KR20240043679A - Styrenic copolymer, feed liquid, and method for producing styrenic copolymer - Google Patents
Styrenic copolymer, feed liquid, and method for producing styrenic copolymer Download PDFInfo
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- KR20240043679A KR20240043679A KR1020230115659A KR20230115659A KR20240043679A KR 20240043679 A KR20240043679 A KR 20240043679A KR 1020230115659 A KR1020230115659 A KR 1020230115659A KR 20230115659 A KR20230115659 A KR 20230115659A KR 20240043679 A KR20240043679 A KR 20240043679A
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- KR
- South Korea
- Prior art keywords
- group
- styrene
- less
- based copolymer
- copolymer
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- 239000007788 liquid Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 229920006249 styrenic copolymer Polymers 0.000 title 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 131
- 229920001577 copolymer Polymers 0.000 claims abstract description 91
- 239000000178 monomer Substances 0.000 claims abstract description 60
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical group CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 34
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 230000008859 change Effects 0.000 claims abstract description 12
- 125000005843 halogen group Chemical group 0.000 claims abstract description 11
- 238000012360 testing method Methods 0.000 claims abstract description 9
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 238000010551 living anionic polymerization reaction Methods 0.000 claims abstract description 8
- 238000002834 transmittance Methods 0.000 claims abstract description 8
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 62
- 239000002904 solvent Substances 0.000 claims description 20
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 18
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 claims description 16
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 16
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 8
- 239000012527 feed solution Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 35
- 238000000034 method Methods 0.000 description 31
- -1 1-ethyl-2-methylpropyl group Chemical group 0.000 description 26
- 229920000642 polymer Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
- 229920005989 resin Polymers 0.000 description 22
- 239000000203 mixture Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical class C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 229920001400 block copolymer Polymers 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000010550 living polymerization reaction Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000005917 3-methylpentyl group Chemical group 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- 125000005926 1,2-dimethylbutyloxy group Chemical group 0.000 description 1
- 125000005923 1,2-dimethylpropyloxy group Chemical group 0.000 description 1
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 description 1
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-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
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-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
- XKMDZVINHIFHLY-UHFFFAOYSA-N 1-ethenyl-3,5-dimethylbenzene Chemical compound CC1=CC(C)=CC(C=C)=C1 XKMDZVINHIFHLY-UHFFFAOYSA-N 0.000 description 1
- XHUZSRRCICJJCN-UHFFFAOYSA-N 1-ethenyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1 XHUZSRRCICJJCN-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
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-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
- 125000003858 2-ethylbutoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])O*)C([H])([H])C([H])([H])[H] 0.000 description 1
- ZIXLDMFVRPABBX-UHFFFAOYSA-N 2-methylcyclopentan-1-one Chemical compound CC1CCCC1=O ZIXLDMFVRPABBX-UHFFFAOYSA-N 0.000 description 1
- 125000005924 2-methylpentyloxy group Chemical group 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- 125000005925 3-methylpentyloxy group Chemical group 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-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
- NTFPWILHWUWYEZ-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-2-tert-butyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1CCCC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C NTFPWILHWUWYEZ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-UHFFFAOYSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- ICKXMDGNIZPYRS-UHFFFAOYSA-N [Li]CCCCCC[Li] Chemical compound [Li]CCCCCC[Li] ICKXMDGNIZPYRS-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000005921 isopentoxy group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- YNXURHRFIMQACJ-UHFFFAOYSA-N lithium;methanidylbenzene Chemical compound [Li+].[CH2-]C1=CC=CC=C1 YNXURHRFIMQACJ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 238000004806 packaging method and process 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
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001470 polyketone Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- TURAMGVWNUTQKH-UHFFFAOYSA-N propa-1,2-dien-1-one Chemical group C=C=C=O TURAMGVWNUTQKH-UHFFFAOYSA-N 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
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
-
- 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
- C08F2438/00—Living radical polymerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
내후성이 우수한 스티렌계 공중합체와, 스티렌계 공중합체를 제조하기 위한 공급액과, 공급액을 이용하여 제조하는 스티렌계 공중합체의 제조 방법을 제공하는 것을 목적으로 한다.
목적은 리빙 음이온 중합법에 의해 얻어지는 α-메틸스티렌 단위와 하기 일반식(1)로 표시되는 비닐 방향족 단량체 단위를 포함하는 공중합체로서, 선샤인 웨더 미터에 의한 내후성 시험에 있어서 조사 시간 1000시간 후의 전 광선투과율의 변화량이 5% 이하, 또 황색도의 변화량이 5 이하인 스티렌계 공중합체에 의해 달성되었다.
[화학식 1]
(화학식 1에 있어서, R1은 수소 원자, 탄소수 2 이상의 알킬기 또는 페닐기를 나타내고, R2는 수소 원자, 할로겐 원자, 히드록실기, C1-C6 알킬기, C1-C6 알콕시기, 카르복실기, 또는 할로 C1-C6 알킬기를 나타낸다.)The purpose is to provide a styrene-based copolymer with excellent weather resistance, a supply liquid for producing the styrene-based copolymer, and a method for producing the styrene-based copolymer using the supply solution.
The object is a copolymer containing an α-methylstyrene unit obtained by living anionic polymerization and a vinyl aromatic monomer unit represented by the following general formula (1), which has a pre-irradiation value of 1000 hours in a weather resistance test using a Sunshine Weather Meter. This was achieved using a styrene-based copolymer with a change in light transmittance of 5% or less and a change in yellowness of 5 or less.
[Formula 1]
(In Formula 1, R 1 represents a hydrogen atom, an alkyl group having 2 or more carbon atoms, or a phenyl group, and R 2 represents a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a carboxyl group, or a halo C1 -C6 represents an alkyl group.)
Description
본 발명은 내후성이 우수한 스티렌계 공중합체, 스티렌계 공중합체를 제조하기 위한 공급액, 및 공급액을 사용하여 제조하는 스티렌계 공중합체의 제조 방법에 관한 것이다.The present invention relates to a styrene-based copolymer with excellent weather resistance, a feed liquid for producing a styrene-based copolymer, and a method for producing a styrene-based copolymer using the feed liquid.
스티렌계 수지는 투명성, 강성, 치수 안정성 등의 재료 성능이 우수할 뿐만 아니라 사출 성형, 연신 시트, 필름, 발포 시트, 발포 보드, 블로우 성형 등의 다양한 성형 가공이 가능한 것, 또 스티렌계 수지의 대부분은 라디칼 중합법에 의한 괴상 중합, 높은 단량체 농도에 의한 용액 중합, 현탁 중합, 유화 중합에 의해 대량으로 저렴하게 제조할 수 있으므로 매우 다종 다양한 용도로 이용되고 있다.Styrene-based resin not only has excellent material performance such as transparency, rigidity, and dimensional stability, but is also capable of various molding processes such as injection molding, stretched sheet, film, foam sheet, foam board, and blow molding. In addition, most of the styrene-based resins Since it can be manufactured inexpensively in large quantities through bulk polymerization using radical polymerization, solution polymerization using high monomer concentration, suspension polymerization, and emulsion polymerization, it is used for a wide variety of purposes.
스티렌계 수지는 리빙 음이온 중합에 의해서도 제조할 수 있지만, 이 리빙 음이온 중합은 원료에 포함되는 불순물의 영향을 받기 쉬운 중합법이다(특허문헌 1). 특히, 활성 음이온은 물, 알데히드, 케톤, 알콜 등의 극성 물질과 반응하기 쉬운 것으로 알려져 있다. 극성 물질이 미량이라도 음이온 중합의 반응계 내에 존재하면, 활성 음이온은 극성 물질과 반응하여 안정적인 결합을 형성하므로, 중합이 정지하는 문제가 발생한다. 이 때문에, 리빙 음이온 중합을 실시할 때에는, 원료 중의 극성 물질을 줄이고, 반응계 내로의 극성 물질의 혼입을 가능한 한 억제해야 한다.Styrene-based resin can also be manufactured by living anionic polymerization, but this living anionic polymerization is a polymerization method that is easily affected by impurities contained in raw materials (Patent Document 1). In particular, active anions are known to easily react with polar substances such as water, aldehydes, ketones, and alcohols. If even a trace amount of a polar substance is present in the anionic polymerization reaction system, the active anion reacts with the polar substance to form a stable bond, resulting in the polymerization stopping. For this reason, when carrying out living anionic polymerization, the polar substances in the raw materials must be reduced and the mixing of polar substances into the reaction system must be suppressed as much as possible.
이상과 같은 문제점을 해결하는 α-메틸스티렌의 정제 방법으로서, 염기성 물질의 존재하에 α-메틸스티렌 중에 포함되는 극성 물질을 반응시키고, 반응에 의해 발생하는 저비점의 부생물을 극성 물질의 반응물과 분리함으로써, α-메틸스티렌을 정제하는 방법이 제안되어 있다(예를 들면, 특허문헌 2).As a method for purifying α-methylstyrene that solves the above problems, polar substances contained in α-methylstyrene are reacted in the presence of a basic substance, and low-boiling by-products generated by the reaction are separated from the polar substance reactants. By doing so, a method for purifying α-methylstyrene has been proposed (for example, patent document 2).
최근, 수지의 유효 이용화가 중요시되어, 각종 리사이클법이 성립하여 시행되어 왔다. 수지가 리사이클, 리워크, 리유즈할 수 있다는 것은, 향후 수지 시장에서는 필수 불가결한 요구가 된다 .In recent years, effective utilization of resins has become important, and various recycling laws have been established and implemented. The fact that resin can be recycled, reworked, and reused will become an essential requirement in the future resin market.
향후 개발되는 수지 재료는, 수회의 용융 가공을 거쳐도 고분자쇄의 절단에 의한 분자량의 저하나 단량체의 발생이 거의 일어나지 않고, 또한 장기 사용에 의한 물성의 내후 열화가 적고, 유효하게 재이용할 수 있는 수지인 것이 필요하다.Resin materials that will be developed in the future rarely experience a decrease in molecular weight or generate monomers due to cutting of the polymer chain even after several rounds of melt processing, and also have little weathering deterioration of physical properties due to long-term use, and can be effectively reused. It needs to be resin.
이 때문에, 지금까지의 스티렌계 공중합체보다 용융 안정성이 높고, 내후성이 우수한 수지 재료의 개발이 요구되고 있다.For this reason, there is a demand for the development of a resin material that has higher melt stability and excellent weather resistance than conventional styrene-based copolymers.
본 발명은 중합에 제공하는 공급액 중의 특정 화합물의 함유량을 제어함으로써, 내후성이 우수한 스티렌계 공중합체와, 스티렌계 공중합체를 제조하기 위한 공급액과, 공급액을 이용하여 제조하는 스티렌계 공중합체의 제조 방법을 제공하는 것을 목적으로 한다.The present invention provides a styrene-based copolymer with excellent weather resistance by controlling the content of a specific compound in the feed liquid used for polymerization, a feed liquid for producing the styrene-based copolymer, and a method for producing a styrene-based copolymer using the feed liquid. The purpose is to provide.
본 발명자는 상기 과제를 해결하기 위해 예의 연구를 거듭한 결과, 중합에 제공하는 공급액 중에 미량 함유되는 특정 화합물의 함유량을 특정의 범위로 제어함으로써, 내후성이 우수한 스티렌계 공중합체가 얻어지는 것을 발견하여, 본 발명의 완성에 이르렀다.As a result of extensive research to solve the above problems, the present inventor discovered that a styrene-based copolymer with excellent weather resistance can be obtained by controlling the content of a specific compound contained in trace amounts in the feed liquid used for polymerization to a specific range, The present invention has been completed.
즉, 본 발명은 이하의 여러가지 양태를 갖는다.That is, the present invention has the following various aspects.
(1) 리빙 음이온 중합법에 의해 얻어지는, α-메틸스티렌 단위와 하기 일반식(1)로 표시되는 비닐 방향족 단량체 단위를 포함하는 공중합체로서, 선샤인 웨더 미터에 의한 내후성 시험에 있어서 조사 시간 1000시간 후의 전 광선투과율의 변화량이 5% 이하, 또 황색도의 변화량이 5 이하인 스티렌계 공중합체.(1) A copolymer containing an α-methylstyrene unit and a vinyl aromatic monomer unit represented by the following general formula (1), obtained by living anionic polymerization, and having an irradiation time of 1000 hours in a weather resistance test using a Sunshine Weather Meter. A styrene-based copolymer with a change in total light transmittance of 5% or less and a change in yellowness of 5 or less.
[화학식 1][Formula 1]
(화학식 1에 있어서, R1은 수소 원자, 탄소수 2 이상의 알킬기 또는 페닐기를 나타내고, R2는 수소 원자, 할로겐 원자, 히드록실기, C1-C6 알킬기, C1-C6 알콕시기, 카르복실기, 또는 할로 C1-C6 알킬기를 나타낸다.)(In Formula 1, R 1 represents a hydrogen atom, an alkyl group having 2 or more carbon atoms, or a phenyl group, and R 2 represents a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a carboxyl group, or a halo C1 -C6 represents an alkyl group.)
(2) 상기 공중합체 중의 α-메틸스티렌 단위의 함유량이 10~65 질량%이고, 중량 평균 분자량(Mw)은 Mw=5만~30만의 범위이며, 중량 평균 분자량(Mw)과 수평균 분자량(Mn)의 비(Mw/Mn)가 1.6~2.5의 범위에 있고, 또한 잔존하는 단량체 및 중합 용매의 총 질량이 500ppm 이하인, 상기 (1)에 기재된 스티렌계 공중합체.(2) The content of α-methylstyrene units in the copolymer is 10 to 65% by mass, the weight average molecular weight (Mw) is in the range of Mw = 50,000 to 300,000, and the weight average molecular weight (Mw) and number average molecular weight ( The styrene-based copolymer according to (1) above, wherein the ratio (Mw/Mn) of Mn is in the range of 1.6 to 2.5, and the total mass of the remaining monomer and polymerization solvent is 500 ppm or less.
(3) 단량체 및 중합 용매로 이루어진 스티렌계 공중합체를 제조하기 위한 공급액으로서, 상기 공급액 중의 아세토닐아세톤의 함유량이 2ppm 이하, 벤즈알데히드의 함유량이 10ppm 이하, 또 페닐아세틸렌의 함유량이 15ppm 이하인 스티렌계 공중합체를 제조하기 위한 공급액.(3) A feed liquid for producing a styrene-based copolymer consisting of a monomer and a polymerization solvent, wherein the feed liquid contains an acetonylacetone content of 2 ppm or less, a benzaldehyde content of 10 ppm or less, and a styrene-based copolymer containing a phenylacetylene content of 15 ppm or less. Feed liquid for producing the composite.
(4) 단량체 및 중합 용매로 이루어진 공급액에 의한 스티렌계 공중합체의 제조 방법으로서, 상기 공급액 중의 아세토닐아세톤의 함유량이 2ppm 이하, 벤즈알데히드의 함유량이 10ppm 이하, 또 페닐아세틸렌의 함유량이 15ppm 이하인 공급액을 사용하여 제조하는 스티렌계 공중합체의 제조 방법.(4) A method for producing a styrene-based copolymer using a feed liquid consisting of a monomer and a polymerization solvent, wherein the feed liquid has an acetonylacetone content of 2 ppm or less, a benzaldehyde content of 10 ppm or less, and a phenylacetylene content of 15 ppm or less. A method for producing a styrene-based copolymer using:
본 발명의 스티렌계 공중합체는, 중합에 제공하는 공급액 중의 특정 화합물의 함유량을 특정 범위로 제어함으로써, 내후성이 우수한 특성을 갖는다. 또한, 본 발명의 스티렌계 공중합체를 함유하는 성형품은 가온용 식품 용기, 주택용 부품, 자동차 실내용 부품, 광학용 부품으로서 매우 적합하게 사용할 수 있다.The styrene-based copolymer of the present invention has excellent weather resistance by controlling the content of a specific compound in the supply liquid used for polymerization to a specific range. Additionally, molded articles containing the styrene-based copolymer of the present invention can be suitably used as food containers for warming, parts for houses, parts for automobile interiors, and parts for optical purposes.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
〈스티렌계 공중합체〉〈Styrene-based copolymer〉
본 발명의 스티렌계 공중합체에 대해 설명한다. 본 발명에 있어서의 스티렌계 공중합체는, 중합에 제공하는 공급액 중의 특정 화합물의 함유량을 제어함으로써 얻어지는 공중합체로서, α-메틸스티렌 단위와 하기 식(1)로 표시되는 비닐 방향족 단량체 단위를 구성 단위로서 포함하고, 선샤인 웨더 미터에 의한 내후성 시험에 있어서 조사 시간 1000시간 후의 전 광선투과율의 변화량이 5% 이하, 또 황색도의 변화량이 5 이하의 스티렌계 공중합체이다. 이에 의해, 내후성이 우수한 특성을 갖는다. 또한, 내열성, 용융 안정성, 성형성, 강도, 강성도 우수한 특성을 갖는다.The styrene-based copolymer of the present invention will be described. The styrene-based copolymer in the present invention is a copolymer obtained by controlling the content of a specific compound in the feed liquid used for polymerization, and consists of an α-methylstyrene unit and a vinyl aromatic monomer unit represented by the following formula (1) as structural units. It is a styrene-based copolymer in which the change in total light transmittance after 1000 hours of irradiation is 5% or less and the change in yellowness is 5 or less in a weather resistance test using a Sunshine Weather Meter. As a result, it has excellent weather resistance properties. In addition, it has excellent heat resistance, melt stability, formability, strength, and rigidity.
[화학식 2][Formula 2]
(화학식 2에 있어서, R1은 수소 원자, 탄소수 2 이상의 알킬기 또는 페닐기를 나타내고, R2는 수소 원자, 할로겐 원자, 히드록실기, C1-C6 알킬기, C1-C6 알콕시기, 카르복실기, 또는 할로 C1-C6 알킬기를 나타낸다.)(In Formula 2, R 1 represents a hydrogen atom, an alkyl group having 2 or more carbon atoms, or a phenyl group, and R 2 represents a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a carboxyl group, or a halo C1 -C6 represents an alkyl group.)
본 명세서에서 사용하는 용어 「C1-C6알킬기」란, 탄소수가 1 내지 6개의 직쇄상 또는 분지상 알킬기를 의미하며, 구체적으로는 메틸기, 에틸기, n-프로필기, iso-프로필기, n-부틸기, iso-부틸기, sec-부틸기, tert-부틸기, n-펜틸기, 1,1-디메틸프로필기, 1,2-디메틸프로필기, 2,2-디메틸프로필기, 1-에틸프로필기, n-헥실기, 1-에틸-2-메틸프로필기, 1,1,2-트리메틸프로필기, 1-에틸부틸기, 1-메틸부틸기, 2-메틸부틸기, 1,1-디메틸부틸기, 1,2-디메틸부틸기, 2,2-디메틸부틸기, 1,3-디메틸부틸기, 2,3-디메틸부틸기, 2-에틸부틸기, 2-메틸펜틸기, 3-메틸펜틸기 등을 들 수 있고, 바람직하게는 메틸기, 에틸기, n-프로필기, iso-프로필기, n-부틸기, iso-부틸기, sec-부틸기, tert-부틸기, n-펜틸기, n-헥실기 등을 들 수 있다.The term “C1-C6 alkyl group” used in this specification refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms, specifically methyl group, ethyl group, n-propyl group, iso-propyl group, and n-butyl group. group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group group, n-hexyl group, 1-ethyl-2-methylpropyl group, 1,1,2-trimethylpropyl group, 1-ethylbutyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethyl Butyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, 3-methyl pentyl group, etc. are mentioned, and preferably methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, etc. can be mentioned.
본 명세서에서 사용하는 용어 「C1-C6알콕시기」란, 상기에서 정의된 「C1-C6알킬기」가 결합된 옥시기를 의미하며, 구체적으로는 메톡시기, 에톡시기, n-프로폭시 기, iso-프로폭시기, n-부톡시기, iso-부톡시기, sec-부톡시기, tert-부톡시기, n-펜틸옥시기, iso-펜틸옥시기, sec-펜틸옥시기, n-헥실옥시기, iso-헥실옥시기, 1,1-디메틸프로폭시기, 1,2-디메틸프로폭시기, 2,2-디메틸프로폭시기, 2-메틸부톡시기, 1-에틸-2-메틸프로폭시기, 1,1,2-트리메틸프로폭시기, 1,1-디메틸부톡시기, 1,2-디메틸부톡시기, 2,2-디메틸부톡시기, 2,3-디메틸부톡시기, 1,3-디메틸부톡시기, 2-에틸부톡시기, 2-메틸펜틸옥시기, 3-메틸펜틸옥시기 등을 들 수 있고, 바람직하게는 메톡시기, 에톡시기, n-프로폭시기, iso-프로폭시기이고, 보다 바람직하게는 메톡시기,에톡시기이다.The term “C1-C6 alkoxy group” used in this specification refers to an oxy group to which the “C1-C6 alkyl group” defined above is bonded, and specifically, methoxy group, ethoxy group, n-propoxy group, iso- Propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, iso-pentyloxy group, sec-pentyloxy group, n-hexyloxy group, iso- Hexyloxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 2,2-dimethylpropoxy group, 2-methylbutoxy group, 1-ethyl-2-methylpropoxy group, 1, 1,2-trimethylpropoxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2 -Ethylbutoxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, etc. are mentioned, preferably methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, more preferably They are methoxy group and ethoxy group.
본 명세서에서 사용하는 용어 「탄소수 2 이상의 알킬기」란, 탄소수가 2개 이상(바람직하게는 2 내지 6개)의 직쇄상 또는 분지상의 알킬기를 의미하고, 구체적으로는 에틸기, n-프로필기, iso-프로필기, n-부틸기, iso-부틸기, sec-부틸기, tert-부틸기, n-펜틸기, 1,1-디메틸프로필기, 1,2-디메틸프로필기, 2,2-디메틸프로필기, 1-에틸프로필기, n-헥실기, 1-에틸-2-메틸프로필기, 1,1,2-트리메틸프로필기, 1-에틸부틸기, 1-메틸부틸기, 2-메틸부틸기, 1,1-디메틸부틸기, 1,2-디메틸부틸기, 2,2-디메틸부틸기, 1,3-디메틸부틸기, 2,3-디메틸부틸기, 2-에틸부틸기, 2-메틸펜틸기, 3-메틸펜틸기 등을 들 수 있고, 바람직하게는 에틸기, n-프로필기, iso-프로필기, n-부틸기, iso-부틸기, sec-부틸기, tert-부틸기, n-펜틸기 등을 들 수 있다.The term “alkyl group having 2 or more carbon atoms” used in this specification refers to a straight-chain or branched alkyl group having 2 or more carbon atoms (preferably 2 to 6 carbon atoms), and specifically includes ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2- Dimethylpropyl group, 1-ethylpropyl group, n-hexyl group, 1-ethyl-2-methylpropyl group, 1,1,2-trimethylpropyl group, 1-ethylbutyl group, 1-methylbutyl group, 2-methyl Butyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 2 -methylpentyl group, 3-methylpentyl group, etc., preferably ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group. , n-pentyl group, etc.
본 명세서에서 사용하는 용어 「할로겐 원자」란, 불소 원자, 염소 원자, 브롬 원자, 요오드 원자 등을 의미한다.The term “halogen atom” used in this specification means a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.
본 명세서에서 사용하는 용어 「할로 C1-C6 알킬기」란, 상기에서 정의된 「C1-C6 알킬기」에 상기에서 정의된 「할로겐 원자」가 결합된 기를 의미한다.The term “halo C1-C6 alkyl group” used in this specification refers to a group in which a “halogen atom” as defined above is bonded to a “C1-C6 alkyl group” as defined above.
본 발명에서 사용하는 비닐 방향족 단량체란, 예를 들면, 스티렌, p-메틸스티렌, m-메틸스티렌, o-메틸스티렌, 2,4-디메틸스티렌, 2,5-디메틸스티렌, 3,4-디메틸스티렌, 3,5-디메틸스티렌, p-에틸스티렌, m-에틸스티렌, o-에틸스티렌 등의 알킬 치환 스티렌류, p-히드록시스티렌, p-메톡시스티렌, p-클로로스티렌, 1,1-디페닐에틸렌 등의 그 외의 스티렌 유도체를 들 수 있다. 바람직한 비닐 방향족 단량체는 스티렌이다. 이들 비닐 방향족 단량체는, 각 1종류씩 사용해도 되고, 2종류 이상을 혼합하여 사용해도 된다. 본 발명에 있어서, 가장 바람직한 조합은 α-메틸스티렌과 스티렌의 조합이다.Vinyl aromatic monomers used in the present invention include, for example, styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, and 3,4-dimethyl. Alkyl-substituted styrenes such as styrene, 3,5-dimethylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, p-hydroxystyrene, p-methoxystyrene, p-chlorostyrene, 1,1 -Other styrene derivatives such as diphenylethylene can be mentioned. A preferred vinyl aromatic monomer is styrene. These vinyl aromatic monomers may be used one type each, or two or more types may be mixed and used. In the present invention, the most preferred combination is the combination of α-methylstyrene and styrene.
스티렌계 공중합체 중에 포함되는 α-메틸스티렌 단위의 함유량은, 바람직하게는 10~65질량%(이하, wt%라고도 함), 보다 바람직하게는, 12~63wt%, 더 바람직하게는 15~60wt%이다. α-메틸스티렌 단위가 10wt% 이상이면 실사용상 내열성 향상의 효과가 보다 크고, 65wt% 이하이면 용융 성형 가공시의 열안정성이 보다 높아지며, 성형시의 가스의 발생을 보다 억제할 수 있고, 또한, 수지 중의 분해에 수반되는 단량체 성분량을 보다 억제할 수도 있다.The content of α-methylstyrene units contained in the styrene-based copolymer is preferably 10 to 65 wt% (hereinafter also referred to as wt%), more preferably 12 to 63 wt%, and still more preferably 15 to 60 wt. %am. If the α-methylstyrene unit is 10 wt% or more, the effect of improving heat resistance in actual use is greater, and if it is 65 wt% or less, the thermal stability during melt molding processing is higher, and the generation of gas during molding can be further suppressed. The amount of monomer components accompanying decomposition in the resin can also be further suppressed.
상기 단량체 이외에 본 발명의 목적을 손상시키지 않는 범위에 있어서 다른 중합 가능한 단량체를 함께 사용할 수 있다. 공중합 가능한 단량체류로서는, 부타디엔, 이소프렌 등의 공액 디엔계 단량체, 메틸메타크릴레이트, 에틸메타크릴레이트, 프로필메타크릴레이트, 부틸메타크릴레이트 등의 메타크릴산알킬에스테르류, 메틸아크릴레이트, 에틸아크릴레이트, 프로필아크릴레이트, 부틸아크릴레이트 등의 아크릴산에스테르 등을 들 수 있다. 이들 단량체는 수지의 충격 강도, 신장, 내약품성 등을 개량 또는 조정하는 경우에 유용하다 .In addition to the above monomers, other polymerizable monomers may be used together as long as they do not impair the purpose of the present invention. Monomers that can be copolymerized include conjugated diene monomers such as butadiene and isoprene, methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate, methyl acrylate, and ethyl acrylate. Acrylic acid esters such as acrylate, propyl acrylate, and butyl acrylate can be mentioned. These monomers are useful for improving or adjusting the impact strength, elongation, chemical resistance, etc. of the resin.
본 발명에 있어서의 스티렌계 공중합체는 리빙 음이온 중합법으로 합성된다. 리빙 음이온 중합법으로서는 공지된 방법을 이용할 수 있다. 예를 들면, 개시제로서 유기 리튬 화합물이 사용되고, 구체적으로는 n-부틸리튬, sec-부틸리튬, t-부틸리튬, 에틸리튬, 벤질리튬, 1,6-디리티오헥산, 스티릴리튬, 부타디에니릴리튬 등이 사용된다. 이 중에서 바람직하게는 n-부틸리튬, sec-부틸리튬을 들 수 있다.The styrene-based copolymer in the present invention is synthesized by living anionic polymerization. As a living anion polymerization method, a known method can be used. For example, an organic lithium compound is used as an initiator, specifically n-butyllithium, sec-butyllithium, t-butyllithium, ethyllithium, benzyllithium, 1,6-dilithiohexane, styryllithium, butadilithium. Enyl lithium, etc. are used. Among these, n-butyllithium and sec-butyllithium are preferred.
중합 용매로서는, 헤테로 원자를 함유하지 않는 탄화수소계 화합물이 좋다. 구체적으로는, n-헥산, 시클로헥산, 헵탄 등의 지방족 탄화수소 화합물, 벤젠, 톨루엔, 에틸벤젠, 크실렌 등의 방향족 탄화수소 화합물을 들 수 있다. 이들 탄화수소 화합물은 1종류 또는 2종류 이상 사용해도 된다. 특히, 바람직한 화합물은 시클로헥산이다.As a polymerization solvent, a hydrocarbon-based compound that does not contain a hetero atom is good. Specific examples include aliphatic hydrocarbon compounds such as n-hexane, cyclohexane, and heptane, and aromatic hydrocarbon compounds such as benzene, toluene, ethylbenzene, and xylene. These hydrocarbon compounds may be used one type or two or more types. A particularly preferred compound is cyclohexane.
중합 온도는 생산성 및 제조 후의 수지의 착색, 내후성의 관점에서 40℃~110℃의 범위가 바람직하고, 보다 바람직하게는 50℃~100℃의 범위, 더 바람직하게는 55℃~95℃의 범위이다.The polymerization temperature is preferably in the range of 40°C to 110°C, more preferably in the range of 50°C to 100°C, and even more preferably in the range of 55°C to 95°C from the viewpoint of productivity, coloring of the resin after production, and weather resistance. .
본 발명에 있어서의 스티렌계 공중합체는, 예를 들면, 완전 혼합형의 중합 반응기를 사용하여 연속 리빙 중합법에 의해 제조할 수 있다. 또는, 완전 혼합형의 중합 반응기와 비완전 혼합형의 중합 반응기의 조합이어도 된다. 특히, 랜덤 공중합체를 얻기 위해서는, 완전 혼합형의 중합 반응기가 바람직하다. 완전 혼합형의 중합이란, 리빙 중합의 반응계 내에 존재하는 α-메틸스티렌, 비닐 방향족 단량체, 리빙 공중합체의 농도가 항상 일정하게 되는 연속식 완전 혼합형 반응기를 사용하여 중합하는 방법 등을 말한다.The styrene-based copolymer in the present invention can be produced, for example, by a continuous living polymerization method using a completely mixed polymerization reactor. Alternatively, it may be a combination of a completely mixed polymerization reactor and a non-completely mixed polymerization reactor. In particular, to obtain a random copolymer, a completely mixed polymerization reactor is preferable. Completely mixed polymerization refers to a method of polymerizing using a continuous completely mixed reactor in which the concentrations of α-methylstyrene, vinyl aromatic monomer, and living copolymer present in the living polymerization reaction system are always constant.
원료 용액 중의 단량체 농도를 올려 생산성을 높이고 싶은 경우는, 중합 반응의 제열을 효율적으로 실시하기 위해 중합 반응기에 컨덴서를 부착하고, 용매의 증발 잠열로 중합 열을 제열하는 것이 바람직하다. 특히, 중합 용매에 주로 시클로헥산(n-헥산이 혼입되어 있어도 관계없음)을 사용하면, 비점이 82℃이므로 중합 온도를 80℃ 내지 90℃ 부근에서 제어하기 쉽다.When it is desired to increase productivity by increasing the monomer concentration in the raw material solution, it is desirable to attach a condenser to the polymerization reactor and remove the heat of polymerization using the latent heat of evaporation of the solvent in order to efficiently remove heat from the polymerization reaction. In particular, when mainly cyclohexane (even if n-hexane is mixed) is used as the polymerization solvent, the polymerization temperature is easy to control around 80°C to 90°C because the boiling point is 82°C.
비완전 혼합형의 튜브형 중합 반응기를 사용하는 경우는, 예를 들면, 반응기의 길이(L)와 내부직경(D)의 비(L/D)가 1 이상인 경우, 또는 교반 효율이 나쁜 경우 등, 중합 반응기 내에서 완전 혼합 상태를 취하기 어려운 경우에는, 반응기의 도중으로부터 비닐 방향족 단량체의 용액을 첨가함으로써 본 발명의 스티렌계 공중합체를 제조할 수 있다.When using a non-completely mixed tubular polymerization reactor, for example, when the ratio (L/D) of the length (L) and internal diameter (D) of the reactor is 1 or more, or when the stirring efficiency is poor, etc., polymerization When it is difficult to achieve complete mixing in the reactor, the styrene-based copolymer of the present invention can be produced by adding a solution of vinyl aromatic monomer from the middle of the reactor.
또한, 비완전 혼합형 중합기를 2기 이상 직렬로 연결하고, 1기째의 중합 후 2기째의 중합 반응기에 비닐 방향족 단량체의 용액을 첨가함으로써 본 발명의 공중합체를 얻을 수도 있다. 또한, 1기째의 중합 반응기에서 비닐 방향족 단량체만을 중합하고, 계속해서 2기째의 중합 반응기 내에서 α-메틸스티렌과 비닐 방향족 단량체의 공중합을 실시하여, 비닐 방향족 단위의 단독 중합체와 공중합체의 블록 공중합체를 얻는 것도 가능하다.Additionally, the copolymer of the present invention can be obtained by connecting two or more non-completely mixed polymerization reactors in series and adding a solution of vinyl aromatic monomer to the second polymerization reactor after polymerization in the first reactor. In addition, only the vinyl aromatic monomer is polymerized in the first polymerization reactor, and then α-methylstyrene and the vinyl aromatic monomer are copolymerized in the second polymerization reactor to form a block copolymer of the homopolymer and copolymer of the vinyl aromatic unit. It is also possible to obtain a merger.
본 발명의 스티렌계 공중합체를 얻기 위해 사용하는 단량체에 함유되는 미량 성분으로, 본 발명에 있어서 제어 대상으로 하는 특정 화합물은 카르보닐기 함유 화합물, 페놀, 중합 금지제인 t-부틸카테콜을 포함하는 카테콜류, 및 페닐아세틸렌이다. 카르보닐기 함유 화합물의 구체적인 예로서는 아세토닐아세톤, 3-메틸-2-시클로펜타논, 벤즈알데히드, 아세토페논 등을 들 수 있다.A trace component contained in the monomer used to obtain the styrene-based copolymer of the present invention, and specific compounds subject to control in the present invention include carbonyl group-containing compounds, phenol, and catechols including t-butylcatechol, a polymerization inhibitor. , and phenylacetylene. Specific examples of carbonyl group-containing compounds include acetonylacetone, 3-methyl-2-cyclopentanone, benzaldehyde, and acetophenone.
이들 화합물은 음이온 중합 등에 의해 폴리α-메틸스티렌 및 그 공중합체를 제조할 때, 중합 저해, 중합체 착색, 및 내후성 저하의 원인 물질이 되므로, 가능한 한 제외하는 것이 바람직하다 .When producing poly-α-methylstyrene and its copolymers by anionic polymerization, etc., these compounds become substances that inhibit polymerization, cause polymer coloring, and reduce weather resistance, so it is desirable to exclude them as much as possible.
α-메틸스티렌으로부터 제어 대상으로 하는 특정 화합물을 제거하는 방법으로서는 α-메틸스티렌에 특정 염기성 물질을 첨가하고, 반응에서 생성된 고비점 화합물과 저비점 화합물을 증류에 의해 α-메틸스티렌으로부터 분리하는 방법이 바람직하다.A method of removing a specific compound to be controlled from α-methylstyrene is a method of adding a specific basic substance to α-methylstyrene and separating the high-boiling point compounds and low-boiling compounds generated in the reaction from α-methylstyrene by distillation. This is desirable.
그 때 사용되는 염기성 물질로서는, 나트륨에톡시드, 칼륨에톡시드, 나트륨메톡시드 등의 금속 알콕시드, 수산화나트륨, 수산화칼륨, 수산화마그네슘 등의 금속 수산화물, 산화나트륨, 산화칼륨, 산화마그네슘 등의 금속 산화물, 리튬디이소프로필아미드 등의 금속 아미드, 부틸리튬, 메틸리튬 등의 알킬 금속 등의 알칼리 금속 또는 알칼리 토류 금속을 함유하는 염기성 화합물을 사용할 수 있다.Basic substances used at that time include metal alkoxides such as sodium ethoxide, potassium ethoxide, and sodium methoxide, metal hydroxides such as sodium hydroxide, potassium hydroxide, and magnesium hydroxide, and sodium oxide, potassium oxide, and magnesium oxide. A basic compound containing an alkali metal or an alkaline earth metal such as a metal oxide, a metal amide such as lithium diisopropylamide, or an alkyl metal such as butyllithium or methyllithium can be used.
스티렌 및 중합 용매로부터 제어 대상으로 하는 특정 화합물을 제거하는 방법으로서는 통상의 정제 방법을 적용할 수 있고, 질소 버블링을 한 후에, 활성 알루미나를 충전한 정제탑 내를 통과시켜 정제하는 방법 등이 있다 .As a method of removing the specific compound to be controlled from styrene and the polymerization solvent, a normal purification method can be applied, including a method of purifying the compound by bubbling with nitrogen and then passing the compound through a purification tower filled with activated alumina. .
상기 방법 등에 의해, 단량체와 중합 용매로 이루어진 중합에 제공하는 공급액 중의 특정 화합물의 함유량을 제어하는 것이 가능하다. 이들 특정 화합물을 일정 범위로 제어한 경우, 중합 컨트롤, 폴리머의 황색화 방지에 유효하고, 특히 폴리머의 내후성 개량에 매우 유효하다.By the above method or the like, it is possible to control the content of a specific compound in the feed liquid used for polymerization consisting of a monomer and a polymerization solvent. When these specific compounds are controlled to a certain range, they are effective in controlling polymerization and preventing yellowing of the polymer, and are particularly effective in improving the weather resistance of the polymer.
제어 대상으로 하는 공급액 중의 특정 화합물의 함유량으로서는, 적으면 적을수록 좋지만, 아세토닐아세톤 2ppm 이하, 벤즈알데히드 10ppm 이하, 및 페닐아세틸렌 15ppm 이하가 바람직하다. 또한, 페닐아세틸렌은 10ppm 이하가 보다 바람직하다. 또한, 본 명세서에서의 ppm은 질량 단위이다. 이들 수치를 초과하면, 얻어진 폴리머의 내후성의 저하가 현저해지고, 경우에 따라서는 리빙 중합을 저해한다.As for the content of the specific compound in the supply liquid to be controlled, the lower the content, the better, but preferably 2 ppm or less of acetonylacetone, 10 ppm or less of benzaldehyde, and 15 ppm or less of phenylacetylene. Additionally, phenylacetylene is more preferably 10 ppm or less. In addition, ppm in this specification is a mass unit. If these values are exceeded, the weather resistance of the obtained polymer decreases significantly, and living polymerization is inhibited in some cases.
본 발명에 있어서의 스티렌계 공중합체의 황색도(Yellow Index)의 값은 3 이하가 바람직하고, 보다 바람직하게는 2 이하, 가장 바람직하게는 1.5 이하이다. 황색도를 저하시키기 위해서는 전술한 바와 같이, 공급액 중의 특정 화합물의 함유량을 저감시키는 것이 유효하다. 특히, 식품 포장 분야에서 이용되는 2축 연신 시트(OPS)나 발포 시트(PSP)의 제조시에는, 시트를 감아 회수하므로 수지의 황색화는 현저하게 눈에 띄어 품질상의 문제를 일으키는 경우가 있다. 따라서, 이와 같은 용도의 사용자는 수지의 황색화에 대해서는 특히 민감하고 중요한 요구 성능 중 하나이다.The yellow index value of the styrene-based copolymer in the present invention is preferably 3 or less, more preferably 2 or less, and most preferably 1.5 or less. In order to reduce the yellowness, it is effective to reduce the content of a specific compound in the supply liquid as described above. In particular, when manufacturing biaxially stretched sheets (OPS) or foam sheets (PSP) used in the food packaging field, since the sheets are rolled and collected, yellowing of the resin is noticeably noticeable and may cause quality problems. Therefore, users of such applications are particularly sensitive to yellowing of the resin and it is one of the important performance requirements.
본 발명에 있어서의 스티렌계 공중합체는, 선샤인 웨더 미터에 의한 내후성 시험에 있어서 조사 시간 1000시간 후의 전 광선투과율의 변화량이 5% 이하, 또 황색도의 변화량이 5 이하이다.The styrene-based copolymer in the present invention has a change in total light transmittance of 5% or less and a change in yellowness of 5 or less after 1000 hours of irradiation in a weather resistance test using a Sunshine Weather Meter.
본 명세서에 있어서, 선샤인 웨더 미터에 의한 내후성 시험에 있어서 조사 시간 1000시간 후의 전 광선투과율의 변화량, 및 황색도의 변화량은 후술하는 실시예에 기재된 방법에 의해 측정되는 값이다. .In this specification, the amount of change in total light transmittance and the amount of change in yellowness after 1000 hours of irradiation in the weather resistance test using the Sunshine Weather Meter are values measured by the method described in the examples described later. .
본 발명의 스티렌계 공중합체의 중량 평균 분자량(Mw)은 바람직하게는, Mw=5만~30만의 범위, 보다 바람직하게는, Mw=6만~29만, 더 바람직하게는, Mw=7만~ 28만의 범위이다. 기계 강도의 점에서 Mw가 5만 이상인 것이 바람직하고, 성형시의 수지의 유동성의 점에서 30만 이하인 것이 바람직하다. 그 결과, 정밀 부품의 성형이 보다 용이해질 뿐만 아니라, 고분자쇄의 분자 배향이 보다 억제되어, 광학 특성의 이방성의 발현이나 시트상 압출 성형품이나 시트상 사출 성형품의 면 충격 강도의 저하, 또 대형 성형품의 성형이 곤란하다는 여러 가지 문제를 보다 억제할 수 있다.The weight average molecular weight (Mw) of the styrene-based copolymer of the present invention is preferably in the range of Mw = 50,000 to 300,000, more preferably, Mw = 60,000 to 290,000, and even more preferably, Mw = 70,000. The range is ~280,000. In terms of mechanical strength, Mw is preferably 50,000 or more, and in terms of resin fluidity during molding, it is preferably 300,000 or less. As a result, not only does the molding of precision parts become easier, but the molecular orientation of the polymer chain is further suppressed, resulting in the development of anisotropy in optical properties, a decrease in surface impact strength of sheet-shaped extrusion molded products and sheet-shaped injection molded products, and large molded products. Various problems such as difficulty in forming can be further suppressed.
또한, 중량 평균 분자량(Mw)과 수 평균 분자량(Mn)의 비(Mw/Mn)가 1.6~2.5의 범위인 것이 바람직하다. 보다 바람직하게는, Mw/Mn=1.8~2.4의 범위가 바람직하다. Mw/Mn이 1.6~2.5에서는, 수지의 유동성과 기계 물성의 밸런스가 좋아지고, 수지 성형체로서 충분한 성능을 낼 수 있어, 상기와 같은 문제의 발생을 동시에 억제할 수 있는 경향에 있다.Moreover, it is preferable that the ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is in the range of 1.6 to 2.5. More preferably, the range of Mw/Mn=1.8 to 2.4 is desirable. When Mw/Mn is 1.6 to 2.5, the balance between the fluidity and mechanical properties of the resin improves, sufficient performance can be achieved as a resin molded body, and the occurrence of the above problems tends to be suppressed at the same time.
본 발명의 유리 전이 온도는 DSC에 의해 구할 수 있고, JIS-K71 21에 나타낸 방법으로 구한 온도를 유리 전이 온도로 한다.The glass transition temperature of the present invention can be determined by DSC, and the temperature determined by the method shown in JIS-K71 21 is taken as the glass transition temperature.
본 발명에 있어서의 스티렌계 공중합체의 α-메틸스티렌 단위와 비닐 방향족 단량체 단위의 결합 양식은 특별히 제한되지 않지만, 가장 바람직한 결합 양식은 랜덤 결합으로 이루어진 공중합체이다. 일반적으로 α-메틸스티렌 단위의 연쇄가 많이 존재하면 열분해되기 쉬워지는 경향에 있다. 따라서, 용도에 따라서는 α-메틸스티렌 단위의 연쇄는 2 내지 4연쇄 이하로 제어하는 것이 바람직하다.The bonding style between the α-methylstyrene unit and the vinyl aromatic monomer unit of the styrene-based copolymer in the present invention is not particularly limited, but the most preferable bonding style is a copolymer composed of random bonds. In general, if there are many chains of α-methylstyrene units, thermal decomposition tends to become easier. Therefore, depending on the application, it is preferable to control the number of α-methylstyrene units to 2 to 4 or less.
비닐 방향족 단량체 단위는, 연쇄되어 있어도 특별히 열 안정성을 손상시킬 우려가 없기 때문에, 장쇄의 연쇄 구조를 취해도 관계없다. 본 발명자들은 비닐 방향족 단량체 단위의 장쇄의 연쇄가, 공중합체의 분자쇄의 말단에 존재하는 AB형, 또는 ABA형의 블록 공중합체(A는 주로 비닐 방향족 단량체 단위 성분으로 이루어진 단독 중합체 성분, B는 α-메틸스티렌 단위와 비닐 방향족 단량체 단위를 함유하는 랜덤 공중합체 성분)가 내열성, 열안정성, 기계 물성, 유동성을 포함하는 그 외의 성능이 랜덤 공중합체와 동등하고, 또한 블록의 일 성분인 비닐 방향족 단량체 단위와 동일한 구조로 이루어진 단독 중합체와 상용성이 매우 양호하다는 특성를 발견했다. 이 특성을 살려, 본 발명의 스티렌계 공중합체를 리사이클재로서 재이용하고 싶은 경우, 예를 들면 폴리스티렌과 용융 혼련하여 재이용하고 싶은 경우에는, 공중합체의 고분자쇄 말단에 폴리스티렌쇄를 블록한 공중합체를 이용할 수 있다.Since the vinyl aromatic monomer unit is not particularly likely to impair thermal stability even if it is chained, it may have a long chain chain structure. The present inventors have discovered an AB-type or ABA-type block copolymer in which a long chain of vinyl aromatic monomer units is present at the terminal of the molecular chain of the copolymer (A is a homopolymer component mainly composed of vinyl aromatic monomer unit components, and B is (a random copolymer component containing an α-methylstyrene unit and a vinyl aromatic monomer unit) has heat resistance, thermal stability, mechanical properties, and other properties, including fluidity, that are equivalent to the random copolymer, and vinyl aromatic is a component of the block. It was discovered that it has very good compatibility with homopolymers with the same structure as the monomer units. Taking advantage of this characteristic, when it is desired to reuse the styrene-based copolymer of the present invention as a recycling material, for example, when it is desired to reuse it by melt-kneading it with polystyrene, a copolymer in which polystyrene chains are blocked at the polymer chain ends of the copolymer is used. Available.
비닐 방향족 단량체 단위의 블록 연쇄 길이는 특별히 제한은 없고, 바람직하게는 블록 연쇄 부분의 수 평균 분자량이 1000 내지 25만의 범위이면 된다. 또한, 비닐 방향족 단량체 단위로 이루어진 블록 성분의 Mw/Mn은 1.0 내지 2.5의 범위인 것이 바람직하다.The block chain length of the vinyl aromatic monomer unit is not particularly limited, and preferably the number average molecular weight of the block chain portion is in the range of 1,000 to 250,000. In addition, Mw/Mn of the block component made of vinyl aromatic monomer units is preferably in the range of 1.0 to 2.5.
비닐 방향족 단량체 단위를 블록 성분으로 하는 공중합체의 제조 방법은, 예를 들면, 배치형 반응기, 연속 튜브형 반응기, 연속 스태틱 믹서형 반응기, 연속 교반 날개 장착의 조형 반응기, 연속 코일형 반응기 등으로 비닐 방향족 단량체 단위로 이루어진 단독 중합체를 제조하고, 계속해서 연속 완전 혼합형 반응기 내에 α-메틸스티렌과 비닐 방향족 단량체 및 리빙의 비닐 방향족 단량체 단위로 이루어진 단독 중합체를 공급하여 공중합함으로써, AB형 블록 공중합체를 얻을 수 있다. ABA형 블록 공중합체를 얻는 경우에는, AB형 블록 공중합체를 제조한 후에, 다른 반응기 내에서 비닐 방향족 단량체 단위를 리빙 중합함으로써 제조할 수 있다. 또는, AB형 리빙 공중합체를 제조한 후에, 다른 반응기 내에서 리빙 성장 종과 반응하는 2관능성 화합물을 첨가함으로써, ABA형 블록 공중합체를 얻을 수 있다.Methods for producing a copolymer containing a vinyl aromatic monomer unit as a block component include, for example, a batch reactor, a continuous tubular reactor, a continuous static mixer reactor, a tank reactor equipped with continuous stirring blades, and a continuous coil reactor. An AB block copolymer can be obtained by preparing a homopolymer composed of monomer units and then copolymerizing the homopolymer composed of α-methylstyrene, vinyl aromatic monomer, and Living's vinyl aromatic monomer units by supplying them in a continuous completely mixed reactor. there is. When obtaining an ABA type block copolymer, it can be produced by living polymerization of a vinyl aromatic monomer unit in another reactor after producing the AB type block copolymer. Alternatively, after preparing the AB-type living copolymer, an ABA-type block copolymer can be obtained by adding a bifunctional compound that reacts with the living growth species in another reactor.
본 발명자들은 예의 연구를 거듭한 결과, 연속 리빙 중합법에 의해 얻어지는 α-메틸스티렌 단위와 비닐 방향족 단량체 단위를 함유하는 공중합체이고, 원료 중의 α-메틸스티렌과 상기 식(1)로 표시되는 비닐 방향족 단량체의 조성 비율을 연속적으로 또는 단속적으로 변화시켜 중합 반응기 내에 공급하여 얻어지는 공중합체 중의 구성 조성비가 적어도 2종 이상의 상이한 공중합체로 이루어진 스티렌계 공중합체가 내열성, 열안정성, 기계 물성, 유동성을 포함하는 기타 성능이 랜덤 공중합체와 동등하고, 또한 비닐 방향족 단량체 단위를 주 성분으로 하는 중합체와 상용성이 매우 양호하다는 특성을 발견했다.As a result of extensive research, the present inventors have found that it is a copolymer containing α-methylstyrene units and vinyl aromatic monomer units obtained by a continuous living polymerization method, and that α-methylstyrene in the raw materials and vinyl represented by the above formula (1) A styrene-based copolymer composed of at least two different copolymers with different composition ratios in the copolymer obtained by continuously or intermittently changing the composition ratio of the aromatic monomer and supplying it to the polymerization reactor has heat resistance, thermal stability, mechanical properties, and fluidity. It was discovered that other properties of the polymer were equivalent to those of random copolymers, and that it had very good compatibility with polymers containing vinyl aromatic monomer units as their main component.
이는 상기 공중합체의 성형품을 리사이클로 사용하는 경우, 비닐 방향족 단량체 단위를 주 성분으로 하는 중합체, 예를 들면, 폴리스티렌에도 리사이클재로서 블렌드하여 재이용이 가능한 것을 시사하고 있다. 다른 공중합체란, 유리 전이 온도가 적어도 3℃ 이상 다른 공중합체를 가리킨다.This suggests that when molded products of the above copolymer are recycled, it is possible to blend and reuse polymers containing vinyl aromatic monomer units as a main component, such as polystyrene, as a recycling material. Different copolymers refer to copolymers whose glass transition temperatures differ by at least 3°C.
단량체 중의 α-메틸스티렌과 비닐 방향족 단량체의 조성 비율을 연속적 또는 단속적으로 변화시켜 중합 반응기 내에 공급한다는 것은, 즉 중합 반응계에 도입되는 각 단량체의 농도가 연속적으로 또는 단속적으로 변화하는 것이며, 그 결과, 얻어지는 공중합체의 각 방향족 단위의 조성비가 연속적으로 변화하여, 적어도 2종 이상의 상이한 구성 조성비로 이루어진 공중합체가 순차적으로 얻어진다.Changing the composition ratio of α-methylstyrene and vinyl aromatic monomers in the monomers continuously or intermittently and supplying them into the polymerization reactor means that the concentration of each monomer introduced into the polymerization reaction system changes continuously or intermittently, and as a result, The composition ratio of each aromatic unit of the obtained copolymer is continuously changed, and copolymers composed of at least two different composition ratios are sequentially obtained.
2종 이상의 다른 구성 조성비를 갖는 공중합체는, 배치형의 조 내에서 용액 상태로 혼합하고, 그 후 진공하에 가열된 탱크 내에 플러싱시켜 용매를 제거해도 되고, 또는 압출기나 니더를 사용하여 용매를 제거하여 펠릿 상태로 회수할 수 있다. 또는, 배치형의 조 내에 모이지 않고 그대로 펠릿 상태로 회수하여, 배치형 또는 연속형 혼합 용기에서 펠릿을 혼합하여, 균일화하는 것도 가능하다. 또는, 혼합 용기에서 펠릿을 균일한 상태로 한 후, 또 압출기를 사용하여 용융 혼합하는 것도 가능하다.Copolymers having two or more different composition ratios may be mixed in a solution state in a batch tank and then flushed into a heated tank under vacuum to remove the solvent, or the solvent may be removed using an extruder or kneader. It can be recovered in pellet form. Alternatively, it is also possible to collect the pellets as they are without collecting them in a batch tank, and mix the pellets in a batch or continuous mixing vessel to homogenize them. Alternatively, it is also possible to uniformize the pellets in a mixing container and then melt and mix them using an extruder.
구체적인 제조예를 들면, α-메틸스티렌(M1)과 비닐 방향족 단량체(M2)의 성분 조성비가 M1/M2=50/50(wt%)의 원료를 반응기 내에 공급하여 중합시킨 후, 다른 조성비, 예를 들면 M1/M2=40/60(wt%)의 원료로 전환하여 계속해서 반응기에 도입하여 중합을 실시한다. 이 경우, 단속적으로 원료 조성을 변화시켰다고 말한다. 이와 같이 중합하면, M1/M2=50/50(wt%)로 중합하여 얻어지는 공중합체의 조성으로부터 M1/M2=40/60(wt%)로 얻어지는 공중합체의 조성까지 연속적으로 변화된 조성을 갖는 공중합체가 순차적으로 얻어진다. 얻어진 공중합체를 배치형의 조내에서 용액 혼합 또는 펠릿 상태로 교반 혼합하고, 그 후 용융 혼련되어 있는 일정한 조성의 공중합체를 얻는다.For a specific manufacturing example, raw materials with a composition ratio of α-methylstyrene (M1) and vinyl aromatic monomer (M2) of M1/M2 = 50/50 (wt%) are supplied into the reactor for polymerization, and then polymerized at a different composition ratio, e.g. For example, the raw material is converted to M1/M2 = 40/60 (wt%) and continuously introduced into the reactor to perform polymerization. In this case, it is said that the raw material composition was changed intermittently. When polymerized in this way, the copolymer has a composition that continuously changes from the composition of the copolymer obtained by polymerizing with M1/M2 = 50/50 (wt%) to the composition of the copolymer obtained with M1/M2 = 40/60 (wt%). are obtained sequentially. The obtained copolymer is stirred and mixed in a solution-mixed or pelletized state in a batch-type tank, and then a copolymer of a certain composition is obtained by melt-kneading.
이와 같은 방법에 의해 얻어진 공중합체는, α-메틸스티렌 단위 성분과 비닐 방향족 단량체 단위 성분의 조성비가 다른 공중합체의 조성물이라고 생각할 수 있다. 이에 의해 얻어진 공중합체는, 비닐 방향족 단량체의 단독 중합체와 매우 상용성이 좋고, 기계 물성의 저하를 초래하지 않으며, 또 투명성을 유지할 수 있으므로 리사이클재로서 매우 이용 가치가 높은 공중합체인 것을 이해할 수 있다.The copolymer obtained by such a method can be considered to be a copolymer composition with different composition ratios of the α-methylstyrene unit component and the vinyl aromatic monomer unit component. It can be understood that the copolymer thus obtained is very compatible with homopolymers of vinyl aromatic monomers, does not cause deterioration in mechanical properties, and can maintain transparency, so it is a copolymer with great usability as a recycling material.
본 발명의 공중합체의 제조 방법인 리빙 음이온 중합법에서는, 중합 반응의 완결은 비닐 방향족 단량체의 반응률이 99% 이상에 도달한 경우에 실시하는 것이 바람직하고, α-메틸스티렌이 반응계에 남아 있어도 된다. 중합 반응의 정지는, 정지제로서 물, 알콜, 페놀, 카르복실산 등의 산소-수소 결합을 갖는 화합물의 첨가,에폭시 화합물, 에스테르 화합물, 케톤 화합물, 카르복실산 무수물, 탄소-할로겐 결합을 갖는 화합물 등도 동일한 효과를 기대할 수 있다. 이들 첨가물의 사용량은 성장 종의 당량으로부터 10배 당량 정도가 바람직하다. 너무 많으면 비용면에서 불리할 뿐만 아니라, 잔존하는 첨가제의 혼입이 장애가 되는 경우도 많다.In the living anionic polymerization method, which is a method for producing the copolymer of the present invention, completion of the polymerization reaction is preferably carried out when the reaction rate of the vinyl aromatic monomer reaches 99% or more, and α-methylstyrene may remain in the reaction system. . The polymerization reaction can be stopped by adding a compound having an oxygen-hydrogen bond such as water, alcohol, phenol, or carboxylic acid as a stopper, an epoxy compound, an ester compound, a ketone compound, a carboxylic acid anhydride, or a compound having a carbon-halogen bond. Compounds, etc. can also be expected to have the same effect. The amount of these additives used is preferably about 10 times the equivalent of the growing species. If there is too much, not only is it disadvantageous in terms of cost, but mixing of remaining additives often becomes an obstacle.
리빙 성장 종을 이용하여 다관능 화합물로 커플링 반응시켜, 폴리머 분자량을 증대, 또는 폴리머쇄를 분지 구조화시킬 수도 있다. 이와 같은 커플링 반응에 사용하는 다관능 화합물은 공지의 것으로부터 선택할 수 있다. 다관능 화합물이란 폴리할로겐 화합물, 폴리에폭시 화합물, 모노 또는 폴리카르복실산에스테르, 폴리케톤 화합물, 모노 또는 폴리카르복실산 무수물 등을 예로 들 수 있다. 구체예로서는 실리콘테트라클로라이드, 디(트리클로로시릴)에탄, 1,3,5-트리브로모벤젠, 에폭시화 대두유, 테트라글리시딜 1,3-비스아미노메틸시클로헥산, 옥살산디메틸, 트리멜리트산 트리-2-에틸헥실, 피로멜리트산 2무수물, 디에틸카보네이트 등을 들 수 있다.Living growth species can be used to carry out a coupling reaction with a multifunctional compound to increase the polymer molecular weight or branch the polymer chain. The polyfunctional compound used in such a coupling reaction can be selected from known compounds. Examples of multifunctional compounds include polyhalogen compounds, polyepoxy compounds, mono- or polycarboxylic acid esters, polyketone compounds, and mono- or polycarboxylic acid anhydrides. Specific examples include silicon tetrachloride, di(trichlorosylyl)ethane, 1,3,5-tribromobenzene, epoxidized soybean oil, tetraglycidyl 1,3-bisaminomethylcyclohexane, dimethyl oxalate, and trimellitic acid. -2-ethylhexyl, pyromellitic dianhydride, diethyl carbonate, etc. are mentioned.
중합 종료 후, 미반응 모노머나 용매는 회수하여 재생 사용하기 위해서 폴리머로부터 휘발 제거된다. 휘발 제거에는 공지된 방법을 이용할 수 있다. 휘발 제거 장치로서는, 예를 들면 진공 탱크에 플러시시키는 방법 및/또는 압출기나 니더를 이용하여 진공 하 가열 증발시키는 방법 등을 바람직하게 이용할 수 있다. 용매의 휘발성에도 의존하지만, 일반적으로는 온도를 180~300℃, 진공도 100Pa~50KPa로 용매나 잔존 모노머 등의 휘발성 성분을 휘발 제거시킨다.After completion of polymerization, unreacted monomers and solvents are volatilized and removed from the polymer for recovery and reuse. Known methods can be used to remove volatilization. As a volatilization removal device, for example, a method of flushing into a vacuum tank and/or a method of heating and evaporating under vacuum using an extruder or kneader can be preferably used. It also depends on the volatility of the solvent, but in general, volatile components such as solvent and remaining monomers are volatilized and removed at a temperature of 180 to 300°C and a vacuum of 100 Pa to 50 KPa.
휘발 제거 장치를 직렬로 접속하여, 2단 이상으로 나열하는 방법도 효과적이다. 또한, 1단째와 2단째의 사이에 물을 첨가하여 2단째의 모노머의 휘발 능력을 높이는 방법도 이용할 수 있다. 플러싱 탱크에서 휘발 성분의 제거 후, 잔여 휘발 성분을 제거하기 위해, 추가로 벤트 장착 압출기를 사용할 수도 있다. 용매가 제거된 스티렌계 공중합체는 공지된 방법으로 펠릿상으로 마무리할 수 있다.It is also effective to connect the volatilization removal devices in series and arrange them in two or more stages. Additionally, a method of increasing the volatilization ability of the monomer in the second stage by adding water between the first and second stages can also be used. After removal of volatile components from the flushing tank, a vented extruder may additionally be used to remove remaining volatile components. The styrene-based copolymer from which the solvent has been removed can be finished into pellet form by a known method.
본 발명에서는, 펠릿상의 스티렌계 공중합체 중에 잔존하는 단량체 및 중합 용매의 총 질량이 500ppm 이하인 것이 바람직하다. 더 바람직하게는, 400ppm 이하이다.In the present invention, it is preferable that the total mass of monomers and polymerization solvent remaining in the pellet-shaped styrene-based copolymer is 500 ppm or less. More preferably, it is 400ppm or less.
본 발명의 스티렌계 공중합체에는 필요에 따라서 열적, 기계적 안정성, 유동성, 착색성을 개량할 목적으로, 스티렌계 수지에서 사용되고 있는 공지의 화합물을 첨가할 수 있다. 그 예로서 1차 산화방지제로서, 예를 들면, 2,6-디-t-부틸-4-메틸페놀, 트리에틸렌글리콜-비스-[3-(3-t-부틸-5-메틸-4-히드록시페닐)프로피오네이트], 펜타에리스톨테트라키스[-(3,5-디t-부틸-4-히드록시페닐)프로피오네이트], 옥타데실-3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트, 1,3,5-트리메틸-2,4,6-트리스(3,5-디-t-부틸-4-히드록시벤질)벤젠, n-옥타데실3-(3,5-디-t-부틸-4-히독시페닐)프로피오네이트, 2-t-부틸-6-(3-t-부틸-2-히드록시-5-메틸벤질)-4-메틸페닐아크릴레이트, 2[1-(2-히드록시3,5-디-t-펜틸페닐)]-4,6-디-t-펜틸페닐아크릴레이트, 테트라키스[메틸렌3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트]메탄, 3,9 비스[2-{3-(t-부틸-4-히드록시-5-메틸페닐)프로피닐옥시}-1,1-디메틸에틸]-2,4,8,10-테트라옥사[5,5]운데칸, 1,3,5-트리스(3’, 5’-디-t-부틸-4’-히드록시벤질)-s-트리아진-2,4,6(1H,2H,3H)-트리온, 1,1,4-트리스(2-메틸-4-히드록시-5-t-부틸페닐)부탄, 4,4’-부틸리덴비스(3-메틸-6-t-부틸페놀) 등의 2,4,6-3 치환 페놀류를 들 수 있다.To the styrene-based copolymer of the present invention, if necessary, known compounds used in styrene-based resins can be added for the purpose of improving thermal and mechanical stability, fluidity, and colorability. Examples of primary antioxidants include, for example, 2,6-di-t-butyl-4-methylphenol, triethylene glycol-bis-[3-(3-t-butyl-5-methyl-4-) hydroxyphenyl)propionate], pentaerytholtetrakis[-(3,5-dit-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t -Butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, n-octa Decyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)- 4-methylphenylacrylate, 2[1-(2-hydroxy3,5-di-t-pentylphenyl)]-4,6-di-t-pentylphenylacrylate, tetrakis[methylene 3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 3,9 bis[2-{3-(t-butyl-4-hydroxy-5-methylphenyl)propynyloxy}-1 ,1-dimethylethyl]-2,4,8,10-tetraoxa[5,5]undecane, 1,3,5-tris(3', 5'-di-t-butyl-4'-hydroxy Benzyl)-s-triazine-2,4,6(1H,2H,3H)-trione, 1,1,4-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, and 2,4,6-3 substituted phenols such as 4,4'-butylidenebis(3-methyl-6-t-butylphenol).
또한, 2차 산화방지제로서 인계 산화방지제, 황계 산화방지제, 내후제로서 힌더드 아민의 안정제, UV 흡수제를 첨가하는 것도 가능하다. 그 외에, 미네랄 오일 등의 가소제, 장쇄 지방족 카르복실산 및/또는 그 금속염 등의 활제, 착색성 개량으로서 유기 염료, 유기 안료를 첨가하는 것도 가능하다.In addition, it is also possible to add phosphorus-based antioxidants and sulfur-based antioxidants as secondary antioxidants, and hindered amine stabilizers and UV absorbers as weathering agents. In addition, it is also possible to add plasticizers such as mineral oil, lubricants such as long-chain aliphatic carboxylic acids and/or their metal salts, and organic dyes and organic pigments to improve coloring properties.
착색성 개량용의 안스라퀴논계 유기 염료는, 공중합체의 열안정성을 손상시키는 것이 적으므로 특히 바람직하다.Anthraquinone-based organic dyes for improving colorability are particularly preferable because they rarely impair the thermal stability of the copolymer.
실리콘계, 불소계의 이형제, 대전 방지제 등도 스티렌계 수지에서 이용되고 있는 공지의 기술을 그대로 응용할 수 있다.Silicone-based and fluorine-based mold release agents and antistatic agents can also be applied using known techniques used in styrene-based resins.
이들 안정제는 중합이 완결된 후의 폴리머 용액 중에 첨가하여 혼합하거나 또는 폴리머 회수 후에 압출기를 사용하여 용융 혼합할 수 있다.These stabilizers can be added and mixed into the polymer solution after polymerization is completed, or can be melt-mixed using an extruder after polymer recovery.
본 발명의 스티렌계 공중합체는, 가공 방법으로서는 저렴하게 대량 생산이 가능한 용융 가공법이 바람직하고, 사출 성형, 압출 성형, 발포 압출 성형, 블로우 성형 등을 적합하게 사용할 수 있다.As a processing method for the styrene-based copolymer of the present invention, a melt processing method that enables mass production at low cost is preferable, and injection molding, extrusion molding, foam extrusion molding, blow molding, etc. can be suitably used.
또한, 본 발명의 스티렌계 공중합체는 투명성, 내열성, 내후성, 치수 안정성, 강성이 우수한 재료이므로, 광학용 부품으로서 적합하게 이용된다. 광학용 부품으로서는, 예를 들면 도광판, 확산판, 반사판, 반사 필름, 반사 방지 필름, 편광판, 편광 필름, 위상차 필름, 렌즈, 프레넬 렌즈 등을 들 수 있다. 이들 광학 부품은 액정 디스플레이나 프로젝터의 대형화에 따라, 종래 이상으로 치수 안정성과 높은 가공성이 요구되고, 또한 광원에 가까운 곳에서 사용되기 때문에 내광성과 내열성도 점점 중요시된다. 본 발명의 스티렌계 공중합체는, 종래의 문제점을 일거에 해결하여 향후의 성능 요구를 만족할 수 있는 우수한 재료이며, 가온용 식품 용기, 주택용 부품, 자동차 실내용 부품, 광학용 부품의 각 용도 이외에도 이용할 수 있는 용도는 많이 있다고 기대할 수 있다.Additionally, the styrene-based copolymer of the present invention is a material excellent in transparency, heat resistance, weather resistance, dimensional stability, and rigidity, and is therefore suitably used as optical components. Examples of optical components include light guide plates, diffusion plates, reflectors, reflective films, anti-reflection films, polarizing plates, polarizing films, retardation films, lenses, Fresnel lenses, and the like. As liquid crystal displays and projectors become larger, these optical components require greater dimensional stability and higher processability than before, and since they are used close to the light source, light resistance and heat resistance are also becoming increasingly important. The styrene-based copolymer of the present invention is an excellent material that can meet future performance requirements by solving all of the conventional problems at once, and can be used for various purposes other than food containers for warming, housing parts, automobile interior parts, and optical parts. It can be expected that there are many possible uses.
[실시예][Example]
이하, 실시예, 비교예를 들어 본 발명의 양태를 구체적으로 설명한다. 그러나, 이들은 예로서, 본 발명의 범위를 전혀 한정하는 것은 아니다.Hereinafter, embodiments of the present invention will be described in detail through examples and comparative examples. However, these are examples and do not limit the scope of the present invention at all.
실시예 및 비교예에 있어서 사용한 분석·평가 방법에 대해 설명한다.The analysis and evaluation methods used in the examples and comparative examples will be described.
〈분석·평가 방법〉〈Analysis/Evaluation Method〉
(1) 공급액 중의 특정 화합물의 함유량(1) Content of specific compounds in the supply solution
공급액 중의 아세토닐아세톤, 벤즈알데히드, 페닐아세틸렌을 가스 크로마토그래피(장치: 시마즈 제작소(주)제 GC-14A, 칼럼: DB-WAX 30m)로 정량했다Acetonylacetone, benzaldehyde, and phenylacetylene in the feed solution were quantified by gas chromatography (equipment: GC-14A manufactured by Shimadzu Corporation, column: DB-WAX 30m).
(2) 펠릿 중의 잔존 휘발분(단량체 및 중합 용매의 총 질량)(2) Residual volatile matter in the pellet (total mass of monomer and polymerization solvent)
시마즈 제작소사제의 GC-MS를 사용하여 이하의 조건으로 측정했다.Measurement was performed under the following conditions using GC-MS manufactured by Shimadzu Corporation.
기기：GC-2010, MS-QP2010, 헤드스페이스 샘플러 장착Equipment: GC-2010, MS-QP2010, equipped with headspace sampler
칼럼：Rtx-1, 0.25mm, 1.00μm, 60m(시마즈 지엘시사제)Column: Rtx-1, 0.25mm, 1.00μm, 60m (manufactured by Shimadzu GLsi)
온도 조건: 60℃에서 2분 유지 후, 10℃/분에서 145℃까지 승온하고, 그 후 3℃/분에서 160℃까지 승온했다.Temperature conditions: After holding at 60°C for 2 minutes, the temperature was raised to 145°C at 10°C/min, and then the temperature was raised to 160°C at 3°C/min.
측정 샘플의 제작: 폴리머 0.4g을 전용 바이알병에 넣어, DMF 10ml와 내부 표준(n-노난)이 들어간 클로로포름을 1ml 첨가하여 마개를 막아 시료를 용해 후, 수지 중의 미량 단량체와 시클로헥산(중량ppm)을 측정했다.Preparation of measurement sample: Put 0.4 g of polymer into a dedicated vial, add 10 ml of DMF and 1 ml of chloroform containing the internal standard (n-nonane), close the stopper, and dissolve the sample. Trace monomers in the resin and cyclohexane (ppm by weight) ) was measured.
검량선은 스티렌, α-메틸스티렌, 시클로헥산을 사용하여 작성했다.The calibration curve was prepared using styrene, α-methylstyrene, and cyclohexane.
(3) 분자량 측정(Mn, Mw, Mw/Mn)(3) Molecular weight measurement (Mn, Mw, Mw/Mn)
토소(주)제의 HLC-8220에 칼럼(TSKgel SuperHZM-H, 40℃)을 2개 접속하고, RI 검출기가 장착된 SEC 장치로 측정했다. 이동상은 THF를 사용했다. 분자량의 계산은 폴리스티렌 스탠다드(토소(주)제)를 사용하여 검량선을 작성하고, 폴리스티렌 환산으로 실시했다.Two columns (TSKgel SuperHZM-H, 40°C) were connected to HLC-8220 manufactured by Tosoh Corporation, and measurement was performed using an SEC device equipped with an RI detector. THF was used as the mobile phase. Calculation of molecular weight was performed by creating a calibration curve using a polystyrene standard (manufactured by Tosoh Corporation) and converting it to polystyrene.
(4) 유리 전이 온도(Tg)(4) Glass transition temperature (Tg)
퍼킨엘머(주)제의 DSC-7을 사용하여, JIS-K-7121에 준거하여 구했다. 구체적으로는, 질소하, 10℃/min에서 실온에서 250℃까지 승온하고, 그 후 10℃/min에서 실온까지 복귀하고, 다시 10℃/min에서 250℃까지 승온했다. 2번째의 승온 과정에서 측정되는 유리 전이 온도를 Tg로 했다.It was determined based on JIS-K-7121 using DSC-7 manufactured by PerkinElmer Co., Ltd. Specifically, under nitrogen, the temperature was raised from room temperature to 250°C at 10°C/min, then returned to room temperature at 10°C/min, and then raised again to 250°C at 10°C/min. The glass transition temperature measured during the second temperature increase process was set to Tg.
(5) 스티렌계 공중합체 중의 α-메틸스티렌의 조성(5) Composition of α-methylstyrene in styrene-based copolymer
BRUKER사제의 NMR(DPX-400)을 사용하여 구했다. 스티렌계 공중합체 중의 α-메틸스티렌의 조성(질량%)을 스티렌계 공중합체의 1H-NMR을 측정하여 메틸, 메틸렌, 메틴의 피크 면적비로 계산하여 구했다.It was determined using NMR (DPX-400) manufactured by BRUKER. The composition (% by mass) of α-methylstyrene in the styrene-based copolymer was determined by measuring 1 H-NMR of the styrene-based copolymer and calculating the peak area ratio of methyl, methylene, and methine.
(6) 사출 성형 방법(6) Injection molding method
PNX60(닛세이 쥬시 고교(주)제)을 사용하여 다음과 같은 조건으로 성형했다. 실린더 온도는 호퍼측으로부터 215℃, 225℃, 230℃, 230℃로 설정했다. 금형 온도는 50℃, 사출 시간을 10초, 냉각 시간을 10초로 설정했다. 용융 수지는 수지가 금형에 충전되는 사출 압력으로, 추가로 5MPa 높은 압력을 가해 충전했다. 시험편의 형상은 80mm×80mm×3mm의 평판 형상으로, 내후성 시험용 샘플로서 사용했다.It was molded using PNX60 (manufactured by Nissei Juushi Kogyo Co., Ltd.) under the following conditions. The cylinder temperature was set to 215°C, 225°C, 230°C, and 230°C from the hopper side. The mold temperature was set at 50°C, the injection time was set at 10 seconds, and the cooling time was set at 10 seconds. The molten resin was filled by applying an additional 5 MPa higher pressure than the injection pressure at which the resin is filled into the mold. The shape of the test piece was a flat plate of 80 mm x 80 mm x 3 mm, and was used as a sample for weather resistance testing.
(7) 전 광선투과율(Tt)(7) Total light transmittance (Tt)
헤이즈 가드 II((주)도요 세이키 세이사쿠쇼제)를 이용하여, ASTM D1003에 준거하여 광원 D65의 조건으로 측정했다.Haze Guard II (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used to measure under the conditions of light source D65 in accordance with ASTM D1003.
(8) 황색도(Yi)(8) Yellowness (Yi)
SD6000(닛폰덴쇼쿠고교(주)제)을 이용하여, 광원: D65, 시야: 10°의 조건으로 측정했다.Measurement was performed using SD6000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) under the conditions of light source: D65 and field of view: 10°.
(9) 내후성 평가(SWOM 조사 시험)(9) Weatherability evaluation (SWOM survey test)
듀사이클 선샤인 웨더미터 S80DHBBR형(스가시험기(주)제)를 이용하여 광원:선샤인 카본 아크, 블랙패널 온도 63℃, 강우 조건 18min/120min으로 조사를 실시하여, 조사 전 및 1000시간 조사 후의 전광선 투과율(Tt) 및 황색도(Yi)를 측정했다.Irradiation was conducted using a DuCycle Sunshine Weather Meter S80DHBBR type (manufactured by Suga Tester Co., Ltd.) at a light source: sunshine carbon arc, black panel temperature of 63°C, and rainfall conditions of 18 min/120 min. Total light transmittance before and after 1000 hours of irradiation. (Tt) and yellowness (Yi) were measured.
[제조예][Manufacturing example]
(1) 원료(1) Raw materials
스티렌(St)과 시클로헥산(CH: 이데미츠코산(주)제)은 저장 탱크에 모아 질소 버블링한 후, 용액을 활성 알루미나(스미카아르켐(주)제 KHD-24)를 충전한 5L 용적의 정제탑 내를 통과시켜 정제했다. 또한, St로서는 스미토모카가쿠(주)제와 대만 카가쿠센이사제를 사용했다.Styrene (St) and cyclohexane (CH: manufactured by Idemitsu Kosan Co., Ltd.) were collected in a storage tank and bubbled with nitrogen, and then the solution was placed in a 5L volume filled with activated alumina (KHD-24 manufactured by Sumika Archem Co., Ltd.). It was purified by passing through a purification tower. In addition, as St, products made by Sumitomo Chemical Co., Ltd. and Taiwan Kagakusen Corporation were used.
α-메틸스티렌(αMeSt)은 하기의 조건으로 정제했다. 또한, αMeSt로서는 미츠이카가쿠(주)사제와 신쇼우카가쿠고교사제를 사용했다.α-Methylstyrene (αMeSt) was purified under the following conditions. Additionally, as αMeSt, products manufactured by Mitsui Chemical Co., Ltd. and Shinsho Chemical Industry Co., Ltd. were used.
〈αMeSt 정제 방법〉〈αMeSt Purification Method〉
증류는 단 증류로 실시했다. 구체적으로는 회전자가 들어있는 300ml 반응솥 플라스크에 액온 측정용 온도계를 장착하고, 거기에 증기 온도 측정용 온도계를 장착한 크라이젠 헤드, 리비히 냉각기, 후타마타 어댑터, 받침 플라스크를 연결했다. 또한, 어댑터부에 바큠 컨트롤러((주)오카노세이사쿠쇼제, VC-30S)를 통해 진공 펌프를 접속하여, 감압도를 조절할 수 있도록 했다. 열원은 오일 배스를 사용했다.Distillation was performed as a simple distillation. Specifically, a thermometer for measuring liquid temperature was attached to a 300 ml reaction flask containing a rotor, and a Krysen head equipped with a thermometer for measuring steam temperature, a Liebig cooler, a Futamata adapter, and a support flask were connected to it. Additionally, a vacuum pump was connected to the adapter unit through a vacuum controller (VC-30S, manufactured by Okano Seisakusho Co., Ltd.), allowing the degree of pressure reduction to be adjusted. An oil bath was used as the heat source.
αMeSt 200ml를 반응솥 플라스크에 넣고, 액온을 80℃로 승온했다. 그 후, 염기성 물질로서 나트륨에톡시드(20질량% 에탄올 용액, 후지 필름 와코쥰야쿠(주)제) 0.08질량%를 반응솥 플라스크 내에 회전자로 교반하면서 첨가했다. 감압도를 230mmHg로 조절하고, 액온이 120℃~125℃가 되기까지 천천히 승온했다.200 ml of αMeSt was placed in a reaction flask, and the liquid temperature was raised to 80°C. After that, 0.08% by mass of sodium ethoxide (20% by mass ethanol solution, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a basic substance was added into the reaction flask while stirring with a rotor. The degree of decompression was adjusted to 230 mmHg, and the temperature was slowly raised until the liquid temperature reached 120°C to 125°C.
승온 중에 비점에 도달하여, 냉각된 저비점 유분은 초기 유분으로서 회수했다.The boiling point was reached during the temperature increase, and the cooled low-boiling fraction was recovered as the initial fraction.
액온이 120℃~125℃에 도달하고, 증기 온도도 120℃~125℃에 도달한 시점을 주 유분으로서 회수했다 .The main fraction was recovered when the liquid temperature reached 120°C to 125°C and the steam temperature also reached 120°C to 125°C.
또한, 주 유분은 10 유분으로 분할하여 회수하고, 실시예에서는 아세토닐아세톤의 함유량이 2ppm 이하, 벤즈알데히드의 함유량이 10ppm 이하, 또 페닐아세틸렌의 함유량이 15ppm 이하인 유분만을 사용했다.In addition, the main fraction was divided into 10 fractions and recovered, and in the examples, only fractions with an acetonylacetone content of 2 ppm or less, a benzaldehyde content of 10 ppm or less, and a phenylacetylene content of 15 ppm or less were used.
(2) 공급액의 조정(2) Adjustment of supply amount
상기 (1)의 방법으로 정제한 원료를 St/αMeSt/CH=12.5/19.5/68(wt%)의 비율로 혼합하여, 중합에 제공하는 공급액으로 했다.The raw materials purified by the method (1) above were mixed at a ratio of St/αMeSt/CH=12.5/19.5/68 (wt%) to serve as a feed liquid for polymerization.
(3) 개시제(3) Initiator
n-부틸리튬(15wt%의 n-헥산 용액, 와코 쥰야쿠 가부시키가이샤제)을 1/61배로 시클로헥산으로 희석했다.n-Butyllithium (15 wt% n-hexane solution, manufactured by Wako Pure Chemical Industries, Ltd.) was diluted 1/61 times with cyclohexane.
(4) 정지제(4) Stopping agent
메탄올(특급, 와코 쥰야쿠(주)제)을 3wt%의 농도가 되도록 시클로헥산으로 희석했다.Methanol (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) was diluted with cyclohexane to a concentration of 3 wt%.
(5) 중합 방법(5) Polymerization method
중합 반응기는, 교반 날개(스미토모쥬키(주)제 맥스 블렌드 날개)와 컨덴서가 장착되고, 또 원료 도입 노즐, 개시제 도입 노즐과 중합 용액 배출 노즐이 장착된 재킷 부착 5L의 반응기(R1)를 사용했다. 컨덴서의 출구는 질소 가스로 밀봉하여, 외부로부터 공기가 혼입되지 않도록 했다. 중합 반응기 내의 중합 용액의 용량은 항상 3L가 되도록 제어했다. 중합 용액으로부터는 항상 용액의 일부가 끓고 있는 상태로 하고, 내온을 79℃~81℃의 사이로 제어했다. 교반 날개의 회전수는 320rpm으로 했다. 중합 반응기의 원료 입구와 출구에는 각각 기어 펌프가 장착되어 있고, 조정이 완료된 공급액을 1.5L/Hr의 일정 유량으로 흐를 수 있도록 제어했다. 또한, 개시제 용액은 0.09L/Hr로 중합 반응기 내에 도입했다.The polymerization reactor was a 5L jacketed reactor (R1) equipped with a stirring blade (Max Blend blade manufactured by Sumitomo Juki Co., Ltd.) and a condenser, and also equipped with a raw material introduction nozzle, an initiator introduction nozzle, and a polymerization solution discharge nozzle. . The outlet of the condenser was sealed with nitrogen gas to prevent air from entering from the outside. The capacity of the polymerization solution in the polymerization reactor was always controlled to be 3 L. A portion of the polymerization solution was always kept boiling, and the internal temperature was controlled between 79°C and 81°C. The rotation speed of the stirring blade was 320 rpm. Gear pumps were installed at the raw material inlet and outlet of the polymerization reactor, and the adjusted feed liquid was controlled to flow at a constant flow rate of 1.5 L/Hr. Additionally, the initiator solution was introduced into the polymerization reactor at 0.09 L/Hr.
중합 반응기로부터 배출된 리빙 폴리머의 용액은, 또한 기어 펌프로 10mm 직경의 배관을 통해 중합 정지제 용액의 도입구까지 인도했다. 반응기로부터 정지제 혼합점까지의 배관의 길이는 약 2m, 배관은 65~70℃에서 보온했다. 정지제 용액은, 0.13L/Hr에서의 유속으로 중합 반응액 내에 도입하고, 그 후에는 1.2L 용량의 정적 믹서(Sulzer(주)제, SMX형)를 거쳐 완전히 중합 반응을 정지시켰다. 또한, 폴리머 용액을 예열기로 260℃까지 가열하고, 그 후 60torr의 감압하, 설정 260℃로 가온 된 약 50L의 용기 내로 플러싱하고, 용매와 미반응 모노머를 폴리머로부터 분리, 회수했다. 플러싱 용기 내의 폴리머 온도는 약 240~250℃, 폴리머의 탱크 내의 체류 시간은 약 20~30분이었다. 충분히 휘발 성분이 제거된 폴리머는 그 후, 로프 형상으로 배출되어 수중 하에서 냉각 후, 컷터로 펠레타이징하여 스티렌계 공중합체를 회수했다.The solution of the living polymer discharged from the polymerization reactor was further guided by a gear pump to the inlet of the polymerization terminator solution through a pipe with a diameter of 10 mm. The length of the pipe from the reactor to the stopping agent mixing point was about 2 m, and the pipe was kept warm at 65 to 70°C. The stopper solution was introduced into the polymerization reaction liquid at a flow rate of 0.13 L/Hr, and then the polymerization reaction was completely stopped through a 1.2 L capacity static mixer (Sulzer Co., Ltd., SMX type). Additionally, the polymer solution was heated to 260°C with a preheater, and then flushed into a container of approximately 50 L heated to 260°C under reduced pressure of 60 torr, and the solvent and unreacted monomer were separated and recovered from the polymer. The temperature of the polymer in the flushing vessel was about 240 to 250°C, and the residence time of the polymer in the tank was about 20 to 30 minutes. The polymer from which volatile components were sufficiently removed was then discharged in the form of a rope, cooled in water, and then pelletized with a cutter to recover the styrene-based copolymer.
[실시예 1~3, 비교예 1~3][Examples 1 to 3, Comparative Examples 1 to 3]
원료 로트를 바꾸어 조정한 공급액을 중합하여 얻어진 펠릿을 사용하여, 다양한 분석·평가를 실시했다. 그 결과를 표 1 및 표 2에 나타낸다. 또한, 얻어진 공중합체 중의 αMeSt 단위의 조성은 52질량%였다.Various analyzes and evaluations were performed using pellets obtained by polymerizing the feed liquid adjusted by changing the raw material lot. The results are shown in Table 1 and Table 2. Additionally, the composition of αMeSt units in the obtained copolymer was 52% by mass.
[표 1][Table 1]
[표 2][Table 2]
표 1 및 표 2로부터 명확한 바와 같이, 본 발명의 스티렌계 공중합체는 내후성이 우수한 것을 알 수 있다.As is clear from Tables 1 and 2, the styrene-based copolymer of the present invention has excellent weather resistance.
본 발명의 스티렌계 공중합체는 중합에 제공하는 공급액 중의 특정 화합물의 함유량을 특정 범위로 제어하는 것에 의해, 내후성이 우수한 특성을 갖는다. 또한, 본 발명의 스티렌계 공중합체를 함유하는 성형품은 가온용 식품 용기, 주택용 부품, 자동차 실내용 부품, 광학용 부품으로서 매우 적합하게 사용할 수 있다.The styrene-based copolymer of the present invention has excellent weather resistance by controlling the content of a specific compound in the feed liquid used for polymerization to a specific range. Additionally, molded articles containing the styrene-based copolymer of the present invention can be suitably used as food containers for warming, parts for houses, parts for automobile interiors, and parts for optical purposes.
Claims (4)
[화학식 1]
(화학식 1에 있어서, R1은 수소 원자, 탄소수 2 이상의 알킬기 또는 페닐기를 나타내고, R2는 수소 원자, 할로겐 원자, 히드록실기, C1-C6 알킬기, C1-C6 알콕시기, 카르복실기, 또는 할로 C1-C6 알킬기를 나타낸다.)A copolymer containing an α-methylstyrene unit obtained by living anionic polymerization and a vinyl aromatic monomer unit represented by the following general formula (1), which has a total light transmittance after 1000 hours of irradiation in a weather resistance test using a Sunshine Weather Meter. A styrene-based copolymer with a change of 5% or less and a change in yellowness of 5 or less.
[Formula 1]
(In Formula 1, R 1 represents a hydrogen atom, an alkyl group having 2 or more carbon atoms, or a phenyl group, and R 2 represents a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a carboxyl group, or a halo C1 -C6 represents an alkyl group.)
상기 공중합체 중의 α-메틸스티렌 단위의 함유량이 10~65 질량%이고, 중량 평균 분자량(Mw)은 Mw=5만~30만의 범위이며, 중량 평균 분자량(Mw)과 수평균 분자량(Mn)의 비(Mw/Mn)가 1.6~2.5의 범위에 있고, 또 잔존하는 단량체 및 중합 용매의 총 질량이 500ppm 이하인, 스티렌계 공중합체.According to claim 1,
The content of α-methylstyrene units in the copolymer is 10 to 65% by mass, the weight average molecular weight (Mw) is in the range of Mw = 50,000 to 300,000, and the weight average molecular weight (Mw) and number average molecular weight (Mn) are in the range. A styrene-based copolymer wherein the ratio (Mw/Mn) is in the range of 1.6 to 2.5, and the total mass of remaining monomers and polymerization solvent is 500 ppm or less.
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| JP4306682B2 (en) | 2003-11-06 | 2009-08-05 | 旭化成ケミカルズ株式会社 | Styrene copolymer and process for producing the same |
| JP4327239B2 (en) | 2006-04-17 | 2009-09-09 | 旭化成ケミカルズ株式会社 | Method for producing α-methylstyrene, and method for producing heat-resistant styrene copolymer using the α-methylstyrene |
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- 2023-08-31 KR KR1020230115659A patent/KR20240043679A/en unknown
- 2023-09-22 CN CN202311231686.0A patent/CN117777340A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4306682B2 (en) | 2003-11-06 | 2009-08-05 | 旭化成ケミカルズ株式会社 | Styrene copolymer and process for producing the same |
| JP4327239B2 (en) | 2006-04-17 | 2009-09-09 | 旭化成ケミカルズ株式会社 | Method for producing α-methylstyrene, and method for producing heat-resistant styrene copolymer using the α-methylstyrene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117777340A (en) | 2024-03-29 |
| JP2024048074A (en) | 2024-04-08 |
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