CN114437274A - Styrene-halogenated phenyl maleimide copolymer and preparation method and application thereof - Google Patents
Styrene-halogenated phenyl maleimide copolymer and preparation method and application thereof Download PDFInfo
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- CN114437274A CN114437274A CN202011130578.0A CN202011130578A CN114437274A CN 114437274 A CN114437274 A CN 114437274A CN 202011130578 A CN202011130578 A CN 202011130578A CN 114437274 A CN114437274 A CN 114437274A
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- styrene
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 34
- 150000002367 halogens Chemical class 0.000 claims abstract description 32
- 239000003063 flame retardant Substances 0.000 claims abstract description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 24
- 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 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 85
- 238000006116 polymerization reaction Methods 0.000 claims description 72
- 239000003999 initiator Substances 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 39
- -1 R9Is H Chemical group 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 19
- 150000002978 peroxides Chemical class 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000012662 bulk polymerization Methods 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
- ZHKCHSNXUCRFSM-UHFFFAOYSA-N 4-[2-[4,4-bis(tert-butylperoxy)cyclohexyl]propan-2-yl]-1,1-bis(tert-butylperoxy)cyclohexane Chemical group C1CC(OOC(C)(C)C)(OOC(C)(C)C)CCC1C(C)(C)C1CCC(OOC(C)(C)C)(OOC(C)(C)C)CC1 ZHKCHSNXUCRFSM-UHFFFAOYSA-N 0.000 claims description 3
- XXSPGBOGLXKMDU-UHFFFAOYSA-M 2-bromo-2-methylpropanoate Chemical compound CC(C)(Br)C([O-])=O XXSPGBOGLXKMDU-UHFFFAOYSA-M 0.000 claims description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 23
- 238000012512 characterization method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- ONEIBTGSNPDDSB-UHFFFAOYSA-N 1-(2,4,6-tribromophenyl)pyrrole-2,5-dione Chemical compound BrC1=CC(Br)=CC(Br)=C1N1C(=O)C=CC1=O ONEIBTGSNPDDSB-UHFFFAOYSA-N 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 4
- 239000004795 extruded polystyrene foam Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- CQNPSIAJXGEDQS-VURMDHGXSA-N (z)-2-phenylbut-2-enedioic acid Chemical class OC(=O)\C=C(/C(O)=O)C1=CC=CC=C1 CQNPSIAJXGEDQS-VURMDHGXSA-N 0.000 description 2
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 2
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 2
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 239000004283 Sodium sorbate Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002635 aromatic organic solvent Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- PBGVMIDTGGTBFS-UHFFFAOYSA-N but-3-enylbenzene Chemical compound C=CCCC1=CC=CC=C1 PBGVMIDTGGTBFS-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002356 laser light scattering Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 description 1
- KQJQPCJDKBKSLV-UHFFFAOYSA-N 1-bromo-3-ethenylbenzene Chemical compound BrC1=CC=CC(C=C)=C1 KQJQPCJDKBKSLV-UHFFFAOYSA-N 0.000 description 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- HLOUDBQOEJSUPI-UHFFFAOYSA-N 1-ethenyl-2,3-dimethylbenzene Chemical group CC1=CC=CC(C=C)=C1C HLOUDBQOEJSUPI-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- GOAHRBQLKIZLKG-UHFFFAOYSA-N 1-tert-butylperoxybutane Chemical compound CCCCOOC(C)(C)C GOAHRBQLKIZLKG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- OWRKXOZFTROHSH-UHFFFAOYSA-N 2-ethenyl-1,3-dimethylbenzene Chemical group CC1=CC=CC(C)=C1C=C OWRKXOZFTROHSH-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- ZVNDSQGHZLPKQV-UHFFFAOYSA-N 4-methylpenta-1,3-dienylbenzene Chemical compound CC(C)=CC=CC1=CC=CC=C1 ZVNDSQGHZLPKQV-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- 229920001634 Copolyester Polymers 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- JUIBLDFFVYKUAC-UHFFFAOYSA-N [5-(2-ethylhexanoylperoxy)-2,5-dimethylhexan-2-yl] 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C(CC)CCCC JUIBLDFFVYKUAC-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000003960 organic solvent Substances 0.000 description 1
- 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 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical group C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of flame-retardant materials, and discloses a styrene-halogenated phenyl maleimide copolymer, and a preparation method and application thereof. The copolymer comprises a structural unit A shown in a formula (1) and a structural unit B shown in a formula (2);
wherein R is1Is H or methyl, R2Is H or halogen, R3Is H or halogen, R4Is linear alkyl or isomeric alkyl of H, C1-C5, linear alkenyl of C2-C5Or isomeric alkenyl radicals, R5、R6And R7Each independently is H or halogen; based on the total weight of the copolymer, the content of the structural unit A is 50-95 wt%, and the content of the structural unit B is 5-50 wt%. The copolymer has excellent flame retardant property, heat resistance and high weight average molecular weight, and the copolymer has excellent processability in a molten state.
Description
Technical Field
The invention relates to the field of flame-retardant materials, in particular to a styrene-halogenated phenyl maleimide copolymer and a preparation method and application thereof.
Background
The extruded polystyrene foam plastic (XPS) plate is a third-generation hard foaming heat-insulating material, overcomes the complex production process of the polystyrene foam plastic (EPS) plate from the technical aspect, and has the superior performance which can not be replaced by the EPS plate. The plate material with continuous uniform surface layer and closed-cell honeycomb structure is produced by polystyrene resin and other additives through an extrusion process, is a novel building material which is generally popularized and applied in China, has excellent high strength, pressure resistance, excellent heat insulation and heat insulation, light weight, convenient use, high-quality hydrophobicity, moisture resistance and environmental protection performance, and good stability and corrosion resistance, and becomes a novel building material which is generally popularized in the building industry. However, the base material of XPS, polystyrene resin, is easy to burn and has poor fire resistance, so a certain amount of flame retardant is added when preparing XPS boards to improve the flame retardant property of the materials.
Halogenated Flame Retardants (HFRs), particularly Brominated Flame Retardants (BFRs), are the most widely produced and used flame retardants in the world today, but additive-type halogenated flame retardants are combined with a matrix by intermolecular forces and easily migrate and diffuse into the environment in the matrix, causing environmental pollution, so that the application of non-polymeric halogenated flame retardants in certain fields is legally limited in many regions of the world. On the other hand, additive halogen flame retardants, including inorganic flame retardants and phosphorus flame retardants developed later, have not only exhibited flame retardant properties but also deteriorated heat resistance, melt strength and other properties of the material, and the compatibility was difficult to solve.
Therefore, it is necessary to design a flame retardant styrenic polymer, which solves the problem of environmental pollution caused by migration of flame retardant from the substrate, and has high mechanical properties, such as heat resistance and melt strength.
Disclosure of Invention
The invention aims to solve the problems of environmental pollution and reduced flame retardance caused by migration of a flame retardant in a styrene polymer for a flame-retardant insulation board in the prior art and the problem of reduced mechanical properties of a styrene polymer material caused by addition of the flame retardant, and provides a styrene-halogenated phenyl maleimide copolymer, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a styrene-halogenophenyl maleimide copolymer, characterized in that the copolymer comprises a structural unit a represented by formula (1) and a structural unit B represented by formula (2);
wherein R is1Is H or methyl, R2Is H or halogen, R3Is H or halogen, R4Is a linear or isomeric alkyl radical of H, C1-C5, a linear or isomeric alkenyl radical of C2-C5, R5、R6And R7Each independently is H or halogen;
based on the total weight of the copolymer, the content of the structural unit A is 50-95 wt%, and the content of the structural unit B is 5-50 wt%.
A second aspect of the present invention provides a method for preparing a styrene-halogenophenyl-maleic acid imide copolymer, characterized in that the method comprises: polymerizing monomers comprising a monomer M1 shown in a formula (4) and a monomer M2 shown in a formula (5) in the presence of an initiator to obtain the styrene-halogenated phenyl maleimide copolymer,
wherein R is1' is H or methyl, R2' is H or halogen, R3' is H or halogen, R4' is a linear or isomeric alkyl radical of H, C1 to C5, a linear or isomeric alkenyl radical of C2 to C5, R5’、R6' and R7' are each independently H or halogen;
based on the total weight of the monomer M1 and the monomer M2, the monomer M1 is used in an amount of 50-95 wt%, and the monomer M2 is used in an amount of 5-50 wt%.
The third aspect of the present invention provides a styrene-halophenylmaleimide copolymer obtained by the above-mentioned process.
The fourth aspect of the present invention provides the use of the above styrene-halophenyl maleimide copolymer in a flame retardant and heat insulating board.
Through the technical scheme, the styrene-halogenated phenyl maleimide copolymer, the preparation method and the application thereof provided by the invention have the following beneficial effects:
the styrene-halogenated phenyl maleic acid imide copolymer provided by the invention has excellent flame retardant property and heat resistance, the weight average molecular weight of the copolymer can reach more than 15 ten thousand, and the molecular chain of the copolymer has a long branched chain structure, so that the entanglement capacity among the molecular chains is improved, the processing performance of the material in a molten state can be obviously improved, and the copolymer has excellent air hole forming capacity in the extrusion foaming process.
In addition, the preparation method of the styrene-halogenated phenyl maleic acid imide copolymer provided by the invention has the advantages of simple process flow and easiness in operation. The multistage reactor can ensure stable production of the device, high single-pass conversion rate and effectively reduced operation cost.
Drawings
FIG. 1 is a flow chart of the preparation process of the styrene-halogenated phenyl maleimide copolymer of the present invention.
Description of the reference numerals
X101-first static mixer; r101-first reactor; r102-second reactor; r103-third reactor; r104-fourth reactor; P101/P102/P103/P104-polymerization liquid transfer pump; E201-Heater before flash vaporization; v201-first flash tank; v202-second flash tank.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, one or more new ranges of values may be obtained from combinations of values between the endpoints of each range, the endpoints of each range and the individual values, and the individual values of the points, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides a styrene-halogenophenylmaleimide copolymer characterized in that the copolymer comprises a structural unit a represented by formula (1) and a structural unit B represented by formula (2);
wherein R is1Is H or methyl, R2Is H or halogen, R3Is H or halogen, R4Is a linear or isomeric alkyl radical of H, C1-C5, a linear or isomeric alkenyl radical of C2-C5, R5、R6And R7Each independently is H or halogen;
based on the total weight of the copolymer, the content of the structural unit A is 50-95 wt%, and the content of the structural unit B is 5-50 wt%.
In the present invention, the styrene-halophenyl maleimide copolymer comprising the structural unit a and the structural unit B has excellent flame retardancy and heat resistance.
Furthermore, the molecular chain of the styrene-halogenated phenyl maleimide copolymer has a long branched chain structure, so that the entanglement capability among the molecular chains is improved, the processing performance of the material in a molten state can be obviously improved, and the styrene-halogenated phenyl maleimide copolymer has excellent air hole forming capability in the extrusion foaming process.
Further, when the contents of the structural unit a and the structural unit B satisfy the above ranges, the copolymer has excellent flame retardancy, heat resistance, and processability.
In order to further improve the flame retardant property, heat resistance, processability and blow hole moldability of the copolymer, it is preferable that R in the formula (1)1Is methyl, R2And R3Is H, R4Is H, C1-C4 straight-chain alkyl or isomeric alkyl, C2-C4 straight-chain alkenyl or isomeric alkenyl.
Preferably, in the formula (1), R1Is H, R2Is H or halogen, R3Is H or halogen; in the formula (2), R5、R6And R7Is halogen, preferably Br.
Further, the content of the structural unit A is 60 to 90 wt%, preferably 60 to 80 wt%, based on the total weight of the copolymer; when the content of the structural unit B is 10 to 50 wt%, preferably 15 to 40 wt%, the flame retardant property, heat resistance and processability of the copolymer are further improved.
In the present invention, the total content of the structural unit a and the structural unit B is 90 wt% or more.
According to the invention, the copolymer also comprises structural units C of formula (3);
R8is H or methyl, R9Is H, -CN, -COOR10or-CONHR11Wherein R is10Is a straight-chain alkyl, branched-chain alkyl or cyclic alkyl of C1-C5, an aromatic radical of C6-C10, R11Is H or methyl.
According to the invention, the content of structural unit C is less than 10 wt%, based on the total weight of the copolymer.
In the present invention, the total content of the structural unit A, the structural unit B and the structural unit C is 100 wt%.
In the present invention, the introduction of the structural unit C can further improve the heat resistance of the copolymer.
According to the invention, the weight-average molecular weight Mw1 of the copolymer is more than 15 ten thousand, preferably more than 18 ten thousand; the copolymer has a ratio Mw2/Mw1 of the absolute molecular weight Mw2 to the weight-average molecular weight Mw1 of 1.05 to 2.5, preferably 1.2 to 1.4.
In the present invention, Mw2/Mw1 is used to characterize the degree of branching of the polymer, with greater Mw2/Mw1 indicating greater degrees of branching in the polymer.
In the present invention, the weight average molecular weight Mw1 of the copolymer was measured by Agilent high temperature gel permeation chromatograph (PL-GPC 220); the absolute molecular weight Mw2 of the polymer was determined using a WyattTRI STAR Mini DAWN multiangular laser light scattering instrument (MALLS).
According to the present invention, the melt strength of the styrene-halogenophenylmaleimide copolymer is 0.15N or more, preferably 0.20N or more.
In the present invention, the melt strength of the copolymer was measured by a melt strength tester model Rheotens 97 from GOTTFERT, Germany.
The second aspect of the present invention provides a method for producing a styrene-halogenophenylmaleimide copolymer, characterized in that the method comprises:
carrying out polymerization reaction on a polymerization monomer containing a monomer M1 shown in a formula (4) and a monomer M2 shown in a formula (5) in the presence of an initiator to obtain the styrene-halogenated phenyl maleimide copolymer,
wherein R is1' is H or methyl, R2' is H or halogen, R3' is H or halogen, R4' is a linear or isomeric alkyl radical of H, C1 to C5, a linear or isomeric alkenyl radical of C2 to C5, R5’、R6' and R7' are each independently H or halogen;
based on the total weight of the monomer M1 and the monomer M2, the monomer M1 is used in an amount of 50-95 wt%, and the monomer M2 is used in an amount of 5-50 wt%.
According toIn the formula (4), R1' is methyl, R2' and R3' is H, R4' is linear or branched alkyl of H, C1-C4, linear or branched alkenyl of C2-C4.
According to the invention, in the formula (4), R1' is H, R2' is H or halogen, R3' is H or halogen.
In the present invention, the monomer M1 represented by formula (4) may be one or more selected from the group consisting of styrene, α -methylstyrene, vinyltoluene, vinylo-xylene, vinylm-xylene, vinylethylbenzene, isobutenylstyrene, t-butylstyrene, bromostyrene, dibromostyrene, chlorostyrene and dichlorostyrene, and styrene is preferred.
In the present invention, the vinylethylbenzene has the following structure:
in the present invention, the isobutylene-based styrene has the following structure:
in the invention, the tert-butyl styrene has the following structure:
in the invention, the dibromostyrene can be o-bromostyrene, m-bromostyrene or p-bromostyrene; the dichlorostyrene may be o-chlorostyrene, m-chlorostyrene or p-chlorostyrene.
According to the invention, the monomer M2 is a benzene ring halide of N-phenylmaleimide (in formula (5), R5’、R6' and R7' is halogen), preferably N- (2,4,6-Tribromophenyl) maleimide (formula (5), R5’、R6' and R7' is Br).
According to the invention, the monomer M1 is used in an amount of 60 to 90 wt.%, preferably 60 to 80 wt.%, based on the total weight of the monomers to be polymerized; the monomer M2 is used in an amount of 10 to 50 wt%, preferably 15 to 40 wt%.
In the present invention, the total amount of the monomer M1 and the monomer M2 is 90% by weight or more.
According to the invention, the polymerized monomers also comprise a monomer M3 represented by formula (6),
wherein R is8' is H or methyl, R9' is H, -CN, -COOR10' or-CONHR11', wherein R10' is C1-C5 straight-chain alkyl, branched-chain alkyl or cyclic alkyl, C6-C10 aryl, R11' is H or methyl.
According to the present invention, the monomer M3 is used in an amount of 10 wt% or less, based on the total weight of the polymerized monomers.
In the present invention, the monomer M1, the monomer M2 and the monomer M3 are used in a total amount of 100% by weight.
In the present invention, the monomer M3 may be at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylic acid, acrylamide and N-methacrylamide.
According to the invention, the initiator comprises a multifunctional initiator.
In the present invention, the multifunctional initiator refers to an initiator having three or more functional groups capable of forming radicals.
According to the present invention, the multifunctional initiator is contained in an amount of 50 wt% or more, preferably 70 to 100 wt%, based on the total weight of the initiator.
In the invention, the copolymer is prepared by adopting the initiator containing the polyfunctional initiator, and long-chain branches can be introduced into the molecular chain of the copolymer. The multifunctional initiator has more than three functional groups, and a molecular chain grows in multiple directions by taking the multifunctional initiator group as the center to generate a multi-arm molecular chain structure, so that a long-chain branch type polymer is formed in the coupling termination of free radicals at the tail end of the molecular chain.
In the prior art, initiators for styrene polymerization include monofunctional initiators, difunctional initiators, trifunctional initiators and tetrafunctional initiators.
In the present invention, in order to obtain a copolymer having long chain branches, it is preferable that the polyfunctional initiator is a trifunctional peroxide and/or a tetrafunctional peroxide, particularly a tetrafunctional peroxide, and an optimum branching effect can be obtained.
According to the invention, the multifunctional initiator is selected from a tetrafunctional peroxide with a structure shown in a formula I and/or a tetrafunctional peroxide with a structure shown in a formula II;
wherein R is a multifunctional group, preferably cyclohexyl, R1、R2、R3Each independently is C1-C5Alkyl or substituted alkyl.
According to the invention, the initiator is 2, 2-bis (4, 4-di (tert-butylperoxy) cyclohexyl) propane and/or [6, 6-bis (5-alpha-bromoisobutyryloxy-2-oxopentane) -4, 8-dioxoundecanediol 1,11]Di (alpha-bromo-iso-butyrate) (C [ CH ]2O(CH2)3OOCC(Br)(CH3)2]4)(THABI)。
In the present invention, the initiator further comprises a monofunctional peroxide and/or a difunctional peroxide, and the amount of the monofunctional peroxide and/or the difunctional peroxide is less than 50 wt% based on the total weight of the initiator. The monofunctional peroxide and the difunctional peroxide may be selected from one or more of benzoyl peroxide, lauroyl peroxide, cyclohexanone peroxide, dicyclohexyl peroxydicarbonate, diisopropyl peroxydicarbonate, tert-butyl peroxypivalate, tert-butyl peroxybenzoate, 2-bis (tert-butylperoxy) butane, methyl ethyl ketone peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2, 5-bis (2-ethylhexanoylperoxy) -2, 5-dimethylhexane.
According to the invention, the initiator is used in an amount such that the multifunctional initiator is added in an amount of 100-2000ppm, preferably 400-1500ppm, more preferably 600-1200ppm, based on the total weight of the polymerized monomers.
In the present invention, an aromatic organic solvent may be optionally added during the polymerization reaction to adjust the reaction rate and the molecular weight of the final polymer. The aromatic organic solvent is preferably at least one of benzene, toluene, xylene, and ethylbenzene. The aromatic hydrocarbon organic solvent is generally used in an amount of 5 to 12% by weight based on the total weight of the polymerized monomers.
In addition, other additives known in the art, such as antioxidants, melt index modifiers, chain transfer agents, and the like, may also be used during the polymerization reaction. Specifically, antioxidants include, but are not limited to: 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer (RD); tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid ] pentaerythritol ester (1010); tris (2, 4-di-tert-butylphenyl) phosphite (168); dioctadecyl pentaerythritol diphosphite (618); N-cyclohexyl-N' -phenyl-p-phenylenediamine (4010); 2,2' -methylenebis (4-methyl-6-tert-butylphenol) (2246); n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1076). Melt index modifiers include, but are not limited to: mineral oil, Polyisobutylenes (PIB), silicone oil. Chain transfer agents include, but are not limited to: tert-dodecyl mercaptan, n-dodecyl mercaptan.
According to the invention, the polymerization conditions comprise: the polymerization temperature is 60-200 ℃, preferably 90-180 ℃; the polymerization pressure is from 0.01 to 5MPaA, preferably from 0.05 to 3 MPaA; the polymerization conversion is from 60 to 95%, preferably from 80 to 90%.
According to the present invention, the polymerization reaction is one of radical polymerization, bulk polymerization or solution polymerization, preferably bulk polymerization, more preferably continuous bulk polymerization. The continuous bulk polymerization is carried out in multistage reactors connected in series, and the copolymer is obtained by devolatilizing (removing unreacted monomers and possible solvents) and granulating the resulting polymerization solution. The continuous bulk polymerization preparation process has the characteristics of simple flow, easy operation, low energy consumption and high production efficiency.
The multistage series reactor can be freely combined by selecting a full mixing type reactor (CSTR) and a plug flow type reactor (PFR). Generally, when the heat generation of the early polymerization is large, a fully mixed reactor (CSTR) is selected, the reaction heat is removed by gasifying the monomers, and when the viscosity of the late polymerization solution is large, a Plug Flow Reactor (PFR) is selected. The present invention preferably employs 1 to 3 fully mixed reactors (CSTR) and 1 to 4 Plug Flow Reactors (PFR) in series, more preferably 1 to 2 fully mixed reactors (CSTR) and 2 to 3 Plug Flow Reactors (PFR) in series.
In the continuous bulk polymerization of the invention, a prepolymerization stage and a polymerization stage are sequentially carried out, at least one stage of reactor carries out prepolymerization, and the rest reactors carry out polymerization; among them, the polymerization conversion rate of each stage of the reactor is preferably controlled so that the polymerization conversion rate at the end of the preliminary polymerization stage is 30 to 40%.
According to a preferred embodiment of the present invention, as shown in fig. 1, the multi-stage series reactor comprises a four-stage reactor comprising a one-stage CSTR fully mixed reactor and a three-stage plug flow reactor connected in series in sequence. Wherein, the following operation conditions are preferably adopted in each stage of reactor:
the reaction temperature of the first-stage reactor is controlled at 90-130 ℃, preferably at 100-120 ℃; the reaction pressure is controlled to be 0.01-5.0MPaA, preferably 0.05-2 MPaA. Initiator, monomer M1, monomer M2, optional monomer M3, and optional solvent are added thereto and free radical polymerization is carried out. When the polymerization conversion rate reaches 8-30%, preferably 15-25%, the material in the reactor is fed into the second stage reactor.
The reaction temperature of the second-stage reactor is controlled at 100-150 ℃, preferably at 120-140 ℃; the reaction pressure is controlled to be 0.1 to 10MPaA, preferably 0.5 to 3 MPaA. The polymerization temperature can be controlled in a subarea mode, and the reaction temperature is gradually increased. The second reactor may be fed with a make-up of monomer M3. When the polymerization conversion rate reaches 25-50%, preferably 30-40%, the materials in the reactor enter a third-stage reactor.
The reaction temperature of the third-stage reactor is controlled at 110-180 ℃, preferably at 130-160 ℃; the reaction pressure is controlled to be 0.1 to 10MPaA, preferably 0.5 to 3 MPaA. The polymerization temperature can be controlled in a subarea mode, and the reaction temperature is gradually increased. When the polymerization conversion rate reaches 50-70%, the materials in the reactor enter a fourth-stage reactor.
The reaction temperature of the fourth-stage reactor is controlled at 120-200 ℃, preferably at 140-170 ℃; the reaction pressure is controlled to be 0.1 to 10MPaA, preferably 0.5 to 3 MPaA. The polymerization temperature can be controlled in a subarea mode, and the reaction temperature is gradually increased. The final polymerization conversion rate is 80% or more, preferably 85% or more.
The present invention has no specific requirement on the devolatilization mode, and generally, the two-stage flash evaporation is selected to better remove the unreacted monomers and the solvent. In the invention, a two-stage falling strip flash tank is preferably selected, as shown in figure 1, unreacted monomers and solvent are removed under vacuum, and the devolatilization temperature can be 200-250 ℃. The selection of the devolatilization mode and the process conditions are not intended to limit the present invention.
In a third aspect, the present invention provides a styrene monomer-halophenyl maleimide copolymer prepared by the above preparation method.
The fourth aspect of the present invention provides the use of the above styrene-halophenyl maleimide copolymer in a flame retardant and heat insulating board.
The present invention is further illustrated by the following examples. These examples are provided only for illustrating and explaining the present invention and are not intended to limit the present invention.
In the following examples and comparative examples, the polymer-related data were obtained according to the following test methods:
the unnotched impact strength of the simply supported beam is tested according to GB/T1043-;
flexural strength/flexural modulus were tested in GB/T1040-;
heat distortion temperature was tested according to ASTM D648;
the flame retardant grade, namely the property of the substance or the treated material for obviously delaying the flame spread, is classified according to a grading system, and the flame retardant grade is gradually increased from V2 to V1 to V0: v0 shows that after the sample is subjected to two 10-second combustion tests, the flame is extinguished within 30 seconds, and no combustible can fall off; v1 shows that after the sample was subjected to two 10-second combustion tests, the flame was extinguished within 60 seconds and no combustible could fall off, and V2 shows that after the sample was subjected to two 10-second combustion tests, the flame was extinguished within 60 seconds and no combustible could fall off.
Weight average molecular weight Mw1 of the copolymer: the weight average molecular weight Mw1 of the polymer was determined by Agilent high temperature gel permeation chromatography (PL-GPC 220).
Absolute molecular weight Mw2 of the copolymer: the absolute molecular weight Mw2 of the polymer was determined using a WyattTRI STAR Mini DAWN multiangular laser light scattering instrument (MALLS).
The content of each structural unit in the copolymer is obtained by adopting an ARX-500 nuclear magnetic resonance spectrometer of BRUKER company of Switzerland through testing, the solvent is deuterated chloroform (CDCl3), the internal standard is tetramethylsilane, the resolution is less than 0.2Hz, and the signal-to-noise ratio is more than 100.
And (3) testing the melt strength: the melt strength tester of Rheotens 97 model of German GOTTFERT company is adopted, the diameter of a die orifice is 2mm, the gap of a drawing wheel is 0.4mm, the distance between the die orifice and the center of the drawing wheel is 60mm, and the drawing acceleration is 20mm/s2The test temperature was 210 ℃.
The following examples all adopt the process flow as shown in fig. 1, and the multistage series reactors include four-stage reactors connected in series in sequence, wherein the first-stage reactor R101 is a fully mixed reactor, and the second-stage reactor R102, the third-stage reactor R103, and the fourth-stage reactor R104 are plug-flow reactors. An initiator and an optional solvent are mixed in a first static mixer X101, the first static mixer X101 and each polymerization monomer feeding pipeline are connected with an inlet of a first reactor R101, a polymerization liquid delivery pump P101 is arranged on a communicating pipeline between the first reactor R101 and a second reactor R102, a polymerization liquid delivery pump P102 is arranged on a communicating pipeline between the second reactor R102 and a third reactor R103, a polymerization liquid delivery pump P103 is arranged on a communicating pipeline between the third reactor R103 and a fourth reactor R104, the fourth reactor R104 is communicated with a pre-flash-evaporation heater E201, a polymerization liquid delivery pump P104 is arranged on the communicating pipeline, the pre-flash-evaporation heater E201 is sequentially connected with a first flash evaporation tank V201 and a second flash evaporation tank V202, solvent recovery is carried out on tank top material flow, and tank bottom material flow enters a granulator.
Monomer M1: styrene, formula (4) wherein R1’、R2’、R3' and R4' both are H, commercially available;
monomer M2: n- (2,4, 6-tribromophenyl) maleimide of formula (5) wherein R5’、R6' and R7' both are Br, purchased from Kyojiki Biotech development Ltd;
monomer M3: methyl methacrylate, R in formula (3)8' is methyl, R9' is-COOCH3；
Multifunctional initiator I: 2, 2-bis (4, 4-di (t-butylperoxy) cyclohexyl) propane, wherein in the formula (7), R is cyclohexyl R1、R2、R3Methyl, available from aksunobel peroxide (ningbo) ltd;
multifunctional initiator II: [6, 6-bis (5- α -bromoisobutyryloxy-2-oxopentane) -4, 8-Dioxoundecanediol 1,11]Di (. alpha. -bromoisobutyrate) of the formula (8), wherein R is a pentyl group, R1Is Br, R2Is methyl, R3Is methyl, and is made by reference to the literature' Hong C-Y, Pan C-Y, Polymer,2001,42: 9385-;
examples and comparative examples all other materials were commercially available.
Example 1
The mass ratio of styrene to N- (2,4, 6-tribromophenyl) maleimide is 7:3, the total amount is 2000g, the dosage of solvent ethylbenzene accounts for 8 wt% of the total weight of the polymerization monomers, the initiator is a multifunctional initiator I, and the dosage of the multifunctional initiator I is 800ppm relative to the total dosage of the monomers. The polymerization temperature in the first reactor (CSTR) was 106 ℃ and the pressure 0.05MPaA, and when the monomer conversion reached 21%, the reaction mixture was pumped into the second reactor (PFR). The polymerization temperature in the second reactor was 120 ℃ and the pressure 2.1MPaA, at a monomer conversion of 46%, the reaction mixture was pumped into the third reactor (PFR). The third reactor polymerization temperature was 150 ℃, pressure 1.5MPaA, monomer conversion 71%, the reaction mixture was pumped into the fourth reactor (PFR); the fourth polymerization reactor had a polymerization temperature of 168 ℃, a pressure of 0.7MPaA, a monomer conversion of 84%, and copolymers obtained by removing monomers and solvents, and the characterization results are shown in Table 1.
In the copolymer, the content of the structural unit A was 76.6% by weight, and the content of the structural unit B was 23.4% by weight.
Comparative example 1
The same conditions as in example 1 were used except that styrene was used as a reactive monomer, and the results of characterization of the obtained copolymer are shown in Table 1.
Comparative example 2
The monofunctional initiator di-tert-butyl peroxide was used to initiate the free radical polymerization, the other conditions were the same as in example 1, and the characterization results of the resulting copolymer are shown in Table 1. In the copolymer, the content of the structural unit A was 82.5% by weight, and the content of the structural unit B was 17.5% by weight.
Example 2
The mass ratio of styrene monomer to N- (2,4, 6-tribromophenyl) maleimide was 8:2, the other conditions were the same as in example 1, and the results of characterization of the obtained copolymer are shown in Table 1. In the copolymer, the content of the structural unit A was 86.2% by weight, and the content of the structural unit B was 13.8% by weight.
Example 3
The amount of polyfunctional initiator I used was 400 ppm. Other conditions were the same as in example 1, and the characterization results of the obtained copolymer are shown in Table 1. In the copolymer, the content of the structural unit A was 79.3% by weight, and the content of the structural unit B was 20.7% by weight.
Example 4
By using the process scheme shown in FIG. 1, the mass ratio of styrene to N- (2,4, 6-tribromophenyl) maleimide is 7:3, the total amount of monomers is 2000g, the amount of solvent ethylbenzene is 8 wt% of the total weight of the polymerized monomers, and the initiator is multifunctional initiator II in an amount of 1000ppm of the polymerized monomers. The first reactor (CSTR) was pumped into the second reactor (PFR) at a polymerization temperature of 112 ℃ and a pressure of 0.05MPaA, at a monomer conversion of 20%. The second reactor had a polymerization temperature of 120 ℃ and a pressure of 2.1MPaA, and a monomer conversion of 45%, and the reaction mixture was pumped into the third reactor (PFR). The third reactor had a polymerization temperature of 150 ℃ and a pressure of 1.5MPaA, and when the monomer conversion was 72%, the reaction mixture was pumped into the fourth reactor (PFR); the fourth polymerization reactor had a polymerization temperature of 170 ℃ and a pressure of 0.7MPaA, a monomer conversion of 83%, and copolymers obtained by removing the monomers and the solvent, and the characterization results thereof are shown in Table 1. In the copolymer, the content of the structural unit A was 75.1% by weight, and the content of the structural unit B was 24.9% by weight
Example 5
The reaction monomers also included monomer M3 in an amount of 8% by weight based on the total weight of the polymerized monomers, the other conditions being the same as in example 1, and the results of characterization of the resulting copolymer are shown in Table 1. In the copolymer, the content of the structural unit A was 72.2% by weight, the content of the structural unit B was 21.1% by weight, and the content of the structural unit C was 6.7% by weight.
Example 6
The initiator is multifunctional initiator I and di-tert-butyl peroxide, wherein the multifunctional initiator I is used in an amount of 70 wt% of the initiator, other conditions are the same as in example 1, and the characterization results of the obtained copolymer are shown in Table 1. In the copolymer, the content of the structural unit A was 77.4% by weight, and the content of the structural unit B was 22.6% by weight.
Example 7
The initiator is multifunctional initiator II and di-tert-butyl peroxide, wherein the amount of the multifunctional initiator II is 70 wt% of the initiator (the amount of the multifunctional initiator II is less than 50 wt%), other conditions are the same as those in example 1, and the characterization results of the obtained copolymer are shown in Table 1. In the copolymer, the content of the structural unit A was 76.1% by weight, and the content of the structural unit B was 23.9% by weight.
Example 8
The polymerization process was different from that of example 1, specifically, one-step polymerization was carried out at a temperature of 106 ℃ and a pressure of 0.5MPaA, and the monomer conversion was 84%. The characterization results of the obtained copolymer are shown in Table 1. In the copolymer, the content of the structural unit A was 79.1% by weight, and the content of the structural unit B was 20.9% by weight.
TABLE 1
As can be seen from Table 1, the copolymer provided by the present invention has a high weight average molecular weight and a ratio of Mw2/Mw1, indicating that a branched structure exists on the molecular chain of the polymer.
Test example
Examples and comparative copolymers were tested for their properties after testing the copolymers according to the test standards, and the results are shown in table 2.
TABLE 2
| Numbering | Simply supported beam (without gap) KJ/m2 | Flexural modulus of elasticity GPa | Flame retardant rating | Heat distortion temperature DEG C | Melt strength N |
| Example 1 | 14.7 | 2.32 | V0 | 93.1 | 0.23 |
| Comparative example 1 | 15.9 | 2.29 | V2 | 87.1 | 0.22 |
| Comparative example 2 | 14.1 | 2.27 | V2 | 90.7 | 0.15 |
| Example 2 | 14.9 | 2.31 | V1 | 91.6 | 0.23 |
| Example 3 | 13.7 | 2.23 | V0 | 91.0 | 0.19 |
| Example 4 | 15.7 | 2.28 | V0 | 93.4 | 0.22 |
| Example 5 | 15.3 | 2.26 | V0 | 93.6 | 0.20 |
| Example 6 | 14.8 | 2.27 | V0 | 92.1 | 0.18 |
| Example 7 | 14.6 | 2.29 | V0 | 92.4 | 0.19 |
| Example 8 | 13.5 | 2.34 | V0 | 91.8 | 0.17 |
As can be seen from Table 2, the styrene-maleic acid copolyester of the present invention has good mechanical properties, high melt strength, excellent flame retardancy and excellent heat resistance.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (18)
1. A styrene-halogenophenylmaleimide copolymer, characterized in that the copolymer comprises a structural unit a represented by formula (1) and a structural unit B represented by formula (2);
wherein R is1Is H or methyl, R2Is H or halogen, R3Is H or halogen, R4Is a linear or isomeric alkyl radical of H, C1-C5, a linear or isomeric alkenyl radical of C2-C5, R5、R6And R7Each independently is H or halogen;
based on the total weight of the copolymer, the content of the structural unit A is 50-95 wt%, and the content of the structural unit B is 5-50 wt%.
2. The styrene-halogenophenylmaleimide copolymer according to claim 1, wherein, in the formula (1), R is1Is methyl, R2And R3Is H, R4Is a linear or isomeric alkyl group from H, C1 to C4, a linear or isomeric alkenyl group from C2 to C4;
preferably, in the formula (1), R1Is H, R2Is H or halogen, R3Is H or halogen;
preferably, in the formula (2), R5、R6And R7Is a halogen, preferably Br.
3. The styrene-halophenylmaleimide copolymer according to claim 1 or 2, wherein the content of said structural unit A is from 60 to 90% by weight, and the content of said structural unit B is from 10 to 50% by weight, based on the total weight of the copolymer;
preferably, the content of the structural unit A is 60-80 wt% and the content of the structural unit B is 15-40 wt% based on the total weight of the copolymer as a container.
4. The styrene-halogenophenylmaleimide copolymer according to any one of claims 1 to 3, wherein the copolymer further comprises a structural unit C represented by the formula (3);
R8is H or methyl, R9Is H, -CN, -COOR10or-CONHR11Wherein R is10Is a straight-chain alkyl, branched-chain alkyl or cyclic alkyl of C1-C5, an aromatic radical of C6-C10, R11Is H or methyl;
preferably, the content of the structural unit C is 10 wt% or less based on the total weight of the copolymer.
5. The styrene-halophenylmaleimide copolymer according to any one of claims 1 to 4, wherein the weight-average molecular weight Mw1 of said copolymer is ten thousand or more, preferably 18 ten thousand or more;
preferably, the copolymer has a ratio Mw2/Mw1 of the absolute molecular weight Mw2 to the weight-average molecular weight Mw1 of from 1.05 to 2.5, preferably from 1.2 to 1.4.
6. The styrene-halophenylmaleimide copolymer according to any one of claims 1 to 4, wherein said copolymer has a melt strength of 0.15N or more, preferably 0.20N or more.
7. A method for preparing a styrene-halophenyl maleimide copolymer, comprising:
carrying out polymerization reaction on polymerization monomers containing a monomer M1 shown in a formula (4) and a monomer M2 shown in a formula (5) in the presence of an initiator to obtain the styrene-halogenated phenyl maleimide copolymer,
wherein R is1' is H or methyl, R2' is H or halogen, R3' is H or halogen, R4' is a linear or isomeric alkyl radical of H, C1 to C5, a linear or isomeric alkenyl radical of C2 to C5, R5’、R6' and R7' are each independently H or halogen;
based on the total weight of the monomer M1 and the monomer M2, the monomer M1 is used in an amount of 50-95 wt%, and the monomer M2 is used in an amount of 5-50 wt%.
8. The method according to claim 7, wherein in the formula (4), R1' is methyl, R2' and R3' is H, R4' is a linear or branched alkyl of H, C1-C4, linear or branched alkenyl of C2-C4;
preferably, in formula (4), R1' is H, R2' is H or halogen, R3' is H or halogen;
preferably, in formula (5), R5’、R6' and R7' is halogen, preferably Br.
9. The process according to claim 7 or 8, wherein the monomer M1 is used in an amount of 60 to 90 wt% and the monomer M2 is used in an amount of 10 to 50 wt%, based on the total weight of the polymerized monomers;
preferably, the monomer M1 is used in an amount of 60 to 80 wt% and the monomer M2 is used in an amount of 15 to 40 wt%, based on the total weight of the polymerized monomers.
10. The method according to any one of claims 7 to 9, wherein the polymerized monomers further comprise a monomer M3 represented by formula (6),
wherein R is8' is H or methyl, R9' is H, -CN, -COOR10' or-CONHR11', wherein R10' is C1-C5 straight-chain alkyl, branched-chain alkyl or cyclic alkyl, C6-C10 aryl, R11' is H or methyl;
preferably, the monomer M3 is used in an amount of 10 wt% or less, based on the total weight of the polymerized monomers.
11. A method according to any one of claims 7-10, wherein the initiator comprises a multifunctional initiator, preferably a multifunctional initiator having three or more free-radical-forming groups;
preferably, the multifunctional initiator is selected from a trifunctional peroxide and/or a tetrafunctional peroxide;
preferably, the multifunctional initiator is contained in an amount of 50 wt% or more based on the total weight of the initiator.
12. The process of claim 11, wherein the multifunctional initiator is selected from a tetrafunctional peroxide of the structure of formula (7) and/or a tetrafunctional peroxide of the structure of formula (8);
wherein R is a multifunctional group, preferably cyclohexyl, R1、R2、R3Each independently is C1-C5Alkyl or substituted alkyl;
preferably, the multifunctional initiator is selected from 2, 2-bis (4, 4-di (tert-butylperoxy) cyclohexyl) propane and/or [6, 6-bis (5- α -bromoisobutyryloxy-2-oxopentane) -4, 8-dioxaundecanediol 1,11] bis (α -bromoisobutyrate).
13. The process according to claim 11 or 12, wherein the amount of the initiator is such that the amount of the multifunctional initiator is 100-2000ppm, preferably 400-1500ppm, more preferably 600-1200ppm, based on the total weight of the polymerized monomers.
14. The method of any one of claims 7-13, wherein the polymerization conditions comprise: the polymerization temperature is 60-200 ℃, preferably 90-180 ℃; the polymerization pressure is from 0.01 to 5MPaA, preferably from 0.05 to 3 MPaA; the polymerization conversion is 60 to 95%, preferably 80 to 90%;
preferably, the polymerization reaction is one of radical polymerization, bulk polymerization or solution polymerization, preferably bulk polymerization;
preferably, the bulk polymerization is carried out in multiple reactors in series.
15. The method of any one of claims 7-14, wherein the polymerization reaction comprises the steps of:
s1, adding an initiator, a monomer M1, a monomer M2, an optional monomer M3 and an optional solvent into a first-stage reactor, and carrying out first polymerization to obtain a first polymer;
s2, adding the first polymer and an optional monomer M3 into a second-stage reaction, and carrying out second polymerization to obtain a second polymer;
s3, adding the second polymer into a third-stage reaction, and carrying out third polymerization to obtain a third polymer;
s4, adding the third polymer into a fourth-stage reaction, and carrying out fourth polymerization to obtain the styrene-halogenated phenyl maleimide copolymer.
16. The method of claim 15, wherein the conditions of the first polymerization comprise: the polymerization temperature is 90-130 ℃, preferably 100-120 ℃; the polymerization pressure is from 0.01 to 5MPaA, preferably from 0.05 to 2 MPaA; the polymerization conversion is 8 to 30%, preferably 15 to 25%;
preferably, the conditions of the second polymerization include: the polymerization temperature is 100-150 ℃, preferably 120-140 ℃; the polymerization pressure is from 0.1 to 10MPaA, preferably from 0.5 to 3 MPaA; the polymerization conversion is 25 to 50%, preferably 30 to 40%;
preferably, the conditions of the third polymerization include: the polymerization temperature is 110-180 ℃, preferably 130-160 ℃; the polymerization pressure is from 0.1 to 10MPaA, preferably from 0.5 to 3 MPaA; the polymerization conversion rate is 50-70%;
preferably, the conditions of the fourth polymerization include: the polymerization temperature is 120-200 ℃, preferably 140-170 ℃; the polymerization pressure is from 0.1 to 10MPaA, preferably from 0.5 to 3 MPaA; the polymerization conversion is 80% or more, preferably 85% or more.
17. A styrene-halophenylmaleimide copolymer produced by the process of any one of claims 7 to 16.
18. Use of a styrene-halophenyl maleimide copolymer according to any one of claims 1 to 6 and 17 in flame retardant insulation panels.
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