CN117642440A - Method for preparing graft copolymer, and resin composition comprising the same - Google Patents
Method for preparing graft copolymer, and resin composition comprising the same Download PDFInfo
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- CN117642440A CN117642440A CN202280049457.4A CN202280049457A CN117642440A CN 117642440 A CN117642440 A CN 117642440A CN 202280049457 A CN202280049457 A CN 202280049457A CN 117642440 A CN117642440 A CN 117642440A
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- acrylonitrile
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- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 132
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000011342 resin composition Substances 0.000 title claims abstract description 57
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000011347 resin Substances 0.000 claims abstract description 52
- 239000011159 matrix material Substances 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims description 257
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 221
- 239000000203 mixture Substances 0.000 claims description 127
- 229920000642 polymer Polymers 0.000 claims description 64
- 150000001993 dienes Chemical class 0.000 claims description 62
- 229920002554 vinyl polymer Polymers 0.000 claims description 47
- 238000002347 injection Methods 0.000 claims description 41
- 239000007924 injection Substances 0.000 claims description 41
- 239000003607 modifier Substances 0.000 claims description 29
- 239000004816 latex Substances 0.000 claims description 28
- 229920000126 latex Polymers 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 claims description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical group CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 11
- 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 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 230000000379 polymerizing effect Effects 0.000 claims description 9
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 claims description 9
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 6
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 6
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 5
- HSNHLHNSJCYPNU-UHFFFAOYSA-N o-propan-2-yl propan-2-ylsulfanylmethanethioate Chemical compound CC(C)OC(=S)SC(C)C HSNHLHNSJCYPNU-UHFFFAOYSA-N 0.000 claims description 5
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 claims description 4
- 230000000149 penetrating effect Effects 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 153
- 239000000463 material Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 27
- 239000002245 particle Substances 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 21
- 239000002585 base Substances 0.000 description 17
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 10
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 9
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 230000006866 deterioration Effects 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000012966 redox initiator Substances 0.000 description 6
- -1 specifically Chemical compound 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 5
- 239000003125 aqueous solvent Substances 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 238000010559 graft polymerization reaction Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 3
- VDNSZPNSUQRUMS-UHFFFAOYSA-N 1-cyclohexyl-4-ethenylbenzene Chemical compound C1=CC(C=C)=CC=C1C1CCCCC1 VDNSZPNSUQRUMS-UHFFFAOYSA-N 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 2
- RRRXUCMQOPNVAT-UHFFFAOYSA-N 1-ethenyl-4-(4-methylphenyl)benzene Chemical compound C1=CC(C)=CC=C1C1=CC=C(C=C)C=C1 RRRXUCMQOPNVAT-UHFFFAOYSA-N 0.000 description 2
- VVTGQMLRTKFKAM-UHFFFAOYSA-N 1-ethenyl-4-propylbenzene Chemical compound CCCC1=CC=C(C=C)C=C1 VVTGQMLRTKFKAM-UHFFFAOYSA-N 0.000 description 2
- OIEANVCCDIRIDJ-UHFFFAOYSA-N 1-ethenyl-5-hexylnaphthalene Chemical compound C1=CC=C2C(CCCCCC)=CC=CC2=C1C=C OIEANVCCDIRIDJ-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 2
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 2
- RLFXJQPKMZNLMP-UHFFFAOYSA-N 2-phenylprop-2-enenitrile Chemical compound N#CC(=C)C1=CC=CC=C1 RLFXJQPKMZNLMP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229940096818 dipentamethylenethiuram disulfide Drugs 0.000 description 2
- VAAKDLOTVZBUNR-UHFFFAOYSA-L disodium;3-ethyloctan-3-yl phosphate Chemical compound [Na+].[Na+].CCCCCC(CC)(CC)OP([O-])([O-])=O VAAKDLOTVZBUNR-UHFFFAOYSA-L 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- KNBRWWCHBRQLNY-UHFFFAOYSA-N piperidine-1-carbothioylsulfanyl piperidine-1-carbodithioate Chemical compound C1CCCCN1C(=S)SSC(=S)N1CCCCC1 KNBRWWCHBRQLNY-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- UGWOAPBVIGCNOV-UHFFFAOYSA-N 5-ethenyldec-5-ene Chemical compound CCCCC=C(C=C)CCCC UGWOAPBVIGCNOV-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- RZUHBLGLDSYPOM-UHFFFAOYSA-N OP(O)(=O)OP(=O)(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC Chemical compound OP(O)(=O)OP(=O)(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC RZUHBLGLDSYPOM-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- IMJGQTCMUZMLRZ-UHFFFAOYSA-N buta-1,3-dien-2-ylbenzene Chemical compound C=CC(=C)C1=CC=CC=C1 IMJGQTCMUZMLRZ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000012888 cubic function Methods 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The present invention provides a method of preparing a graft copolymer applied to a resin composition comprising a graft copolymer and a matrix resin, and relates to a method of preparing a graft copolymer which maintains impact properties such as impact strength and falling ball impact strength to the same or better level while improving flowability and subsequently improving processability, a graft copolymer prepared by the method, and a resin composition comprising the graft copolymer.
Description
Technical Field
Cross-reference to related applications
The present application claims the benefit of priority based on korean patent application No.10-2021-0104040 filed on 8/6 of 2021, the entire contents of which are incorporated herein by reference.
The present invention relates to a method of preparing a graft copolymer, and a resin composition comprising the same.
Background
Acrylonitrile-butadiene-styrene (ABS) copolymers are prepared by graft copolymerization of styrene and acrylonitrile on butadiene rubber polymers. ABS copolymers have excellent impact resistance, chemical resistance, thermal stability, colorability, fatigue resistance, rigidity and processability when compared to conventional High Impact Polystyrene (HIPS), and are used in parts or toys such as interior and exterior materials of automobiles, office equipment and various electric and electronic products.
ABS copolymers are generally prepared by an emulsion polymerization method and are used as materials for conventional resin compositions, flame-retardant resin compositions, extrusion resin compositions, heat-resistant resin compositions, and transparent resin compositions according to the properties of the mixed matrix resin. Thus, since ABS copolymers can be used as materials in various fields, efforts have been continuously made to satisfy the physical properties required in various fields in addition to matrix resins.
At the same time, ABS copolymers are essentially impact resistant. Therefore, as a method of improving the impact resistance of the ABS copolymer, a method of controlling the proportion of monomers and maximizing the grafting ratio to change the composition of monomers to be graft polymerized to and from rubber particles has been proposed, but in this case, in the process of preparing a resin composition comprising the ABS copolymer and a matrix resin, deterioration of flowability may cause a problem of deterioration of processability.
In addition, although the same ABS copolymer is applied in a resin composition including the ABS copolymer and a matrix resin, physical properties of the ABS copolymer itself may not be completely exhibited according to the type of matrix resin, and defects that individually deteriorate physical properties such as impact resistance and processability may occur.
[ Prior Art literature ]
[ patent literature ]
(patent document 1) JP1994-192346A
Disclosure of Invention
Technical problem
In order to solve the above-mentioned problems mentioned in the background art, an object of the present invention is to prepare a graft copolymer capable of maintaining impact properties at the same or better level regardless of the type of matrix resin and improving flowability and processability in a resin composition comprising the graft copolymer and the matrix resin.
That is, the present invention has been devised to solve the problems of the conventional art, and an object is to provide a method of preparing a graft copolymer which is applied to a resin composition comprising a graft copolymer and a matrix resin, by which impact properties such as impact strength and ball drop impact strength are maintained at the same or better level, and flowability and thus processability are improved.
In addition, it is another object of the present invention to provide a graft copolymer prepared by the preparation method.
In addition, another object of the present invention is to provide a resin composition comprising the graft copolymer.
Technical proposal
In order to solve the above-mentioned task, the present invention provides a method of preparing a graft copolymer, the graft copolymer prepared thereby, and a resin composition comprising the same.
(1) The present invention provides a method for preparing a graft copolymer, comprising: a step (S10) of injecting a first monomer mixture and a first molecular weight modifier in batches and polymerizing in the presence of a conjugated diene-based polymer latex to prepare a preliminary graft copolymer latex containing a preliminary graft copolymer; and a step (S20) of continuously injecting a second monomer mixture, a first molecular weight modifier and a second molecular weight modifier different from the first molecular weight modifier, and polymerizing in the presence of the preliminary graft copolymer latex prepared in step (S10) to prepare a graft copolymer latex comprising a graft copolymer, wherein the first monomer mixture comprises 60 to 85% by weight of an aromatic vinyl monomer and 15 to 40% by weight of a vinyl cyanide monomer, and the second monomer mixture comprises 73 to 99% by weight of an aromatic vinyl monomer and 1 to 27% by weight of a vinyl cyanide monomer.
(2) The present invention provides the method for producing a graft copolymer according to (1), wherein the conjugated diene polymer latex comprises a conjugated diene polymer, and the conjugated diene polymer is injected in an amount of 50 to 80 parts by weight based on 100 parts by weight of the total injection amount of the conjugated diene polymer, the aromatic vinyl monomer and the vinyl cyanide monomer.
(3) The present invention provides the process for producing a graft copolymer according to (1) or (2), wherein the first monomer mixture contains 25 to 40% by weight of a vinyl cyanide-based monomer.
(4) The present invention provides the process for producing a graft copolymer according to any one of (1) to (3), wherein the second monomer mixture contains 15 to 25% by weight of a vinyl cyanide-based monomer.
(5) The present invention provides the process for producing a graft copolymer according to any one of (1) to (4), wherein the first molecular weight regulator is one or more selected from the group consisting of t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan, carbon tetrachloride, methylene chloride, dibromomethane, tetraethylthiuram disulfide, dipentylene thiuram disulfide and diisopropylxanthate disulfide.
(6) The present invention provides the method for producing a graft copolymer according to any one of (1) to (5), wherein the total amount of the first molecular weight modifier in the step (S10) and the step (S20) is 0.20 parts by weight to 0.40 parts by weight based on 100 parts by weight of the total amount of the conjugated diene polymer, the aromatic vinyl monomer and the vinyl cyanide monomer.
(7) The present invention provides the process for producing a graft copolymer according to any one of (1) to (7), wherein the second molecular weight modifier is one or more selected from the group consisting of an α -methylstyrene dimer, n-dodecylmercaptan, octylmercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetraethylthiuram disulfide, dipentamethylenethiuram disulfide and diisopropylxanthate disulfide.
(8) The present invention provides the method for producing a graft copolymer according to any one of (1) to (8), wherein the injection amount of the second molecular weight regulator in step (S20) is 0.01 to 0.40 parts by weight based on 100 parts by weight of the total injection amount of the conjugated diene-based polymer, the aromatic vinyl-based monomer and the vinyl cyanide-based monomer.
(9) The present invention provides a graft copolymer produced according to the process for producing a graft copolymer of any one of (1) to (8), comprising: conjugated diene polymers; a first graft layer formed by infiltration into the conjugated diene-based polymer or externally; and a second graft layer formed by wrapping the first graft layer, wherein the first graft layer comprises 60 to 85 wt% of aromatic vinyl monomer units and 15 to 40 wt% of vinyl cyanide monomer units, and the second graft layer comprises 73 to 99 wt% of aromatic vinyl monomer units and 1 to 27 wt% of vinyl cyanide monomer units.
(10) The present invention provides a resin composition comprising the graft copolymer according to (9) and a matrix resin.
(11) The present invention provides the resin composition according to (10), wherein the base resin comprises an aromatic vinyl monomer unit and a vinyl cyanide monomer unit.
(12) The present invention provides the resin composition according to (10) or (11), wherein the base resin comprises an α -methylstyrene monomer unit and a vinyl cyanide monomer unit.
Advantageous effects
In the resin composition comprising the graft copolymer and the matrix resin, the graft copolymer produced by the process for producing a graft copolymer according to the present invention can maintain impact properties at the same or better level regardless of the type of matrix resin, and can improve flowability and subsequently improve processability.
Detailed Description
Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.
It should be understood that words or terms used in the specification and claims of the present invention should not be construed as meaning defined in a commonly used dictionary. It is to be understood that the words or terms should be construed to have meanings consistent with the meanings in the technical concept of the present invention based on the principle that the inventor can properly define the words to better explain the invention.
The term "monomer unit" in the present invention may refer to a component or structure derived from a monomer or the material itself, and in particular embodiments, may refer to a repeating unit formed in a polymer during polymerization of the polymer by participation of a monomer injected into the polymerization reaction.
The term "latex" in the present invention may refer to a dispersed polymer or copolymer polymerized by polymerization in water, and in particular, may refer to dispersed minute particles of a polymer having a rubber phase or a copolymer having a rubber phase polymerized by emulsion polymerization in a colloidal state in water.
The term "composition" as used in the present invention encompasses reaction products and decomposition products formed from materials of the respective compositions and mixtures comprising materials of the respective compositions.
The present invention provides a process for preparing a graft copolymer.
According to one embodiment of the present invention, the method for preparing a graft copolymer comprises: a step (S10) of injecting the first monomer mixture and the first molecular weight modifier in batches and polymerizing in the presence of the conjugated diene-based polymer latex to prepare a preliminary graft copolymer latex containing a preliminary graft copolymer; and a step (S20) of continuously injecting a second monomer mixture, a first molecular weight modifier, and a second molecular weight modifier different from the first molecular weight modifier, and polymerizing in the presence of the preliminary graft copolymer latex prepared in step (S10) to prepare a graft copolymer latex including a graft copolymer, wherein the first monomer mixture may include 60 to 85 wt% of an aromatic vinyl monomer and 15 to 40 wt% of a vinyl cyanide monomer, and the second monomer mixture may include 73 to 99 wt% of an aromatic vinyl monomer and 1 to 27 wt% of a vinyl cyanide monomer.
According to one embodiment of the present invention, the method of preparing a graft copolymer may prepare a core-shell graft copolymer by preliminarily graft polymerizing a first monomer mixture onto a conjugated diene-based polymer through step (S10), and forming a first graft layer by penetrating monomer units formed from the first monomer mixture into the conjugated diene-based polymer or forming the first graft layer outside, and forming a second graft layer in a wrapping shape of the first graft layer through step (S20).
According to one embodiment of the present invention, the step (S10) and the step (S20) may be continuously performed in the graft copolymerization for preparing the graft copolymer, and in particular, may be performed by continuously injecting the second monomer mixture, the first molecular weight regulator, and the second molecular weight regulator different from the first molecular weight regulator during the batch injection and polymerization of the first monomer mixture and the first molecular weight regulator in the presence of the conjugated diene-based polymer latex according to the step (S10).
According to one embodiment of the present invention, step (S10) may be performed in the presence of the conjugated diene-based polymer latex. Accordingly, the first monomer mixture injected in step (S10) may be graft-polymerized onto the conjugated diene-based polymer contained in the conjugated diene-based polymer latex to prepare a preliminary graft copolymer containing a first graft layer formed by infiltration of monomer units formed from the first monomer mixture into the conjugated diene-based polymer or outside. The conjugated diene polymer latex may be prepared by the step (S1) for preparing the conjugated diene polymer. Step (S1) is a step of polymerizing a conjugated diene-based monomer to prepare a conjugated diene-based polymer, and the conjugated diene-based monomer may be one or more selected from 1, 3-butadiene, 2, 3-dimethyl-1, 3-butadiene, piperylene, 3-butyl-1, 3-octadiene, isoprene, and 2-phenyl-1, 3-butadiene, specifically, 1, 3-butadiene.
According to one embodiment of the present invention, step (S1) may be performed by emulsion polymerization, and thus, a conjugated diene polymer latex type including a conjugated diene polymer may be obtained.
According to an embodiment of the present invention, step (S1) may be performed by radical polymerization using a peroxide-based initiator, a redox initiator, or an azo-based initiator, and the redox initiator may be, for example, one or more selected from t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, and cumene hydroperoxide. In this case, a stable polymerization environment can be provided.
According to one embodiment of the present invention, if a redox initiator is used, ferrous sulfate, sodium ethylenediamine tetraacetate or sodium formaldehyde sulfoxylate may also be included.
According to an embodiment of the present invention, the emulsifier used in the emulsion polymerization process of step (S1) may be one or more selected from anionic emulsifiers, cationic emulsifiers and nonionic emulsifiers, in particular, one or more selected from alkylaryl sulfonates, alkali methylalkyl sulfates, fatty acid soaps, alkali oleates, alkali abietates, alkali laurates, sodium diethylhexyl phosphate, phosphonated polyoxyethylene alcohols and phosphonated polyoxyethylene phenols. In this case, there may be an effect of providing a stable polymerization environment. The emulsifier may be injected, for example, 5.0 parts by weight or less, 3.0 parts by weight or less, or 0.5 parts by weight to 2.5 parts by weight based on 100 parts by weight of the total amount of the conjugated diene-based monomer injected in step (S1).
According to an embodiment of the present invention, the emulsion polymerization in step (S1) may be performed in an aqueous solvent, and the aqueous solvent may be ion-exchanged water.
According to one embodiment of the present invention, the conjugated diene polymer latex may include a conjugated diene polymer, and the conjugated diene polymer may be injected in an amount of 50 to 80 parts by weight based on 100 parts by weight of the total injection amount of the conjugated diene polymer, the aromatic vinyl monomer, and the vinyl cyanide monomer. The injected amount of the conjugated diene polymer is a basic amount of the solid content of the conjugated diene polymer in the conjugated diene polymer latex. In a specific embodiment, the conjugated diene-based polymer may be 50 parts by weight or more, 52 parts by weight or more, 54 parts by weight or more, 56 parts by weight or more, 58 parts by weight or more, or 60 parts by weight or more, and 80 parts by weight or less, 75 parts by weight or less, 70 parts by weight or less, 68 parts by weight or less, 66 parts by weight or less, 64 parts by weight or less, 62 parts by weight or 60 parts by weight or less, based on 100 parts by weight of the total injection amount of the conjugated diene-based polymer, the aromatic vinyl-based monomer, and within this range, the compatibility of the graft copolymer with the matrix resin may be prevented from deteriorating, and the impact resistance may be improved.
According to an embodiment of the present invention, the first monomer mixture injected in step (S10) may include an aromatic vinyl-based monomer and a vinyl cyanide-based monomer. In this case, in the process of preparing the resin composition comprising the graft copolymer, in order to improve flowability and subsequently improve processability while maintaining the same or better level of impact properties such as impact resistance regardless of the type of matrix resin, it is important to control the amount of vinyl cyanide-based monomer in the first monomer mixture. In a specific embodiment, the first monomer mixture may include 15 wt% or more, 16 wt% or more, 17 wt% or more, 18 wt% or more, 19 wt% or more, 20 wt% or more, 21 wt% or more, 22 wt% or more, 23 wt% or more, 24 wt% or more, or 25 wt% or more, and 40 wt% or less, 39 wt% or less, 38 wt% or less, 37 wt% or less, 36 wt% or less, 35 wt% or less, 34 wt% or less, 33 wt% or less, 32 wt% or less, 31 wt% or 30 wt% or less of the vinyl cyanide monomer. Within this range, during the polymerization of the graft copolymer, a significant increase in the middle and end of the polymerization and a deviation from the controlled temperature range during the polymerization can be prevented, the impact strength and flowability to a general-purpose base resin such as a styrene-acrylonitrile copolymer can be sufficiently ensured, and the deterioration of the impact strength to a heat-resistant base resin such as an α -methylstyrene-acrylonitrile copolymer can be prevented.
According to an embodiment of the present invention, the first monomer mixture may include 60 wt% or more, 61 wt% or more, 62 wt% or more, 63 wt% or more, 64 wt% or more, 65 wt% or more, 66 wt% or more, 67 wt% or more, 68 wt% or more, 69 wt% or more, or 70 wt% or more, and 85 wt% or less, 84 wt% or less, 83 wt% or less, 82 wt% or less, 81 wt% or less, 80 wt% or less, 79 wt% or less, 78 wt% or less, 77 wt% or less, 76 wt% or 75 wt% or less of the aromatic vinyl monomer, depending on the amount of the vinyl cyanide monomer. The first monomer mixture may contain, in addition to the aromatic vinyl monomer and the vinyl cyanide monomer, a vinyl monomer copolymerizable with the conjugated diene polymer, the aromatic vinyl monomer and the vinyl cyanide monomer, as required.
According to one embodiment of the present invention, the first monomer mixture may be injected in an amount of 5 to 20 parts by weight based on 100 parts by weight of the total injection amount of the conjugated diene-based polymer, the aromatic vinyl-based monomer, and the vinyl cyanide-based monomer injected in the process of preparing the graft copolymer. In a specific embodiment, the first monomer mixture may be 5 parts by weight or more, 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, or 10 parts by weight or more, and 20 parts by weight or less, 19 parts by weight or less, 18 parts by weight or less, 17 parts by weight or less, 16 parts by weight or less, or 15 parts by weight based on 100 parts by weight of the total injection amount of the conjugated diene polymer, the aromatic vinyl monomer, and the vinyl cyanide monomer, and within this range, the compatibility of the graft copolymer with the matrix resin may be prevented from deteriorating, and the impact resistance may be improved.
According to an embodiment of the present invention, the second monomer mixture injected in step (S20) may include an aromatic vinyl-based monomer and a vinyl cyanide-based monomer. In this case, the aromatic vinyl monomer of the first monomer mixture and the aromatic vinyl monomer of the second monomer mixture may be the same as or different from each other. In addition, the vinyl cyanide monomer of the first monomer mixture and the vinyl cyanide monomer of the second monomer mixture may be the same or different from each other. Meanwhile, in the process of preparing a resin composition comprising a graft copolymer, in order to improve flowability and subsequently improve processability while maintaining impact properties such as impact resistance regardless of the type of matrix resin, it is important to control the vinyl cyanide monomer content in the second monomer mixture in addition to the vinyl cyanide monomer content in the first monomer mixture. If the vinyl cyanide monomer content in the first monomer mixture and the second monomer mixture is not properly controlled in this way, although the impact strength to a general-purpose base resin such as a styrene-acrylonitrile copolymer can be ensured, the impact strength to a heat-resistant base resin such as an α -methylstyrene-acrylonitrile copolymer cannot be ensured. Thus, in a particular embodiment, the second monomer mixture may comprise greater than or equal to 1 wt%, greater than or equal to 5 wt%, greater than or equal to 10 wt%, greater than or equal to 11 wt%, greater than or equal to 12 wt%, greater than or equal to 13 wt%, greater than or equal to 14 wt%, greater than or equal to 15 wt%, greater than or equal to 16 wt%, greater than or equal to 17 wt%, greater than or equal to 18 wt%, greater than or equal to 19 wt%, or greater than or equal to 20 wt%, and less than or equal to 27 wt%, less than or equal to 26 wt%, less than or equal to 25 wt%, less than or equal to 24 wt%, less than or equal to 23 wt%, less than or equal to 22 wt%, less than or equal to 21 wt%, or less than or equal to 20 wt% of the vinyl cyanide monomer.
According to an embodiment of the present invention, the second monomer mixture may contain 73 wt% or more, 74 wt% or more, 75 wt% or more, 76 wt% or more, 77 wt% or more, 78 wt% or more, 79 wt% or more, or 80 wt% or more, and 99 wt% or less, 95 wt% or less, 90 wt% or less, 89 wt% or less, 88 wt% or less, 87 wt% or less, 86 wt% or less, 85 wt% or less, 84 wt% or less, 83 wt% or less, 82 wt% or less, 81 wt% or 80 wt% or less of the aromatic vinyl monomer, depending on the amount of the vinyl cyanide monomer. In addition to the aromatic vinyl monomer and the vinyl cyanide monomer, the second monomer mixture may contain a vinyl monomer copolymerizable with the conjugated diene polymer, the aromatic vinyl monomer, and the vinyl cyanide monomer, as required.
According to one embodiment of the present invention, the second monomer mixture may be injected in 10 to 45 parts by weight based on 100 parts by weight of the total injection amount of the conjugated diene-based polymer, the aromatic vinyl-based monomer, and the vinyl cyanide-based monomer injected in the process of preparing the graft copolymer. In a specific embodiment, the second monomer mixture may be 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, or 25 parts by weight or less, and 45 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, or 30 parts by weight or less, based on 100 parts by weight of the total amount of the conjugated diene polymer, the aromatic vinyl monomer, and the vinyl cyanide monomer injected. Within this range, deterioration in compatibility of the graft copolymer with the matrix resin can be prevented, and impact resistance can be improved.
According to one embodiment of the present invention, the aromatic vinyl-based monomer may be one or more selected from styrene, α -methylstyrene, 3-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene and 1-vinyl-5-hexylnaphthalene, in particular, styrene.
According to an embodiment of the present invention, the vinyl cyanide monomer may be one or more selected from acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile and α -chloroacrylonitrile, in particular, acrylonitrile.
According to one embodiment of the present invention, step (S10) and step (S20) may be performed by injecting the first molecular weight regulator together with the first monomer mixture and the second monomer mixture. Similarly, the first molecular weight modifier may be injected in both step (S10) and step (S20), but may be injected batchwise with the first monomer mixture in step (S10), and may be injected continuously with the second monomer mixture in step (S20). In this case, the absolute amount of the first molecular weight modifier injected during the preparation of the graft copolymer can be reduced, and by injecting in the same amount based on the total injection amount of the first molecular weight modifier as described above, the flowability of the graft copolymer can be improved, while deterioration of mechanical properties such as impact resistance can be prevented.
According to one embodiment of the present invention, the first molecular weight regulator may be one or more selected from the group consisting of tertiary dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetraethylthiuram disulfide, dipentylene thiuram disulfide and diisopropyl xanthogen disulfide, in particular tertiary dodecyl mercaptan.
According to one embodiment of the present invention, the total injection amount of the first molecular weight modifier in the step (S10) and the step (S20) may be 0.20 parts by weight to 0.40 parts by weight based on 100 parts by weight of the total injection amount of the conjugated diene polymer, the aromatic vinyl monomer and the vinyl cyanide monomer. In a specific embodiment, the total amount of the first molecular weight modifier in step (S10) and step (S20) may be 0.20 parts by weight or more, 0.21 parts by weight or more, 0.22 parts by weight or more, 0.23 parts by weight or more, 0.24 parts by weight or more, 0.25 parts by weight or more, 0.26 parts by weight or more, 0.27 parts by weight or more, 0.28 parts by weight or more, 0.29 parts by weight or more, or 0.30 parts by weight or more, and 0.40 parts by weight or less, 0.38 parts by weight or less, 0.36 parts by weight or less, 0.34 parts by weight or less, 0.32 parts by weight or less, 0.30 parts by weight or less, 0.28 parts by weight or less, 0.26 parts by weight or less, 0.24 parts by weight or less, or 0.22 parts by weight or less, based on 100 parts by weight of the total amount of the conjugated diene polymer, the aromatic vinyl monomer and the vinyl cyanide monomer.
According to one embodiment of the invention, step (20) may be performed by continuously injecting the second monomer mixture together with a second molecular weight regulator different from the first molecular weight regulator, in addition to the first molecular weight regulator. In this case, unlike the first molecular weight regulator, the second molecular weight regulator may be injected for the purpose of changing only the grafting ratio without changing the molecular weight. In a specific embodiment, the second molecular weight regulator may be one or more selected from the group consisting of alpha-methylstyrene dimer, n-dodecylmercaptan, octylmercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetraethylthiuram disulfide, dipentamethylenethiuram disulfide, and diisopropylxanthate disulfide. In a specific embodiment, an alpha-methylstyrene dimer may be used, depending on the purpose of injection of the second molecular weight regulator.
According to one embodiment of the present invention, the total injection amount of the second molecular weight modifier in the step (S20) may be 0.01 to 0.40 parts by weight based on 100 parts by weight of the total injection amount of the conjugated diene polymer, the aromatic vinyl monomer and the vinyl cyanide monomer. In a specific embodiment, the total amount of the second molecular weight modifier in step (S20) may be 0.01 parts by weight or more, 0.02 parts by weight or more, 0.03 parts by weight or more, 0.04 parts by weight or more, 0.05 parts by weight or more, 0.06 parts by weight or more, 0.07 parts by weight or more, 0.08 parts by weight or more, 0.09 parts by weight or more, or 0.10 parts by weight or more, and 0.40 parts by weight or less, 0.35 parts by weight or less, 0.30 parts by weight or less, 0.25 parts by weight or less, 0.20 parts by weight or less, 0.18 parts by weight or less, 0.16 parts by weight or less, 0.15 parts by weight or less, 0.14 parts by weight or less, 0.13 parts by weight or less, 0.12 parts by weight or less, 0.11 parts by weight or less, based on 100 parts by weight of the total amount of the conjugated diene polymer, the aromatic vinyl monomer and the vinyl cyanide monomer. Within this range, only the change in the graft ratio can be caused without changing the molecular weight.
According to one embodiment of the present invention, the graft polymerization in step (S10) and step (S20) may be performed by emulsion polymerization, and the emulsion polymerization may be performed in the presence of a modifier. The emulsifier may be one or more selected from anionic, cationic and nonionic emulsifiers, and in a specific embodiment may be one or more selected from alkylaryl sulfonates, alkali methylalkyl sulfates, fatty acid soaps, alkali oleates, alkali rosin salts, alkali laurates, sodium diethylhexyl phosphate, phosphonated polyoxyethylene alcohols and phosphonated polyoxyethylene phenols.
According to an embodiment of the present invention, the graft polymerization in step (S10) and step (S20) may be performed by radical polymerization using a peroxide-based initiator, a redox initiator, or an azo-based initiator, and the redox initiator may be one or more selected from t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, and isopropylbenzene hydroperoxide, and in this case, an effect of providing a stable polymerization environment may be achieved. In addition, if a redox initiator is used, polymerization may be performed by further comprising ferrous sulfate, glucose, or sodium pyrophosphate as a redox catalyst.
According to one embodiment of the present invention, the graft polymerization in step (S10) and step (S20) may be performed in an aqueous solvent, and the aqueous solvent may be ion-exchanged water. Thus, the graft copolymer prepared in step (S20) can be obtained as an example of a latex-type graft copolymer dispersed as a colloidal phase in an aqueous solvent.
The present invention provides a graft copolymer.
According to an embodiment of the present invention, the graft copolymer may be a graft copolymer prepared according to the above-described method for preparing a graft copolymer. In a specific embodiment, the graft copolymer may comprise: conjugated diene polymers; a first graft layer formed by infiltration into the conjugated diene-based polymer or externally; and a second graft layer formed by wrapping the first graft layer, wherein the first graft layer comprises 60 to 85 wt% of aromatic vinyl monomer units and 15 to 40 wt% of vinyl cyanide monomer units, and the second graft layer comprises 73 to 99 wt% of aromatic vinyl monomer units and 1 to 27 wt% of vinyl cyanide monomer units.
According to an embodiment of the present invention, the conjugated diene-based polymer may be derived from a conjugated diene-based polymer contained in the conjugated diene-based polymer latex injected in the step (S10) of the method of preparing a graft copolymer, the first graft layer may be derived from a first monomer mixture injected in the step (S10) of the method of preparing a graft copolymer, and the second graft layer may be derived from a second monomer mixture injected in the step (S20) of the method of preparing a graft copolymer.
According to an embodiment of the present invention, the graft copolymer may include a conjugated diene-based polymer according to an amount of the conjugated diene-based polymer injected in the method of preparing the graft copolymer, and the first and second graft layers may further include an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit according to an amount of the first and second monomer mixtures, an amount of each monomer in the first monomer mixture, and an amount of each monomer in the second monomer mixture injected in the method of preparing the graft copolymer.
According to an embodiment of the present invention, the graft copolymer may be graft polymerized step by step according to the step (S10) and the step (S20) of the above-described method for preparing a graft copolymer, and may exhibit the above-described structural specificity.
According to one embodiment of the present invention, the graft ratio of the graft copolymer may be 34.0% to 44.0%. The grafting ratio may be controlled by the second molecular weight regulator in the process for preparing the graft copolymer, and in one particular embodiment may be 34.0% or more, 36.0% or more, 38.0% or more, 38.5% or more, or 38.6% or more, and 44.0% or less, 43.0% or less, 42.5% or less, or 42.2% or less. Within this range, together with the vinyl cyanide-based monomer unit content in the first graft layer and the second graft layer, impact resistance and flowability to a general-purpose base resin such as a styrene-acrylonitrile copolymer can be sufficiently ensured, and deterioration in impact strength to a heat-resistant base resin such as an α -methylstyrene-acrylonitrile copolymer can be prevented.
According to one embodiment of the invention, the weight average molecular weight of the graft copolymer may be 80,000g/mol to 95,000g/mol. The weight average molecular weight may be controlled by the first molecular weight regulator in the process for preparing the graft copolymer, and may specifically be 80,000g/mol or more, 80,400g/mol or more, 81,000g/mol or more, 81,500g/mol or more, or 81,800g/mol or more, and 95,000g/mol or less, 94,000g/mol or less, 93,000g/mol or less, 92,000g/mol or less, 91,000g/mol or less, 90,000g/mol or less, 89,000g/mol or 88,000g/mol or less. Within this range, together with the vinyl cyanide-based monomer unit content in the first graft layer and the second graft layer, the impact strength and flowability to a general-purpose base resin such as a styrene-acrylonitrile copolymer can be sufficiently ensured, and the deterioration of the impact strength to a heat-resistant base resin such as an α -methylstyrene-acrylonitrile copolymer can be prevented.
The present invention provides a resin composition.
According to one embodiment of the present invention, the resin composition may comprise the graft copolymer and a matrix resin. The graft copolymer can be prepared according to the method of preparing the graft copolymer, and flowability and processability can be improved while maintaining impact properties at the same or better level regardless of the type of matrix resin. Therefore, the resin composition can have excellent impact resistance and processability regardless of the type of matrix resin.
According to an embodiment of the present invention, the resin composition may include 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 21 parts by weight or more, 22 parts by weight or more, 23 parts by weight or more, 24 parts by weight or more, or 25 parts by weight or more, and 40 parts by weight or less, 35 parts by weight or less, 30 parts by weight or less, 29 parts by weight or less, 28 parts by weight or less, 27 parts by weight or less, 26 parts by weight or 25 parts by weight or less, based on 100 parts by weight of the total amount of the graft copolymer and the matrix resin. In this case, the amount of the graft copolymer to be applied in the resin composition may be changed according to the type of the matrix resin.
According to an embodiment of the present invention, the resin composition may include 60 parts by weight to 90 parts by weight of the base resin, specifically, 60 parts by weight or more, 65 parts by weight or more, 70 parts by weight or more, 71 parts by weight or more, 72 parts by weight or more, 73 parts by weight or more, 74 parts by weight or more, or 75 parts by weight or more, and 90 parts by weight or less, 85 parts by weight or less, 80 parts by weight or less, 79 parts by weight or less, 78 parts by weight or less, 77 parts by weight or less, 76 parts by weight or 75 parts by weight or less, based on 100 parts by weight of the total amount of the graft copolymer and the base resin, according to the amount of the graft copolymer. In this case, the amount of the matrix resin applied in the resin composition may be changed according to the type of the matrix resin.
According to one embodiment of the present invention, the base resin may include an aromatic vinyl monomer unit and a vinyl cyanide monomer unit. Here, the aromatic vinyl monomer used to form the aromatic vinyl monomer unit may be one or more selected from styrene, α -methylstyrene, 3-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene and 1-vinyl-5-hexylnaphthalene, specifically styrene or α -methylstyrene. In addition, the vinyl cyanide monomer used to form the vinyl cyanide monomer unit may be one or more selected from acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, and α -chloroacrylonitrile, specifically, acrylonitrile.
According to one embodiment of the present invention, if the resin composition includes a general-purpose base resin as a base resin of the resin composition, the base resin may include a styrene monomer unit and a vinyl cyanide monomer unit, in particular, a styrene-acrylonitrile copolymer.
According to one embodiment of the present invention, if the resin composition includes a styrene monomer unit and a vinyl cyanide monomer unit as a matrix resin, the resin composition may have a flow index of 17.0g/10min or more, 17.5g/10min or more, 18.0g/10min or more, 18.5g/10min or more, 19.0g/10min or more, 19.5g/10min or more, or 20.0g/10min or more, and 25.0g/10min or less, 24.5g/10min or less, 24.0g/10min or less, 23.5g/10min or less, 23.0g/10min or less, 22.5g/10min or less, 22.0g/10min or less, 21.5g/10min or less, 21.0g/10min or 20.5g/10min or 20.0g/10min or less, as measured under conditions of 220 ℃ and 10kg by the ASTM D1238 method.
According to one embodiment of the present invention, if the resin composition contains a styrene monomer unit and a vinyl cyanide monomer unit as a matrix resin, the impact strength of the resin composition measured at room temperature (23 ℃) using a sample having a thickness of 1/4 inch by the ASTM D256 method may be 33.5kgf cm/cm or more, 34.0kgf cm/cm or more, 34.5kgf cm/cm or more, or 35.0kgf cm/cm or more, and 50.0kgf cm/cm or less, 45.0kgf cm/cm or less, 40.0kgf cm/cm or less, 39.0kgf cm/cm or less, 38.0kgf cm/cm or less, 37.0kgf cm/cm or less, or 36.0kgf cm/cm or less.
According to one embodiment of the present invention, if the resin composition contains a heat-resistant matrix resin as the matrix resin, the matrix may contain an α -methylstyrene monomer unit and a vinyl cyanide monomer unit, specifically, an α -methylstyrene-acrylonitrile copolymer.
According to one embodiment of the present invention, if the resin composition includes an α -methylstyrene monomer unit and a vinylcyanide monomer unit as a matrix resin, the flow index of the resin composition measured at 220℃and 10kg by the ASTM D1238 method may be 5.0g/10min or more, 5.1g/10min or more, 5.2g/10min or more, 5.3g/10min or more, 5.4g/10min or more, 5.5g/10min or more, 5.6g/10min or more, 5.7g/10min or more, 5.8g/10min or more, 5.9g/10min or more, 6.0g/10min or more, 6.1g/10min or more, 6.2g/10min or more, 6.3g/10min or more, or 6.4g/10min or less, and 8.0g/10min or less, 7.5g/10min or less, 7.7.7 g/10min or 7.7 g/10min or less, 6.8 g/10min or 6.1g/10min or less, 6.5g/10min or 6.2g/10min or less.
According to one embodiment of the present invention, if the resin composition contains an α -methylstyrene monomer unit and a vinyl cyanide monomer unit as a matrix resin, the impact strength of the resin composition measured at room temperature (23 ℃) using a sample having a thickness of 1/4 inch by the ASTM D256 method may be 13.0 kgf-cm/cm or more, 13.5 kgf-cm/cm or more, 14.0 kgf-cm/cm or more, 14.5 kgf-cm/cm or more, or 15.0 kgf-cm or more, and 20.0 kgf-cm/cm or less, 19.0 kgf-cm/cm or less, 18.0 kgf-cm/cm or less, 17.0 kgf-cm/cm or less, 16.0 kgf-cm/cm or less, 15.0 kgf-cm/cm or 14.0 kgf-cm/cm or less.
According to one embodiment of the present invention, the resin composition may contain conventional amounts of additives known in the art of the present invention, such as antioxidants, heat stabilizers, processing aids, colorants, and lubricants, as desired.
Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. However, the invention may be implemented in various other types and is not limited to the embodiments described herein.
Examples and comparative examples
Example 1
< preparation of graft copolymer >
100 parts by weight of ion-exchanged water and 60 parts by weight (based on the solid content) of polybutadiene latex (polybutadiene average particle diameter: 310 nm) were injected one by one into a polymerization reactor replaced with nitrogen. Then, 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile: 15% by weight) as a first monomer mixture were batch-injected into the polymerization reactor; 0.05 parts by weight of glucose; 0.03 parts by weight of tetrasodium pyrophosphate; 0.001 parts by weight of ferrous sulfate; 0.12 parts by weight of t-butyl hydroperoxide; and 0.20 parts by weight of t-dodecyl mercaptan as a first molecular weight regulator, followed by stirring at 50℃for 30 minutes. Then, 11 parts by weight of ion-exchanged water was continuously injected into the polymerization reactor; 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile 26.4% by weight) as a second monomer mixture; 0.3 parts by weight of potassium oleate; 0.1 parts by weight of cumene hydroperoxide; 0.10 parts by weight of tertiary dodecyl mercaptan as a first molecular weight regulator; and 0.10 parts by weight of an alpha-methylstyrene dimer as a second molecular weight regulator, and polymerizing at a rate of 100 minutes, in which case the temperature of the polymerization reactor was raised to 70℃at a rate.
After the end of the injection, 0.05 parts by weight of glucose, 0.03 parts by weight of tetrasodium pyrophosphate, 0.001 parts by weight of ferrous sulfate and 0.05 parts by weight of cumene hydroperoxide were injected into the polymerization reactor in batch, and in this case, polymerization was performed while raising the temperature of the polymerization reactor to 80℃over 1 hour, and the polymerization was completed to prepare a graft copolymer latex.
< preparation of graft copolymer particle Material >
To 100 parts by weight (based on the solid content) of the graft copolymer latex thus prepared, 2 parts by weight of magnesium sulfate (MgSO 4 ) Followed by coagulation at 82 ℃. Then, aging was performed at 89℃for 10 minutes, washing, dehydration and drying were performed to prepare a graft copolymer particle material.
Example 2
The same procedure as in example 1 was conducted, except that 9.6 parts by weight of styrene and 2.4 parts by weight of acrylonitrile (acrylonitrile: 20% by weight) were injected as the first monomer mixture instead of 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile: 15% by weight) and 21.2 parts by weight of styrene and 6.8 parts by weight of acrylonitrile (acrylonitrile: 24.3% by weight) were injected as the second monomer mixture instead of 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile: 26.4% by weight) in example 1, to prepare a graft copolymer particle material.
Example 3
The same procedure as in example 1 was conducted, except that 9.0 parts by weight of styrene and 3.0 parts by weight of acrylonitrile (acrylonitrile: 25% by weight) were injected as the first monomer mixture instead of 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile: 15% by weight) and 21.8 parts by weight of styrene and 6.2 parts by weight of acrylonitrile (acrylonitrile: 22.1% by weight) were injected as the second monomer mixture instead of 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile: 26.4% by weight) in example 1, to prepare a graft copolymer particle material.
Example 4
The same procedure as in example 1 was conducted, except that 8.4 parts by weight of styrene and 3.6 parts by weight of acrylonitrile (acrylonitrile: 30% by weight) were injected as the first monomer mixture instead of 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile: 15% by weight) and 22.4 parts by weight of styrene and 5.6 parts by weight of acrylonitrile (acrylonitrile: 20.0% by weight) were injected as the second monomer mixture instead of 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile: 26.4% by weight) in example 1, to prepare a graft copolymer particle material.
Example 5
The same procedure as in example 1 was conducted, except that 7.2 parts by weight of styrene and 4.8 parts by weight of acrylonitrile (acrylonitrile: 40% by weight) were injected as the first monomer mixture instead of 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile: 15% by weight) and 23.6 parts by weight of styrene and 4.4 parts by weight of acrylonitrile (acrylonitrile: 15.7% by weight) were injected as the second monomer mixture instead of 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile: 26.4% by weight) in example 1, to prepare a graft copolymer particle material.
Example 6
The same procedure as in example 1 was conducted, except that 8.4 parts by weight of styrene and 3.6 parts by weight of acrylonitrile (acrylonitrile: 30% by weight) were injected as the first monomer mixture instead of 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile: 15% by weight) in example 1, 0.15 parts by weight of t-dodecyl mercaptan was injected as the first molecular weight regulator, and 22.4 parts by weight of styrene and 5.6 parts by weight of acrylonitrile (acrylonitrile: 20.0% by weight) were injected as the second monomer mixture instead of 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile: 26.4% by weight), to prepare a graft copolymer particle material.
Example 7
The same procedure as in example 1 was conducted, except that 8.4 parts by weight of styrene and 3.6 parts by weight of acrylonitrile (acrylonitrile: 30% by weight) were injected as the first monomer mixture instead of 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile: 15% by weight) in example 1, 0.10 parts by weight of t-dodecyl mercaptan was injected as the first molecular weight regulator instead of 0.20 parts by weight of t-dodecyl mercaptan, and 22.4 parts by weight of styrene and 5.6 parts by weight of acrylonitrile (acrylonitrile: 20.0% by weight) were injected as the second monomer mixture instead of 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile: 26.4% by weight), to prepare a graft copolymer particle material.
Example 8
The same method as in example 1 was conducted, except that 8.4 parts by weight of styrene and 3.6 parts by weight of acrylonitrile (acrylonitrile is 30% by weight) were injected as the first monomer mixture instead of 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile is 15% by weight) in example 1, 22.4 parts by weight of styrene and 5.6 parts by weight of acrylonitrile (acrylonitrile is 20.0% by weight) were injected as the second monomer mixture instead of 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile is 26.4% by weight), and 0.05 parts by weight of α -methylstyrene dimer was injected as the second molecular weight regulator during the injection of the second monomer mixture, to prepare a graft copolymer particle material.
Example 9
The same method as in example 1 was conducted, except that 8.4 parts by weight of styrene and 3.6 parts by weight of acrylonitrile (acrylonitrile is 30% by weight) were injected as the first monomer mixture instead of 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile is 15% by weight) in example 1, 22.4 parts by weight of styrene and 5.6 parts by weight of acrylonitrile (acrylonitrile is 20.0% by weight) were injected as the second monomer mixture instead of 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile is 26.4% by weight), and 0.15 parts by weight of α -methylstyrene dimer was injected as the second molecular weight regulator during the second monomer mixture, to prepare a graft copolymer particle material.
Example 10
The same method as in example 1 was conducted, except that 8.4 parts by weight of styrene and 3.6 parts by weight of acrylonitrile (acrylonitrile is 30% by weight) were injected as the first monomer mixture instead of 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile is 15% by weight) in example 1, 22.4 parts by weight of styrene and 5.6 parts by weight of acrylonitrile (acrylonitrile is 20.0% by weight) were injected as the second monomer mixture instead of 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile is 26.4% by weight), and 0.20 parts by weight of α -methylstyrene dimer was injected as the second molecular weight regulator during the injection of the second monomer mixture, to prepare a graft copolymer particle material.
Example 11
The same procedure as in example 1 was conducted, except that 65 parts by weight based on the solid content was injected in example 1 in place of 60 parts by weight of polybutadiene latex, 7.35 parts by weight of styrene and 3.15 parts by weight of acrylonitrile (acrylonitrile is 30% by weight) were injected in place of 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile is 15% by weight) as the first monomer mixture, 0.16 parts by weight in place of 0.20 parts by weight of t-dodecyl mercaptan was injected as the first molecular weight regulator during the injection of the first monomer mixture, 19.6 parts by weight of styrene and 4.9 parts by weight of acrylonitrile (acrylonitrile is 20.0% by weight) in place of 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile is 26.4% by weight) were injected as the second monomer mixture, and 0.05 parts by weight in place of 0.10 parts by weight of t-dodecyl mercaptan was injected as the first molecular weight regulator during the injection of the second monomer mixture, to prepare a graft copolymer particle material.
Example 12
The same procedure as in example 1 was conducted, except that 70 parts by weight of styrene and 2.7 parts by weight of acrylonitrile (acrylonitrile: 30% by weight) were injected as the first monomer mixture instead of 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile: 15% by weight) based on the solid content of 70 parts by weight of the polybutadiene latex instead of 60 parts by weight were injected in example 1, 0.10 parts by weight of t-dodecyl mercaptan instead of 0.20 parts by weight was injected as the first molecular weight regulator during the injection of the first monomer mixture, 16.8 parts by weight of styrene and 4.2 parts by weight of acrylonitrile (acrylonitrile: 20.0% by weight) were injected instead of 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile: 26.4% by weight) were injected as the second monomer mixture, and 0.05 parts by weight of t-dodecyl mercaptan instead of 0.10 parts by weight was injected as the first molecular weight regulator during the injection of the second monomer mixture, to prepare a graft copolymer particle material.
Comparative example 1
The same method as in example 1 was conducted, except that 8.4 parts by weight of styrene and 3.6 parts by weight of acrylonitrile (acrylonitrile is 30% by weight) were injected as the first monomer mixture instead of 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile is 15% by weight) and 22.4 parts by weight of styrene and 5.6 parts by weight of acrylonitrile (acrylonitrile is 20.0% by weight) were injected as the second monomer mixture instead of 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile is 26.4% by weight) in example 1, and that an α -methylstyrene dimer was not injected as the second molecular weight regulator during the injection of the second monomer mixture, to prepare a graft copolymer particle material.
Comparative example 2
The same method as in example 1 was conducted, except that 12.0 parts by weight of styrene was injected instead of injecting acrylonitrile (acrylonitrile was 0% by weight) instead of 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile was 15% by weight) as the first monomer mixture in example 1, and 18.8 parts by weight of styrene and 9.2 parts by weight of acrylonitrile (acrylonitrile was 32.9% by weight) were injected instead of 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile was 26.4% by weight) as the second monomer mixture, to prepare a graft copolymer particle material.
Comparative example 3
The same procedure as in example 1 was conducted, except that 10.8 parts by weight of styrene and 1.2 parts by weight of acrylonitrile (acrylonitrile: 10% by weight) were injected as the first monomer mixture instead of 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile: 15% by weight) and 20.0 parts by weight of styrene and 8.0 parts by weight of acrylonitrile (acrylonitrile: 28.6% by weight) were injected as the second monomer mixture instead of 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile: 26.4% by weight) in example 1, to prepare a graft copolymer particle material.
Comparative example 4
The same procedure as in example 1 was conducted, except that 8.4 parts by weight of styrene and 3.6 parts by weight of acrylonitrile (acrylonitrile: 30% by weight) were injected as the first monomer mixture instead of 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile: 15% by weight) and 19.6 parts by weight of styrene and 8.4 parts by weight of acrylonitrile (acrylonitrile: 30.0% by weight) were injected as the second monomer mixture instead of 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile: 26.4% by weight) in example 1, to prepare a graft copolymer particle material.
Comparative example 5
The same procedure as in example 1 was conducted, except that 8.4 parts by weight of styrene and 3.6 parts by weight of acrylonitrile (acrylonitrile: 30% by weight) were injected as the first monomer mixture instead of 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile: 15% by weight) in example 1, that tertiary dodecyl mercaptan as the first molecular weight regulator was not injected during the injection of the first monomer mixture, 22.4 parts by weight of styrene and 5.6 parts by weight of acrylonitrile (acrylonitrile: 20.0% by weight) were injected instead of 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile: 26.4% by weight) and that 0.40 parts by weight of α -methylstyrene dimer was injected as the second molecular weight regulator during the injection of the second monomer mixture, to prepare a graft copolymer particle material.
Comparative example 6
The same procedure as in example 1 was conducted, except that 8.4 parts by weight of styrene and 3.6 parts by weight of acrylonitrile (acrylonitrile: 30% by weight) were injected as the first monomer mixture instead of 10.2 parts by weight of styrene and 1.8 parts by weight of acrylonitrile (acrylonitrile: 15% by weight) in example 1, 0.1 parts by weight of α -methylstyrene dimer as the second molecular weight regulator was injected as the second molecular weight regulator during the injection of the first monomer mixture, 22.4 parts by weight of styrene and 5.6 parts by weight of acrylonitrile (acrylonitrile: 20.0% by weight) were injected as the second molecular weight regulator instead of 20.6 parts by weight of styrene and 7.4 parts by weight of acrylonitrile (acrylonitrile: 26.4% by weight) were injected as the second monomer mixture, and 0.20 parts by weight of α -methylstyrene dimer instead of 0.10 parts by weight was injected as the second molecular weight regulator during the injection of the second monomer mixture, to prepare a graft copolymer particle material.
Test examples
Test example 1
Regarding the graft copolymers prepared in examples 1 to 12 and comparative examples 1 to 6, the grafting ratio and weight average molecular weight were measured by the following methods, and are shown in tables 1 to 3 together with the composition of each monomer, the weight ratio of vinyl cyanide-based monomer in the monomer mixture, and the injection amounts of the first molecular weight regulator and the second molecular weight regulator.
* Grafting ratio (%): 1g of each of the graft copolymer particle materials prepared in examples 1 to 12 and comparative examples 1 to 6 was poured into 50ml of acetone, followed by stirring for 24 hours, and sol-gel separation was performed using a centrifuge. The precipitate was then dried at 80 ℃ to give a dried product, the weight of the dried product was measured, and the grafting ratio was calculated according to mathematical formula 1.
[ mathematical formula 1]
Grafting ratio (%) = [ { (weight of dried product) - (weight of conjugated diene-based polymer injected during polymerization) }/(weight of conjugated diene-based polymer during polymerization) ]. Times.100
* Weight average molecular weight (Mw, g/mol): each of the dried products in examples 1 to 12 and comparative examples 1 to 6 for measuring the grafting ratio was dissolved in Tetrahydrofuran (THF), and the weight average molecular weight was measured by gel permeation chromatography (GPC, PL GPC220, agilent Technologies) under the following conditions.
-column: polystyrene gel (Styragel)
-a solvent: tetrahydrofuran (THF)
-flow rate: 1.0ml/min
Sample concentration: 1.0mg/ml
Injection amount: 100 μl of
Column temperature: 40 DEG C
-a detector: waters 2414RI detector-standard: polystyrene (calibrated with cubic function) -data processing: empower
TABLE 1
TABLE 2
TABLE 3
As shown in the above tables 1 and 2, it was confirmed that the graft copolymers of examples 1 to 12 prepared according to the present invention exhibited a suitable level of grafting ratio and weight average molecular weight.
In contrast, as shown in table 4, it was confirmed that comparative example 2, which contained no vinyl cyanide monomer in the first monomer mixture and an excess of vinyl cyanide monomer in the second monomer mixture, and comparative example 3, which contained a small amount of vinyl cyanide monomer in the first monomer mixture and an excess of vinyl cyanide monomer in the second monomer mixture, exhibited lower grafting rates and weight average molecular weights than examples 1 to 12.
Further, it was confirmed that comparative example 6 in which the molecular weight modifier was not injected during the injection of the first monomer mixture and the first molecular weight modifier was not injected during the injection of the second monomer mixture, and comparative example 6 in which the second molecular weight modifier was injected during the injection of the first monomer mixture instead of the first molecular weight modifier and the first molecular weight modifier was not injected during the injection of the second monomer mixture exhibited a higher grafting ratio than examples 1 to 12, and in particular, comparative example 6 also exhibited a higher weight average molecular weight.
Test example 2
For each of the graft copolymers prepared in examples 1 to 12 and comparative examples 1 to 6, a first resin composition and a second resin composition were prepared by the following methods, and the impact strength and flow index of each resin composition were measured and are shown in tables 4 to 6.
< preparation of first resin composition >
27.5 parts by weight of each of the graft copolymer particle materials prepared in examples 1 to 12 and comparative examples 1 to 6, 72.5 parts by weight of a styrene-acrylonitrile copolymer (LG chem, 92 HR), 1.0 part by weight of a lubricant (ethylene bis stearamide), 0.2 part by weight of magnesium stearate as a stabilizer, and 0.2 part by weight of distearyl pentaerythritol diphosphate were homogeneously mixed using a Henschel mixer, and then extruded to produce pellets.
< preparation of the second resin composition >
24 parts by weight of each of the graft copolymer particle materials prepared in examples 1 to 12 and comparative examples 1 to 6, 76 parts by weight of an α -methylene styrene-acrylonitrile copolymer (LG Chem,200 UH), 1.0 part by weight of a lubricant (ethylene bis stearamide), 0.2 part by weight of sonnox 1076 (SONGWON Industrial co.) as a stabilizer, and 0.2 part by weight of wingstand-L were homogeneously mixed using a Henschel mixer, and then extruded to produce pellets.
* Impact strength (kgf. Cm/cm): notched Izod impact strength was measured using a 1/4 inch thick specimen according to ASTM D256, notched at room temperature (23 ℃) on the specimen.
* Flow index (g/10 min): the measurements were made according to ASTM D1238 at 220℃and 10 kg.
TABLE 4
TABLE 5
TABLE 6
As shown in tables 4 to 6, it was confirmed that each of the first resin composition and the second resin composition comprising each of the graft copolymers of examples 1 to 12 prepared according to the present invention exhibited the same level or improved level of flowability and improved impact strength, although comprising different types of base resins, when compared with the first resin composition and the second resin composition comprising the graft copolymer of comparative example 1 in which the second molecular weight regulator was not injected during the injection of the second monomer mixture. In particular, in the case of examples 3 to 10 in which the amount of the vinyl cyanide monomer in the first monomer mixture was controlled to 25% by weight or more and the amount of the vinyl cyanide monomer in the second monomer mixture was controlled to 24% by weight or less, it was confirmed that the effect was further maximized when compared with comparative example 1 even when compared with examples 1 and 2.
In contrast, it was confirmed that both the first resin composition and the second resin composition comprising the graft copolymer of comparative example 2 in which the vinyl cyanide-based monomer was not contained in the first monomer mixture and the vinyl cyanide-based monomer was contained in the second monomer mixture in excess, and comprising the graft copolymer of comparative example 3 in which the vinyl cyanide-based monomer was contained in the first monomer mixture in a small amount and the vinyl cyanide-based monomer was contained in the second monomer mixture, exhibited rapidly decreased impact strength. The result is that the grafting ratio and the weight average molecular weight of the graft copolymer are not sufficiently ensured.
Further, comparative example 4 in which an excess of vinyl cyanide-based monomer was contained in the second monomer mixture; comparative example 5 in which the molecular weight modifier was not injected during the injection of the first monomer mixture and the first molecular weight modifier was not injected during the injection of the second monomer mixture; and comparative example 6 in which the second molecular weight modifier was injected in place of the first molecular weight modifier during the injection of the first monomer mixture, and in which the second molecular weight modifier was not injected during the injection of the second monomer mixture, it was confirmed that the flow index was rapidly lowered, and in particular, it was confirmed that the impact strength of the first resin composition was deteriorated in the cases of comparative example 5 and comparative example 6.
From these results, it was confirmed that the resin composition comprising the graft copolymer prepared according to the method for preparing a graft copolymer of the present invention and a matrix resin exhibited improved flowability and subsequently improved processability while maintaining the same or better level of impact properties regardless of the type of matrix resin.
Claims (12)
1. A method of making a graft copolymer, the method comprising:
step S10, injecting the first monomer mixture and the first molecular weight regulator in batches and polymerizing in the presence of the conjugated diene polymer latex to prepare a preliminary graft copolymer latex containing a preliminary graft copolymer; and
a step S20 of continuously injecting a second monomer mixture, a first molecular weight regulator and a second molecular weight regulator different from the first molecular weight regulator, and polymerizing in the presence of the preliminary graft copolymer latex prepared in the step S10 to prepare a graft copolymer latex comprising a graft copolymer,
wherein the first monomer mixture comprises 60 to 85 wt% of an aromatic vinyl monomer and 15 to 40 wt% of a vinyl cyanide monomer,
the second monomer mixture includes 73 to 99 wt% of an aromatic vinyl monomer and 1 to 27 wt% of a vinyl cyanide monomer.
2. The method for producing a graft copolymer according to claim 1, wherein,
the conjugated diene polymer latex comprises a conjugated diene polymer, and
the conjugated diene polymer is injected in an amount of 50 to 80 parts by weight based on 100 parts by weight of the total injection amount of the conjugated diene polymer, the aromatic vinyl monomer and the vinyl cyanide monomer.
3. The method of preparing a graft copolymer of claim 1, wherein the first monomer mixture comprises 25 to 40 weight percent of the vinyl cyanide-based monomer.
4. The method of preparing a graft copolymer of claim 1, wherein the second monomer mixture comprises 15 to 25 weight percent of the vinyl cyanide-based monomer.
5. The method of preparing a graft copolymer of claim 1, wherein the first molecular weight regulator is one or more selected from the group consisting of t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan, carbon tetrachloride, methylene chloride, dibromomethane, tetraethylthiuram disulfide, dipentylene thiuram disulfide, and diisopropylxanthate disulfide.
6. The method for producing a graft copolymer according to claim 1, wherein the total amount of the first molecular weight modifier in step S10 and step S20 is 0.20 to 0.40 parts by weight based on 100 parts by weight of the total amount of the conjugated diene polymer, the aromatic vinyl monomer and the vinyl cyanide monomer.
7. The method for preparing a graft copolymer according to claim 1, wherein the second molecular weight regulator is one or more selected from the group consisting of α -methylstyrene dimer, n-dodecylmercaptan, octylmercaptan, carbon tetrachloride, methylene chloride, dibromomethane, tetraethylthiuram disulfide, dipentylene thiuram disulfide, and diisopropylxanthate disulfide.
8. The method for producing a graft copolymer according to claim 1, wherein the injection amount of the second molecular weight regulator in step S20 is 0.01 to 0.40 parts by weight based on 100 parts by weight of the total injection amount of the conjugated diene-based polymer, the aromatic vinyl-based monomer, and the vinyl cyanide-based monomer.
9. A graft copolymer comprising:
conjugated diene polymers; a first graft layer formed by penetrating into or outside the conjugated diene-based polymer; and a second graft layer formed by wrapping the first graft layer, wherein,
the first graft layer comprises 60 to 85 wt% of aromatic vinyl monomer units and 15 to 40 wt% of vinyl cyanide monomer units,
The second graft layer includes 73 to 99 wt% of an aromatic vinyl monomer unit and 1 to 27 wt% of a vinyl cyanide monomer unit.
10. A resin composition comprising the graft copolymer of claim 9 and a matrix resin.
11. The resin composition according to claim 10, wherein the base resin comprises the aromatic vinyl monomer unit and the vinyl cyanide monomer unit.
12. The resin composition according to claim 10, wherein the matrix resin comprises an α -methylstyrene monomer unit and a vinyl cyanide monomer unit.
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| KR1020220097471A KR20230022128A (en) | 2021-08-06 | 2022-08-04 | Method for preparing graft copolymer, graft copolymer and resin composition comprising the copolymer |
| KR10-2022-0097471 | 2022-08-04 | ||
| PCT/KR2022/011635 WO2023014154A1 (en) | 2021-08-06 | 2022-08-05 | Method for manufacturing graft copolymer, graft copolymer, and resin composition comprising same |
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