass of maleic anhydride, 0.45 part by mass of alpha-methylstyrene dimer, and 39 parts by mass of methyl ethyl ketone were placed in an autoclave having a capacity of about 120 liters equipped with a stirrer, the gas phase part was replaced with nitrogen, and then the temperature was raised to 92 ℃ over 40 minutes while stirring. After raising the temperature, the temperature was maintained at 92 ℃ and a solution prepared by dissolving 41 parts by mass of styrene, 23 parts by mass of maleic anhydride, and 0.42 part by mass of t-butyl-2-ethylhexanoate into 116 parts by mass of methyl ethyl ketone was continuously added over 5 hours. After the addition, the temperature was raised to 120 ℃ to complete the polymerization within 1 hour. Subsequently, 23 parts by mass of aniline and 0.4 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ℃ for 7 hours. The imidization reaction solution after the completion of the reaction was fed into a vented screw extruder, and volatile components were removed to obtain a granular maleimide-based copolymer B-7. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
< preparation example of Maleimide-based copolymer (B-8) >
79 parts by mass of styrene, 9 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride, 1.00 parts by mass of alpha-methylstyrene dimer and 33 parts by mass of methyl ethyl ketone were charged into an autoclave having a capacity of about 120 liters equipped with a stirrer, the gas phase portion was replaced with nitrogen, and then the temperature was raised to 92 ℃ over 40 minutes under stirring. After the temperature was raised, the mixture was kept at 92 ℃ and a solution prepared by dissolving 9 parts by mass of maleic anhydride and 0.60 part by mass of t-butyl peroxy-2-ethylhexanoate in 47 parts by mass of methyl ethyl ketone was continuously added over 5 hours. After the completion of the addition, the temperature was raised to 120 ℃ to complete the polymerization within 1.5 hours. Subsequently, 9 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ℃ for 7 hours. The imidized reaction solution after the completion of the reaction was fed into a vented screw extruder, and volatile components were removed to obtain a granular maleimide-based copolymer B-8. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
< preparation example of Maleimide-based copolymer (B-9) >
79 parts by mass of styrene, 9 parts by mass of acrylonitrile, 2 parts by mass of maleic anhydride and 33 parts by mass of methyl ethyl ketone were charged into an autoclave having a capacity of about 120 liters equipped with a stirrer, the gas phase part was replaced with nitrogen gas, and then the temperature was raised to 92 ℃ over 40 minutes under stirring. After the temperature was raised, the mixture was kept at 92 ℃ and a solution prepared by dissolving 9 parts by mass of maleic anhydride and 0.60 part by mass of t-butyl peroxy-2-ethylhexanoate in 47 parts by mass of methyl ethyl ketone was continuously added over 5 hours. After the completion of the addition, the temperature was raised to 120 ℃ to complete the polymerization within 1.5 hours. Subsequently, 9 parts by mass of aniline and 0.2 parts by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ℃ for 7 hours. The imidization reaction solution after the completion of the reaction was fed into a vented screw extruder, and volatile components were removed to obtain a granular maleimide-based copolymer B-9. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
< preparation example of Maleimide-based copolymer (B-10) >
84 parts by mass of styrene, 12 parts by mass of acrylonitrile, 1 part by mass of maleic anhydride, 0.57 part by mass of alpha-methylstyrene dimer, and 26 parts by mass of methyl ethyl ketone were charged into an autoclave having a capacity of about 120 liters equipped with a stirrer, and after the gas phase portion was replaced with nitrogen, the temperature was raised to 92 ℃ over 40 minutes while stirring. After the temperature was raised, the mixture was kept at 92 ℃ for 4.5 hours, and a solution prepared by dissolving 3 parts by mass of maleic anhydride and 0.82 part by mass of t-butyl peroxy-2-ethylhexanoate in 24 parts by mass of methyl ethyl ketone was continuously added. After the end of the addition of maleic anhydride, a solution of 0.18 parts by mass of t-butyl peroxide-2-ethylhexanoate dissolved in 1 part by mass of methyl ethyl ketone was continuously added for 1 hour. After the addition, the temperature was raised to 120 ℃ to complete the polymerization within 1 hour. Subsequently, 3 parts by mass of aniline and 0.1 part by mass of triethylamine were added to the polymerization solution, and the mixture was reacted at 140 ℃ for 7 hours. The imidization reaction solution after the completion of the reaction was fed into a vented screw extruder, and volatile components were removed to obtain a granular maleimide-based copolymer B-10. The analysis results of the obtained maleimide-based copolymer are shown in Table 2.
< chlorine-containing Polymer-based resin composition >
(use of raw materials) the raw materials used in each example and each comparative example are as follows.
(1) Chlorine-containing Polymers (PVC)
Product name: TH-1000 (manufactured by Taiyo Vinyl Corporation).
(2) Maleimide copolymer
The compounds (A-1 to A-6 and B-1 to B-10) obtained in the above production examples were used.
Examples 1 to 6 and comparative examples 1 to 10 (kneading and mixing of Maleimide copolymer and chlorine-containing Polymer)
The maleimide-based copolymers A-1 to A-6 and B-1 to B-10 were mixed with a commercially available chlorine-containing polymer (product name: TH-1000, manufactured by Taiyo Vinyl Corporation) previously added with a combination of a stabilizer and a lubricant in the compounding ratios shown in tables 1 to 2 and mixed by a Henschel mixer, and then the mixture was rolled up into a ROLL sheet by a test ROLL (phi 6X L15 test ROLL, kansai ROLL Co., ltd.), and the ROLL sheet was overlapped and subjected to extrusion molding, cutting or molding to prepare a test piece, and then the physical property values thereof were measured. The results are shown in tables 1 and 2.
(component analysis)
The analysis of the composition of each monomer unit was carried out by C-13NMR method under the following measurement conditions.
Device name: FT-NMR AVANCE300 (manufactured by BRUKER Co., ltd.)
Solvent: deuterated chloroform
Temperature: 14% by mass
Temperature: 27 ℃ C
And (4) accumulating times: 8000 times
(weight average molecular weight)
The weight average molecular weight is a value in terms of polystyrene measured by Gel Permeation Chromatography (GPC) and is measured using the following conditions.
The measurement name: SYSTEM-21Shodex (manufactured by Showa Denko K.K.)
And (3) chromatographic column: 3 PL gel MIXED-B (manufactured by Polymer Laboratories) were used in series
Temperature: 40 deg.C
And (3) detection: differential refractive index
Solvent: tetrahydrofuran (THF)
Temperature: 2% by mass
And (3) correcting a curve: prepared using a standard Polystyrene (PS) (manufactured by Polymer Laboratories, inc.)
(melt viscosity)
The melt viscosity was measured by a capillary die with L =40mm and D =1mm at 190 ℃ and a shear rate of 100/sec. The measuring apparatus used was a capillary rheometer 1D manufactured by Toyo Seiki Seisaku-Sho.
(Vicat softening temperature)
The vicat softening temperature is based on JIS K7206:1999 50 method (load: 50N, heating rate: 50 ℃/hr), using a test piece 20 mm. Times.20 mm, thickness: 4 mm. The HDT & VSPT test apparatus manufactured by the toyo seiko corporation was used as the measuring apparatus.
(yellowness (YI))
Measured according to JIS K-7373. The specific procedure is as follows.
1g of maleimide copolymer was dissolved in 25mL of tetrahydrofuran. After dissolution, it was transferred to a square cell for assay. The color difference was determined by using a CIE standard D65 light source under conditions of a temperature of 23 ℃ and a humidity of 50% using a transmission method with a square pool of tetrahydrofuran solution as a blank, and the value was defined as the yellowness.
Device name: SE7700 spectrocolorimeter (manufactured by Nippon Denshoku industries Co., ltd.)
A square pool: A02277A 10X 36X 55H double-sided transmission type square pool
(maximum Torque)
The maximum torque of each example and comparative example was measured as follows.
20 parts by mass of the maleimide-based copolymers in the examples and comparative examples were added to 80 parts by mass of a chlorine-containing polymer (TH-1000, manufactured by Taiyo Vinyl Corporation) to which additives such as a stabilizer and a lubricant were previously added and mixed by a Henschel mixer. In melt-kneading the maleimide-based copolymer and the chlorine-containing polymer, the maximum torque (kneading torque, in N · m) in kneading was measured by a laboratory plastic mill (model 4C150, mixer model R60, manufactured by Toyo Seiki Seisaku-Sho K.K.) under the conditions of a filling amount of 60.0g, a temperature of 190 ℃ and a rotation speed of 60 rpm.
When the value of the maximum torque is low, melt kneading is facilitated, and therefore extrusion molding can be appropriately performed.
TABLE 1
TABLE 2
In examples 1 to 6 (using the chlorine-containing polymer resin compositions using the maleimide-based copolymers according to the present invention), the heat resistance of the chlorine-containing polymer was sufficiently improved. Further, the yellowness of the maleimide-based copolymer to be used is controlled to a low level, whereby the coloring of the resin composition and the molded article thereof can be suppressed. Further, the maximum torque at the time of melt-kneading the maleimide-based copolymer and the chlorine-containing polymer is suppressed to a low level. It is expected that extrusion molding of the molded article can be carried out without any problem.
In contrast, in comparative examples 1 to 10 (using the chlorine-containing polymer resin compositions not satisfying the maleimide-based copolymer specified in the present invention), the heat resistance of the chlorine-containing polymer may not be sufficiently improved. Further, the maleimide-based copolymer to be used has a high yellowness, and there is a possibility that the resin composition and the molded article thereof are colored. Further, the maleimide-based copolymer and the chlorine-containing polymer are not melted and cannot be kneaded, and therefore the maximum torque may become high during melt kneading.
Industrial applicability
The present invention provides a maleimide copolymer which can provide a chlorine-containing polymer resin composition having improved heat resistance of a chlorine-containing polymer and suppressed coloration, a chlorine-containing polymer resin composition containing the maleimide copolymer and the chlorine-containing polymer, and a molded article thereof. It is suitable for use in molded articles requiring heat resistance and appearance properties such as gutters and air-conditioning duct covers. The chlorine-containing polymer resin composition of the present invention is also suitable for extrusion molding.
Claims (10)
1. A maleimide copolymer for chlorine-containing polymers, wherein,
the maleimide-based copolymer for chlorine-containing polymers comprises 50 to 90 mass% of the aromatic vinyl monomer unit, 0.5 to 25 mass% of the vinyl cyanide monomer unit, 0 to 10 mass% of the unsaturated acid anhydride monomer unit and 5 to 25 mass% of the maleimide monomer unit, based on 100 mass% of the total amount of the aromatic vinyl monomer unit, vinyl cyanide monomer unit, unsaturated acid anhydride monomer unit and maleimide monomer unit,
a melt viscosity of 200 to 100000Pa · sec as measured at 190 ℃ and a shear rate of 100/sec, and a weight average molecular weight of 2.5 to 12 ten thousand.
2. A chlorine-containing polymer-based resin composition, wherein,
comprising 5 to 50% by mass of the maleimide copolymer of claim 1 and 50 to 95% by mass of a chlorine-containing polymer.
3. The chlorine-containing polymer-based resin composition according to claim 2, wherein
The melt viscosity is 200 to 70000Pa sec.
4. The chlorine-containing polymer-based resin composition according to claim 2 or 3, wherein
The weight average molecular weight of the maleimide copolymer is 5 to 10 ten thousand.
5. The chlorine-containing polymer resin composition according to any one of claims 2 to 4, wherein
The maleimide copolymer contains 50 to 80 mass% of aromatic vinyl monomer units.
6. The chlorine-containing polymer resin composition according to any one of claims 2 to 5, wherein
The maleimide copolymer contains 5 to 20 mass% of vinyl cyanide monomer units.
7. The chlorine-containing polymer resin composition according to any one of claims 2 to 6, wherein
The maleimide copolymer contains 0.3 to 5 mass% of unsaturated acid anhydride monomer units.
8. The chlorine-containing polymer resin composition according to any one of claims 2 to 7, wherein
The maleimide copolymer contains 5 to 24 mass% of maleimide monomer units.
9. The chlorine-containing polymer resin composition according to any one of claims 2 to 8, wherein
The maleimide monomer unit is N-aryl maleimide.
10. A molded article obtained by molding the chlorine-containing polymer resin composition according to any one of claims 2 to 9.
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| PCT/JP2021/029721 WO2022039099A1 (en) | 2020-08-19 | 2021-08-12 | Maleimide copolymer, and chlorine-containing polymer resin composition including maleimide copolymer and chlorine-containing polymer |
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| TW202402837A (en) * | 2022-03-31 | 2024-01-16 | 日商電化股份有限公司 | Heat-resistance imparter for chlorinated polymers, resin composition, and molded object formed from said resin composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02265944A (en) * | 1989-04-05 | 1990-10-30 | Nippon Oil & Fats Co Ltd | Vinyl chloride resin composition |
| JPH04122759A (en) * | 1990-09-14 | 1992-04-23 | Sekisui Chem Co Ltd | Vinyl chloride resin composition |
| JPH11302482A (en) * | 1998-04-22 | 1999-11-02 | Mitsui Chem Inc | Vinyl chloride resin composition and molded product using the same |
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| JP2006265373A (en) * | 2005-03-24 | 2006-10-05 | Denki Kagaku Kogyo Kk | Vinyl chloride resin composition comprising maleimide copolymer and vinyl chloride polymer |
| JP6475501B2 (en) | 2015-01-26 | 2019-02-27 | デンカ株式会社 | Vinyl chloride resin heat-resistant reforming copolymer, molded body, vinyl chloride piping |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02265944A (en) * | 1989-04-05 | 1990-10-30 | Nippon Oil & Fats Co Ltd | Vinyl chloride resin composition |
| JPH04122759A (en) * | 1990-09-14 | 1992-04-23 | Sekisui Chem Co Ltd | Vinyl chloride resin composition |
| JPH11302482A (en) * | 1998-04-22 | 1999-11-02 | Mitsui Chem Inc | Vinyl chloride resin composition and molded product using the same |
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