CN115989247A - 马来酰亚胺系共聚物 - Google Patents
马来酰亚胺系共聚物 Download PDFInfo
- Publication number
- CN115989247A CN115989247A CN202180051433.8A CN202180051433A CN115989247A CN 115989247 A CN115989247 A CN 115989247A CN 202180051433 A CN202180051433 A CN 202180051433A CN 115989247 A CN115989247 A CN 115989247A
- Authority
- CN
- China
- Prior art keywords
- maleimide
- mass
- copolymer
- resin
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 92
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000002245 particle Substances 0.000 claims abstract description 50
- 229920005989 resin Polymers 0.000 claims description 65
- 239000011347 resin Substances 0.000 claims description 65
- 239000011342 resin composition Substances 0.000 claims description 19
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 18
- 239000000155 melt Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229920006015 heat resistant resin Polymers 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 6
- 238000004898 kneading Methods 0.000 abstract description 16
- 238000001125 extrusion Methods 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 description 77
- 238000000034 method Methods 0.000 description 46
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 35
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000006116 polymerization reaction Methods 0.000 description 25
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 22
- 229920000578 graft copolymer Polymers 0.000 description 20
- 229920000638 styrene acrylonitrile Polymers 0.000 description 19
- 229920001971 elastomer Polymers 0.000 description 16
- 239000003963 antioxidant agent Substances 0.000 description 15
- 150000008064 anhydrides Chemical class 0.000 description 14
- 230000003078 antioxidant effect Effects 0.000 description 14
- -1 azo compound Chemical class 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000012986 chain transfer agent Substances 0.000 description 11
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 11
- 239000003505 polymerization initiator Substances 0.000 description 11
- 239000000839 emulsion Substances 0.000 description 10
- 238000010559 graft polymerization reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000012662 bulk polymerization Methods 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000004816 latex Substances 0.000 description 8
- 229920000126 latex Polymers 0.000 description 8
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000003141 primary amines Chemical class 0.000 description 6
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RRTJOAHJZQVSSE-UHFFFAOYSA-N 1,3,2-dioxaphosphepine Chemical compound C=1C=COPOC=1 RRTJOAHJZQVSSE-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 3
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 3
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 3
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical compound CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 description 3
- 229940087305 limonene Drugs 0.000 description 3
- 235000001510 limonene Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 3
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 3
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 description 2
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 2
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ONOVRUOVXNSEDQ-UHFFFAOYSA-N C(C)(C)(C)C1=CC=C(C(=C1)C(C)(C)C)OC(C(CCCC)CC)O[P] Chemical compound C(C)(C)(C)C1=CC=C(C(=C1)C(C)(C)C)OC(C(CCCC)CC)O[P] ONOVRUOVXNSEDQ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- STLLXWLDRUVCHL-UHFFFAOYSA-N [2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl]-4,6-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)(C)CC)C(C)(C)CC)OC(=O)C=C)=C1O STLLXWLDRUVCHL-UHFFFAOYSA-N 0.000 description 2
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- 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
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 description 1
- IMYCVFRTNVMHAD-UHFFFAOYSA-N 1,1-bis(2-methylbutan-2-ylperoxy)cyclohexane Chemical compound CCC(C)(C)OOC1(OOC(C)(C)CC)CCCCC1 IMYCVFRTNVMHAD-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- SXTILEHINBCKSS-UHFFFAOYSA-N 1-chloro-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(Cl)C(=O)C=C1C1=CC=CC=C1 SXTILEHINBCKSS-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- QCOLXFOZKYRROA-UHFFFAOYSA-N 1-methoxy-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(OC)C(=O)C=C1C1=CC=CC=C1 QCOLXFOZKYRROA-UHFFFAOYSA-N 0.000 description 1
- IYBPIDAYDPNCTP-UHFFFAOYSA-N 1-methyl-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(C)C(=O)C=C1C1=CC=CC=C1 IYBPIDAYDPNCTP-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- WVGXBYVKFQJQGN-UHFFFAOYSA-N 1-tert-butylperoxy-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1OOC(C)(C)C WVGXBYVKFQJQGN-UHFFFAOYSA-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
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- TZJQCUDHKUWEFU-UHFFFAOYSA-N 2,2-dimethylpentanenitrile Chemical compound CCCC(C)(C)C#N TZJQCUDHKUWEFU-UHFFFAOYSA-N 0.000 description 1
- VTFXHGBOGGGYDO-UHFFFAOYSA-N 2,4-bis(dodecylsulfanylmethyl)-6-methylphenol Chemical compound CCCCCCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCCCCCC)=C1 VTFXHGBOGGGYDO-UHFFFAOYSA-N 0.000 description 1
- GVJRTUUUJYMTNQ-UHFFFAOYSA-N 2-(2,5-dioxofuran-3-yl)acetic acid Chemical compound OC(=O)CC1=CC(=O)OC1=O GVJRTUUUJYMTNQ-UHFFFAOYSA-N 0.000 description 1
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 1
- TVWGHFVGFWIHFN-UHFFFAOYSA-N 2-hexadecan-2-yl-4,6-dimethylphenol Chemical compound CCCCCCCCCCCCCCC(C)C1=CC(C)=CC(C)=C1O TVWGHFVGFWIHFN-UHFFFAOYSA-N 0.000 description 1
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 1
- YAQDPWONDFRAHF-UHFFFAOYSA-N 2-methyl-2-(2-methylpentan-2-ylperoxy)pentane Chemical compound CCCC(C)(C)OOC(C)(C)CCC YAQDPWONDFRAHF-UHFFFAOYSA-N 0.000 description 1
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 1
- RFSCGDQQLKVJEJ-UHFFFAOYSA-N 2-methylbutan-2-yl benzenecarboperoxoate Chemical compound CCC(C)(C)OOC(=O)C1=CC=CC=C1 RFSCGDQQLKVJEJ-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- WXDJDZIIPSOZAH-UHFFFAOYSA-N 2-methylpentan-2-yl benzenecarboperoxoate Chemical compound CCCC(C)(C)OOC(=O)C1=CC=CC=C1 WXDJDZIIPSOZAH-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- BQARUDWASOOSRH-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-yl hydrogen carbonate Chemical compound CC(C)(C)OOC(C)(C)OC(O)=O BQARUDWASOOSRH-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide 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
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- DRBUOMRBZPMETF-UHFFFAOYSA-N chlorobenzene;n,n-dimethylformamide Chemical compound CN(C)C=O.ClC1=CC=CC=C1 DRBUOMRBZPMETF-UHFFFAOYSA-N 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- HARQWLDROVMFJE-UHFFFAOYSA-N ethyl 3,3-bis(tert-butylperoxy)butanoate Chemical compound CCOC(=O)CC(C)(OOC(C)(C)C)OOC(C)(C)C HARQWLDROVMFJE-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 150000008301 phosphite esters Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229940066769 systemic antihistamines substituted alkylamines Drugs 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YOEYNURYLFDCEV-UHFFFAOYSA-N tert-butyl hydroxy carbonate Chemical compound CC(C)(C)OC(=O)OO YOEYNURYLFDCEV-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/48—Isomerisation; Cyclisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/18—Plasticising macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2055/00—Use of specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of main groups B29K2023/00 - B29K2049/00, e.g. having a vinyl group, as moulding material
- B29K2055/02—ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
- B29K2079/08—PI, i.e. polyimides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/08—Copolymers of styrene
- C08J2425/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/50—Aqueous dispersion, e.g. containing polymers with a glass transition temperature (Tg) above 20°C
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
本发明的课题为,提供一种熔融挤出混炼时的分散性优异的马来酰亚胺系共聚物。根据本发明可提供一种平均粒子直径为75μm以上,1000μm的筛子上小于5质量%的粉状的马来酰亚胺系共聚物(A)。
Description
技术领域
本发明涉及熔融挤出混炼时的分散性优异的马来酰亚胺系共聚物。
背景技术
ABS树脂是以丙烯腈、丁二烯、苯乙烯为主成分的热塑性树脂,凭借其优异的机械强度、外观、耐化学性、成型性等被广泛应用于汽车、家电、OA设备、住宅建材、日用品等领域。但在汽车内装材料等要求耐热性的用途中,耐热性可能会不足。作为提高耐热性的技术,可使用马来酰亚胺系共聚物或α-甲基苯乙烯系共聚物等(专利文献1、2)。此外,近年来,在双轴挤出机的高扭矩化和螺杆深槽化方面取得了进展,使得高排出量成为可能。此外,已知在熔融混炼的初期阶段种固体树脂的塑化进行,但固体树脂引发可塑化需要除去固体树脂周围存在的空气相,并压缩直至接近真正的固体密度。因此,已知熔融混炼粉末时,必须有效消除空气相引发可塑化,必须施加高混炼压力以增加堆积密度。
【现有技术文献】
【专利文献】
【专利文献1】日本特开2003-41080号公报
【专利文献2】WO2010/082617号公报
发明内容
发明要解决的问题
本发明的课题在于提供熔融挤出混炼时的分散性优异的马来酰亚胺系共聚物。
用于解决问题的方案
(1)平均粒子直径为75μm以上,在1000μm的筛子上小于5质量%的粉状的马来酰亚胺系共聚物(A)。
(2)如(1)所述的马来酰亚胺系共聚物(A),其玻璃化转变温度为170~210℃。
(3)如(1)或(2)所述的马来酰亚胺系共聚物(A),其在260℃、剪切速度120/sec下的熔融黏度为1000Pa·s以上。
(4)一种耐热性树脂组合物的制造方法,其特征在于,使用挤出机将(1)~(3)中任一项所述的马来酰亚胺系共聚物(A)和选自ABS树脂、ASA树脂、AES树脂、SAN树脂中的至少一种的树脂(B)熔融混炼。
发明的效果
本发明的马来酰亚胺系共聚物由于马来酰亚胺系共聚物的分散性优异,因此在ABS树脂等树脂中的分散性也充分。因此,即使在使用分散性稍差的深槽螺杆的高排出量条件下,也可以获得马来酰亚胺系共聚物的分散状态良好且无外观缺陷的成型品。
附图说明
图1是本发明的实施方式所涉及的双轴挤出装置的螺杆构成图。
具体实施方式
<术语说明>
本说明书中,例如“A~B”这样的记载是指A以上且B以下。
以下对本发明的实施方式进行详细说明。以下所示的实施方式可以相互组合。
本发明的马来酰亚胺系共聚物的平均粒子直径为70μm以上,筛子上1000μm以上的小于5质量%。
马来酰亚胺系共聚物(A)是具有马来酰亚胺系单体单元、苯乙烯系单体单元的共聚物。在本发明中,还可以具有丙烯腈系单体单元、不饱和二羧酸酐系单体单元。
马来酰亚胺系单体单元例如为N-甲基马来酰亚胺、N-丁基马来酰亚胺、N-环己基马来酰亚胺等N-烷基马来酰亚胺;以及N-苯基马来酰亚胺、N-氯苯基马来酰亚胺、N-甲基苯基马来酰亚胺、N-甲氧基苯基马来酰亚胺、N-三溴苯基马来酰亚胺等。其中优选N-苯基马来酰亚胺。马来酰亚胺系单体单元可以单独使用也可以将2种以上并用。马来酰亚胺系单体单元例如可以使用由马来酰亚胺系单体组成的原料。或者可通过使用氨或伯胺将由不饱和二羧酸单体单元组成的原料酰亚胺化来获得。
马来酰亚胺系共聚物(A)优选在马来酰亚胺系共聚物(A)100质量%中含有马来酰亚胺系单体单元40~70质量%,更优选含有45~60质量%。马来酰亚胺系单体单元的含量具体而言例如为40、41、42、43、44、45、50、55、60或70质量%,也可以是任意2个所例示数值之间的范围内。如果马来酰亚胺系单体单元的含量在该范围内,则可提高与下文中选自ABS树脂、ASA树脂、AES树脂、SAN树脂中的至少一种树脂(B)的相容性,树脂组合物的冲击强度优异。马来酰亚胺系单体单元的含量为由13C-NMR测得的值。
苯乙烯系单体单元为苯乙烯、邻甲基苯乙烯、间甲基苯乙烯、对甲基苯乙烯、2,4-二甲基苯乙烯、乙基苯乙烯、对叔丁基苯乙烯、α-甲基苯乙烯、α-甲基-对甲基苯乙烯等。其中,优选苯乙烯。苯乙烯系单体单元可以单独使用也可以将2种以上并用。
马来酰亚胺系共聚物(A)100质量%中优选含有苯乙烯系单体单元20~60质量%,更优选含有35~55质量%。具体而言例如为20、30、40、45、46、47、48、49、50、55或60质量%,也可以是任意2个所例示数值之间的范围内。如果苯乙烯系单体单元的含量在该范围内,则可提高与下文中选自ABS树脂、ASA树脂、AES树脂、SAN树脂中的至少一种树脂(B)的相容性,树脂组合物的冲击强度优异。苯乙烯系单体单元的含量是采用13C-NMR测得的值。
丙烯腈系单体单元为丙烯腈、甲基丙烯腈、乙基丙烯腈、富马腈等。其中,优选丙烯腈。丙烯腈系单体单元可以单独使用也可以将2种以上并用。
马来酰亚胺系共聚物(A)100质量%中优选含有丙烯腈系单体单元0~20质量%,更优选含有0~15质量%。具体而言例如为0、5、6、7、8、9、10、15或20质量%,也可以是任意2个所例示数值之间的范围内。如果丙烯腈系单体单元的含量在该范围内,则树脂组合物的耐化学性优异。丙烯腈系单体单元的含量是采用13C-NMR测得的值。
不饱和二羧酸酐系单体单元为马来酸酐、衣康酸酐、柠康酸酐、乌头酸酐等。其中优选马来酸酐。不饱和二羧酸酐系单体单元可以单独使用也可以将2种以上并用。
马来酰亚胺系共聚物(A)100质量%中优选含有不饱和二羧酸酐系单体单元0~10质量%,更优选含有0~5质量%。具体而言例如为0、1、2、3、4、5、6、7、8、9或10质量%,也可以是任意2个所例示数值之间的范围内。如果不饱和二羧酸酐系单体单元的含量在该范围内,则马来酰亚胺系共聚物的热稳定性优异。不饱和二羧酸酐系单体单元的含量是采用滴定法测得的值。
本发明的一个方式中的马来酰亚胺系共聚物(A)100质量%中优选含有马来酰亚胺系单体单元40~70质量%、苯乙烯系单体单元20~60质量%、丙烯腈系单体单元0~20质量%、不饱和二羧酸酐系单体单元0~10质量%。马来酰亚胺系共聚物(A)100质量%中更优选含有马来酰亚胺系单体单元45~60质量%、苯乙烯系单体单元35~55质量%、丙烯腈系单体单元0~15质量%、不饱和二羧酸酐系单体单元0~5质量%。若构成单元在上述范围内,则马来酰亚胺系共聚物(A)的流动性、耐热性、热稳定性优异。
从有效提高选自后述的ABS树脂、ASA树脂、AES树脂、SAN树脂的至少1种树脂(B)的耐热性的方面考虑,马来酰亚胺系共聚物(A)的玻璃化转变温度(Tmg)优选为170~210℃,更优选为185~205℃。玻璃化转变温度是采用DSC,在下述测得条件下测得的测定值。
装置名:Seiko Instruments株式会社制的Robot DSC6200
升温速度:10℃/分钟
马来酰亚胺系共聚物(A)的重均分子量(Mw)优选为6万~15万,更优选为7万~14万。具体而言例如为6、7、8、9、10、11、12、13、14或15万,也可以是任意2个所例示数值之间的范围内。若马来酰亚胺系共聚物(A)的重均分子量(Mw)为上述范围内,则通过与后述的树脂(B)熔融混炼而得到的树脂组合物的流动性和冲击强度的平衡优异。。为了控制马来酰亚胺系共聚物(A)的重均分子量(Mw),除了调整聚合温度、聚合时间以及聚合引发剂添加量之外,还有调整溶剂浓度和链转移剂添加量等的方法。马来酰亚胺系共聚物(A)的重均分子量是采用凝胶渗透色谱(GPC)测得的聚苯乙烯换算值,在以下条件下测定。
装置名:SYSTEM-21Shodex(昭和电工株式会社制)
柱:PL gel MIXED-B 3根串联
温度:40℃
检测:差示折射率
溶剂:四氢呋喃
浓度:2质量%
标准曲线:使用标准聚苯乙烯(PS)(PL公司制)绘制。
作为马来酰亚胺系共聚物(A)的制造方法,可采用公知方法。例如有如下方法:将由苯乙烯系单体、马来酰亚胺系单体、不饱和二羧酸酐系单体、其他可共聚的单体构成的单体混合物共聚;或者将由苯乙烯系单体、不饱和二羧酸酐系单体、其他可共聚的单体构成的单体混合物共聚后,使不饱和二羧酸酐系单体单元的一部分与氨或伯胺反应进行酰亚胺化而转变为马来酰亚胺系单体单元(以下称为“后酰亚胺化法”)。
马来酰亚胺系共聚物(A)的聚合方式例如有溶液聚合、本体聚合等。从通过一边分批添加一边聚合可得到聚合组成更均匀的马来酰亚胺系共聚物(A)的观点考虑,优选溶液聚合。溶液聚合的溶剂从不易产生副产物、不良影响小的观点考虑优选为非聚合性。例如为丙酮、甲乙酮、甲基异丁基酮、苯乙酮等酮类;四氢呋喃、1,4-二噁烷等醚类;苯、甲苯、二甲苯、氯苯等芳香族烃;N,N-二甲基甲酰胺、二甲基亚砜、N-甲基-2-吡咯烷酮等。从对马来酰亚胺系共聚物(A)进行脱挥回收时容易去除溶剂的观点考虑,优选甲乙酮、甲基异丁基酮。对于聚合工艺,连续聚合式、批次式(分批式)、半分批式均可适用。聚合方法没有特别限定,但从可通过简单的工艺生产率良好地进行制造的观点考虑,优选自由基聚合。
溶液聚合或本体聚合中可使用聚合引发剂、链转移剂。聚合温度优选为80~150℃的范围。聚合引发剂例如为偶氮二异丁腈、偶氮二环己基甲腈、偶氮二甲基丙腈、偶氮二甲基丁腈等偶氮系化合物;过氧化苯甲酰、过氧化苯甲酸叔丁酯、1,1-二(叔丁基过氧化)环己烷、叔丁基过氧化异丙基单碳酸酯、过氧化-2-乙基己酸叔丁酯、二叔丁基过氧化物、过氧化二异丙苯、乙基-3,3-二(叔丁基过氧化)丁酸酯等过氧化物类。可以使用其中1种也可以将2种以上组合使用。从控制聚合反应速度和聚合率的观点考虑,优选使用10小时半衰期为70~120℃的偶氮系化合物或有机过氧化物。聚合引发剂的使用量没有特别限定,相对于全部单体单元100质量%优选使用0.1~1.5质量%,进一步优选为0.1~1.0质量%。如果聚合引发剂的使用量为0.1质量%以上,则可得到足够的聚合速度,因而优选。如果聚合引发剂的使用量为1.5质量%以下,则可抑制聚合速度,因此容易控制反应,容易得到目标分子量。链转移剂例如有正辛硫醇、正十二烷基硫醇、叔十二烷基硫醇、α-甲基苯乙烯二聚体、巯基乙酸乙酯、柠檬烯、萜品油烯等。链转移剂量的使用量只要可得到目标分子量就没有特别限定,但相对于全部单体单元100质量%优选为0.1~0.8质量%,更优选为0.15~0.5质量%。如果链转移剂的使用量为0.1质量%~0.8质量%,则可容易得到目标分子量。
马来酰亚胺系共聚物(A)的马来酰亚胺系单体单元的导入有使马来酰亚胺系单体共聚的方法和后酰亚胺化法。后酰亚胺化法由于马来酰亚胺系共聚物(A)中的残留马来酰亚胺系单体量少而优选。后酰亚胺化法是将由苯乙烯系单体、不饱和二羧酸酐系单体、其他可共聚单体构成的单体混合物共聚后,使不饱和二羧酸酐系单体单元的一部分与氨或伯胺反应进行酰亚胺化而转变为马来酰亚胺系单体单元的方法。作为伯胺,例如有甲胺、乙胺、正丙胺、异丙胺、正丁胺、正戊胺、正己胺、正辛胺、环己胺、癸胺等烷基胺类以及氯或溴取代的烷基胺;苯胺、甲苯胺、萘胺等芳香族胺,其中优选苯胺。这些伯胺可以单独使用也可以将2种以上并用。采用后酰亚胺化时,在伯胺与不饱和二羧酸酐系单体单元的反应中,为了提高脱水闭环反应可使用催化剂。催化剂例如为三甲胺、三乙胺、三丙胺、三丁胺、N,N-二甲基苯胺、N,N-二乙基苯胺等叔胺。后酰亚胺化的温度优选为100~250℃,更优选为120~200℃。如果后酰亚胺化反应的温度为100℃以上,则可提高反应速度,从生产率的观点考虑优选。如果酰亚胺化反应的温度为250℃以下,则能够抑制马来酰亚胺系共聚物(A)的热劣化导致的物性下降,因而优选。
马来酰亚胺系共聚物(A)的溶液聚合结束后的溶液或酰亚胺化结束后的溶液去除溶液聚合所使用的溶剂和未反应单体等挥发成分的方法(脱挥方法)可采用公知方法。例如可使用带加热器的真空脱挥槽或者带排气孔的脱挥挤出机。经脱挥的熔融状态的马来酰亚胺系共聚物(A)被转移至造粒工序,从多孔模呈绳状挤出,采用冷切方式、空中热切方式、水中热切方式加工成颗粒状。
颗粒状的马来酰亚胺系共聚物(A)可以使用公知的粉碎机加工成粉末状。粉碎机例如可列举筛网式微粉碎机和冲击型粉碎机。
马来酰亚胺系共聚物(A)是粉末状,其平均粒子直径为75μm以上,优选为80~300μm,更优选为100~250μm。具体而言例如为75、80、95、100、110、120、130、140、150、160、170、180、190、200、210、220、230、240、250、260、270、280、290或300μm,也可以是任意2个所例示数值之间的范围内。通过使其呈现粉末状,熔融挤出混炼时的分散性大幅提高,但平均粒子直径小于75μm时,当从料斗进料时,挤出机供应区可能会堵塞。它还增加了粉尘爆发性的风险。粉末的平均粒子直径可使用JIS Z 8801的试验筛子测定。使用网孔为1000、850、500、355、250、150、106、75、50μm的筛子,将喷洒抗静电剂混合的马来酰亚胺系共聚物的粉末50g放入网孔最大的筛子中盖上盖子,将筛子置于摇床上,摇晃20分钟后,测定包含粉末的各筛子的质量,减去筛子的质量,即可计算出筛子上的粒度分布。从粒度分布的结果来看,质量从网孔大的开始依次相加,平均粒子直径是从夹住累积质量50%的两点网孔(粒子直径)和50%的交点求出的粒子直径。例如,使用筛网式微粉碎机时,平均粒子直径可根据筛网直径和旋转数调节。
粉状的马来酰亚胺系共聚物(A)的1000μm的筛子上小于5质量%,优选为小于3质量%。本发明中马来酰亚胺系共聚物的粒子量规定的“筛子上”是指一种积酸分布,表示特定粒子直径以上的粒子量占整体的百分比。
另外,本发明中马来酰亚胺系共聚物的粒子量规定的“筛子下”是指一种积酸分布,表示特定粒子直径以下的粒子量占整体的百分比。具体而言例如为,1000μm的筛子上小于5、4、3、2或1质量%,也可以是任意2个所例示数值之间的范围内。若1000μm的筛子上大于5质量%,则即使是粉末状熔融挤出混炼时的分散性也会变差。1000μm的筛子上的含量可通过粉碎条件和粉碎后的分级调节。另外,75μm的筛子上至850μm的筛子下的含量优选为60~90质量%,更优选65~90质量%。具体而言例如为60、65、70、75、80、85或90质量%,也可以是任意2个所例示数值之间的范围内。
作为马来酰亚胺系共聚物(A),从赋予树脂(B)耐热性的观点出发,可以使用含有大量马来酰亚胺系单体单元的共聚物。此时,伴随马来酰亚胺系单体单元的含量的增加,马来酰亚胺系共聚物(A)的熔融黏度提高,与树脂(B)熔融混炼时会导致分散性的问题。在本发明所涉及的马来酰亚胺系共聚物(A)的情况下,从赋予树脂(B)耐热性的观点出发,即使采用含有大量马来酰亚胺系单体单元的共聚物,与树脂(B)熔融混炼时的分散性也优异。
从赋予树脂(B)耐热性的观点出发,使用含有大量马来酰亚胺系单体单元的马来酰亚胺系共聚物(A)时,马来酰亚胺系共聚物(A)在260℃、剪切速度120/sec下的熔融黏度优选为1000Pa·s以上,在260℃、剪切速度120/sec下的熔融黏度更优选为1000Pa·s以上,且在280℃、剪切速度120/sec下的熔融黏度为500Pa·s以上。马来酰亚胺系共聚物(A)的熔融黏度越高,熔融挤出混炼时的分散性变差,通过将其制成粉末状而提高分散性的效果也增加。另外,从分散性的观点出发,马来酰亚胺系共聚物(A)在280℃、剪切速度120/sec下的熔融黏度优选为3000Pa·s以下,更优选为2000Pa·s以下。熔融黏度是使用毛细管流变仪,用L=40mm、D=1mm的毛细管模测定的值。
树脂(B)只要是选自ABS树脂、ASA树脂、AES树脂、SAN树脂,可以使用1种也可以使用2种以上。
ABS树脂、ASA树脂、AES树脂是使橡胶状聚合物至少与苯乙烯系单体和丙烯腈系单体接枝共聚而成的接枝共聚物。例如,使用聚丁二烯、苯乙烯-丁二烯共聚物等丁二烯系橡胶作为橡胶状聚合物时为ABS树脂;使用由丙烯酸丁酯或丙烯酸乙酯等构成的丙烯酸系橡胶时为ASA树脂;使用乙烯-α-烯烃共聚物等乙烯系橡胶时为AES树脂。进行接枝共聚时,可以组合使用这些橡胶状聚合物中的2种以上。
作为ABS树脂等的接枝共聚物的制造方法,可采用公知方法。例如可举出采用乳化聚合或连续本体聚合的制造方法。采用乳化聚合的方法容易调整最终树脂组合物中的橡胶状聚合物的含量,因而优选。
采用乳化聚合的接枝共聚物的制造方法是使橡胶状聚合物的乳胶与苯乙烯系单体和丙烯腈系单体乳化接枝聚合的方法(以下称为“乳化接枝聚合法”)。采用乳化接枝聚合法可得到接枝共聚物的乳胶。
乳化接枝聚合法中,使用水、乳化剂、聚合引发剂、链转移剂,聚合温度优选为30~90℃的范围。乳化剂例如有阴离子表面活性剂、阳离子表面活性剂、两性表面活性剂等。聚合引发剂例如有异丙苯过氧化氢、过氧化二异丙苯、过氧化乙酸叔丁酯、过氧化苯甲酸叔己酯、过氧化苯甲酸叔丁酯等有机过氧化物;过硫酸钾、过硫酸铵等过硫酸盐类;偶氮二异丁腈等偶氮系化合物;铁离子等还原剂;甲醛次硫酸氢钠等二次还原剂;以及乙二胺四乙酸二钠等螯合剂等。链转移剂例如有正辛硫醇、正十二烷基硫醇、叔十二烷基硫醇、α-甲基苯乙烯二聚体、巯基乙酸乙酯、柠檬烯、萜品油烯等。
接枝共聚物的乳胶可采用公知方法凝固并回收接枝共聚物。例如向接枝共聚物的乳胶中加入凝固剂使其凝固,使用脱水机清洗脱水,经过干燥工序得到粉末状的接枝共聚物。
从抗冲击性的观点考虑,采用乳化接枝聚合法得到的接枝共聚物中橡胶状聚合物的含量优选为40~70质量%,更优选为45~65质量%。橡胶状聚合物的含量例如可通过在乳化接枝聚合时调整苯乙烯系单体和丙烯腈系单体相对于橡胶状聚合物的使用比例来调整。
从抗冲击性或耐化学性的观点考虑,除了采用乳化接枝聚合法得到的接枝共聚物的橡胶状聚合物之外的构成单元优选为苯乙烯系单体单元65~85质量%、丙烯腈系单体单元15~35质量%。
接枝共聚物的凝胶成分优选为粒子状。凝胶成分为苯乙烯系单体与丙烯腈系单体接枝共聚合而成的橡胶状聚合物的粒子,是不溶于甲乙酮、甲苯等有机溶剂,可通过离心而分离的成分。有时可形成为在橡胶状聚合物的粒子内部呈粒子状内包有苯乙烯-丙烯腈系共聚物的包藏结构。若将接枝共聚物与苯乙烯-丙烯腈共聚物熔融共混,则凝胶成分以粒子状作为分散相存在于苯乙烯-丙烯腈共聚物的连续相中。凝胶成分是将质量W的接枝共聚物溶解在甲乙酮中,使用离心机以20000rpm离心沉淀不溶物,倾析除去上清液,得到不溶成分,由真空干燥后干燥的不溶成分的质量S,根据式凝胶成分(质量%)=(S/W)×100计算出的值。此外,凝胶成分可以通过同样地将接枝共聚物和苯乙烯-丙烯腈共聚物熔融共混的树脂组合物溶解在甲乙酮中并离心来计算。
从抗冲击性和成型品外观的观点考虑,接枝共聚物的凝胶成分的体积平均粒径优选为0.10~1.0μm的范围,更优选为0.15~0.50μm。体积平均粒径是如下计算得到的值:将接枝共聚物与苯乙烯-丙烯腈共聚物熔融共混得到树脂组合物的颗粒,从该颗粒切出超薄切片,使用透射电子显微镜(TEM)进行观察,根据分散于连续相的粒子的图像解析进行计算。体积平均粒径例如可通过调整乳化接枝聚合时使用的橡胶状聚合物的乳胶粒径来调整。橡胶状聚合物的乳胶粒径可通过在乳化聚合时调整乳化剂的添加方法或水的使用量等来调整,但为了得到优选的范围需要延长聚合时间而生产率降低,因此可采用如下方法:使粒径0.1μm左右的橡胶状聚合物短时间聚合,再采用化学凝集法或物理凝集法使橡胶粒子肥大化。
从抗冲击性的观点考虑,接枝共聚物的接枝率优选为10~100质量%,更优选为20~70质量%。接枝率是由凝胶成分(G)与橡胶状聚合物的含量(RC)采用接枝率(质量%)=[(G-RC)/RC]×100计算得到的值。接枝率表示每单位质量橡胶状聚合物中含有的通过接枝而键合的苯乙烯-丙烯腈共聚物和粒子中内包的苯乙烯-丙烯腈共聚物的量。接枝率例如可通过在乳化接枝聚合时调整单体与橡胶状聚合物的比例、引发剂的种类和量、链转移剂量、乳化剂量、聚合温度、投料方法(一次性/多次/连续)、单体的添加速度等来调整。
从抗冲击性和成型品外观的观点考虑,接枝共聚物的甲苯膨润度优选为5~20倍。甲苯膨润度表示橡胶状聚合物的粒子的交联度,通过如下方式算出:将接枝共聚物溶解于甲苯,将不溶成分离心或过滤分离,由用甲苯膨润后的状态的质量与真空干燥去除甲苯后的干燥状态的质量之比算出。甲苯膨润度例如收到乳化接枝聚合时使用的橡胶状聚合物的交联度的影响,可通过在橡胶状聚合物的乳化聚合時添加引发剂、乳化剂、调整聚合温度、添加二乙烯基苯等多官能单体来调整。
SAN树脂是具有苯乙烯系单体单元和丙烯腈系单体单元的共聚物,例如有苯乙烯-丙烯腈共聚物。
作为SAN树脂的其他可共聚单体,可使用甲基丙烯酸甲酯等(甲基)丙烯酸酯系单体、丙烯酸丁酯、丙烯酸乙酯等丙烯酸酯系单体、甲基丙烯酸等(甲基)丙烯酸系单体、丙烯酸等丙烯酸系单体、N-苯基马来酰亚胺等N-取代马来酰亚胺系单体。
SAN树脂的构成单元优选为苯乙烯系单体单元60~90质量%、乙烯基氰单体单元10~40质量%,更优选为苯乙烯系单体单元65~80质量%、乙烯基氰单体单元20~35质量%。如果构成单元为上述范围内,则所得树脂组合物的冲击强度与流动性的平衡优异。苯乙烯系单体单元、乙烯基氰单体单元的含量是采用13C-NMR测得的值。
作为SAN树脂的制造方法,可采用公知方法。例如可采用本体聚合、溶液聚合、悬浮聚合、乳化聚合等来制造。作为反应装置的操作方法,连续式、分批式(批次式)、半批次式均可适用。从品质和生产率的方面考虑,优选本体聚合或溶液聚合,优选连续式。作为本体聚合或溶液聚合的溶剂,例如有苯、甲苯、乙苯和二甲苯等烷基苯类;丙酮、甲乙酮等酮类;己烷、环己烷等脂肪族烃等。
SAN树脂的本体聚合或溶液聚合中可使用聚合引发剂、链转移剂,聚合温度优选为120~170℃的范围。聚合引发剂例如有1,1-二(叔丁基过氧化)环己烷、2,2-二(叔丁基过氧化)丁烷、2,2-二(4,4-二叔丁基过氧化环己基)丙烷、1,1-二(叔戊基过氧化)环己烷等过氧缩醛类、异丙苯过氧化氢、叔丁基过氧化氢等氢过氧化物类、过氧化乙酸叔丁酯、过氧化苯甲酸叔戊酯等烷基过氧化物类、叔丁基过氧化异丙苯、二叔丁基过氧化物、过氧化二异丙苯、二叔己基过氧化物等二烷基过氧化物类、过氧化乙酸叔丁酯、过氧化苯甲酸叔丁酯、叔丁基过氧化异丙基单碳酸酯等过氧化物酯类、叔丁基过氧异丙基碳酸酯、聚醚四(叔丁基过氧碳酸酯)等过氧碳酸酯类、N,N’-偶氮双(环己烷-1-腈)、N,N’-偶氮双(2-甲基丁腈)、N,N’-偶氮双(2,4-二甲基戊腈)、N,N’-偶氮双[2-(羟甲基)丙腈]等,可使用其中1种或者将2种以上组合使用。链转移剂例如有正辛硫醇、正十二烷基硫醇、叔十二烷基硫醇、α-甲基苯乙烯二聚体、巯基乙酸乙酯、柠檬烯、萜品油烯等。
从SAN树脂聚合结束后的溶液中去除未反应单体或用于溶液聚合的溶剂等挥发成分的脱挥方法可采用公知方法。例如可使用带预热器的真空脱挥槽或带排气口的脱挥挤出机。经脱挥的熔融状态的SAN树脂可被移送至造粒工序,由多孔模呈绳状挤出,采用冷切方式、空中热切方式、水中热切方式加工成颗粒状。
从树脂组合物的抗冲击性和成型性的观点考虑,SAN树脂的重均分子量优选为5万~25万,更优选为7万~20。具体而言例如为5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20万,也可以是任意2个所例示数值之间的范围内。SAN树脂的重均分子量是使用凝胶渗透色谱(GPC)在THF溶剂中测定得到的聚苯乙烯换算值,是采用与马来酰亚胺系共聚物(A)相同的方法测定得到的值。重均分子量可通过调整聚合时链转移剂的种类和量、溶剂浓度、聚合温度、聚合引发剂的种类和量来调整。
作为树脂(B),例如可举出使用采用乳化聚合法得到的粉末状ABS树脂以及采用连续式本体聚合法得到的颗粒状SAN树脂这两种树脂的方法。另外可举出将采用乳化聚合法得到的粉末状ABS树脂和采用连续本体聚合得到的颗粒状SAN树脂用挤出机等熔融混合后,制成颗粒状的ABS树脂的方法。
使用挤出机将马来酰亚胺系共聚物(A)和选自ABS树脂、ASA树脂、AES树脂、SAN树脂中的至少一种的树脂(B)熔融混炼的方法可采用公知方法。挤出机可使用公知的装置,例如可举出双螺杆挤出机、单螺杆挤出机、多螺杆挤出机、带双轴转子的连续混炼机等。优选使用双轴挤出机,更优选被广泛使用的啮合式同向双螺杆挤出机。
作为本发明的实施方式中双轴挤出机的螺杆,从生产性的观点来看优选使用螺杆深沟比大的。螺杆深沟比由螺杆外径(D)和谷径(d)之比D/d规定。螺杆深沟比在整个螺杆上可以是均匀的,也可以在每个区域中不同。本发明的混炼部中螺杆深沟比是指,混炼熔融混炼的材料的区域中,配置有混合元件温度最高的区域的螺杆深沟比。本发明的实施方式中,从生产性的观点考虑,双轴挤出机的混炼部中螺杆深沟比优选为1.55以上。
熔融混炼优选在抗氧化剂(C)的存在下进行。抗氧化剂优选使用受阻酚系抗氧化剂,也可并用磷系抗氧化剂。
受阻酚系抗氧化剂是在其基本骨架中具有酚性羟基的抗氧化剂。受阻酚系抗氧化剂例如可列举,十八烷基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯、亚乙基双(氧乙烯基)双〔3-(5-叔丁基-4-羟基-间-甲苯基)丙酸酯〕、3,9-双[2-〔3-(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基〕-1,1-二甲基乙基]-2,4,8,10-四氧杂螺[5.5]十一烷、季戊四醇四[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、4,6-双(辛基硫甲基)-邻甲酚、4,6-双〔(正十二烷硫基)甲基〕-邻甲酚、2,4-二甲基-6-(1-甲基十五烷基)酚、四〔亚甲基-3-(3,5-二-叔丁基-4-羟基苯基)丙酸〕甲烷、4,4’-硫代双(6-叔丁基-3-甲基酚)、1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷、4,4’-亚丁基双(3-甲基-6-叔丁基酚)、双-[3,3-双-(4’-羟基-3’-tert―丁基苯基)-丁酸]-乙二醇酯、2-叔丁基-6-(3-叔丁基-2-羟基-5-甲基苄基)-4-甲基苯基丙烯酸酯、2-〔1-(2-羟基-3,5-二-叔戊基苯基)乙基〕-4,6-二-叔戊基苯基丙烯酸酯等。优选为,十八烷基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯、亚乙基双(氧乙烯基)双〔3-(5-叔丁基-4-羟基-间-甲苯基)丙酸酯〕、季戊四醇四[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]。更优选为,十八烷基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯。受阻酚系抗氧化剂可以单独使用也可以组合2种以上来使用。
磷系抗氧化剂是三价磷化合物的亚磷酸酯类。磷系抗氧化剂例如可列举,6-[3-(3-叔丁基-4-羟基-5-甲基苯基)丙氧基]-2,4,8,10-四-叔丁基苯[d,f][1,3,2]二噁磷杂庚英、3,9-双(2,6-二-叔丁基-4-甲基苯氧基)-2,4,8,10-四氧杂-3,9-二磷杂螺〔5.5〕十一烷、双(2,4-枯基苯基)季戊四醇二亚磷酸酯、2,2’-亚甲基双(4,6-二-叔丁基-1-苯氧基)(2-乙基己氧基)磷、三(2,4-二-叔丁基苯基)亚磷酸酯、双〔2,4-双(1,1-二甲基乙基)-6-甲基苯基〕亚磷酸乙基酯、双(2,4-二-叔丁基苯基)季戊四醇二亚磷酸酯、环辛戊烷四基双(十八烷基亚磷酸酯)、双(壬基苯基)季戊四醇二亚磷酸酯、4,4’-亚联苯基二次磷酸四(2,4-二-叔丁基苯基)、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物、四(2,4-二-叔丁基-5-甲基苯基)-4,4’-联苯二亚磷酸酯等。优选为,6-[3-(3-叔丁基-4-羟基-5-甲基苯基)丙氧基]-2,4,8,10-四-叔丁基苯[d,f][1,3,2]二噁磷杂庚英、3,9-双(2,6-二-叔丁基-4-甲基苯氧基)-2,4,8,10-四氧杂-3,9-二磷杂螺〔5.5〕十一烷、双(2,4-枯基苯基)季戊四醇二亚磷酸酯、2,2’-亚甲基双(4,6-二-叔丁基-1-苯氧基)(2-乙基己氧基)磷、三(2,4-二-叔丁基苯基)亚磷酸酯、双(2,4-二-叔丁基苯基)季戊四醇二亚磷酸酯。更优选为,6-[3-(3-叔丁基-4-羟基-5-甲基苯基)丙氧基]-2,4,8,10-四-叔丁基苯[d,f][1,3,2]二噁磷杂庚英、双(2,4-枯基苯基)季戊四醇二亚磷酸酯、三(2,4-二-叔丁基苯基)亚磷酸酯、双(2,4-二-叔丁基苯基)季戊四醇二亚磷酸酯,进一步优选为6-[3-(3-叔丁基-4-羟基-5-甲基苯基)丙氧基]-2,4,8,10-四-叔丁基苯[d,f][1,3,2]二噁磷杂庚英、双(2,4-枯基苯基)季戊四醇二亚磷酸酯、双(2,4-二-叔丁基苯基)季戊四醇二亚磷酸酯。磷系抗氧化剂可以单独使用也可以组合2种以上来使用。
混炼部的气缸温度为290℃以上时,作为抗氧化剂(C)更有选使用游离基清除剂。作为游离基清除剂可列举,2-叔丁基-6-(3'-叔丁基-5'-甲基-2'-羟基苄基)-4-甲基苯基丙烯酸酯、2,4-二叔戊基-6-[1-(3,5-二叔戊基-2-羟基苯基)乙基]苯基丙烯酸酯。
相对于马来酰亚胺系共聚物(A)和树脂(B)的总计100质量份,抗氧化剂(C)的添加量优选为0.1~0.5质量份,更优选为0.3~0.5质量份。具体而言例如为0.1、0.2、0.3、0.4或0.5质量份,也可以是任意2个所例示数值之间的范围内。
将马来酰亚胺系共聚物(A)和树脂(B)的总量作为100质量%时,树脂组合物中马来酰亚胺系共聚物(A)的含量优选为5~45质量%,更优选为7~35质量%,进一步优选为10~30质量%。具体而言例如为5、10、15、20、21、22、23、24、25、26、27、28、29、30、35、40或45质量%,也可以是任意2个所例示数值之间的范围内。马来酰亚胺系共聚物(A)的含量过少,则树脂组合物的耐热性提高不充分。过多则流动性降低,成型性变差。应予说明,包含于树脂组合物的树脂实质上可以仅是马来酰亚胺系共聚物(A)和树脂(B)。
耐热性树脂组合物的制造中在不损害本发明效果的范围内可以含有其他树脂成分、抗冲击改性剂、流动性改性剂、硬度改性剂、抗氧化剂、无机填充剂、消光剂、阻燃剂、阻燃助剂、防滴剂、滑动性赋予剂、放热剂、电磁波吸收剂、增塑剂、润滑剂、脱模剂、紫外线吸收剂、光稳定剂、抗菌剂、抗霉剂、抗静电剂、炭黑、氧化钛、颜料、染料等。
【实施例】
以下使用实施例对详细内容进行说明,但本发明并不限定于以下实施例。
<马来酰亚胺系共聚物(A-1)的制造例>
采用以下方法制造马来酰亚胺系共聚物(A-1)。
向具备搅拌机的容积约120升的高压釜中投入苯乙烯62质量份、马来酸酐11质量份、2、4-二苯基-4-甲基-1-戊烯0.2质量份、甲乙酮31质量份,用氮气对系内进行置换后,升温至92℃,历时7小时连续添加将马来酸酐28质量份和过氧化-2-乙基己酸叔丁酯0.19质量份溶解于甲乙酮110质量份的溶液。添加之后升温至120℃,使其反应30分钟完成聚合。其后向聚合液加入苯胺35质量份、三乙胺0.6质量份在140℃反应7小时。将反应结束后的酰亚胺化反应液投入于排气式挤出机,除去挥发成分得到了约3mm的颗粒状的马来酰亚胺系共聚物(A-1)。A-1的苯乙烯单元为48质量%、N-苯基马来酰亚胺单元为51质量%、马来酸酐单元为1质量%,重均分子量Mw为13万,玻璃化转变温度Tmg为202℃。另外,在260℃、剪切速度120/sec下的熔融黏度为3420Pa·s,在280℃、剪切速度120/sec下的熔融黏度为1780Pa·s。
<马来酰亚胺系共聚物(A-2~A-8)的制造例>
使用筛网式微粉碎机将马来酰亚胺系共聚物(A-1)粉碎为粉末状。用筛网直径1mm,改变旋转数得到了平均粒子直径不同的A-2~A-5。A-6使用了除去A-4的筛子(850μm)上的。A-7仅使用了筛子(75μm)下的。A-8使用了混合了A-2 80质量%和A-6的筛子(1000μm)上10质量%的。粉末的平均粒子直径使用JIS Z 8801的试验筛子测定。使用网孔为1000、850、500、355、250、150、106、75、50μm的筛子,将喷洒抗静电剂混合的马来酰亚胺系共聚物的粉末50g放入网孔最大的筛子中盖上盖子,将筛子置于摇床上,摇晃20分钟。摇晃后,测定包含粉末的各筛子的质量,减去筛子的质量,即可计算出筛子上的粒度分布。从粒度分布的结果来看,质量从网孔大的开始依次相加,平均粒子直径是从夹住累积质量50%的两点网孔(粒子直径)和50%的交点求出的粒子直径。应予说明,因为用本测定法无法测定A-7的平均粒子直径,因此为小于75μm,但通过激光衍射/散射法获得的平均粒子直径为37μm。
<马来酰亚胺系共聚物(A-9)的制造例>
采用以下方法制造马来酰亚胺系共聚物(A-9)。
向具备搅拌机的容积约120升的高压釜中投入苯乙烯42质量份、丙烯腈10质量份、马来酸酐4质量份、2、4-二苯基-4-甲基-1-戊烯0.03质量份、甲乙酮27质量份,用氮气对气相部进行置换后,搅拌同时历时40分钟升温至92℃。升温后维持92℃,历时4.5小时连续添加将马来酸酐21质量份和过氧化-2-乙基己酸叔丁酯0.15质量份溶解于甲乙酮85质量份的溶液以及苯乙烯20质量份。进一步,添加完马来酸酐之后,历时30分钟连续添加将过氧化-2-乙基己酸叔丁酯0.02质量份溶解于甲乙酮9质量份的溶液以及苯乙烯3质量份。添加之后升温至120℃,使其反应30分钟完成聚合。后向聚合液中加入苯胺23质量份、三乙胺0.4质量份在140℃反应7小时。将反应结束后的酰亚胺化反应液投入于排气式挤出机,除去挥发成分得到了颗粒状的马来酰亚胺系共聚物(A-9)进一步,与(A-2)~(A-8)相同的方式,使用筛网式微粉碎机将马来酰亚胺系共聚物(A-9)粉碎为粉末状。(A-9)的苯乙烯单元为52质量%、丙烯腈单元为8质量%、N-苯基马来酰亚胺单元为39质量%、马来酸酐单元为1质量%,重均分子量Mw为14万、玻璃化转变温度Tmg为177℃。另外,在260℃、剪切速度120/sec下的熔融黏度为1660Pa·s,在280℃、剪切速度120/sec下的熔融黏度为710Pa·s。
<ABS树脂(B-1)>
使用市售的ABS树脂(电化株式会社制DENKAABS GR-3500)。
<SAN树脂(B-2)>
使用市售的SAN树脂(电化株式会社制DENKAAS AS-EXS)。
<实施例·比较例>
使用挤出机按表1所示的配合以及条件将马来酰亚胺系共聚物、ABS树脂熔融混炼,进行了耐热性树脂组合物的制造。挤出机使用了L/D=48、螺杆深沟比1.56的双螺杆挤出机(东芝机械株式会社制TEM-26SX)。应予说明,作为抗氧化剂,相对于马来酰亚胺系共聚物(A)和树脂(B)的总量100质量份,混合了下述(C-1)0.3质量份、(C-2)0.15质量份。评价结果示于表1。
(C-1)季戊四醇四[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯](BASF日本株式会社制造Irganox1010)
(C-2):三(2,4-二-叔丁基苯基)亚磷酸酯(BASF日本株式会社制造Irganox168)
(熔体流动速率)
熔体流动速率基于JIS K7210在220℃以98N负载进行测定。
(维卡软化温度)
维卡软化点基于JIS K7206,采用50法(负载50N、升温速度50℃/小时)使用10mm×10mm、厚4mm的实验片进行测定。应予说明,测定设备使用东洋精机制作所社制的HDT&VSPT试验装置。
(夏比冲击强度)
夏比冲击强度基于JIS K7111-1,使用带缺口实验片,打击方向采用沿边进行测定。应予说明,测定设备使用东洋精机制作所社制的数显冲击试验机。
(分散等级)
使用射出成型机(东芝机械株式会社制造,IS-50EP),将在气缸温度220℃、模具温度60℃的成型条件下成型的长90mm、宽55mm、厚2mm的镜板,肉眼观察马来酰亚胺系共聚物的分散状态。若马来酰亚胺系共聚物的分散状态差,则在成型品的表面观察到沿树脂流动的条纹。
分散等级5:外观非常干净没有瑕疵
分散等级4:可以看到细微的条纹
分散等级3:可以看到细微的条纹
分散等级2:存在导致明显不良外观的条纹。
分散等级1:有明显被认为整体外观较差的条纹。
【表1】
由表1的结果可知,通过使用平均粒子直径为75μm以上、1000μm的筛子上小于5质量%的粉状的马来酰亚胺系共聚物,可得到马来酰亚胺系共聚物的分散性优异的耐热性树脂组合物。
应予说明,虽然没有示于表1,但比较例2在制造耐热性树脂组合物时,马来酰亚胺系共聚物在挤出机的供给区堵塞二工作效率差。
产业上的可利用性
根据本发明的马来酰亚胺系共聚物,可以得到生产率高、马来酰亚胺系共聚物的分散性优异的耐热性树脂组合物,其成型品的外观也优异。
Claims (4)
1.一种马来酰亚胺系共聚物(A),其平均粒子直径为75μm以上,在1000μm的筛子上小于5质量%的粉状。
2.根据权利要求1所述的马来酰亚胺系共聚物(A),其玻璃化转变温度为170~210℃。
3.根据权利要求1或2所述的马来酰亚胺系共聚物(A),其在260℃、剪切速度120/sec下的熔融黏度为1000Pa·s以上。
4.一种耐热性树脂组合物的制造方法,其特征在于,
使用挤出机将权利要求1~3中任一项所述的马来酰亚胺系共聚物(A)和选自ABS树脂、ASA树脂、AES树脂、SAN树脂中的至少一种的树脂(B)熔融混炼。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020-163987 | 2020-09-29 | ||
JP2020163987 | 2020-09-29 | ||
PCT/JP2021/034756 WO2022071051A1 (ja) | 2020-09-29 | 2021-09-22 | マレイミド系共重合体 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115989247A true CN115989247A (zh) | 2023-04-18 |
Family
ID=80950475
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202180051433.8A Pending CN115989247A (zh) | 2020-09-29 | 2021-09-22 | 马来酰亚胺系共聚物 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20230294346A1 (zh) |
EP (1) | EP4223797A4 (zh) |
JP (1) | JP7199595B2 (zh) |
KR (1) | KR20230075476A (zh) |
CN (1) | CN115989247A (zh) |
TW (1) | TW202222859A (zh) |
WO (1) | WO2022071051A1 (zh) |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03244652A (ja) * | 1990-02-22 | 1991-10-31 | Nippon Oil & Fats Co Ltd | 熱可塑性樹脂組成物及びその製造方法 |
JPH1036614A (ja) * | 1996-05-22 | 1998-02-10 | Denki Kagaku Kogyo Kk | 耐熱性マスターバッチ樹脂、それを用いた耐熱性樹脂成形体及びその製造方法 |
JP3637694B2 (ja) * | 1996-09-03 | 2005-04-13 | 大日本インキ化学工業株式会社 | 粉末成形用樹脂組成物及び成形品 |
JP4044161B2 (ja) * | 1996-09-27 | 2008-02-06 | 株式会社日本触媒 | 粒体状マレイミド類およびその取扱い方法 |
JP2001055449A (ja) | 1999-08-20 | 2001-02-27 | Nippon Shokubai Co Ltd | 熱可塑性樹脂組成物の製造方法およびその樹脂成形品 |
JP2003041080A (ja) | 2001-05-23 | 2003-02-13 | Denki Kagaku Kogyo Kk | マレイミド系耐熱付与材 |
ES2525809T3 (es) | 2009-01-16 | 2014-12-30 | Denki Kagaku Kogyo Kabushiki Kaisha | Maleimida copolímero, proceso para la producción del mismo, y composiciones de resina resistente al calor que los contienen |
CN107614598B (zh) * | 2015-05-19 | 2020-12-18 | 电化株式会社 | 耐热性树脂组合物及其制造方法 |
-
2021
- 2021-09-22 TW TW110135124A patent/TW202222859A/zh unknown
- 2021-09-22 EP EP21875353.1A patent/EP4223797A4/en active Pending
- 2021-09-22 KR KR1020237013423A patent/KR20230075476A/ko unknown
- 2021-09-22 JP JP2022505604A patent/JP7199595B2/ja active Active
- 2021-09-22 WO PCT/JP2021/034756 patent/WO2022071051A1/ja unknown
- 2021-09-22 CN CN202180051433.8A patent/CN115989247A/zh active Pending
- 2021-09-22 US US18/017,974 patent/US20230294346A1/en active Pending
Also Published As
Publication number | Publication date |
---|---|
TW202222859A (zh) | 2022-06-16 |
JP7199595B2 (ja) | 2023-01-05 |
US20230294346A1 (en) | 2023-09-21 |
EP4223797A1 (en) | 2023-08-09 |
WO2022071051A1 (ja) | 2022-04-07 |
JPWO2022071051A1 (zh) | 2022-04-07 |
EP4223797A4 (en) | 2024-05-01 |
KR20230075476A (ko) | 2023-05-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7021319B2 (ja) | 耐熱性樹脂組成物及びその製造方法 | |
CN107614546B (zh) | 聚合物共混物相容剂用共聚物和树脂组合物 | |
EP4212584A1 (en) | Heat resistance resin composition and injection molded body thereof | |
EP3960814B1 (en) | Thermoplastic resin composition and molded article thereof | |
JP7199595B2 (ja) | マレイミド系共重合体 | |
WO2022071050A1 (ja) | 耐熱性樹脂組成物の製造方法 | |
WO2022176756A1 (ja) | 耐熱性樹脂組成物の製造方法 | |
CN116323798A (zh) | 耐热性树脂组合物 | |
JP2022173868A (ja) | 抗菌性耐熱樹脂組成物 | |
CN116964148A (zh) | Abs树脂改质剂、树脂组合物、成型体、以及树脂组合物的制造方法 | |
TW202309179A (zh) | 透明之橡膠改質苯乙烯系樹脂組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |