CN104203990B - Macromolecular compound and manufacture method thereof and molding - Google Patents
Macromolecular compound and manufacture method thereof and molding Download PDFInfo
- Publication number
- CN104203990B CN104203990B CN201380015726.6A CN201380015726A CN104203990B CN 104203990 B CN104203990 B CN 104203990B CN 201380015726 A CN201380015726 A CN 201380015726A CN 104203990 B CN104203990 B CN 104203990B
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- Prior art keywords
- transfer agent
- macromolecular compound
- mass parts
- manufacture method
- chain transfer
- Prior art date
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- 229920002521 macromolecule Polymers 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000000465 moulding Methods 0.000 title claims description 17
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 68
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 21
- 239000007858 starting material Substances 0.000 claims abstract description 17
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- 238000012546 transfer Methods 0.000 claims description 22
- 125000000524 functional group Chemical group 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 230000003287 optical effect Effects 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 16
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 11
- -1 alkyl methacrylate Chemical compound 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 238000009826 distribution Methods 0.000 description 6
- 239000012458 free base Substances 0.000 description 6
- 238000012662 bulk polymerization Methods 0.000 description 5
- 239000000113 methacrylic resin Substances 0.000 description 5
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical group SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229940051250 hexylene glycol Drugs 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 230000001902 propagating effect Effects 0.000 description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-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
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-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
- MFGALGYVFGDXIX-UHFFFAOYSA-N 2,3-Dimethylmaleic anhydride Chemical compound CC1=C(C)C(=O)OC1=O MFGALGYVFGDXIX-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 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
- 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 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- DBWWINQJTZYDFK-UHFFFAOYSA-N 2-ethenyl-1,4-dimethylbenzene Chemical compound CC1=CC=C(C)C(C=C)=C1 DBWWINQJTZYDFK-UHFFFAOYSA-N 0.000 description 1
- VSZSIEBALNXIFG-UHFFFAOYSA-N 2-hydroxyethyl 2,2-bis(sulfanyl)acetate Chemical compound OCCOC(=O)C(S)S VSZSIEBALNXIFG-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
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- PMZXJPLGCUVUDN-UHFFFAOYSA-N 4-ethenyl-1,2-dimethylbenzene Chemical compound CC1=CC=C(C=C)C=C1C PMZXJPLGCUVUDN-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GIDPEPYGDXWNPR-UHFFFAOYSA-N C(C)(C)(C)C(=C(C(=O)O)C)C1CCCCC1.C(=C)C(=O)O Chemical compound C(C)(C)(C)C(=C(C(=O)O)C)C1CCCCC1.C(=C)C(=O)O GIDPEPYGDXWNPR-UHFFFAOYSA-N 0.000 description 1
- VYBUOUBVHOCIBD-UHFFFAOYSA-N C(C)(C)(C)C(=C(C(=O)O)C)C1CCCCC1.C(C(=C)C)(=O)O Chemical compound C(C)(C)(C)C(=C(C(=O)O)C)C1CCCCC1.C(C(=C)C)(=O)O VYBUOUBVHOCIBD-UHFFFAOYSA-N 0.000 description 1
- QDMMAJNKZYLYAC-UHFFFAOYSA-N C=C.C(CCCCC)C1=CC=CC=C1 Chemical compound C=C.C(CCCCC)C1=CC=CC=C1 QDMMAJNKZYLYAC-UHFFFAOYSA-N 0.000 description 1
- NOEMSRWQFGPZQS-UHFFFAOYSA-N CCC(O)=S.CCC(O)=S.CCC(O)=S.CCC(CO)(CO)CO Chemical compound CCC(O)=S.CCC(O)=S.CCC(O)=S.CCC(CO)(CO)CO NOEMSRWQFGPZQS-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005012 alkyl thioether group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- QWYVTJQFFVAOFP-UHFFFAOYSA-N dec-1-en-2-ylbenzene Chemical compound CCCCCCCCC(=C)C1=CC=CC=C1 QWYVTJQFFVAOFP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- YJSSCAJSFIGKSN-UHFFFAOYSA-N hex-1-en-2-ylbenzene Chemical compound CCCCC(=C)C1=CC=CC=C1 YJSSCAJSFIGKSN-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- SKEQOTBKQUCUGK-UHFFFAOYSA-N o-(2-hydroxyethyl) propanethioate Chemical compound CCC(=S)OCCO SKEQOTBKQUCUGK-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- ANGVCCXFJKHNDS-UHFFFAOYSA-N pent-1-en-2-ylbenzene Chemical compound CCCC(=C)C1=CC=CC=C1 ANGVCCXFJKHNDS-UHFFFAOYSA-N 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical group CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F20/00—Homopolymers and 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
Abstract
The invention provides the method can with the transparency of applicable optical applications and the macromolecular compound of mobility and excellent impact resistance.The invention provides a kind of manufacture method of macromolecular compound, under the chain-transfer agent of the specified quantitative containing Polyfunctional chain transfer agent and the coexisting of polymerization starter, carry out radical polymerization by by methacrylic ester and the monomer mixture that can form with the vinyl monomer of its copolymerization.
Description
Technical field
The present invention relates to the macromolecular compound of the transparency, mobility and excellent impact resistance and the manufacture method that can manufacture this macromolecular compound with high efficiency and the molding be made up of this macromolecular compound.
Background technology
The macromolecular compound manufactured by radical polymerization with the form of molding for multiple uses such as OA apparatus field, automotive field, electrical/electronic fields.Such as, be that the macromolecular compound with the transparency of representative is widely used in the such optical applications of the front panel of display unit, light guiding plate with methacrylic resin.
In recent years, with the maximization, thin-walled property etc. of display unit, require the plasticity improving the thermoplastic resins such as macromolecular compound, the particularly methacrylic resin used in display unit.
If improve mobility by reducing weight-average molecular weight, then can improve the plasticity of macromolecular compound, but the shock-resistance that can produce obtained molding reduces such problem.
In order to realize plasticity and the shock-resistance of methacrylic resin simultaneously, the method for known interpolation shock-resistance modifying agent.Known such as following method: the specific segmented copolymer as shock-resistance modifying agent is coexisted, by polymerize monomer mixtures, obtains the methacrylic resin composition (referenced patent document 1) of excellent impact resistance thus.But the method exists the miscellaneous and problem that the transparency that the is methacrylic resin composition obtained is impaired of production process, still there is the leeway of improvement further.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2011-12236 publication
Summary of the invention
Invent problem to be solved
So, the industrial favourable manufacture method that the object of the present invention is to provide the macromolecular compound of the transparency and plasticity and the excellent impact resistance with applicable optical applications and the macromolecular compound obtained by this manufacture method.In addition, another object of the present invention is to the molding that the good appearance obtained by this macromolecular compound is provided.
For the method for dealing with problems
According to the present invention, above-mentioned purpose realizes by providing following invention.
[1] a kind of manufacture method of macromolecular compound, radical polymerization is carried out under the existence by methacrylic ester (A) and the monomer mixture (C) that can form with the vinyl monomer (B) of methacrylic ester (A) copolymerization and more than one Polyfunctional chain transfer agents (D) and polymerization starter (E), the feature of described manufacture method is, above-mentioned Polyfunctional chain transfer agent (D) meets the relation of following formula (1) relative to the usage quantity of the above-mentioned monomer mixture of 100 mass parts (C)
(in formula (1), a and p represents the integer of more than 1, M
p, n
pand W
prepresent any Polyfunctional chain transfer agent (D in a kind Polyfunctional chain transfer agent (D) respectively
p) molecular weight, functional group number and amount (mass parts)).
[2] a kind of manufacture method of macromolecular compound, by methacrylic ester (A) and the monomer mixture (C) that can form with the vinyl monomer (B) of methacrylic ester (A) copolymerization and more than one Polyfunctional chain transfer agents (D), radical polymerization is carried out under the existence of more than one simple function chain-transfer agents (D ') and polymerization starter (E), the feature of described manufacture method is, above-mentioned Polyfunctional chain transfer agent (D) and above-mentioned simple function chain-transfer agent (D ') meet the relation of following formula (2) and formula (3) relative to the usage quantity of the above-mentioned monomer mixture of 100 mass parts (C),
(in formula (2), (3), a, b and p represent the integer of more than 1 respectively, M
p, n
pand W
prepresent any Polyfunctional chain transfer agent (D in a kind Polyfunctional chain transfer agent (D) respectively
p) molecular weight, functional group number and amount (mass parts), M '
pand W '
prepresent respectively any simple function chain-transfer agent in b kind simple function chain-transfer agent (D ') (D '
p) molecular weight and amount (mass parts)).
The manufacture method of the macromolecular compound [3] as described in above-mentioned [1] or [2], is characterized in that, uses above-mentioned polymerization starter (E) in the scope of 0.001 ~ 0.01 mass parts.
[4] macromolecular compound, it is obtained by the manufacture method according to any one of above-mentioned [1] ~ [3].
[5] molding, it is made up of the macromolecular compound described in above-mentioned [4].
Invention effect
Manufacturing method according to the invention, does not need to add shock-resistance modifying agent, industrially advantageously can manufacture the transparency and the macromolecular compound of plasticity and excellent impact resistance with applicable optical applications.In addition, utilize the macromolecular compound obtained by this manufacture method, the molding of mechanical strength and good appearance can be provided.
Embodiment
In the manufacture method of macromolecular compound of the present invention, under the existence by methacrylic ester (A) and the monomer mixture (C) that can form with the vinyl monomer of its copolymerization (B) and more than one Polyfunctional chain transfer agents (D) and polymerization starter (E), carry out radical polymerization.
Radical polymerization in manufacture method of the present invention can applying soln polymerization, suspension polymerization, mass polymerization, emulsion polymerization etc., in addition, can any one mode in a batch manner, in successive polymerization mode implement.Wherein, from use optical applications obtained macromolecular compound in, preferably do not use the mass polymerization of dispersion agent, emulsifying agent, solvent etc., from the view point of productivity, more preferably utilize the mass polymerization (continuous bulk polymerization method) of successive polymerization mode.
As the methacrylic ester (A) that can use in manufacture method of the present invention, can enumerate such as: the alkyl methacrylate such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, N-Hexyl methacrylate, methacrylic acid (2-ethylhexyl); The methacrylic acid cycloalkanes esters such as cyclohexyl methacrylate, methacrylic acid (t-butyl cyclohexyl methacrylate); The methacrylic acid aralkyl esters such as benzyl methacrylate; The arylmethacrylate such as phenyl methacrylate; Deng.Wherein, from the view point of the transparency of obtained macromolecular compound, preferably alkyl methacrylate is used.These methacrylic esters (A) can be used alone one, also can be used together multiple.
As can use in manufacture method of the present invention can with the vinyl monomer (B) of methacrylic ester (A) copolymerization, can enumerate such as: the acrylate such as methyl acrylate, ethyl propenoate, propyl acrylate, isopropyl acrylate, butyl acrylate, Ethyl acrylate, vinylformic acid (2-ethylhexyl), cyclohexyl acrylate, vinylformic acid (t-butyl cyclohexyl methacrylate), benzyl acrylate, phenyl acrylate; Vinylbenzene, alpha-methyl styrene, α-ethyl styrene, α-propylstyrene, α-butylstyrene, α-amylbenzene ethene, α-hexyl benzene ethene, α-octyl styrene, a vinyl toluene, an ethyl styrene, p-methylstyrene, p-ethyl-styrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene, 3,4-dimethyl styrene, 3, the aromatic ethenyl compounds such as 5-dimethyl styrene, p-tert-butylstyrene, α, α-diphenylethlene; The unsaturated carboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, dimethyl maleic anhydride, itaconic anhydride, aconitic anhydride, trimellitic acid 1,2-anhydride; The maleimides such as N-methylmaleimido, NEM, N-phenylmaleimide, N-N-cyclohexylmaleimide; The acid amides such as acrylamide, Methacrylamide; The vinyl cyanide such as vinyl cyanide, methacrylonitrile based compound etc.Wherein, from the view point of the transparency of obtained macromolecular compound, preferred acrylate, more preferably uses the alkyl acrylate of carbonatoms 1 ~ 6.These vinyl monomers (B) can be used alone one, also can be used together multiple.
In the monomer mixture (C) used in manufacture method of the present invention, from the view point of the transparency and plasticity, preferably in the scope of 50 ~ 99.9 quality %, contain methacrylic ester (A), more preferably in the scope of 70 ~ 99.5 quality % containing methacrylic ester (A), further preferred in the scope of 85 ~ 99 quality % containing methacrylic ester (A).In addition, monomer mixture (C) preferably contains vinyl monomer (B) in the scope of 0.1 ~ 50 quality %, more preferably in the scope of 0.5 ~ 30 quality % containing vinyl monomer (B), further preferred in the scope of 1 ~ 15 quality % containing vinyl monomer (B).
In addition, above-mentioned monomer mixture (C) preferably contains monofunctional monomer in the scope of 99 ~ 100 quality %, more preferably in the scope of 99.5 ~ 100 quality %, monofunctional monomer is contained, further preferred in the scope of 99.9 ~ 100 quality % containing monofunctional monomer, most preferably containing 100 quality % monofunctional monomers.When comprising polyfunctional monomer, molecular weight distribution broadens, and cannot fully obtain effect of the present invention, and the transmissivity of molding also reduces.
In manufacture method of the present invention, by making the usage quantity of Polyfunctional chain transfer agent (D) meet the relation of following general formula (1) relative to the above-mentioned monomer mixture of 100 mass parts (C), plasticity and the shock-resistance of obtained macromolecular compound can be improved.
(in formula (1), a and p represents the integer of more than 1, M
p, n
pand W
prepresent any Polyfunctional chain transfer agent (D in a kind Polyfunctional chain transfer agent (D) respectively
p) molecular weight, functional group number and amount (mass parts))
The Polyfunctional chain transfer agent (D) used in manufacture method of the present invention refers to have the chain-transfer agent that plural chain transfer constant under radical polymerization condition is the functional group of more than 0.01 in a part.In addition, above-mentioned chain transfer constant refers to the chain transfer constant of the functional group that the growth end free base of the polymkeric substance be made up of monomer mixture (C) at radical polymerization temperature and this Polyfunctional chain transfer agent (D) have, with the velocity constant k with chain transfer reaction
trdivided by the velocity constant k of reaction of propagation
pand the value obtained defines.As this functional group, sulfydryl, disulfide base, halogen group etc. can be enumerated.
As Polyfunctional chain transfer agent (D), can enumerate such as: 1,4-succinimide mercaptans, 1,6-ethanthiol, 1,10-the last of the ten Heavenly stems two mercaptan, ethylene glycol bis thiopropionate, the two mercaptoacetate of butyleneglycol, the two thiopropionate of butyleneglycol, the two mercaptoacetate of hexylene glycol, the alkyl sulfhydryl such as hexylene glycol two thiopropionate, trimethylolpropane tris thiopropionate, tetramethylolmethane tetrathio propionic ester, Dipentaerythritol six thiopropionates.These Polyfunctional chain transfer agents (D) can be used alone, and also can be used together multiple.
Polyfunctional chain transfer agent (D) is relative to the above-mentioned formula of usage quantity demand fulfillment (1) of 100 mass parts monomer mixtures (C).That is, the Wn of the whole Polyfunctional chain transfer agents (D) used
0.5/ M's (wherein, W, n, M represent the molecular weight of each Polyfunctional chain transfer agent (D), functional group number and amount (mass parts)) and (hereinafter referred to as " constant f ") be more than 0.0015 and less than 0.0045.When using Polyfunctional chain transfer agent (D) of W mass parts molecular weight M, functional group number n relative to 100 mass parts monomer mixtures (C), it is Wn that the substituting group of the chain tra nsfer of the generation growth end free base in radical polymerization is estimated as every 100 mass parts monomer mixtures (C)
0.5/ M mole.Therefore, constant f refers to the summation of the mole number of the functional group of the Polyfunctional chain transfer agent (D) that the chain tra nsfer increasing end free base occurs when 100 mass parts monomer mixtures (C) being carried out radical polymerization.When constant f is less than 0.0015, there is the tendency that mobility reduces, when being greater than 0.0045, there is the tendency that shock-resistance reduces.Constant f is preferably the scope of 0.0020 ~ 0.0040, is more preferably the scope of 0.0025 ~ 0.0035.
In addition, in the radical polymerization carried out in manufacture method of the present invention, all right simple function of use further chain-transfer agent (D ').The simple function chain-transfer agent that uses in manufacture method of the present invention (D ') refers in a part, only to have the chain-transfer agent that a chain transfer constant is the functional group of 0.01 more than under radical polymerization condition.In addition, above-mentioned chain transfer constant refers to the chain transfer constant of the functional group that the growth end free base of the polymkeric substance be made up of monomer mixture (C) at radical polymerization temperature and this simple function chain-transfer agent (D ') have, with the velocity constant k with chain transfer reaction
trdivided by the velocity constant k of reaction of propagation
pand the value obtained defines.As this functional group, sulfydryl, disulfide base, halogen group etc. can be enumerated.
As simple function chain-transfer agent (D '), can enumerate: the alkyl sulfhydryls such as n octylmercaptan, n-dodecyl mercaptan, tertiary lauryl mercaptan; Mercaptoacetate; 3-mercaptopropionic acid ester; Thiophenol; Alkyl thioether; α-methylstyrenedimer etc., wherein, preferred alkyl mercaptan.These simple function chain-transfer agents (D ') can be used alone, also can be used together multiple.
When using simple function chain-transfer agent (D '), the usage quantity of Polyfunctional chain transfer agent (D) and simple function chain-transfer agent (D ') needs the relation meeting following formula (2) and formula (3) relative to 100 mass parts monomer mixtures (C).
(in formula (2), (3), a, b and p represent the integer of more than 1 respectively, M
p, n
pand W
prepresent any Polyfunctional chain transfer agent (D in a kind Polyfunctional chain transfer agent (D) respectively
p) molecular weight, functional group number and amount (mass parts), M '
pand W '
prepresent respectively any simple function chain-transfer agent in b kind simple function chain-transfer agent (D ') (D '
p) molecular weight and amount (mass parts)).
Use simple function chain-transfer agent (D ') when, from the view point of plasticity and the shock-resistance of obtained macromolecular compound, the above-mentioned formula of usage quantity demand fulfillment (2) of Polyfunctional chain transfer agent (D) and simple function chain-transfer agent (D ').That is, constant f and the W ' n of whole simple function chain-transfer agents (D ') that uses
0.5the molecular weight that/M ' (wherein, W ', M ' is each simple function chain-transfer agent (D ') and amount (mass parts)) and (hereinafter referred to as " constant f ' ") add up to more than 0.0015 and less than 0.0045.When using simple function chain-transfer agent (D ') of W ' mass parts molecular weight M ' relative to 100 mass parts monomer mixtures (C), the functional group that the generation in radical polymerization increases the chain tra nsfer of end free base thinks that every 100 mass parts monomer mixtures (C) are W '/M ' mole.Therefore, constant f ' refers to the total of the substituent mole number of the simple function chain-transfer agent (D ') that the chain tra nsfer increasing end free base occurs when use 100 mass parts monomer mixture (C) carries out radical polymerization.In addition, the total of constant f and constant f ' refers to the generation when 100 mass parts monomer mixtures (C) being carried out radical polymerization and the total of mole number with the functional group of chain tra nsfer time Polyfunctional chain transfer agent (D) and simple function chain-transfer agent (D ').When the total of constant f and constant f ' is less than 0.0015, the plasticity of the macromolecular compound obtained reduces, and on the other hand, when being greater than 0.0045, shock-resistance reduces.The total of constant f and constant f ' is preferably the scope of 0.0020 ~ 0.0040, is more preferably the scope of 0.0025 ~ 0.0035.
In addition, when using simple function chain-transfer agent (D '), from the view point of plasticity and the shock-resistance of obtained macromolecular compound, the above-mentioned formula of usage quantity demand fulfillment (3) of Polyfunctional chain transfer agent (D) and simple function chain-transfer agent (D ').That is, constant f ' and the ratio of f need to be less than 1.This means that Propagating Radical end in radical polymerization can not exceed the movement of Propagating Radical end to Polyfunctional chain transfer agent (D) to the movement in simple function chain-transfer agent (D ').Preferably constant f ' is less than 0.8 with the ratio of constant f further, is more preferably less than 0.5.
The polymerization starter (E) used in manufacture method of the present invention is as long as can cause the polymerization starter of radical polymerization at the polymerization temperature, then be not particularly limited, can enumerate such as: Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 1,1-azo two (1-cyclohexanenitrile), 2, two (the 4-methoxyl group-2 of 2 '-azo, 4-methyl pentane nitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 2, the azo compounds such as the two-2-methylbutyronitriles of 2 '-azo; 1,1-bis(t-butylperoxy) cyclohexane, tertiary hexyl peroxy sec.-propyl monocarbonate, 1, the organo-peroxides etc. such as 1,3,3-tetramethyl butyl peroxy-2-ethylhexanoate, lauroyl peroxide, decoyl superoxide, isobutyryl superoxide.These polymerization starters (E) can be used alone one, also can be used together multiple.
10 hr half-life temperature of polymerization starter (E) are preferably less than 90 DEG C, are more preferably less than 80 DEG C, more preferably less than 70 DEG C.When 10 hr half-life temperature of polymerization starter (E) are more than 90 DEG C, the ratio of the low-molecular-weight polymkeric substance in the macromolecular compound obtained increases, and therefore, there is mold fouling when causing shaping, tendency that the intensity of molding reduces.
The usage quantity of above-mentioned polymerization starter (E) is preferably the scope of 0.001 ~ 0.01 mass parts relative to 100 mass parts monomer mixtures (C).In addition, from the view point of productivity, polymerization stability, be preferably 1.0 × 10 relative to 1 mole of monomer mixture (C)
-6~ 1.0 × 10
-4mole scope, be more preferably 3.0 × 10
-5~ 7.0 × 10
-5mole scope.Polymerization starter is less than 1.0 × 10 relative to the usage quantity of 1 mole of monomer mixture (C)
-6mole time, there is the tendency that speed of response is slow, productivity reduces, the usage quantity of polymerization starter is more than 1.0 × 10
-4mole time, exist be difficult to control polymerization tendency.
Polymerization temperature in the radical polymerization carried out in manufacture method of the present invention is preferably 110 ~ 170 DEG C, is more preferably the scope of 120 ~ 160 DEG C, more preferably the scope of 130 ~ 150 DEG C.When polymerization temperature is lower than 110 DEG C, the viscosity of reaction solution increases, and there is the tendency needing large power in order to mix, when polymerization temperature is more than 170 DEG C, and the tendency that the thermostability that there is the macromolecular compound obtained reduces.
Polymerization time in radical polymerization is preferably the scope of 0.5 ~ 4 hour, is more preferably the scope of 1 ~ 3 hour, more preferably the scope of 1.5 ~ 2.5 hours.When polymerization time is less than 0.5 hour, the requirement of polymerization starter (E) increases, and exists and is difficult to control polyreaction and the tendency being difficult to Molecular regulator amount.On the other hand, constantly little more than 4 at polymerization time, there is the tendency that productivity reduces.
The molecular weight distribution of the macromolecular compound obtained by manufacture method of the present invention is preferably the scope of 1.6 ~ 1.8.When molecular weight distribution is less than 1.6, there is the tendency that plasticity reduces, during more than 1.8, there is the tendency that shock-resistance reduces.
The weight-average molecular weight of the macromolecular compound obtained by manufacture method of the present invention is preferably the scope of 40,000 ~ 100,000, is more preferably the scope of 4.5 ten thousand ~ 80,000, more preferably the scope of 50,000 ~ 60,000.
The transparency of the macromolecular compound obtained by manufacture method of the present invention, plasticity, excellent impact resistance, therefore, useful as various molding.Such as, be shaped by the known melting heating such as injection forming, compression molding, extrusion molding, vacuum forming, the mechanical strength of different shape and the molding of good appearance can be obtained.As the purposes of molding, can enumerate such as: the billboards such as advertising tower, vertical billboard, side billboard (sleeve billboard), lattice window billboard, roof billboard; The display such as display stands, dividing plate, store display plate articles for use; The illumination such as fluorescent lamp shade, situation illuminating cover, lampshade, luminous ceiling, Luminous wall, chandelier articles for use; The in-built articles for use such as pendent lamp, mirror; The building components such as the roof of door, dome, safety window glass, partition wall, stair skirtboard, balcony skirtboard, amusement buildings; Frontal windshield, pilot are with the transfer roller associated member such as sun visor, motorcycle, motorboat windscreen, tinted shade used for buses, automobile side sun visor, rear sun visor, the head wing (ヘ ッ De ウ ィ Application グ), head lamp case, metering watch glasses, rear light cover; The electronic equipment parts such as sound equipment image label, photography hood, TV protective guard, automatic selling-machine; The medical device part such as foster-mother, X-ray part; Equipment associated member such as machinery cover, gauger cover, experimental installation, chi, scale card, viewing window etc.; The optical association parts such as front panel, diffuser plate of liquid crystal protecting sheet, light guiding plate, light guiding film, Fresnel lens, biconvex lens, various indicating meter; The traffic associated members such as road sign, signpost, curved mirror, soundproof wall; The film structural component such as surfacing, label film of automobile inside surfacing, mobile phone; Family's electrical article parts such as the top board of the cap material of washing machine or control panel, pot for cooking rice; And greenhouse, large-scale tank, case tank, dial plate, bathtub, sanitary apparatus, mat applying, game part, toy, welding time face's protection face shield etc.
Embodiment
Below, by embodiment etc., the present invention is specifically described, but the invention is not restricted to these embodiments.
(making of test film)
(Corporation Japan Steel Works manufactures to use injection machine, J75SAV), H1/H2/HV/H3/MH=200/210/230/250/250 DEG C, under the condition of die temperature 60 DEG C, injection forming is carried out to the macromolecular compound obtained in embodiment, comparative example, makes test film thus.Use this test film, measure the physics value of molding.
The physics value of the macromolecular compound obtained in embodiment 1 ~ 4 and comparative example 1 ~ 5 and the molding made by these macromolecular compounds is measured by following method.
(weight-average molecular weight, molecular weight distribution)
Utilization possesses chromatographic column, and (TOSOH Co., Ltd manufactures, TSKgelSUPERHZM-M and TSKguardcolumnSUPERHZ-H) and (the TOSOH Co., Ltd's manufacture of differential refraction rate meter, RI-8020) (TOSOH Co., Ltd manufactures gel permeation chromatograph, HLC-8020), 40 DEG C, obtain weight-average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the macromolecular compound obtained in embodiment, comparative example in tetrahydrofuran solvent with polystyrene conversion.
(MFR)
Based on JISK7210, under the condition of temperature 230 DEG C, load 37.3N, measure the MFR of the macromolecular compound obtained in embodiment, comparative example.
(shock-resistance)
Use the test film of the 80mm × 10mm × 4mm made by the macromolecular compound obtained in embodiment, comparative example, evaluated by the flexural strength measured based on JISK7203.
(transmittance)
To make the mode that path length is 200mm cut test film from the flat board of thickness 6mm, measure the transmissivity of light under path length 200mm of wavelength 550nm.
Below, methyl methacrylate is expressed as MMA, methyl acrylate is expressed as MA, Diisopropyl azodicarboxylate is expressed as AIBN, n octylmercaptan is expressed as n-OM, tetramethylolmethane tetrathio propionic ester is expressed as PETP, ethylene glycol bis mercaptoacetate is expressed as EGTG, by 1,2,3-propane three mercaptan is expressed as PTT, and ethylene glycol dimethacrylate is expressed as EGDMA.In addition, mentioned reagent is pure pharmaceutical worker's industry company manufacture with light.
(embodiment 1)
In the polymerization reactor possessing agitator, supply comprises the monomer mixture (C) (1 molar part), the AIBN0.007 mass parts (4.2 × 10 as polymerization starter (E) that are made up of MMA89 mass parts (0.87 molar part) and MA11 mass parts (0.13 molar part) continuously
-5molar part), as the mixed solution of the PETP0.66 mass parts of Polyfunctional chain transfer agent (D).Under this condition, constant f is 0.0029.These materials are implemented mass polymerization under polymerization temperature 140 DEG C, the mean residence time condition of 2 hours, extracts polymerization liquid out continuously.Then, the reaction mixture extracted out from polymerization reactor is heated to 230 DEG C, is supplied to the twin screw extruder that control is 260 DEG C.In this twin screw extruder, be separated the volatile component of removing using unreacted monomer as principal constituent, by polymer-extruded one-tenth material strip shape.This material strip tablets press is cut, obtains granular macromolecular compound.The evaluation result of obtained macromolecular compound is shown in table 1.
(embodiment 2)
Use EGTG0.44 mass parts replaces the PETP in embodiment 1 as Polyfunctional chain transfer agent (D), in addition, operate similarly to Example 1, obtain granular macromolecular compound.In addition, under this condition, constant f is 0.0030.The evaluation result of obtained macromolecular compound is shown in table 1.
(embodiment 3)
By the quantitative change of the PETP in embodiment 1 more 0.52 mass parts, and be used as the n-OM0.13 mass parts of simple function chain-transfer agent (D ') in the lump, in addition, operate similarly to Example 1, obtain granular macromolecular compound.In addition, under this condition, constant f is 0.0023, and constant f ' is 0.0009, and constant f and constant f ' sum are 0.0032.In addition, the ratio (f '/f) of constant f ' and constant f is 0.39.The evaluation result of this obtained macromolecular compound is shown in table 1.
(embodiment 4)
Use PTT0.22 mass parts replaces the PETP in embodiment 1 as Polyfunctional chain transfer agent (D), in addition, operate similarly to Example 1, obtain granular macromolecular compound.In addition, under this condition, constant f is 0.0027.The evaluation result of obtained macromolecular compound is shown in table 1.
(comparative example 1)
Use the PETP that n-OM0.44 mass parts replaces as simple function chain-transfer agent (D ') in embodiment 1, in addition, operate similarly to Example 1, obtain granular macromolecular compound.In addition, under this condition, constant f ' is 0.0030.The evaluation result of obtained macromolecular compound is shown in table 1.
(comparative example 2)
Use EGTG0.16 mass parts replaces the PETP in embodiment 1 as Polyfunctional chain transfer agent (D), in addition, operate similarly to Example 1, obtain granular macromolecular compound.In addition, under this condition, constant f is 0.0011.The evaluation result of obtained macromolecular compound is shown in table 1.
(comparative example 3)
Use after the quantitative change of the PETP in embodiment 1 more 1.1 mass parts, in addition, operate similarly to Example 1, obtain granular macromolecular compound.In addition, under this condition, constant f is 0.0049.The evaluation result of obtained macromolecular compound is shown in table 1.
(comparative example 4)
Use EGTG0.22 mass parts replaces the PETP in embodiment 1 as Polyfunctional chain transfer agent (D), and use n-OM0.35 mass parts as simple function chain-transfer agent (D ') in the lump, in addition, operate in the same manner as comparative example 1, obtain granular macromolecular compound.In addition, under this condition, constant f is 0.0015, and constant f ' is 0.0024, and constant f and constant f ' sum are 0.0039.In addition, the ratio (f '/f) of constant f ' and constant f is 1.6.The evaluation result of obtained macromolecular compound is shown in table 1.
(comparative example 5)
Use by MMA89 mass parts (0.87 molar part), MA11 mass parts (0.13 molar part) and EGDMA0.10 mass parts (5.0 × 10
-4molar part) monomer mixture (C) (1.0005 molar part) that forms, EGTG0.70 mass parts is used to replace PETP as Polyfunctional chain transfer agent (D), in addition, operate similarly to Example 1, obtain granular macromolecular compound.In addition, under this condition, constant f is 0.0047.The evaluation result of obtained macromolecular compound is shown in table 1.
Known, comparative examples 1 different from the present invention in manufacturing only utilizing simple function chain-transfer agent (D '), although demonstrate the MFR equal with embodiment, flexural strength is poor.
In addition we know, the usage quantity of Polyfunctional chain transfer agent (D) is lower than the comparative example 2 of the scope specified by formula (1) compared with embodiment, although flexural strength is excellent, MFR significantly reduces, poor fluidity.
In addition we know, the usage quantity of Polyfunctional chain transfer agent (D) exceedes the comparative example 3 of the scope specified by formula (1) compared with embodiment, although MFR is high, flexural strength is poor.
In addition we know, the usage rate of Polyfunctional chain transfer agent (D) and simple function chain-transfer agent (D ') do not meet formula (3) although comparative example 4 demonstrate the MFR value equal with embodiment, flexural strength is poor.
In addition we know, the usage quantity of Polyfunctional chain transfer agent (D) exceed the scope that specified by formula (1) and comparative example 5 containing polyfunctional monomer in monomer mixture (C) compared with embodiment, molecular weight distribution is wide, flexural strength and ght transmission rate variance.
As mentioned above, both the MFR of the macromolecular compound obtained by manufacture method of the present invention and flexural strength are excellent, therefore, and mobility and excellent impact resistance.Thus, the macromolecular compound of the application of the invention, can obtain the molding of mechanical strength and good appearance.
Claims (4)
1. the manufacture method of a macromolecular compound, by methacrylic ester (A) and the monomer mixture (C) that can form with the vinyl monomer (B) of methacrylic ester (A) copolymerization and more than one Polyfunctional chain transfer agents (D), radical polymerization is carried out under the existence of more than one simple function chain-transfer agents (D ') and polymerization starter (E), the feature of described manufacture method is, described Polyfunctional chain transfer agent (D) and described simple function chain-transfer agent (D ') meet the relation of following formula (2) and formula (3) relative to the usage quantity of monomer mixture (C) described in 100 mass parts,
(in formula (2), (3), a, b and p represent the integer of more than 1 respectively, M
p, n
pand W
prepresent any Polyfunctional chain transfer agent (D in a kind Polyfunctional chain transfer agent (D) respectively
p) molecular weight, functional group number and amount (mass parts), M '
pand W '
prepresent respectively any simple function chain-transfer agent in b kind simple function chain-transfer agent (D ') (D '
p) molecular weight and amount (mass parts)).
2. the manufacture method of macromolecular compound as claimed in claim 1, is characterized in that, use described polymerization starter (E) in the scope of 0.001 ~ 0.01 mass parts.
3. a macromolecular compound, it is obtained by the manufacture method described in claim 1 or 2.
4. a molding, it is made up of macromolecular compound according to claim 3.
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| PCT/JP2013/056959 WO2013141106A1 (en) | 2012-03-22 | 2013-03-13 | Polymer compound, method for producing same, and molded article of same |
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| JP2010235648A (en) * | 2009-03-30 | 2010-10-21 | Toray Ind Inc | Gum-containing thermoplastic resin composition |
-
2013
- 2013-03-13 WO PCT/JP2013/056959 patent/WO2013141106A1/en active Application Filing
- 2013-03-13 JP JP2014506167A patent/JP6231980B2/en not_active Expired - Fee Related
- 2013-03-13 CN CN201380015726.6A patent/CN104203990B/en not_active Expired - Fee Related
- 2013-03-21 TW TW102109964A patent/TWI551614B/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102833A (en) * | 1993-11-05 | 1995-05-24 | 住友化学工业株式会社 | Process for production of methacrylate polymers |
| CN1605593A (en) * | 2003-09-08 | 2005-04-13 | 三菱丽阳株式会社 | Production method of (methyl) acrylic acid polymer |
| CN101006106A (en) * | 2004-11-08 | 2007-07-25 | Lg化学株式会社 | Method for producing an (meth)acrylate syrup |
| CN101939391A (en) * | 2007-12-28 | 2011-01-05 | E.I.内穆尔杜邦公司 | Thermally and actinically curable adhesive composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201343680A (en) | 2013-11-01 |
| TWI551614B (en) | 2016-10-01 |
| WO2013141106A1 (en) | 2013-09-26 |
| CN104203990A (en) | 2014-12-10 |
| JPWO2013141106A1 (en) | 2015-08-03 |
| JP6231980B2 (en) | 2017-11-15 |
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