KR20020042964A - 유동성이 우수한 고무변성 스티렌계 공중합 투명수지의제조방법 - Google Patents
유동성이 우수한 고무변성 스티렌계 공중합 투명수지의제조방법 Download PDFInfo
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- KR20020042964A KR20020042964A KR1020000072334A KR20000072334A KR20020042964A KR 20020042964 A KR20020042964 A KR 20020042964A KR 1020000072334 A KR1020000072334 A KR 1020000072334A KR 20000072334 A KR20000072334 A KR 20000072334A KR 20020042964 A KR20020042964 A KR 20020042964A
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- 229920005989 resin Polymers 0.000 title claims abstract description 57
- 239000011347 resin Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 32
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229920001577 copolymer Polymers 0.000 claims abstract description 37
- 229920001971 elastomer Polymers 0.000 claims abstract description 30
- 239000005060 rubber Substances 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 18
- 229920000126 latex Polymers 0.000 claims abstract description 16
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 15
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 13
- 239000004816 latex Substances 0.000 claims abstract description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000005453 pelletization Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 150000003440 styrenes Chemical class 0.000 claims description 36
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 239000012986 chain transfer agent Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- -1 alkyl styrene Chemical compound 0.000 claims description 9
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical group CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 7
- 229920006249 styrenic copolymer Polymers 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 235000012830 plain croissants Nutrition 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000578 graft copolymer Polymers 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 claims description 2
- KQJQPCJDKBKSLV-UHFFFAOYSA-N 1-bromo-3-ethenylbenzene Chemical compound BrC1=CC=CC(C=C)=C1 KQJQPCJDKBKSLV-UHFFFAOYSA-N 0.000 claims description 2
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 claims description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- LWZNQGJGMBRAII-UHFFFAOYSA-N 2-methylhexyl prop-2-enoate Chemical compound CCCCC(C)COC(=O)C=C LWZNQGJGMBRAII-UHFFFAOYSA-N 0.000 claims description 2
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 238000012662 bulk polymerization Methods 0.000 claims description 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229920006026 co-polymeric resin Polymers 0.000 claims description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 2
- 230000000593 degrading effect Effects 0.000 abstract 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 16
- 230000000704 physical effect Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/06—Vinyl aromatic monomers and methacrylates as the only monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
| 구분 | 실시예 1 | 실시예 2 | 실시예 3 | 실시예 4 | 실시예 5 | 비교예 1 | 비교예 2 |
| 헤이즈값 (%) | 4.6 | 4.3 | 4.5 | 5.0 | 6.0 | 7.5 | 3.9 |
| 전광선투과율 (%) | 89.2 | 88.3 | 89.1 | 89.1 | 89.2 | 88.6 | 89.1 |
| 아이조드 충격강도(㎏ ㎝/㎝) | 7.0 | 7.5 | 8.3 | 7.1 | 7.2 | 5.1 | 8.5 |
| MI (g/10 min) | 8.9 | 6.3 | 4.6 | 4.5 | 3.1 | 9.3 | 2.1 |
| 열변형온도 (℃) | 81 | 82 | 83 | 83 | 87 | 80 | 83 |
| 고무 평균입경 (㎛) | 0.7 | 0.6 | 0.6 | 0.7 | 0.8 | 1.3 | 0.6 |
Claims (10)
- 스티렌-부타디엔 고무라텍스의 존재 하에 스티렌계 모노머와 메타크릴레이트 모노머를 그라프트 공중합시켜서 제조되는 유동성이 우수한 고무변성 스티렌계 투명수지의 제조방법에 있어서, 상전환한 이후에 머캅탄계 연쇄이동제를 투입하고, 더욱 중합시키는 단계를 포함하는 고무변성 스티렌계 공중합 투명수지의 제조방법.
- 제 1 항에 있어서,a) 스티렌-부타디엔 고무라텍스를 스티렌계 모노머와 메타크릴레이트 모노머혼합용액에 용해시켜 원료 혼합용액을 제조하는 단계;b) 상기 a) 단계의 혼합용액을 3 개 이상의 교반 반응기가 직렬로 연결된 연속 중 합장치의 제 1 반응기에 투입하여 그라프트 공중합시켜서 고무상으로상전환시키는 단계;c) 상기 b) 단계의 상전환된 공중합체를 제 2 반응기로 연속투입하고, 여기에 머캅탄계 연쇄이동제를 투입하여 그라프트 공중합시키는 단계;d) 상기 c) 단계의 공중합체를 제 3 이상의 반응기에 연속투입하여 그라프트공중합시키는 단계; 및e) 상기 d) 단계의 공중합체를 탈휘발, 및 펠렛화시키는 단계를 포함하는 고무변성 스티렌계 공중합 투명수지의 제조방법.
- 제 1 항에 있어서,a) 스티렌-부타디엔 고무라텍스 3 내지 15 중량부를ⅰ) 스티렌계 모노머 30∼60 중량부; 및ⅱ) 메틸메타크릴레이트 모노머 40∼70 중량부의 중량비로 혼합되는 모노머 혼합용액 85∼97 중량부에 용해시켜 원료 혼합용액을 제조하는 단계;b) 상기 a) 단계의 혼합용액을 3 개 이상의 교반 반응기가 직렬로 연결된 연속 중 연속 중합장치의 제 1 반응기에 온도 120∼135 ℃로 투입하여 그라프트 공중합시켜 고무상으로 상전환시키는 단계;c) 상기 b) 단계의 상전환된 공중합체를 제 2 반응기로 연속투입하고, 여기에 ⅲ) 머캅탄계 연쇄이동제 250∼1200 ppm를 투입하여 그라프트 공중합하는 단계;e) 상기 d) 단계의 공중합체를 제 3 이상의 반응기에 연속투입하여 중합전환률이 70∼90 %가 될 때까지 그라프트 공중합시키는 단계; 및f) 상기 e) 단계의 공중합체를 탈휘발, 및 펠렛화시키는 단계를 포함하는 고무변성 스티렌계 공중합 투명수지의 제조방법.
- 제 1 항 내지 제 3 항 중 어느 한 항에 있어서,상기 a) 스티렌-부타디엔 고무라텍스가 25 ℃에서 5 % 톨루엔 용액점도가 20∼40 cp이고, 스티렌 골격 함유율이 10∼50 %인 블록, 및 랜던 공중합체로 이루어진 군으로부터 선택되는 고무변성 스티렌계 공중합 투명수지의 제조방법.
- 제 1 항 내지 제 3 항 중 어느 한 항에 있어서,상기 a)ⅰ)스티렌계 모노머가 스티렌, α-메틸 스티렌,o-메틸 스티렌,p-메틸 스티렌,m-메틸 스티렌, 에틸 스티렌,i-부틸 스티렌,t-부틸 스티렌 등의 알킬 스티렌; 및o-브로모 스티렌,p-브로모 스티렌,m-브로모 스티렌,o-크로로 스티렌,p-크로로 스티렌,m-크로로 스티렌 등의 할로겐화 스티렌으로 이루어진 군으로부터 1 종 이상 선택되는 고무변성 스티렌계 공중합 투명수지의 제조방법.
- 제 1 항 내지 제 3 항 중 어느 한 항에 있어서,상기 a) 모노머 혼합용액은 a)ⅱ) 메틸메타크릴레이트 100 중량부에 대하여 알킬 아크릴산 에스테르계 모노머 1 내지 6 중량부를 더욱 포함하여 혼합되는 고무변성 스티렌계 공중합 투명수지의 제조방법.
- 제 6 항에 있어서,상기 알킬 아크릴산 에스테르계 모노머는 메틸 아크릴레이트, 에틸 아크릴레이트,n-부틸 아크릴레이트, 2-메틸 헥실 아크릴레이트, 및 2-에틸 헥실 아크릴레이트로 이루어진 군으로부터 선택되는 고무변성 스티렌계 공중합 투명수지의 제조방법.
- 제 1 항 내지 제 3 항 중 어느 한 항에 있어서,상기 c)ⅲ) 머캅탄 연쇄이동제가n-옥틸 머캅탄,n-도데실 머캅탄, 및t-도데실 머캅탄으로 이루어진 군으로부터 1 종 이상 선택되는 고무변성 스티렌계 공중합 투명수지의 제조방법.
- 제 1 항 내지 제 3 항 중 어느 한 항에 있어서,상기 고무변성 스티렌계 제조 공정이 연속, 또는 회분식의 괴상중합, 용액중합, 및 괴상-현탁중합으로 이루어진 군으로부터 1 종 이상 선택되어 실시되는 고무변성 스티렌계 공중합 투명수지의 제조방법.
- 제 1 항 내지 제 3 항 중 어느 한 항에 있어서,상기 고무변성 스티렌계 제조방법으로 제조되는 고무변성 스티렌계 공중합 수지 중 분산된 고무입자의 평균입경이 1.2 ㎛ 이하인 고무변성 스티렌계 공중합 투명수지의 제조방법.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190060499A (ko) * | 2017-11-24 | 2019-06-03 | 주식회사 엘지화학 | 무광 열가소성 수지의 제조방법 및 이로부터 제조된 무광 열가소성 수지 |
| CN119638899A (zh) * | 2024-11-05 | 2025-03-18 | 大连理工大学 | 一种mbs树脂的制备方法 |
| CN119638900A (zh) * | 2024-11-05 | 2025-03-18 | 大连理工大学 | 一种mabs树脂的制备方法 |
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| KR100600566B1 (ko) | 2004-12-27 | 2006-07-13 | 제일모직주식회사 | 유동성이 우수한 분지구조의 메타크릴계 수지의 제조방법 |
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| DE3023721A1 (de) * | 1980-06-25 | 1982-01-21 | Basf Ag, 6700 Ludwigshafen | Verfahren zur kontinuierlichen herstellung von mit kautschuk modifizierten polymerisaten von vinylaromaten |
| DE3047303A1 (de) * | 1980-12-16 | 1982-07-29 | Basf Ag, 6700 Ludwigshafen | Verfahren zur kontinuierlichen herstellung von mit kautschuk modifizierten polymerisaten von vinylaromaten, verwendung derselben zum spritzgiessen, sowie formteile aus diesen |
| JPS5891707A (ja) * | 1981-11-27 | 1983-05-31 | Dainippon Ink & Chem Inc | ラテックスポリマ−の製造方法 |
| JPS6094414A (ja) * | 1983-10-28 | 1985-05-27 | Mitsui Toatsu Chem Inc | ゴム変性耐衝撃性樹脂の連続的製造方法 |
| KR950012365B1 (ko) * | 1991-10-17 | 1995-10-17 | 주식회사코오롱 | 주행 및 내구성이 우수한 자기기록매체 및 그의 제조방법 |
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| KR20190060499A (ko) * | 2017-11-24 | 2019-06-03 | 주식회사 엘지화학 | 무광 열가소성 수지의 제조방법 및 이로부터 제조된 무광 열가소성 수지 |
| CN119638899A (zh) * | 2024-11-05 | 2025-03-18 | 大连理工大学 | 一种mbs树脂的制备方法 |
| CN119638900A (zh) * | 2024-11-05 | 2025-03-18 | 大连理工大学 | 一种mabs树脂的制备方法 |
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