CN101503554B - Weather-resistant halogen substituent maleimide heat-resistant flame-retardant resin composition and preparation method thereof - Google Patents
Weather-resistant halogen substituent maleimide heat-resistant flame-retardant resin composition and preparation method thereof Download PDFInfo
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- CN101503554B CN101503554B CN200810057628XA CN200810057628A CN101503554B CN 101503554 B CN101503554 B CN 101503554B CN 200810057628X A CN200810057628X A CN 200810057628XA CN 200810057628 A CN200810057628 A CN 200810057628A CN 101503554 B CN101503554 B CN 101503554B
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- monomer
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- maleimide
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- 238000002360 preparation method Methods 0.000 title claims abstract description 80
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000003063 flame retardant Substances 0.000 title claims abstract description 48
- 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 title claims abstract description 35
- 239000011342 resin composition Substances 0.000 title claims abstract description 34
- 125000005843 halogen group Chemical group 0.000 title claims abstract 13
- 239000000178 monomer Substances 0.000 claims abstract description 145
- -1 aryl ethylene Chemical compound 0.000 claims abstract description 108
- 229920005989 resin Polymers 0.000 claims abstract description 73
- 239000011347 resin Substances 0.000 claims abstract description 73
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 58
- 229920001971 elastomer Polymers 0.000 claims abstract description 40
- 239000000806 elastomer Substances 0.000 claims abstract description 35
- 229920001577 copolymer Polymers 0.000 claims abstract description 17
- 239000000839 emulsion Substances 0.000 claims description 118
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 59
- 239000000203 mixture Substances 0.000 claims description 48
- 239000012752 auxiliary agent Substances 0.000 claims description 34
- 239000004816 latex Substances 0.000 claims description 33
- 229920000126 latex Polymers 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- 238000006116 polymerization reaction Methods 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 25
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 19
- 239000003643 water by type Substances 0.000 claims description 19
- 239000003995 emulsifying agent Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- 238000004945 emulsification Methods 0.000 claims description 16
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical group CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 239000004902 Softening Agent Substances 0.000 claims description 12
- 230000009466 transformation Effects 0.000 claims description 12
- 238000005054 agglomeration Methods 0.000 claims description 11
- 230000002776 aggregation Effects 0.000 claims description 11
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 10
- 125000001475 halogen functional group Chemical group 0.000 claims description 10
- 230000002829 reductive effect Effects 0.000 claims description 10
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 238000005496 tempering Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- 238000012423 maintenance Methods 0.000 claims description 8
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000344 soap Substances 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
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- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 5
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000005189 flocculation Methods 0.000 claims description 4
- 230000016615 flocculation Effects 0.000 claims description 4
- 229940114930 potassium stearate Drugs 0.000 claims description 4
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
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- 239000006174 pH buffer Substances 0.000 claims description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 3
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 claims description 2
- MHUFITQZKOMYKX-UHFFFAOYSA-N 2,5-dioxo-4-phenylpyrrole-3-carboxylic acid Chemical compound O=C1NC(=O)C(C(=O)O)=C1C1=CC=CC=C1 MHUFITQZKOMYKX-UHFFFAOYSA-N 0.000 claims description 2
- QRNSUDYQQKOCPW-UHFFFAOYSA-N 3-(2-methylpropyl)pyrrole-2,5-dione Chemical compound CC(C)CC1=CC(=O)NC1=O QRNSUDYQQKOCPW-UHFFFAOYSA-N 0.000 claims description 2
- USICVVZOKTZACS-UHFFFAOYSA-N 3-butylpyrrole-2,5-dione Chemical group CCCCC1=CC(=O)NC1=O USICVVZOKTZACS-UHFFFAOYSA-N 0.000 claims description 2
- QUKZJBQJUYHRON-UHFFFAOYSA-N 3-ethylpyrrole-2,5-dione Chemical class CCC1=CC(=O)NC1=O QUKZJBQJUYHRON-UHFFFAOYSA-N 0.000 claims description 2
- IVGGIBCLIRGTRS-UHFFFAOYSA-N 3-methoxy-4-phenylpyrrole-2,5-dione Chemical class O=C1NC(=O)C(OC)=C1C1=CC=CC=C1 IVGGIBCLIRGTRS-UHFFFAOYSA-N 0.000 claims description 2
- NMXSDUSRXRNRLK-UHFFFAOYSA-N 3-methyl-4-phenylpyrrole-2,5-dione Chemical class O=C1NC(=O)C(C)=C1C1=CC=CC=C1 NMXSDUSRXRNRLK-UHFFFAOYSA-N 0.000 claims description 2
- ZLPORNPZJNRGCO-UHFFFAOYSA-N 3-methylpyrrole-2,5-dione Chemical group CC1=CC(=O)NC1=O ZLPORNPZJNRGCO-UHFFFAOYSA-N 0.000 claims description 2
- JDDMPHKHKQRDPT-UHFFFAOYSA-N 3-naphthalen-1-ylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C3=CC=CC=C3C=CC=2)=C1 JDDMPHKHKQRDPT-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 2
- JTUOMQJVPHRJHA-UHFFFAOYSA-N [C].C(CCCCCCCCCCC)S Chemical compound [C].C(CCCCCCCCCCC)S JTUOMQJVPHRJHA-UHFFFAOYSA-N 0.000 claims description 2
- ZJUBYYLSWUNRRH-UHFFFAOYSA-M [Na].[Cl-].[K+] Chemical compound [Na].[Cl-].[K+] ZJUBYYLSWUNRRH-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 235000011128 aluminium sulphate Nutrition 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 claims description 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 150000005181 nitrobenzenes Chemical class 0.000 claims description 2
- 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 claims description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- ONQDVAFWWYYXHM-UHFFFAOYSA-M potassium lauryl sulfate Chemical compound [K+].CCCCCCCCCCCCOS([O-])(=O)=O ONQDVAFWWYYXHM-UHFFFAOYSA-M 0.000 claims description 2
- 229940096992 potassium oleate Drugs 0.000 claims description 2
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 2
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 150000003440 styrenes Chemical class 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- XNYYNDAEXFUXBD-UHFFFAOYSA-N tert-butylbenzene ethene Chemical compound C=C.C(C)(C)(C)C1=CC=CC=C1 XNYYNDAEXFUXBD-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims 2
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- CGKQZIULZRXRRJ-UHFFFAOYSA-N Butylone Chemical compound CCC(NC)C(=O)C1=CC=C2OCOC2=C1 CGKQZIULZRXRRJ-UHFFFAOYSA-N 0.000 claims 1
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- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 16
- 238000002485 combustion reaction Methods 0.000 description 9
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 2
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- AQPHBYQUCKHJLT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4,5,6-pentabromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br AQPHBYQUCKHJLT-UHFFFAOYSA-N 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- XCMSBWQTZVVGIC-UHFFFAOYSA-N 2-bromo-1-phenylpropane-1,1-diol Chemical compound C1(=CC=CC=C1)C(C(C)Br)(O)O XCMSBWQTZVVGIC-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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- 229920003006 Polybutadiene acrylonitrile Polymers 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-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
- ZGBSOTLWHZQNLH-UHFFFAOYSA-N [Mg].S(O)(O)(=O)=O Chemical compound [Mg].S(O)(O)(=O)=O ZGBSOTLWHZQNLH-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- QSMOHLASMMAGIB-UHFFFAOYSA-N butyl prop-2-enoate;prop-2-enenitrile Chemical compound C=CC#N.CCCCOC(=O)C=C QSMOHLASMMAGIB-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000005502 peroxidation Methods 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
- VPRUMANMDWQMNF-UHFFFAOYSA-N phenylethane boronic acid Chemical compound OB(O)CCC1=CC=CC=C1 VPRUMANMDWQMNF-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a weather-resistant halogen substituent maleimide heat-resistant flame-retardant resin composition and a preparation method thereof, wherein the weather-resistant halogen substituent maleimide heat-resistant flame-retardant resin composition comprises 10-65 parts of halogen substituent maleimide heat-resistant flame-retardant resin, 30-55 parts of a graft polymer of an acrylate elastomer grafted aryl ethylene monomer and a nitrile vinyl monomer, and 5-35 parts of a binary copolymer of the aryl ethylene monomer and the nitrile vinyl monomer. The prepared weather-resistant heat-resistant flame-retardant resin composition has the advantages of good appearance, good weather resistance, high heat resistance and flame retardance, and is a heat-resistant flame-retardant material with good performance. The prepared weather-resistant heat-resistant flame-retardant resin can be widely used for modifying heat resistance and flame retardance of ABS, PC, PBT and other materials. As a material with excellent heat-resistant flame-retardant property, the material can be independently used for preparing high heat-resistant flame-retardant parts of automobiles and household electrical appliances.
Description
Technical field
The present invention relates to a kind of Weather resistant heat resisting flame retardant resin composition and preparation method, particularly a kind of Weather-resistant halogen substituent maleimide heat resisting fire-proof resin composition and preparation method.
Background technology
The monomeric free-radical polymerized thing of halogen substituent maleimide, because of containing the plane five-membered ring structure on its molecular chain, can effectively suppress the rotation of chain, thereby have very high structure rigidity and thermostability, simultaneously because of containing halogen on its molecular chain, on stable on heating basis, have good flame retardancy again, thereby be subjected to extensive concern.
The preparation of heat-proof combustion-resistant ABS resin comprises two kinds of alloyage and modification by copolymerization methods, and wherein the modification by copolymerization method is a kind of reasonable technological line.The modification by copolymerization method mainly is made up of two portions technology, what a part was a halogen substituent maleimide (XIMID) with the monomeric terpolymer XSMIA of halogen substituent maleimide of aryl ethylene class monomer (AEM) itrile group vinyl monomer (NEM) is synthetic, and another part is the synthetic of ABS graft copolymer.The synthetic of the monomeric terpolymer of halogen substituent maleimide is the stable on heating assurance of superelevation heat-resisting ABS resin, and the ABS graft copolymer is determining the balance of its over-all properties.But, be to exist that weathering resistance is poor, the fireballing shortcoming of performance degradation being applied to outdoor products because the ABS graft copolymer contains not complete reaction double bond structure.
The synthetic of XSMIA then can be adopted various polymerization processs such as body, suspension, emulsion and solution polymerization.Halogen substituent maleimide monomer and AEM and or NEM and three's copolyreaction have and the general different characteristics of copolyreaction, polymerization rate is very fast, reaction is difficult to control.Though high temperature suspension polymerization also may address this problem, its to the requirement of equipment than higher.The molecular weight of the monomeric terpolymer of emulsion polymerisation process synthetic halogen substituent maleimide is with respect to various polymerization processs such as body, suspension and solution polymerizations, the molecular weight of polymerisate is bigger, helps improving the physical strength and the resistance toheat (especially heat-drawn wire performance) of product.
GB1026912 has described the multipolymer for preparing maleimide and MMA with the method for mass polymerization, and the initiator of employing is an organo-peroxide.GB1062872 has described the multipolymer for preparing vinylchlorid and maleimide with method of emulsion polymerization, adopts redox initiation system.CA2078337 etc. have reported the method for its solution polymerization, and its solvent generally uses organic solvents such as benzene, and initiator adopts the oil soluble thermal decomposition initiating, as azo-initiator.What GB1086673 and GB1213061 introduced is that what it adopted is water soluble starter with the method for the multipolymer of emulsion polymerization prepared maleimide and vinylbenzene etc.In " polymer material science and engineering " 2001 (17) .1, reported in " second-order transition temperature of St-AN-PMI emulsion copolymers and the rheological " that people such as Liu Guodong deliver and described its general emulsion polymerisation process, promptly adopt emulsifying agent, and be the polymerization process of initiator with the persulphate.
US4757109 has described a kind of technology with emulsion polymerisation process synthesizing styrene, vinyl cyanide, maleimide terpolymer, employing has the anionic emulsifier of well emulsify ability in pH value is 3～9 scopes, initiator adopts redox system or Potassium Persulphate initiator, when this patent is pointed out with the Potassium Persulphate initiator, speed of response is slower, its polymerization technique is fairly simple, does not discuss in view of polymerization process.KR9510550 has also introduced a kind of technology that adopts method of emulsion polymerization synthesizing styrene, vinyl cyanide, maleimide terpolymer, what adopt is used water soluble starter of typical letex polymerization or redox initiation system, does not also discuss in view of polymerization process.
CN101007894 " PBT and ABS fire retardant material " adopts fire retardant to prepare a kind of PBT and ABS fire retardant material; CN1962751 " a kind of heat-proof combustion-resistant ABS resin and preparation method thereof " discloses a kind of method that adopts fire retardant to prepare heat-proof combustion-resistant ABS resin; CN1412238 " fire-resisting ABS special-purpose material " prepares heat-proof combustion-resistant ABS resin by the method for polyvinyl chloride, decabromodiphenyl oxide, antimonous oxide, properties-correcting agent chlorinatedpolyethylene, stablizer, lubricant and ABS resin blend.
KR20040047992 has described a kind of preparation method of heat resistant resin composition, and wherein the fire retardant of Cai Yonging is the halogenated compound of weight-average molecular weight at 2000-10000; KR 950002892B has described a kind of employing tetrabromo-bisphenol, and ten bromines connect the method that phenylate prepares heat resisting flame retardant resin composition; KR930004282B has described a kind of bromostyrene and has done the method that comonomer prepares the ABS heat resisting and flame-retardant alloy; JP8108137 has described a kind of patented method of utilizing the blend of small molecules fire retardant to prepare maleimide modified styrene resin/PC/ABS flame-proof heat-resistant alloy; JP3146542 has described a kind of by carrying out the method that blend prepares the flame-proof heat-resistant resin combination with PVC; JP63039953 has described and has a kind ofly prepared fire-retardant by carrying out blend with PVC and bromo dihydroxyphenyl propane; JP62143960 has described a kind of CPVC of utilization and has carried out the method that blend prepares the heat-proof combustion-resistant heat-resistant composition; JP63081152 has described a kind of method by mass polymerization and has prepared bromo maleimide and cinnamic multipolymer, carries out blend with bromo aryl organic fire-retardant ABS then, preparation heat-proof combustion-resistant method for compositions.
JP2003327777A discloses a kind of thermoplastic resin composition, it is a kind of existing thermotolerance, shock resistance, satisfy the resin material of high levels weathering resistance again simultaneously, this thermoplastic resin composition that contains A and B, comprise N-substituted maleimide amine, aromatic ethenyl compound, (methyl) acrylate and other maleimide based copolymer A that can make, and the graft copolymer B of the multipolymer formation of the compounded rubber of conjugated diolefine hydrocarbon system rubber polymer and acrylate rubber polymer composition and unsaturated cyanogen compound and aromatic ethenyl compound with the monomer of its copolymerization.A adopts suspension polymerization synthetic, and B is the unsaturated cyanogen compound of acrylate rubber polymer latex agglomeration conjugated diolefine hydrocarbon system rubber polymer latex and the graftomer of aromatic ethenyl compound, and weather resistance relies on the blend auxiliary agent to obtain.
More than these patented methods, adopt small molecules fire retardant or small molecules halogen containing flame-retardant, weathering resistance auxiliary agent, in various degree exist the auxiliary agent transport phenomena, the Weather resistant heat resistant flame retardant performance is not good, prepares the shortcoming that alloy exists poor heat stability again with PVC or CPVC.
Summary of the invention
At the problems referred to above, the object of the present invention is to provide a kind of Weather-resistant halogen substituent maleimide heat resisting fire-proof resin composition and preparation method.Can be comparatively convenient, under the situation of easy handling, the synthetic relatively XSMIA (aryl ethylene class monomer base vinyl monomer and the monomeric terpolymer of halogen substituted maleimide) of homogeneous that distributes that forms in the monomer ratio scope of broad, and by the synthetic acrylic ester elastomer grafting aryl ethylene class monomer that is complementary with it and the graft latex of itrile group vinyl monomer, graft latex and heat-proof flame-proof resin emulsion carry out common cohesion then, the method that the multipolymer of dry back and aryl ethylene class monomer and itrile group vinyl monomer carries out blend obtains the good Weather resistant heat resisting flame retardant resin composition of over-all properties.
Weather-resistant halogen substituent maleimide heat resisting fire-proof resin composition of the present invention, in Weather resistant heat resisting flame retardant resin composition is 100 mass parts, contain: 10～65 parts of A. halogen substituent maleimide heat-proof flame-proof resins, the halogen substituent maleimide unit accounts for 10～45 quality % in the halogen substituent maleimide heat-proof flame-proof resin, aryl ethylene class unit accounts for 30～65 quality %, and the itrile group vinyl units accounts for 0～30 quality %; B. the graftomer of acrylic ester elastomer grafting aryl ethylene class monomer and itrile group vinyl monomer is 30～55 parts, acrylic ester elastomer accounts for 35～60 quality % in the graftomer, aryl ethylene class unit accounts for 26～49 quality %, and the itrile group vinyl units accounts for 10～20 quality %; C. the copolymer of aryl ethylene class monomer and itrile group vinyl monomer is 5～35 parts, and aryl ethylene class unit accounts for 65～78 quality % in the copolymer, and the itrile group vinyl units accounts for 22～35 quality %; Wherein the emulsion of halogen substituent maleimide heat-proof flame-proof resin is to obtain (being 100 mass parts in the polymerization single polymerization monomer total amount, as follows) by the following method:
(a) preparation of monomer mixed solution
In 25～35 ℃ with 10～45 parts of halogen substituent maleimide monomers, 30～65 parts of aryl ethylene class monomers, 0～30 part of itrile group vinyl monomer, 0.1～0.6 part of oil soluble thermal decomposition initiating, 0.01～0.65 part of molecular weight regulator adds tempering tank, open to stir and mix, form homogeneous phase monomer mixed solution (a).
Optimum condition is: in 25～35 ℃ with 15～45 parts of halogen substituent maleimide monomers, 35～60 parts of aryl ethylene class monomers, 0.2～0.5 part of oil soluble thermal decomposition initiating, 0～25 part of itrile group vinyl monomer, 0.05～0.45 part of molecular weight regulator adds tempering tank, open to stir and mix, form homogeneous phase monomer mixed solution (a).
(b) preparation of halogen substituent maleimide heat-proof flame-proof resin emulsion
With 100～200 parts of de-salted waters, 2.0～10.0 parts of emulsifying agents join in the reactor that whipping appts is housed in 25～35 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.Emulsification can heat up and carry out polymerization in 20～75 minutes.The temperature of maintenance system was carried out polyreaction 3～8 hours under 55～95 ℃.System temperature is risen to 90～100 ℃ then, polyreaction was carried out 0.5～2.0 hour again, the sampling and measuring total solid content, and qualified back (〉=37%, as follows) promptly forms halogen substituent maleimide heat-proof flame-proof resin emulsion (b).The solids that emulsion filtered out after reaction finished and the ratio of total monomer charging capacity are lower than 3.0%.
Optimum condition is: with 140～180 parts of de-salted waters, 2.5～8.5 parts of emulsifying agents join in the reactor in 25～35 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.Emulsification can heat up and carry out polymerization in 20～75 minutes.The temperature of maintenance system was carried out polyreaction 4～6 hours under 70～85 ℃.System temperature is risen to 90～100 ℃ then, polyreaction was carried out 0.5～1.5 hour again, and the sampling and measuring total solid content promptly forms halogen substituent maleimide heat-proof flame-proof resin emulsion (b) after qualified.
Used initiator is the oil soluble thermal decomposition initiating in the synthetic method of halogen substituent maleimide heat-proof flame-proof resin emulsion of the present invention, it is the general initiator of radical polymerization, at 100 ℃ half life of decompositions less than 4 hours, as azo class, organo-peroxide class etc.The most frequently used initiator has: Diisopropyl azodicarboxylate, and 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide etc., owing to be general general type, just no longer for example many.Wherein preferred Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
Also can add common agent such as softening agent, thermo-stabilizer etc. among the present invention after polymerization finishes, they can be mixed with the emulsion of auxiliary agent with emulsifying agent and de-salted water in emulsifying tank, and the mode with emulsion after copolyreaction finishes adds.The emulsion of described auxiliary agent, be meant the emulsion that softening agent, thermo-stabilizer, emulsifying agent and de-salted water is mixed with auxiliary agent in emulsifying tank, mode that can emulsion after copolyreaction finishes adds, and makes their degrees of scatter in polymkeric substance more even, thus better effects if.Used auxiliary agent can be a softening agent in emulsion, thermo-stabilizer etc., be employed softening agent such as DOP in the general plastic working process, DCP, Magnesium Stearate etc., thermo-stabilizer is as 1076,1010,2246, emulsifying agent such as potassium stearate, potassium oleate, synthetic fatty acid potassium etc., proportioning also is to adopt general proportioning in the prior art, as softening agent: thermo-stabilizer: the weight ratio of emulsifying agent is (1～5): (1～5): (3～10), emulsifying agent, initiator, water, softening agent, the consumption of thermo-stabilizer is identical with general letex polymerization, be conventional amount used, no longer describe in detail.Certainly the present invention also can not add the emulsion of auxiliary agent, and use directly is provided after the polymerization.
Because the solubleness of XMI in the ST/AN mixed solution is limited, after the XMI formula ratio reaches certain umber, temperature is lower than 25 ℃, XMI will separate out with solid-state from solution, so the starting temperature of emulsion polymerization should be more than 25 ℃, and temperature is higher than 35 ℃, the part initiator will begin to decompose, thereby the configuration temperature condition of emulsion polymerization chemical generally fixes within 25～35 ℃ the scope.
The graftomer of the aryl ethylene of acrylic ester elastomer grafting in the present invention class monomer and itrile group vinyl monomer, the copolymer of aryl ethylene class monomer and itrile group vinyl monomer all can adopt commercially available product or utilize mature industrial technology to obtain, graftomer as acrylic ester elastomer grafting aryl ethylene class monomer and itrile group vinyl monomer can be taked CN1223272, methods such as JP4185663 obtain, perhaps use the present commercially available prod AAS757RE of BASF AG, SKR2842 etc., the copolymer of aryl ethylene class monomer and itrile group vinyl monomer can be taked
Method such as CN1455786, CN85101103 obtains, and perhaps uses present commercially available prod, BHF, the CHF etc. that have Lanzhou Petrochemical Company to produce.
Among the present invention, when describing the monomer link configuration on the polymer chain structure, adopt " unit of the same name " to be used as its title, be called styrene units as the corresponding with it macromolecule chain section structure of styrene monomer, other same appellation with monomeric compound.
The halogen substituent maleimide monomer that the preparation method adopted of halogen substituent maleimide of the present invention unit or halogen substituent maleimide heat-proof flame-proof resin emulsion has following structural formula:
(Rn contains the halo-alkyl of 1-15 carbon in the formula, cycloalkyl, and substituted alkyl, aryl, substituted aryl, wherein, halogens is bromine, chlorine)
Concrete example has: N-halogenated methyl maleimide, N-halogenated ethyl maleimide, N-halo tertiary butyl maleimide, N-halo isobutyl-maleimide, N-halo cyclohexyl maleimide, N-halogenophenyl maleimide, N-halogenated methyl phenyl maleimide, N-halogenated methoxy phenyl maleimide, N-halo carboxyl phenyl maleimide, N-halogenated nitrobenzene base maleimide, N-halo naphthyl maleimide etc., can be wherein one or more.Wherein preferred N-tribromo cyclohexyl maleimide and N-tribromo phenyl maleimide.
Aryl ethylene class unit or aryl ethylene class monomer are the compounds that contains aryl hydrocarbon or substituted arene in the vinyl monomer.Mainly contain: vinylbenzene, right/adjacent/-vinyl toluene (being also referred to as Vinyl toluene), 1.3-dimethyl styrene, 2.4-dimethyl styrene, ethyl styrene is to tert-butylbenzene ethene, alpha-methyl styrene, α-ethyl styrene, Alpha-Methyl p-methylstyrene, halogenated styrenes, haloalkyl vinylbenzene, vinyl naphthalene or the like.The combination of one or more in these monomers all can be used.Optimization styrene wherein, Vinyl toluene.
Itrile group vinyl units or itrile group vinyl monomer are the compounds of nitrile group-containing in the vinyl monomer.Mainly contain: vinyl cyanide, methacrylonitrile etc.
The emulsifying agent that the present invention uses, mainly contain anion surfactant, nonionogenic tenside or their compound system, for example: sodium lauryl sulphate, dodecyl sulphate potassium, Sodium dodecylbenzene sulfonate, Potassium dodecylbenzenesulfonate, potassium stearate, synthetic fatty acid potassium, disproportionated rosin acid soap, anion surfactants such as sodium oleate, OP (alkylphenol polyoxyethylene), Tween, polyoxyethylene nonionogenic tensides such as Span, wherein preferably sodium dodecyl sulfate, disproportionated rosin acid soap, Sodium dodecylbenzene sulfonate or synthetic fatty acid potassium or their compound system.
The acrylic ester elastomer latex that the present invention uses, mainly be meant the homopolymer of acrylic ester monomer or the multipolymer of acrylic ester monomer and energy and the formation of its monomer that reacts, as butyl polyacrylate (BA) latex (PBA), BA-St (3～10%) copolymer emulsion (PBAS), butyl acrylate-vinyl cyanide (3～8%) copolymer emulsion (PBAN) etc., preferably PBA latex.The present invention to the homopolymer of acrylic ester monomer or acrylic ester monomer and can and the preparation method of the multipolymer that forms of its monomer that reacts do not limited, common preparation method all can, but particle diameter is preferably between 260～400nm; The graftomer of acrylic ester elastomer grafting aryl ethylene class monomer and itrile group vinyl monomer is vinyl cyanide-PBA-styrene-grafted polymer A BAS, vinyl cyanide-PBAS-styrene-grafted polymkeric substance, vinyl cyanide-PBAN-styrene-grafted polymkeric substance etc. preferably, general designation AAS graftomer, preferably vinyl cyanide-PBA-styrene-grafted polymer A BAS.The copolymer of aryl ethylene class monomer and itrile group vinyl monomer is SAN, α-MSAN, styrene methacrylonitrile copolymer (SMAN) etc. preferably, its nitrile content is preferably in 22～35% (preferred 26～30%), and molecular weight is preferably in 60000～120000 (preferred 80000～100000).
Acrylic ester monomer is meant ethyl propenoate, methyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl acrylate, butyl methacrylate (MBA), ethyl propylene acid butyl ester (EBA) etc. can be wherein one or more, wherein preferred butyl acrylate (BA).
The present invention also provides the preparation method of a kind of acrylic ester elastomer grafting aryl ethylene class monomer of the suitable especially preparation present composition and the graftomer of itrile group vinyl monomer (or claiming graft copolymer): the summation in acrylic ester elastomer, aryl ethylene class monomer and itrile group vinyl monomer is 100 mass parts:
Under 25～35 ℃ with 35～60 parts particle diameter acrylic ester elastomer latex (in butt) at 260～400nm, 0.2～0.8 part of emulsifying agent, 0.1～0.6 part of pH buffer reagent, 0.1～0.5 part of complexing agent, 0.1～0.6 part is helped reductive agent, 120～200 parts of de-salted waters join in the reactor, begin to stir, the itrile group vinyl monomer that adds 2～6.5 parts then, 0.1～0.3 part oxygenant, 6～14 parts aryl ethylene class monomer and 0.1～0.5 part of molecular weight regulator join in the reactor, heat up after 5～15 minutes, be warmed up to 60～70 ℃ and add 0.01～0.05 part of reductive agent, add 6～13.5 parts of itrile group vinyl monomers after 0.5～2.5 hour, 20～39 parts aryl ethylene class monomer and 0.1～0.3 part oxygenant.Record the graft latex transformation efficiency by the method for surveying dry-matter and finish reaction more than 95%, finish the preparation of the multipolymer of acrylic ester elastomer grafting aryl ethylene class monomer and itrile group vinyl monomer.
Optimum condition:
Under 25～35 ℃ with 40～55 parts particle diameter acrylic ester elastomer latex at 300～350nm, 0.4～0.6 part of emulsifying agent, 0.2～0.5 part of pH buffer reagent, 0.2～0.4 part of complexing agent, 0.2～0.4 part is helped reductive agent, 150～180 parts of de-salted waters join in the reactor, begin to stir, the itrile group vinyl monomer that adds 3.0～6.0 parts then, 0.2～0.3 part oxygenant, 7～13.5 parts aryl ethylene class monomer and 0.2～0.5 part of molecular weight regulator join in the reactor, heat up after 5～15 minutes, be warmed up to 60～70 ℃ and add 0.01～0.03 part of reductive agent, add 7.0～13.5 parts of itrile group vinyl monomers after 0.5～2.0 hour, 21～32 parts aryl ethylene class monomer and 0.2～0.3 part oxygenant.Record the graft latex transformation efficiency by the method for surveying dry-matter and finish reaction more than 95%, finish the preparation of the multipolymer of acrylic ester elastomer grafting aryl ethylene class monomer and itrile group vinyl monomer.
Both can provide use with emulsion form among the present invention, and also the graftomer emulsion of acrylic ester elastomer grafting aryl ethylene class monomer and itrile group vinyl monomer can be condensed, provide use after the drying the graft polymer latex (or claiming emulsion) that generates acrylic ester elastomer grafting aryl ethylene class monomer and itrile group vinyl monomer.Dry auxiliary agent, the condition of using of cohesion is prior art, universal method.
The preparation method of the acrylic ester elastomer grafting aryl ethylene class monomer that in the present invention, provides and the graftomer of itrile group vinyl monomer, other preparation method that can effectively prepare the graftomer of acrylic ester elastomer grafting aryl ethylene class monomer and itrile group vinyl monomer also can adopt, and commercially available in addition toughness properties-correcting agent such as 757RE, SKR2842 or the like also can directly select for use.
The molecular weight regulator that the present invention uses is not particularly limited, as being general tert-dodecyl mercaptan, dodecyl mercaptan carbon etc.
Used flocculation agent is the normal coagulation agent among the present invention, as sulfuric acid, calcium chloride, sal epsom, sodium-chlor, potassium aluminium sulfate, polymeric flocculant etc., preferably sulfuric acid magnesium.
The reductive agent that uses during the graftomer of preparation acrylic ester elastomer grafting aryl ethylene class monomer and itrile group vinyl monomer in the invention, help reductive agent as the general reductive agent of redox system, help reductive agent, as using ferrous sulfate, sodium sulfoxylate formaldehyde, glucose, S-WAT, organism such as alcohol, amine, oxalic acid, preferably sulfuric acid is ferrous, sodium sulfoxylate formaldehyde.
Complexing agent also is the general complexing agent of redox system, as being sodium ethylene diamine tetracetate (EDTA), trisodium phosphate etc.
Oxygenant is the general oxygenant of redox system, as being hydrogen peroxide, hydrogen phosphide cumene, di-isopropylbenzene hydroperoxide, tertbutyl peroxide, isopropyl benzene hydroperoxide, peroxidation 2,4 dichloro benzene formyl, 1,1 two (tert-butyl peroxy base) hexanaphthene etc., preferred hydrogen phosphide cumene, di-isopropylbenzene hydroperoxide.
The present invention is not specially limited the preparation method of Weather-resistant halogen substituent maleimide heat resisting fire-proof resin composition, as adopting the most frequently used mixing method: each is formed blending, extruding pelletization and obtain.Certainly each is formed also and can the blending cohesion of partial tree fat liquor form elder generation dryly to obtain with the mode of other component mixing moulding again.Can adopt specifically and in halogen substituent maleimide heat-proof flame-proof resin emulsion, add common agent such as softening agent, thermo-stabilizer etc., they can be mixed with the emulsion of auxiliary agent with emulsifying agent, de-salted water in emulsifying tank, the mode with emulsion after copolyreaction finishes adds.This emulsion can be carried out blend through the multipolymer of cohesion, dry back and graft copolymer, aryl ethylene class monomer and the itrile group vinyl monomer of acrylic ester elastomer grafting aryl ethylene class monomer and itrile group vinyl monomer and be prepared Weather resistant heat resisting flame retardant resin composition; Also the halogen substituent maleimide heat-proof flame-proof resin emulsion that obtains directly can be mixed the back with the graft latex of acrylic ester elastomer grafting aryl ethylene class monomer and itrile group vinyl monomer and condense altogether, carry out blend with the multipolymer of aryl ethylene class monomer and itrile group vinyl monomer again and prepare Weather resistant heat resisting flame retardant resin composition.
The present invention also provides a kind of preparation method of this Weather-resistant halogen substituent maleimide heat resisting fire-proof resin composition, be specifically a kind of halogen substituent maleimide monomer and aryl ethylene class monomer or and the heat-proof flame-proof resin emulsion of itrile group vinyl monomer and the graftomer emulsion of acrylic ester elastomer grafting aryl ethylene class monomer and the itrile group vinyl monomer copolymer that carries out common cohesion, dry back and aryl ethylene class monomer and itrile group vinyl monomer carry out the method that blend prepares Weather resistant heat resisting flame retardant resin composition:
Heat-proof flame-proof resin emulsion is mixed with the graftomer emulsion of acrylic ester elastomer grafting aryl ethylene class monomer and itrile group vinyl monomer and the emulsion of 0.8～1.2 part of auxiliary agent, 100 parts of these mixed emulsions are under agitation joined temperature continuously under 25～35 ℃ be in 60～70 ℃ 100～500 part 2～8 ‰ the aqueous solution that contains flocculation agent (as sal epsom), added in 30～35 minutes.After emulsion adds mixed solution is warming up to 90～100 ℃ and keeps and to lower the temperature in 1～1.5 hour, finish agglomeration process.Condensing the slurry that dries with de-salted water washing back after filtration; To contain 65～95 parts of heat-proof flame-proof resins and graft polymer mixture, with the copolymer blend of 5～35 parts aryl ethylene class monomer and itrile group vinyl monomer, blend can be extruded through forcing machine and obtain Weather-resistant halogen substituent maleimide heat resisting fire-proof resin composition product.
Among the present invention, do not get rid of during the composition blending and add other common agent, as oxidation inhibitor, softening agent, lubricant, fire retardant or the like.Oxidation inhibitor can be 1010,1076,2246 etc., softening agent can be Magnesium Stearate, DOP, DDP etc., lubricant can be silicone oil, EBS, fire retardant can be a decabromodiphenyl oxide etc., its consumption and ratio are all same as the prior art, to kind, add-on the present invention of auxiliary agent and have no special requirements.The consumption of various common agents is generally about 0.1～0.5 part, is 0.2～0.5 part as oxidation inhibitor, and 0.2～0.5 part in softening agent, lubricant are 0.2～0.5 part.Be preferably in during blend and mix 3～5min in the high speed mixing machine (1300～1500 rev/mins, as follows).
Weather-resistant halogen substituent maleimide heat resisting fire-proof resin composition of the present invention and preparation method's characteristics are as follows:
1. the preparation method of halogen substituent maleimide heat-proof flame-proof resin emulsion of the present invention has thoroughly solved the problem of the unstable and long-time placement variable color of pH of this latex.Polyreaction is very easily controlled, and reaction process is highly stable, and polymerization finishes no a large amount of precipitate and produces.The polymerization reaction monomer transformation efficiency is more than 90%, and the solids that emulsion filtered out after reaction finished and the ratio of total monomer charging capacity are lower than 3.0%, the resin emulsion nondiscoloration.The second-order transition temperature test result of product only shows a second-order transition temperature value, illustrates that its structural homogeneity is good.
2. the method that Weather-resistant halogen substituent maleimide heat resisting fire-proof resin composition of the present invention adopts heat-proof flame-proof resin emulsion and acrylic ester elastomer graft copolymer emulsion to condense has altogether solved the difficult problem that Weather resistant heat resisting flame retardant resin emulsion particle in agglomeration process is thin, yield is low.
3. the acrylic ester elastomer graft copolymer of the present invention's preparation has been adjusted the particle diameter of graft base latex, the nitrile content in the graftomer, the structural parameter such as glue content of graftomer according to the structure and the performance characteristics of Weather resistant heat resisting flame retardant resin, and making it has good consistency with heat-proof flame-proof resin.
4. it is good to have outward appearance with the Weather-resistant halogen substituent maleimide heat resisting fire-proof resin composition that makes of the present invention, good weatherability, and the thermal stability height, fire-retardant advantage is the good heat-proof combustion-resistant material of a kind of performance.The Weather resistant heat resisting flame retardant resin of preparation can be widely used in the heat-proof combustion-resistant modification aspect to materials such as ABS, PC, PBT.As a kind of heat-proof combustion-resistant performance excellent material, its independent use also can be used for preparing automobile, the component of the high-temp resistant fire-retarding of household electrical appliances.
Embodiment
Following examples are to specify of the present invention, and wherein reactor reacts in water-bath for three mouthfuls of glass flask of band stirring, condenser, thermometer; The end opening glass flask that tempering tank stirs for band.Hereinafter " % ", " part " all refers to weight percentage or parts by weight.
Second-order transition temperature Tg:DSC-differential thermal differential method
Vicat softening temperature: GB/T 1633-2000
Flame retardant properties test: UL-94
Molecular weight: GPC model W-150C
Nitrile content: GB/T 4486-84
Melt flow rate (MFR) (g/10min): 3682-2000
Socle girder notched Izod impact strength (J/m): GB/T 1843-1996
The weather resistance test: the socle girder notched Izod impact strength retention rate with 1000 lab scales in the weathering age case characterizes
Resin emulsion whether weighed by variable color after certain hour is weighed and placed to the solids that emulsion filtered out after resin emulsion stability finished with reaction and the ratio magnitude of total monomer charging capacity.
The preparation of the emulsion of auxiliary agent:
Under 75 ℃, 5.0% oleic acid potash soap, 10% antioxidant 1076,5% plasticizer phthalic acid dibutylester and 80% de-salted water are mixed with the emulsion of auxiliary agent in emulsifying tank.
Embodiment:
The preparation of heat-proof flame-proof resin emulsion
The preparation of A1:
A) preparation of monomer mixed solution
Under 30 ℃ with 30 parts of N-tribromo phenyl maleimides, 45 parts of vinylbenzene, 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B) preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.5 parts of sodium lauryl sulphate join in the reactor under 30 ℃, open and stir, and (a) joined carry out emulsification in the reactor.The pH value is surveyed in emulsification after 33 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 5 hours under 75 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (b) after qualified, and surveying the pH value is about 9.
Under 75 ℃, 5.0% oleic acid potash soap, 10% antioxidant 1076,5% plasticizer phthalic acid dibutylester and 80% de-salted water are mixed with the emulsion of auxiliary agent in emulsifying tank.
In (b), add 0.7 part of the emulsion of auxiliary agent at last, be all processes of finishing preparation (b).
Emulsion in the reactor, after filtration, filtrate white heat-proof flame-proof resin emulsion product, placed nondiscoloration 120 hours.The solids that filters out is weighed after the drying, as the criterion (＜3.0% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.8%.
Calculated yield 93.1% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=133 ℃ with the differential calorimeter.Record its vicat softening temperature: 133 ℃, flame retardant properties reaches the V-0 level.
The preparation of A2:
A) preparation of monomer mixed solution
Under 32 ℃ with 45 parts of N-tribromo phenyl maleimides, 55 parts of alpha-methyl styrenes, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B) preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.4 parts of Sodium dodecylbenzene sulfonatees join in the reactor under 32 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.The pH value is surveyed in emulsification after 32 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 5.5 hours under 78 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (b) after qualified, and surveying the pH value is about 9.(b) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (b).
Emulsion in the reactor, after filtration, filtrate white heat-proof flame-proof resin emulsion product, placed nondiscoloration 120 hours.The solids that filters out is weighed after the drying, as the criterion of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.3%.
Calculated yield 91.1% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=155 ℃ with the differential calorimeter.Record its vicat softening temperature: 153 ℃, flame retardant properties reaches the V-0 level.
The preparation of A3:
A) preparation of monomer mixed solution
Under 25 ℃ with 10 parts of N-tribromo cyclohexyl maleimides, 65 parts of vinylbenzene, 25 parts of methacrylonitriles, 0.35 part of 2,2'-Azobis(2,4-dimethylvaleronitrile), 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B) preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 5.5 parts of sodium lauryl sulphate join in the reactor under 25 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.The pH value is surveyed in emulsification after 31 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 5.8 hours under 72 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (b) after qualified, and surveying the pH value is about 9.(b) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (b).
Emulsion in the reactor, after filtration, filtrate white heat-proof flame-proof resin emulsion product, placed nondiscoloration 120 hours.The solids that filters out is weighed after the drying, as the criterion of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 2.7%.
Calculated yield 94.1% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=108 ℃ with the differential calorimeter.Record its vicat softening temperature: 108 ℃, flame retardant properties reaches the HB level.
The preparation of A4:
A) preparation of monomer mixed solution
Under 26 ℃ with 25 parts of N-tribromo phenyl maleimides, 50 parts of vinylbenzene, 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B) preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.5 parts of sodium lauryl sulphate join in the reactor under 28 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.The pH value is surveyed in emulsification after 44 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 4.5 hours under 75 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (b) after qualified, and surveying the pH value is about 9.(b) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (b).
Emulsion in the reactor, after filtration, filtrate white heat-proof flame-proof resin emulsion product, placed nondiscoloration 120 hours.The solids that filters out is weighed after the drying, as the criterion of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 2.0%.
Calculated yield 92.5% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=120 ℃ with the differential calorimeter.Record its vicat softening temperature: 121 ℃, flame retardant properties reaches the V-1 level.
The preparation of acrylic ester elastomer graft copolymer emulsion
The preparation of B1
Under 25 ℃ with the PBA latex of 35 parts particle diameter 320nm (in butt, as follows), 0.8 part sodium lauryl sulphate, 0.1 part yellow soda ash, 0.1 part EDTA, 0.6 part of glucose, 200 parts of de-salted waters join in the reactor, begin to stir, the vinyl cyanide that adds 6 parts then, 0.30 part hydrogen phosphide cumene, 13.5 parts vinylbenzene and 0.45 part of tert-dodecyl mercaptan join in the reactor, heat up after 10 minutes, be warmed up to 60 ℃ and add 0.041 part of ferrous sulfate, begin reaction, in the system since exothermic heat of reaction begin to heat up, 1.5 add 13.5 parts of vinyl cyanide after hour, the hydrogen phosphide cumene of 32 parts vinylbenzene and 0.25 part.Constant temperature is 1 hour when treating that system temperature rises to 75 ℃, records the graft latex transformation efficiency by the method for surveying dry-matter and finishes 95% or more to react, and finishes the preparation of ABAS graft copolymer.The grafting efficiency 52% of the ABAS graft copolymer that obtains, the molecular weight 6.2 * 10 of free styrene-acrylonitrile copolymer in the ABAS graft copolymer
4
The preparation of B2
Under 27 ℃ with vinylbenzene-BA multipolymer (styrene content 5%) latex of 45 parts particle diameter 260nm, 0.5 part Sodium dodecylbenzene sulfonate, 0.4 part sodium bicarbonate, 0.2 part trisodium phosphate, 0.3 part sodium sulfoxylate formaldehyde, 190 parts of de-salted waters join in the reactor, begin to stir, the vinyl cyanide that adds 4.4 parts then, 0.30 the di-isopropylbenzene hydroperoxide of part, 13.5 vinylbenzene and 0.45 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 5 minutes, are warmed up to 60 ℃ and add 0.025 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, treat to add after 1.5 hours 11 parts of vinyl cyanide in the system, the di-isopropylbenzene hydroperoxide of 26.1 parts vinylbenzene and 0.25 part.Constant temperature is 1 hour when treating that system temperature rises to 75 ℃, records the graft latex transformation efficiency by the method for surveying dry-matter and finishes 95% or more to react, and finishes the preparation of ABAS graft copolymer.The grafting efficiency 52% of the ABAS graft copolymer that obtains, the molecular weight 7.1 * 10 of free styrene-acrylonitrile copolymer in the ABAS graft copolymer
4
The preparation of B3
Under 30 ℃ with vinylbenzene-MBA multipolymer (styrene content 10%) latex of 47 parts particle diameter 320nm, 0.2 part Sodium dodecylbenzene sulfonate and 0.3 part of disproportionated rosin acid soap, 0.6 part sodium bicarbonate, 0.5 part trisodium phosphate, 0.1 part glucose, 120 parts of de-salted waters join in the reactor, begin to stir, the vinyl cyanide that adds 4.1 parts then, 0.10 the di-isopropylbenzene hydroperoxide of part, 12.4 vinylbenzene and 0.50 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 10 minutes, are warmed up to 60 ℃ and add 0.05 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, add 9.7 parts of vinyl cyanide after 2.5 hours in the system, the di-isopropylbenzene hydroperoxide of 26.8 parts vinylbenzene and 0.30 part.Constant temperature is 1 hour when treating that system temperature rises to 75 ℃, records the graft latex transformation efficiency by the method for surveying dry-matter and finishes 95% or more to react, and finishes the preparation of ABAS graft copolymer.The grafting efficiency 52% of the ABAS graft copolymer that obtains, the molecular weight 7.3 * 10 of free styrene-acrylonitrile copolymer in the ABAS graft copolymer
4
The preparation of B4
Under 25 ℃ with the PEBA latex of 45 parts particle diameter 400nm, 0.5 part Sodium dodecylbenzene sulfonate and 0.6 part of synthetic fatty acid potassium, 0.5 part sodium bicarbonate, 0.2 part trisodium phosphate, 0.3 part glucose, 200 parts of de-salted waters join in the reactor, begin to stir, and add 3.3 parts vinyl cyanide then, 0.15 the di-isopropylbenzene hydroperoxide of part, 13.2 vinylbenzene and 0.40 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 15 minutes, are warmed up to 60 ℃ and add 0.012 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, add 7.7 parts of vinyl cyanide after 1.5 hours in the system, the di-isopropylbenzene hydroperoxide of 30.8 parts vinylbenzene and 0.25 part.Constant temperature is 1 hour when treating that system temperature rises to 75 ℃, records the graft latex transformation efficiency by the method for surveying dry-matter and finishes 95% or more to react, and finishes the preparation of ABAS graft copolymer.The grafting efficiency 52% of the ABAS graft copolymer that obtains, the molecular weight 7.9 * 10 of free styrene-acrylonitrile copolymer in the ABAS graft copolymer
4
The preparation of B5
Under 25 ℃ with vinyl cyanide-BA multipolymer (acrylonitrile content 5%) latex of 45 parts particle diameter 320nm, 0.5 part Sodium dodecylbenzene sulfonate, 0.4 part sodium bicarbonate, 0.2 part trisodium phosphate, 0.3 part sodium sulfoxylate formaldehyde, 150 parts of de-salted waters join in the reactor, begin to stir, the vinyl cyanide that adds 4.4 parts then, 0.15 the di-isopropylbenzene hydroperoxide of part, 12.0 vinylbenzene and 0.21 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 7 minutes, are warmed up to 60 ℃ and add 0.043 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, add 9 parts of vinyl cyanide after 1.5 hours in the system, the di-isopropylbenzene hydroperoxide of 29.6 parts vinylbenzene and 0.24 part.Constant temperature is 1 hour when treating that system temperature rises to 75 ℃, records the graft latex transformation efficiency by the method for surveying dry-matter and finishes 95% or more to react, and finishes the preparation of ABAS graft copolymer.The grafting efficiency 52% of the ABAS graft copolymer that obtains, the molecular weight 10.5 * 10 of free styrene-acrylonitrile copolymer in the ABAS graft copolymer
4
The preparation of B6
Under 27 ℃ with butyl acrylate-EBA multipolymer (butyl acrylate content 5%) latex of 45 parts particle diameter 320nm, 0.6 part Sodium dodecylbenzene sulfonate, 0.35 part sodium bicarbonate, 0.2 part trisodium phosphate, 0.3 part glucose, 160 parts of de-salted waters join in the reactor, begin to stir, the vinyl cyanide that adds 4.1 parts then, 0.18 the di-isopropylbenzene hydroperoxide of part, 12.4 vinylbenzene and 0.35 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 13 minutes, are warmed up to 60 ℃ and add 0.019 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, add 9.7 parts of vinyl cyanide after 1.0 hours in the system, the di-isopropylbenzene hydroperoxide of 28.8 parts vinylbenzene and 0.25 part.Constant temperature is 1 hour when treating that system temperature rises to 75 ℃, records the graft latex transformation efficiency by the method for surveying dry-matter and finishes 95% or more to react, and finishes the preparation of ABAS graft copolymer.The grafting efficiency 52% of the ABAS graft copolymer that obtains, the molecular weight 8.3 * 10 of free styrene-acrylonitrile copolymer in the ABAS graft copolymer
4
The preparation of B7
Under 28 ℃ with the PBA latex of 55 parts particle diameter 320nm, 0.6 part Sodium dodecylbenzene sulfonate, 0.4 part sodium bicarbonate, 0.24 part trisodium phosphate, 0.34 part glucose, 130 parts of de-salted waters join in the reactor, begin to stir, and add 4.0 parts vinyl cyanide then, 0.15 the di-isopropylbenzene hydroperoxide of part, 9.6 vinylbenzene and 0.22 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 6 minutes, are warmed up to 60 ℃ and add 0.038 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, add 9.0 parts of vinyl cyanide after 0.5 hour in the system, the di-isopropylbenzene hydroperoxide of 22.4 parts vinylbenzene and 0.26 part.Constant temperature is 1 hour when treating that system temperature rises to 75 ℃, records the graft latex transformation efficiency by the method for surveying dry-matter and finishes 95% or more to react, and finishes the preparation of ABAS graft copolymer.The grafting efficiency 52% of the ABAS graft copolymer that obtains, the molecular weight 10.4 * 10 of free styrene-acrylonitrile copolymer in the ABAS graft copolymer
4
The preparation of B8
Under 35 ℃ with the PBA latex of 60 parts particle diameter 320nm, 0.1 part Sodium dodecylbenzene sulfonate, 0.2 part sodium bicarbonate, 0.21 part trisodium phosphate, 0.11 part glucose, 145 parts of de-salted waters join in the reactor, begin to stir, and add 3.0 parts vinyl cyanide then, 0.13 the di-isopropylbenzene hydroperoxide of part, 9.0 vinylbenzene and 0.39 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 14 minutes, are warmed up to 60 ℃ and add 0.016 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, add 7.0 parts of vinyl cyanide after 1.5 hours in the system, the di-isopropylbenzene hydroperoxide of 21 parts vinylbenzene and 0.18 part.Constant temperature is 1 hour when treating that system temperature rises to 75 ℃, records the graft latex transformation efficiency by the method for surveying dry-matter and finishes 95% or more to react, and finishes the preparation of ABAS graft copolymer.The grafting efficiency 52% of the ABAS graft copolymer that obtains, the molecular weight 7.1 * 10 of free styrene-acrylonitrile copolymer in the ABAS graft copolymer
4
B9: commercially available SKR2842
C1: commercially available SAN, the trade mark: BHF, index: in conjunction with nitrile content 25.3%
C2: commercially available SAN, the trade mark: HH, index: in conjunction with nitrile content 28.1%
C3: commercially available SAN, the trade mark: HH-C300, index: in conjunction with nitrile content 30.2%
Blending auxiliary agent: 0.2 part of lubricant (EBS), (1010) 0.4 parts in oxidation inhibitor, 0.2 part and 3 parts decabromodiphenyl oxides of softening agent (Magnesium Stearate), 3 parts of Sb
2O
3
Embodiment 1:
Heat-proof flame-proof resin emulsion A1 is mixed according to 12: 53: 0.82 ratio with the emulsion of ABS emulsion B1 and auxiliary agent, with 100 parts of these mixed emulsions under 25 ℃, under agitation join temperature continuously and be in 65 ℃ the aqueous solution of 300 part 5 ‰ sal epsom, keep uniform feed rate and in 30～35 minutes, add.After emulsion adds mixed solution is warming up to 95 ℃ and keeps and to lower the temperature in 1 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, promptly become A1 and B1 mixture.With A1 after 65.82 parts of oven dry and B1 mixture, with 35 parts C2,5.5 parts of blending auxiliary agents; Mix in the high speed mixing machine, blend can obtain the heat resisting flame retardant resin composition product through twin screw extruder.The performance of product sees Table 2.
Embodiment 2:
Heat-proof flame-proof resin emulsion A2 is mixed according to 24: 51: 0.80 ratio with the emulsion of ABS emulsion B1 and auxiliary agent, 100 parts of these mixed emulsions are under agitation joined temperature continuously under 30 ℃ be in 60 ℃ the aqueous solution of 100 part 2 ‰ sal epsom, keeps uniform feed rate and added in 30～35 minutes.After emulsion adds mixed solution is warming up to 97 ℃ and keeps and to lower the temperature in 1 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, standby.With A1 after 75.80 parts of oven dry and B1 mixture, with 25 parts C1,6.1 parts of blending auxiliary agents; In the high speed mixing machine, mix.Blend can obtain the heat resisting flame retardant resin composition product through twin screw extruder.The performance of product sees Table 2.
Embodiment 3:
Heat-proof flame-proof resin emulsion A3 is mixed according to 36: 39: 1.20 ratio with the emulsion of ABS emulsion B1 and auxiliary agent, 100 parts of these mixed emulsions are under agitation joined temperature continuously under 30 ℃ be in 70 ℃ the aqueous solution of 500 part 8 ‰ sal epsom, keeps uniform feed rate and added in 30～35 minutes.After emulsion adds mixed solution is warming up to 100 ℃ and keeps and to lower the temperature in 1 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, standby.With A1 after 76.2 parts of oven dry and B1 mixture, with 25 parts C3,5.6 parts of blending auxiliary agents; In the high speed mixing machine, mix.Blend can obtain the heat resisting flame retardant resin composition product through twin screw extruder.The performance of product sees Table 2.
Embodiment 4:
Heat-proof flame-proof resin emulsion A1 is mixed according to 45: 40: 1.20 ratio with the emulsion of ABS emulsion B2 and auxiliary agent, 100 parts of these mixed emulsions are under agitation joined temperature continuously under 35 ℃ be in 70 ℃ the aqueous solution of 300 part 8 ‰ sal epsom, keeps uniform feed rate and added in 30～35 minutes.After emulsion adds mixed solution is warming up to 100 ℃ and keeps and to lower the temperature in 1 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, standby.With A1 after 86.2 parts of oven dry and B1 mixture, with 15 parts C2,5.1 parts of blending auxiliary agents; In the high speed mixing machine, mix.Blend can obtain the heat resisting flame retardant resin composition product through twin screw extruder.The performance of product sees Table 2.
Embodiment 5
Heat-proof flame-proof resin emulsion A1100 part under 35 ℃, is under agitation joined temperature continuously and is in 70 ℃ the aqueous solution of 350 part 6 ‰ sal epsom, keep uniform feed rate and in 30～35 minutes, add.After emulsion adds mixed solution is warming up to 100 ℃ and keeps and to lower the temperature in 1 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, standby.
With the A1 after 55 parts of oven dry and 30 parts of commercially available ABS height splicing branch part B9, C2 of 15 parts, 3.1 parts of blending auxiliary agents; In the high speed mixing machine, mix.Blend can obtain the heat resisting flame retardant resin composition product through twin screw extruder.The performance of product sees Table 2.
Embodiment 6～9, and just the kind of A, B, C and consumption see Table 2 listedly, and other are identical with embodiment 4.
Embodiment 10
Heat-proof flame-proof resin emulsion A1100 part under 35 ℃, is under agitation joined temperature continuously and is in 70 ℃ the aqueous solution of 450 part 4 ‰ sal epsom, keep uniform feed rate and in 30～35 minutes, add.After emulsion adds mixed solution is warming up to 100 ℃ and keeps and to lower the temperature in 1 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, standby.
ABS emulsion B6100 part under 25 ℃, is under agitation joined temperature continuously and is in 63 ℃ the aqueous solution of 350 part 5 ‰ sal epsom, keep uniform feed rate and in 30～35 minutes, add.After emulsion adds mixed solution is warming up to 96 ℃ and keeps and to lower the temperature in 1 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, standby.
With ABS grafting part B6,5 parts the C2 after A1 after 65 parts of oven dry and 30 oven dry, 4.1 parts of blending auxiliary agents; Mix in the high speed mixing machine, blend can obtain the heat resisting flame retardant resin composition product through twin screw extruder.The performance of product sees Table 2.
Embodiment 11,12, and just the kind of A, B, C and consumption see Table 2 listedly, and other are identical with embodiment 10.
The performance perameter of table 1 C
Table 2 embodiment weather resistant Weather resistant heat resisting fire-retardant combination blend prescription and The performance test results
Comparative example 1～5:
On the basis of embodiment 1～5, during the preparation Weather resistant heat resisting flame retardant resin composition, the acrylic ester elastomer graft copolymer changes the conjugated diene rubber graft copolymer ABS graft copolymer of corresponding glue content into, is designated as B
0, for example the preparation of B1 changes the acrylic ester elastomer graft copolymer conjugated diene rubber graft copolymer ABS graft copolymer of corresponding glue content into, and other condition is constant, and this preparation is designated as B
01.Add the comparative example A in addition
0Preparation, changing initiator is the water soluble starter Potassium Persulphate.Adopt the method for embodiment 4 to prepare resin combination.
A
01 preparation:
A) preparation of monomer mixed solution
Under 30 ℃ with 30 parts of N-tribromo phenyl maleimides, 45 parts of vinylbenzene, 25 parts of vinyl cyanide, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B) preparation of heat-proof flame-proof resin emulsion
Under 30 ℃ with 160 parts of de-salted waters, 0.35 part of Potassium Persulphate, 3.5 parts of sodium lauryl sulphate join in the reactor, open to stir, and (a) joined carry out emulsification in the reactor.The pH value is surveyed in emulsification after 33 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 5 hours under 75 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (b) after qualified, and surveying the pH value is about 9.
Under 75 ℃, 5.0% oleic acid potash soap, 10% antioxidant 1076,5% plasticizer phthalic acid dibutylester and 80% de-salted water are mixed with the emulsion of auxiliary agent in emulsifying tank.
In (b), add 0.7 part of the emulsion of auxiliary agent at last, be all processes of finishing preparation (b).
Table 3 comparative example Weather resistant heat resisting fire-retardant combination blend prescription and The performance test results
This shows, compare that adopt the composition of water soluble starter and conjugated diene elastomer production, its weather resistance is relatively poor with embodiment.
Claims (17)
1. Weather-resistant halogen substituent maleimide heat resisting fire-proof resin composition, it is characterized in that: in Weather resistant heat resisting flame retardant resin composition is 100 mass parts, contain: 10～65 parts of A. halogen substituent maleimide heat-proof flame-proof resins, the halogen substituent maleimide unit accounts for 10～45 quality % in the halogen substituent maleimide heat-proof flame-proof resin, aryl ethylene class unit accounts for 30～65 quality %, and the itrile group vinyl units accounts for 0～30 quality %; B. the graftomer of acrylic ester elastomer grafting aryl ethylene class monomer and itrile group vinyl monomer is 30～55 parts, acrylic ester elastomer accounts for 35～60 quality % in the graftomer, aryl ethylene class unit accounts for 26～49 quality %, and the itrile group vinyl units accounts for 10～20 quality %; C. the copolymer of aryl ethylene class monomer and itrile group vinyl monomer is 5～35 parts, and aryl ethylene class unit accounts for 65～78 quality % in the copolymer, and the itrile group vinyl units accounts for 22～35 quality %; Wherein the emulsion of halogen substituent maleimide heat-proof flame-proof resin is to obtain by the following method, is 100 mass parts in the polymerization single polymerization monomer total amount:
(A) preparation of monomer mixed solution
In 25～35 ℃ with 10～45 parts of halogen substituent maleimide monomers, 30～65 parts of aryl ethylene class monomers, 0～30 part of itrile group vinyl monomer, 0.1～0.6 part of oil soluble thermal decomposition initiating, 0.01～0.65 part of molecular weight regulator adds tempering tank, open to stir and mix, form homogeneous phase monomer mixed solution (a);
(B) preparation of halogen substituent maleimide heat-proof flame-proof resin emulsion
In 25～35 ℃ with 100～200 parts of de-salted waters, 2.0～10.0 parts of emulsifying agents join in the reactor that whipping appts is housed, the unlatching stirring joins (a) carries out emulsification in the reactor, emulsification can heat up and carry out polymerization in 20～75 minutes, and the temperature of maintenance system was carried out polyreaction 3～8 hours under 55～95 ℃; System temperature is risen to 90～100 ℃ then, polyreaction was carried out 0.5～2.0 hour again, promptly formed halogen substituent maleimide heat-proof flame-proof resin emulsion (b).
2. resin combination according to claim 1, it is characterized in that aryl ethylene class monomer is selected from vinylbenzene, Vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, in tert-butylbenzene ethene, alpha-methyl styrene, α-ethyl styrene, Alpha-Methyl p-methylstyrene, halogenated styrenes, haloalkyl vinylbenzene, the vinyl naphthalene one or more.
3. resin combination according to claim 1 is characterized in that the itrile group vinyl monomer is selected from one or more in vinyl cyanide, the methacrylonitrile.
4. resin combination according to claim 1 is characterized in that acrylic ester elastomer refers to the homopolymer of acrylic ester monomer or the multipolymer of acrylic ester monomer and energy and the formation of its monomer that reacts.
5. resin combination according to claim 4, it is characterized in that acrylic ester monomer is selected from ethyl propenoate, methyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl acrylate, butyl methacrylate, one or more in the ethyl propylene acid butyl ester.
6. resin combination according to claim 1, it is characterized in that the halogen substituent maleimide monomer is selected from N-halogenated methyl maleimide, N-halogenated ethyl maleimide, N-halo tertiary butyl maleimide, N-halo isobutyl-maleimide, N-halo cyclohexyl maleimide, N-halogenophenyl maleimide, N-halogenated methyl phenyl maleimide, N-halogenated methoxy phenyl maleimide, N-halo carboxyl phenyl maleimide, N-halogenated nitrobenzene base maleimide, one or more in the N-halo naphthyl maleimide.
7. resin combination according to claim 1 is characterized in that emulsifying agent is anion surfactant, nonionogenic tenside or their compound system.
8. resin combination according to claim 7, it is characterized in that emulsifying agent is selected from sodium lauryl sulphate, dodecyl sulphate potassium, Sodium dodecylbenzene sulfonate, Potassium dodecylbenzenesulfonate, potassium stearate, synthetic fatty acid potassium, disproportionated rosin acid soap, one or more in sodium oleate, the polyoxyethylene nonionogenic tenside.
9. resin combination according to claim 1 is characterized in that molecular weight regulator is tert-dodecyl mercaptan or dodecyl mercaptan carbon.
10. resin combination according to claim 1 is characterized in that the oil soluble thermal decomposition initiating is azo-initiator or organic peroxide initiator.
11. resin combination according to claim 1, the copolymer molecular weight that it is characterized in that aryl ethylene class monomer and itrile group vinyl monomer is 60000～120000.
12. the preparation method of the described resin combination of claim 1, it is characterized in that heat-proof flame-proof resin emulsion is mixed with the graftomer emulsion of acrylic ester elastomer grafting aryl ethylene class monomer and itrile group vinyl monomer and the emulsion of 0.8～1.2 part of auxiliary agent, 100 parts of these mixed emulsions are under agitation joined temperature continuously under 25～35 ℃ be in 60～70 ℃ 100～500 part 2～8 ‰ the aqueous solution that contains flocculation agent, in 30～35 minutes, add, after emulsion adds mixed solution being warming up to 90～100 ℃ keeps and can lower the temperature in 1～1.5 hour, finish agglomeration process, condense the slurry that and dry with de-salted water washing back after filtration, obtain the mixture of heat-proof flame-proof resin and graftomer; Mixture with 65～95 parts of above-mentioned heat-proof flame-proof resins and graftomer, with the copolymer blend of 5～35 parts aryl ethylene class monomer and itrile group vinyl monomer, blend is extruded through forcing machine can obtain the Weather-resistant halogen substituent maleimide heat resisting fire-proof resin composition.
13. the preparation method of resin combination according to claim 12, the preparation method who it is characterized in that the graftomer of acrylic ester elastomer grafting aryl ethylene class monomer and itrile group vinyl monomer: with acrylic ester elastomer, the summation of aryl ethylene class monomer and itrile group vinyl monomer is 100 mass parts meters, under 25～35 ℃ with 35～60 parts particle diameter acrylic ester elastomer latex at 260～400nm, 0.2～0.8 part of emulsifying agent, 0.1～0.6 part of PH buffer reagent, 0.1～0.5 part of complexing agent, 0.1～0.6 part is helped reductive agent, 120～200 parts of de-salted waters join in the reactor, begin to stir, the itrile group vinyl monomer that adds 2～6.5 parts then, 0.1～0.3 part oxygenant, 6～14 parts aryl ethylene class monomer and 0.1～0.5 part of molecular weight regulator join in the reactor, heat up after 5～15 minutes, be warmed up to 60～70 ℃ and add 0.01～0.05 part of reductive agent, 0.5 add 6～13.5 parts of itrile group vinyl monomers after～2.5 hours, 20～39 parts aryl ethylene class monomer and 0.1～0.3 part oxygenant; Graft latex transformation efficiency 95% finishes reaction when above.
14. the preparation method of resin combination according to claim 12 is characterized in that softening agent in the emulsion of auxiliary agent: thermo-stabilizer: emulsifying agent: the weight ratio of water is (1～5): (1～5): (3～10): (80～200).
15., it is characterized in that emulsifying agent is one or more in potassium stearate, potassium oleate, the synthetic fatty acid potassium according to the preparation method of claim 13 or 14 described resin combinations.
16. the preparation method of resin combination according to claim 12 is characterized in that flocculation agent is selected from one or more in calcium sulfate, calcium chloride, sal epsom, sodium-chlor, potassium aluminium sulfate, the polymeric flocculant.
17. the preparation method of resin combination according to claim 13 is characterized in that the pH buffer reagent is yellow soda ash or sodium bicarbonate.
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