CN101503545B - Halogen substituent maleimide heat-resistant flame-retardant resin composition with improved glossiness and preparation method thereof - Google Patents
Halogen substituent maleimide heat-resistant flame-retardant resin composition with improved glossiness and preparation method thereof Download PDFInfo
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- CN101503545B CN101503545B CN2008100576307A CN200810057630A CN101503545B CN 101503545 B CN101503545 B CN 101503545B CN 2008100576307 A CN2008100576307 A CN 2008100576307A CN 200810057630 A CN200810057630 A CN 200810057630A CN 101503545 B CN101503545 B CN 101503545B
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- maleimide
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- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003063 flame retardant Substances 0.000 title claims abstract description 44
- 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 31
- 239000011342 resin composition Substances 0.000 title claims abstract description 19
- 125000005843 halogen group Chemical group 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 81
- 239000000178 monomer Substances 0.000 claims abstract description 170
- -1 aryl ethylene Chemical compound 0.000 claims abstract description 92
- 239000000203 mixture Substances 0.000 claims abstract description 83
- 229920005989 resin Polymers 0.000 claims abstract description 71
- 239000011347 resin Substances 0.000 claims abstract description 71
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 55
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 47
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 38
- 229920001577 copolymer Polymers 0.000 claims abstract description 21
- 239000005977 Ethylene Substances 0.000 claims abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract 8
- 239000000839 emulsion Substances 0.000 claims description 132
- 238000000034 method Methods 0.000 claims description 70
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 56
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 52
- 229920000126 latex Polymers 0.000 claims description 46
- 239000004816 latex Substances 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 34
- 239000012752 auxiliary agent Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000007334 copolymerization reaction Methods 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 31
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 22
- 239000003643 water by type Substances 0.000 claims description 21
- 239000003995 emulsifying agent Substances 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 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 17
- 239000002245 particle Substances 0.000 claims description 17
- 238000004945 emulsification Methods 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 15
- 230000009466 transformation Effects 0.000 claims description 15
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 13
- 239000004902 Softening Agent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 11
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 11
- 239000005062 Polybutadiene Substances 0.000 claims description 10
- 238000005054 agglomeration Methods 0.000 claims description 10
- 230000002776 aggregation Effects 0.000 claims description 10
- 125000001475 halogen functional group Chemical group 0.000 claims description 10
- 229920002857 polybutadiene Polymers 0.000 claims description 10
- 230000002829 reductive effect Effects 0.000 claims description 10
- 238000005496 tempering Methods 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
- 238000010792 warming Methods 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 238000005070 sampling Methods 0.000 claims description 8
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- 230000000977 initiatory effect Effects 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 5
- 239000000344 soap 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-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
- 239000006174 pH buffer Substances 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
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- 229920001195 polyisoprene Polymers 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
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 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 compound 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
- 229920003171 Poly (ethylene oxide) Polymers 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
- 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 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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001084 poly(chloroprene) Polymers 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
- 150000003440 styrenes Chemical class 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 3
- 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
- CGKQZIULZRXRRJ-UHFFFAOYSA-N Butylone Chemical compound CCC(NC)C(=O)C1=CC=C2OCOC2=C1 CGKQZIULZRXRRJ-UHFFFAOYSA-N 0.000 claims 1
- 239000012934 organic peroxide initiator Substances 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 2
- 229920006015 heat resistant resin Polymers 0.000 abstract 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 55
- 150000002367 halogens Chemical group 0.000 description 40
- 239000000047 product Substances 0.000 description 28
- 238000002156 mixing Methods 0.000 description 20
- 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 18
- 238000002485 combustion reaction Methods 0.000 description 18
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- 230000007704 transition Effects 0.000 description 12
- 235000003891 ferrous sulphate Nutrition 0.000 description 11
- 239000011790 ferrous sulphate Substances 0.000 description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 11
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- 239000001488 sodium phosphate Substances 0.000 description 9
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 9
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 8
- 239000008103 glucose Substances 0.000 description 8
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
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- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 6
- 150000002825 nitriles Chemical class 0.000 description 6
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- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 5
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
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- QBLRHWLVSHLMSP-UHFFFAOYSA-N 3-bromopyrrole-2,5-dione Chemical compound BrC1=CC(=O)NC1=O QBLRHWLVSHLMSP-UHFFFAOYSA-N 0.000 description 2
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- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 2
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
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- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 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
- 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
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- 239000004215 Carbon black (E152) Substances 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
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920007019 PC/ABS 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
- AQFKZIGXHYQDLK-UHFFFAOYSA-N [Na].[S].C(CCCCCCCCCCC)C1=CC=CC=C1 Chemical compound [Na].[S].C(CCCCCCCCCCC)C1=CC=CC=C1 AQFKZIGXHYQDLK-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 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
- 239000008346 aqueous phase Substances 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
- 230000015572 biosynthetic process Effects 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
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 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
- 230000003750 conditioning 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
- 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 1
- 238000000354 decomposition 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
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response 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
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The composition comprises, by 100 parts by mass, 10-65 parts of halogen substituent maleimide heat-resistant resin, 30-55 parts of a conjugated diene rubber grafted aryl ethylene monomer, a nitrile vinyl monomer or a graft polymer of a copolymerizable acrylate monomer, and 5-35 parts of a binary copolymer of the aryl ethylene monomer and the nitrile vinyl monomer. The heat-resistant flame-retardant resin composition prepared by the invention has the advantages of good appearance, flame retardance, good glossiness and high heat resistance, and is a heat-resistant flame-retardant material with good performance. The prepared heat-resistant flame-retardant resin can be widely used for modifying heat resistance and flame retardance of materials such as ABS, PC, PBT and the like. 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 polymer heat resisting flame retardant resin composition and preparation method who has improved glossiness, particularly a kind of composition and method of making the same that has improved the halogen substituent-containing maleimide heat-proof flame-proof resin of glossiness.
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 the basis of heatproof combustion resistance, 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 of halogen substituent maleimide (XSMIA) 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 assurance of superelevation heat-proof combustion-resistant ABS resin heatproof combustion resistance, and the ABS graft copolymer is determining the balance of its over-all properties.
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 heat-proof combustion-resistant performance (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 resisting flame retardant 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 flame-retardant alloy; JP3146542 has described a kind of by carrying out the method that blend prepares the flame-proof heat-resistant fire-proof resin composition 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 blend and prepare heat-proof combustion-resistant heat-proof combustion-resistant method for compositions; JP 63081152 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.
More than these patented methods, adopt small molecules fire retardant or small molecules halogen containing flame-retardant, in various degree exist the auxiliary agent transport phenomena, the heat-proof combustion-resistant performance is not good, prepares the shortcoming that alloy exists poor heat stability again with PVC or CPVC.
In order to obtain the good heat-proof combustion-resistant composition of over-all properties, need the suitable glue content of preparation conjugated diene rubber grafting aryl ethylene class monomer and or the grafting powder of itrile group vinyl monomer, and to preparation conjugated diene rubber grafting aryl ethylene class monomer and or the particle diameter and the gel of the graft base latex of the grafting powder of itrile group vinyl monomer higher requirement is arranged, factors such as grafted monomer proportioning, molecular weight also all can produce considerable influence to the final performance of heat-proof combustion-resistant composition.
For the most of user on the existing market, surface gloss to the heat-proof combustion-resistant composition product all has higher requirement, according to experimental result, but in the graft polymerization prescription, introduce the acrylic ester monomer of copolymerization, can improve the glossiness of composition effectively, satisfy the requirement of market the product glossiness.
Summary of the invention
At the problems referred to above, the object of the present invention is to provide a kind of composition and preparation method who has improved the halogen substituent-containing maleimide heat-proof flame-proof resin of glossiness.Under the situation of comparatively convenient, easy handling, the synthetic relatively heat-proof flame-proof resin XSMIA multipolymer of homogeneous that distributes of forming in the monomer ratio scope of broad, and by the synthetic conjugated diene rubber grafting aryl ethylene class monomer that is complementary with it and or the graft latex of itrile group vinyl monomer, then graft latex and heat-proof flame-proof resin emulsion carry out common cohesion, dry back and aryl ethylene class monomer and or the multipolymer of the itrile group vinyl monomer method of carrying out blend obtain the good heat resisting flame retardant resin composition of over-all properties.
The composition of halogen substituent maleimide heat-proof flame-proof resin of the present invention, composition in the halogen substituent maleimide heat-proof flame-proof resin 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 %; But B. conjugated diene rubber grafting aryl ethylene class monomer, itrile group vinyl monomer or and 30～55 parts of the graftomer of the acrylic ester monomer of copolymerization, conjugated diene rubber accounts for 35～60 quality % in the graftomer, aryl ethylene class unit accounts for 20～45.5 quality %, the itrile group vinyl units accounts for 5.5～22 quality %, but the esters of acrylic acid unit of copolymerization accounts for 0～10 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 heat-proof flame-proof resin emulsion (b).
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.
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 XPMI in the ST/AN mixed solution is limited, after the XPMI formula ratio reaches certain umber, temperature is lower than 25 ℃, XPMI 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.
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.
Used initiator is the used oil soluble thermal decomposition initiating of general radical polymerization in the polymerization process of halogen substituent maleimide heat-proof flame-proof resin emulsion of the present invention, usually oil dissolubility thermal decomposition initiating is meant at the initiator of the half life of decomposition below 100 ℃ less than 4 hours, comprises azo class, organo-peroxide class.The object lesson of 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).Initiator once adds in the present invention, and oil-soluble conditioning agent also must add in (a), and emulsifying agent then must add aqueous phase.
The 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., these halo maleimide monomers can be used alone or in combination.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.
But the acrylic ester monomer of copolymerization mainly contains: ethyl propenoate, methyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, and butyl acrylate, butyl methacrylate etc. can be one or more, wherein the preferable methyl methyl acrylate.
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, anion surfactants such as sodium oleate, OP, Tween, polyoxyethylene nonionogenic tensides such as Span, wherein preferably sodium dodecyl sulfate, Sodium dodecylbenzene sulfonate or synthetic fatty acid potassium or their compound system.
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.
But the aryl ethylene of conjugated diene rubber grafting in the present invention class monomer and itrile group vinyl monomer or and the unitary graftomer of esters of acrylic acid of copolymerization (or claiming multipolymer), 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 conjugated diene rubber grafting aryl ethylene class monomer and itrile group vinyl monomer can be taked CN 1555398, methods such as CN 1394216 obtain, and perhaps use present commercially available prod that 338 of GE is arranged, Daqing petrochemical, the high branch powder that glueds joint of the ABS of Lanzhou petrochemical industry.Conjugated diene rubber latex, mainly be the homopolymer of conjugated diolefine and the multipolymer that can form with the monomer that it reacts, (wherein styrene content 3～10% as polybutadiene latex, polyisoprene latex, polychloroprene latex, butadiene-styrene,) copolymer emulsion, (wherein acrylonitrile content 3～8% for butadiene-acrylonitrile,) copolymer emulsion, (wherein Butyl acrylate content 3～10% for the butadiene-acrylic acid butyl ester,) copolymer emulsion etc., preferably polybutadiene latex.Among the present invention, used graft rubber latex is existing Industrial products on ripe production technology or the market, and preferably structural gel is 70%～90%.The present invention is not limited the preparation method of conjugated diene rubber (as polybutadiene latex), the preparation method of common polybutadiene latex all can, but particle diameter is preferably between 260～400nm; Conjugated diene rubber grafting aryl ethylene class monomer, but the graft copolymer of the acrylic ester monomer of itrile group vinyl monomer and copolymerization is polyhutadiene grafted propylene nitrile/styrene/methacrylic acid methyl esters preferably, butadiene-styrene copolymer grafted propylene nitrile/methyl methacrylate, the graftomer of butadiene-acrylic acid ester copolymer graft phenylethene/methyl methacrylate (general designation ABS graftomer), the graftomer (AIS) of polyisoprene grafted propylene nitrile/styrene/methacrylic acid methyl esters, the graftomer (ACS) of sovprene grafted propylene nitrile/styrene/methacrylic acid methyl esters etc., preferably the graftomer ABS of polyhutadiene grafted propylene nitrile/styrene/methacrylic acid methyl esters.
The copolymer of aryl ethylene class monomer and itrile group vinyl monomer can take methods such as CN1455786, CN85101103 to obtain, BHF, the CHF etc. that perhaps use present commercially available prod to have Lanzhou Petrochemical Company to produce.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).
But the present invention also provide a kind of suitable especially preparation present composition conjugated diene rubber grafting aryl ethylene class monomer, itrile group vinyl monomer or and the preparation method of the graft copolymer of the acrylic ester monomer of copolymerization: but be 100 mass parts in the summation of the acrylic ester monomer of conjugated diene rubber, aryl ethylene class monomer and itrile group vinyl monomer and copolymerization:
Under 25～35 ℃ with 35～60 parts particle diameter conjugated diene rubber 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 2.0～6.5 parts then, 0.1～0.3 part oxygenant, 6～16 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 3.5～15.5 parts of itrile group vinyl monomers after 0.5～2.5 hour, 14～39 parts aryl ethylene class monomer, but the oxygenant of 0～8 part of the acrylic ester monomer of copolymerization and 0.1～0.3 part.Record the graft latex transformation efficiency by the method for surveying dry-matter and finish 95% or more to react, but finish conjugated diene rubber grafting aryl ethylene class monomer and itrile group vinyl monomer or with the preparation of the multipolymer of the acrylic ester monomer of copolymerization.
Optimum condition:
Under 25～35 ℃ with 40～55 parts particle diameter conjugated diene rubber 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, 9～15.5 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 ℃ and add 0.01～0.03 part of reductive agent, add 4.0～15.0 parts of itrile group vinyl monomers after 0.5～2.0 hour, 21～32 parts aryl ethylene class monomer, but the oxygenant of 0～6 part of the acrylic ester monomer of copolymerization and 0.2～0.3 part.Record the graft latex transformation efficiency by the method for surveying dry-matter and finish 95% or more to react, but finish conjugated diene rubber grafting aryl ethylene class monomer and itrile group vinyl monomer or with the preparation of the multipolymer of the acrylic ester monomer of copolymerization.
But among the present invention both can with generate conjugated diene rubber grafting aryl ethylene class monomer and itrile group vinyl monomer or and the graftomer emulsion (or claiming latex) of the acrylic ester monomer of copolymerization provide use with emulsion form, but also can with conjugated diene rubber grafting aryl ethylene class monomer and itrile group vinyl monomer or and the graftomer (or claiming graft copolymer) of the acrylic ester monomer of copolymerization emulsion is condensed, provide use after the drying.Dry auxiliary agent, the condition of using of cohesion is prior art, universal method.
But the conjugated diene rubber grafting aryl ethylene class monomer that in the present invention, provides, itrile group vinyl monomer or and the preparation method of the graft copolymer emulsion of the acrylic ester monomer of copolymerization, but other can effectively prepare conjugated diene rubber grafting aryl ethylene class monomer, itrile group vinyl monomer or and the preparation method of the graft copolymer of the acrylic ester monomer of copolymerization also can adopt, commercially available in addition toughness properties-correcting agent as 338, ABS is high also can directly select for use by the branch powder etc. of glueing joint.
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.
But preparation conjugated diene rubber grafting aryl ethylene class monomer among the present invention, itrile group vinyl monomer or and the oxygenant that uses during the graft copolymer of the acrylic ester monomer of copolymerization be the general oxygenant of redox system, as being hydrogen peroxide, hydrogen phosphide cumene, di-isopropylbenzene hydroperoxide, tertbutyl peroxide, isopropyl benzene hydroperoxide, peroxidation 2, the 4-dichloro-benzoyl, 1,1 two (tert-butyl peroxy base) hexanaphthene etc., preferred hydrogen phosphide cumene, di-isopropylbenzene hydroperoxide.
Employed reduction is reductive agent mutually, helps reductive agent to be the general reductive agent of redox system, to help reductive agent, as using ferrous sulfate, sodium sulfoxylate formaldehyde in the invention, S-WAT, glucose, 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.
The present invention is not specially limited the preparation of compositions method of halogen substituent maleimide heat-proof flame-proof resin, 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.But this emulsion can through cohesion, dry back and conjugated diene rubber grafting aryl ethylene class monomer, itrile group vinyl monomer or and the multipolymer of graft copolymer, aryl ethylene class monomer and the itrile group vinyl monomer of the acrylic ester monomer of copolymerization carry out blend and prepare heat resisting flame retardant resin composition; But also can with the halogen substituent maleimide heat-proof flame-proof resin emulsion that obtains directly with conjugated diene rubber grafting aryl ethylene class monomer, itrile group vinyl monomer or and the graft latex of the acrylic ester monomer of copolymerization mixes and carries out blend with the multipolymer of aryl ethylene class monomer and itrile group vinyl monomer again after condense altogether the back and prepare heat resisting flame retardant resin composition.
The present invention also provides a kind of this to improve the preparation of compositions method of the halogen substituent maleimide heat-proof flame-proof resin of glossiness, is the heat-proof flame-proof resin emulsion and the conjugated diene rubber grafting aryl ethylene class monomer of a kind of halogen substituent maleimide monomer and aryl ethylene class monomer and/or itrile group vinyl monomer specifically, but the itrile group vinyl monomer or and the graft copolymer emulsion of the acrylic ester monomer of copolymerization carry out common cohesion, the copolymer of dry back and aryl ethylene class monomer and itrile group vinyl monomer carries out the method that blend prepares heat resisting flame retardant resin composition:
But with halogen substituent maleimide heat-proof flame-proof resin emulsion and conjugated diene rubber grafting aryl ethylene class monomer, itrile group vinyl monomer or and the graft copolymer emulsion of the acrylic ester monomer of copolymerization and the emulsion of 0.8～1.2 part of auxiliary agent mix, 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), keeps uniform feed rate and 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.Condense the slurry that and dry with de-salted water washing back after filtration, standby.To contain 65～95 parts the halogen substituent maleimide heat-proof flame-proof resin and the mixture of conjugated diolefine graftomer, mix with 5～35 parts the aryl ethylene class monomer and the copolymer and the blending auxiliary agent of itrile group vinyl monomer, blend is extruded the composition of the halogen substituent maleimide heat-proof flame-proof resin of the glossiness that can be improved through forcing machine.
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., and softening agent can be Magnesium Stearate, DOP, DDP etc., and lubricant can be silicone oil, EBS etc., and 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).
The composition of the halogen substituent-containing maleimide heat-proof flame-proof resin that has improved glossiness of the present invention and preparation method's characteristics are as follows:
1. the synthetic method of halogen substituent maleimide heat-proof flame-proof resin emulsion of the present invention has thoroughly solved the instability of emulsion, problems such as pH reduces and emulsion variable color, precipitate be more.Polyreaction is very easily controlled, and reaction process is highly stable, and polymerization finishes not have substantially precipitate and produces.The polymerization reaction monomer transformation efficiency is more than 95%, and the solids that emulsion filtered out after reaction finished and the ratio of total monomer charging capacity are lower than 1.0%.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 the composition of halogen substituent-containing maleimide heat-proof flame-proof resin of the present invention adopts halogen substituent maleimide heat-proof flame-proof resin emulsion and conjugated diene rubber graft copolymer emulsion to condense has altogether solved the difficult problem that heat-proof flame-proof resin emulsion particle in agglomeration process is thin, yield is low.
3. the conjugated diene rubber 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 heat-proof flame-proof resin, and making it has good consistency with heat-proof flame-proof resin.
4. with the preparation of compositions method of halogen substituent-containing maleimide heat-proof flame-proof resin of the present invention, it is good that the heat resisting flame retardant resin composition that makes has outward appearance, fire-retardant, and glossiness is good, the advantage that thermal stability is high is the good heat-proof combustion-resistant material of a kind of performance.The heat-proof flame-proof 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, molecular weight refers to weight-average molecular weight.
Second-order transition temperature Tg:DSC-differential thermal differential method
Vicat softening temperature: GB/T 1633-2000
Flame retardant properties test: UL-94
Glossiness: JIS-Z 8741 GS (60)
Molecular weight: GPC (W-150C)
Nitrile content: GB/T 4486-84
Melting index (g/10min): 3682-2000
Socle girder notched Izod impact strength (J/m): GB/T 1843-1996
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.
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, emulsor stir for band.Hereinafter " % ", " part " all refers to mass percent or mass fraction.
The preparation of the emulsion of auxiliary agent: the emulsion that under 75 ℃, 5.0% oleic acid potash soap, 10% antioxidant 1076,5% plasticizer phthalic acid dibutylester and 80% de-salted water is mixed with auxiliary agent in emulsifying tank.
Embodiment:
The preparation of halogen substituent maleimide 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 halogen substituent maleimide 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 40～45 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 4.5～5 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 alpha-methyl styrenes, 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 140 parts of de-salted waters, 3.3 parts of dodecylbenzene sulphur sodium 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 5.5～6 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 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, 3.7 parts of Sodium dodecylbenzene sulfonatees and 2.0 parts of synthetic fatty acid potassium 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 5.5～6 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, 2.9 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 4～4.5 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 conjugated diene rubber graft copolymer emulsion
The preparation of B1
Under 25 ℃ with the polybutadiene latex of 35 parts particle diameter 320nm, 0.8 part sodium lauryl sulphate, 0.1 part yellow soda ash, 0.1 part EDTA, 0.6 part glucose, 200 parts of de-salted waters join in the reactor, begin to stir, and add 5.8 parts vinyl cyanide then, 0.30 the hydrogen phosphide cumene of part, 13.6 vinylbenzene and 0.45 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 10 minutes, are warmed up to 60 ℃ and add 0.041 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, add 13.7 parts of vinyl cyanide after 1.5 hours in the system, the hydrogen phosphide cumene of 31.9 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 ABS graft copolymer.The grafting efficiency 52% of the ABS graft copolymer that obtains, the molecular weight 6.2 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B2
Under 27 ℃ with vinylbenzene (containing vinylbenzene 5%)-butadienecopolymer latex of 43 parts particle diameter 260nm, 0.5 part Sodium dodecylbenzene sulfonate, 0.4 part sodium bicarbonate, 0.2 part trisodium phosphate, 0.6 part sodium sulfoxylate formaldehyde, 190 parts of de-salted waters join in the reactor, begin to stir, the vinyl cyanide that adds 5.2 parts then, 0.30 the di-isopropylbenzene hydroperoxide of part, 13.8 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 10.4 parts of vinyl cyanide, 23.7 parts vinylbenzene in the system, 3.8 the di-isopropylbenzene hydroperoxide of part MMA 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 ABS graft copolymer.The grafting efficiency 52% of the ABS graft copolymer that obtains, the molecular weight 7.2 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B3
Under 30 ℃ with vinylbenzene (10%)-butadienecopolymer latex of 52 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 3.3 parts then, 0.10 the di-isopropylbenzene hydroperoxide of part, 10.1 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 7.9 parts of vinyl cyanide, 22.5 parts vinylbenzene after 2.5 hours in the system, 4.1 the di-isopropylbenzene hydroperoxide of part MMA 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 ABS graft copolymer.The grafting efficiency 52% of the ABS graft copolymer that obtains, the molecular weight 7.3 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B4
Under 25 ℃ with the polybutadiene latex of 45 parts particle diameter 400nm, 0.2 part Sodium dodecylbenzene sulfonate and 0.6 part of synthetic fatty acid potassium, 0.5 part sodium bicarbonate, 0.2 part trisodium phosphate, 0.5 part glucose, 200 parts of de-salted waters join in the reactor, begin to stir, the vinyl cyanide that adds 3.2 parts then, 0.15 the di-isopropylbenzene hydroperoxide of part, 12.7 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 8.4 parts of vinyl cyanide, 28.7 parts vinylbenzene after 1.5 hours in the system, 1.9 the di-isopropylbenzene hydroperoxide of part MMA 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 ABS graft copolymer.The grafting efficiency 52% of the ABS graft copolymer that obtains, the molecular weight 7.6 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B5
Under 25 ℃ with vinyl cyanide (5%)-butadienecopolymer latex of 46 parts particle diameter 320nm, 0.5 part Sodium dodecylbenzene sulfonate, 0.4 part sodium bicarbonate, 0.2 part trisodium phosphate, 0.33 part sodium sulfoxylate formaldehyde, 150 parts of de-salted waters join in the reactor, begin to stir, the vinyl cyanide that adds 3.8 parts then, 0.15 the di-isopropylbenzene hydroperoxide of part, 12.5 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 7.4 parts of vinyl cyanide, 23.4 parts vinylbenzene after 1.5 hours in the system, 6.9 the di-isopropylbenzene hydroperoxide of part MMA 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 ABS graft copolymer.The grafting efficiency 52% of the ABS graft copolymer that obtains, the molecular weight 10.2 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B6
Under 27 ℃ with butyl acrylate (5%)-butadienecopolymer 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 3.8 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 8.9 parts of vinyl cyanide, 25.4 parts vinylbenzene after 1.0 hours in the system, 4.6 the di-isopropylbenzene hydroperoxide of part methyl acrylate (MA) and 0.22 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 ABS graft copolymer.The grafting efficiency 52% of the ABS graft copolymer that obtains, the molecular weight 8.4 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B7
Under 28 ℃ with the polybutadiene latex of 54 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 3.8 parts vinyl cyanide then, 0.18 the di-isopropylbenzene hydroperoxide of part, 9.2 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 7.6 parts of vinyl cyanide, 22.5 parts vinylbenzene after 0.5 hour in the system, 2.9 the di-isopropylbenzene hydroperoxide of part MMA 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 ABS graft copolymer.The grafting efficiency 52% of the ABS graft copolymer that obtains, the molecular weight 10.1 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B8
Under 35 ℃ with the polybutadiene latex of 60 parts particle diameter 320nm, 0.2 part Sodium dodecylbenzene sulfonate, 0.4 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 2.8 parts vinyl cyanide then, 0.13 the di-isopropylbenzene hydroperoxide of part, 8.4 vinylbenzene and 0.35 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 6.5 parts of vinyl cyanide, 19.5 parts vinylbenzene after 1.5 hours in the system, 2.8 the di-isopropylbenzene hydroperoxide of part MMA 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 ABS graft copolymer.The grafting efficiency 52% of the ABS graft copolymer that obtains, the molecular weight 7.3 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
B9: commercially available GE company produce 338
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 64 ℃ 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 C2,4.1 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 2:
Heat-proof flame-proof resin emulsion A2 is mixed according to 25: 50: 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 75.8 parts of oven dry and B1 mixture, with 25 parts C1,5.0 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 34: 41: 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 68 ℃ 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 C3,4.9 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 47: 38: 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 C2,5.8 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 5～8, and just the kind of A, B, C and consumption see Table 2 listedly, and other are identical with embodiment 4.
Embodiment 9
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 powder B6,5 parts the C2 after the A1 after 65 parts of oven dry and the 30 parts of oven dry, 4.4 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 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 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, 5.3 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 11,12, and just the kind of A, B, C and consumption see Table 2 listedly, and other are identical with embodiment 10.
Table 1 A synthesis condition
| Sequence number | Halogen substituent maleimide | The aryl ethylene class | The itrile group vinyl | Second-order transition temperature, ℃ | The dimension card, ℃ | Yield, % | The solids ratio that leaches, % |
| A1 A2 A3 A4 | 30 45 10 25 | 45 55 65 50 | 25 0 25 25 | 129 148 112 118 | 132 143 108 117 | 93.3 93.6 93.3 94.3 | 1.2 1.2 1.1 1.3 |
Table 2 embodiment heat-resistant composition blend prescription and The performance test results
| The embodiment sequence number | A | B | C | The dimension card, ℃ | Cantilever beam impact strength, J/m | Fire-retardant rank | Glossiness | |||
| Sequence number | Proportioning | Sequence number | Proportioning | Sequence number | Proportioning | |||||
| 1 2 3 4 5 6 7 8 9 10 11 12 | A1 A2 A3 A1 A1 A1 A3 A4 A1 A1 A4 A4 | 12 25 34 47 55 65 25 35 65 55 55 50 | B1 B1 B2 B2 B3 B4 B5 B3 B6 B9 B7 B8 | 53 50 41 38 40 30 40 40 30 30 40 40 | C2 C1 C3 C2 C3 C2 C2 C2 C2 C2 C2 C2 | 35 25 25 15 5 5 35 25 5 15 5 10 | 105 114 106 117 119 122 106 107 122 117 114 113 | 263 201 212 189 175 131 264 208 178 213 198 203 | V-0 V-0 HB V-0 V-0 V-0 HB V-1 V-0 V-0 V-0 V-0 | 63 70 72 69 71 70 73 68 67 62 72 67 |
Comparative example
A
01 preparation:
A) preparation of monomer mixed solution
In the time of 30 ℃, in being housed, the reactor of stirring adds 30 parts of N-tribromo phenyl maleimides, 44.7 parts of vinylbenzene, and 25.3 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 monomer emulsion
30 ℃ with 160 parts of de-salted waters, 0.45 part of Potassium Persulphate, and 3.0 parts of sodium lauryl sulphate join in the emulsor, open and stir, and (a) joined carry out emulsification in the emulsor.Emulsification 42 minutes monomer emulsion (b).Measuring its pH is 9～10.
C) preparation of heat-proof flame-proof resin emulsion
(b) joined in the reactor continuously equably and the temperature of maintenance system is carried out polyreaction under 80 ℃.The feed rate of control (b) added it within 4.8 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (c) after qualified.(c) after polymerization finished, measuring its pH was about 9.5.
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 (d), add 0.7 part of the emulsion of auxiliary agent at last, be all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate heat-proof flame-proof resin emulsion.The solids that filters out is weighed after the drying, as the criterion (≤3.5% is qualified) of emulsion reaction system stability through washing.Under this condition, this emulsion is placed nondiscoloration in 72 hours.The ratio of solids that filters out and monomeric charge amount is 3.45%.
Calculated yield 94.4% after the product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=128 ℃ with the differential calorimeter.Record its vicat softening temperature: 127 ℃, flame retardant properties reaches the V-0 level.
B
01 preparation
Under 25 ℃ with the polybutadiene latex of 35 parts particle diameter 320nm, 0.8 part sodium lauryl sulphate, 0.1 part yellow soda ash, 0.1 part EDTA, 0.6 part glucose, 200 parts of de-salted waters join in the reactor, begin to stir, the vinyl cyanide that adds 15.4 parts then, 5 parts of vinylbenzene, 0.30 hydrogen phosphide cumene and 0.45 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 10 minutes, be warmed up to 60 ℃ and add 0.041 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, add the hydrogen phosphide cumene of 45.6 parts of vinyl cyanide and 0.25 part after 1.5 hours in the system.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 ABS graft copolymer.The grafting efficiency 52% of the ABS graft copolymer that obtains, the molecular weight 6.5 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
B
02 preparation
Under 27 ℃ with vinylbenzene (5%)-butadienecopolymer 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 4.2 parts then, 0.30 the di-isopropylbenzene hydroperoxide of part, 13.8 vinylbenzene and 0.45 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 5 minutes, be 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 34.1 parts vinylbenzene in the system, 2.8 the di-isopropylbenzene hydroperoxide of part MMA 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 ABS graft copolymer.The grafting efficiency 52% of the ABS graft copolymer that obtains, the molecular weight 7.6 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
Comparative example 1～4: the blend method of comparative example 1～4 and embodiment are same, and the result is as shown in table 3.
Table 3 comparative example heat resisting flame retardant resin composition blend prescription and The performance test results
| The embodiment sequence number | A | B | C | Vicat softening point, ℃ | Socle girder impacts, J/m | Fire-retardant rank | Glossiness | |||
| Sequence number | Proportioning | Sequence number | Proportioning | Sequence number | Proportioning | |||||
| 1 2 3 | A 01 A 01 A 01 | 10 25 35 | B 01 B 02 B1 | 55 50 40 | C2 C1 C3 | 35 25 25 | 102.5 113.2 105.7 | 223 164 178 | Not fire-retardant HB | 61 59 67 |
Claims (17)
1. the composition of a halogen substituent-containing maleimide heat-proof flame-proof resin, it is characterized in that: the composition in the halogen substituent maleimide heat-proof flame-proof resin is 100 mass parts, contain: 10～65 parts of A. halogen substituent maleimide heat-proof flame-proof resins, the halogen substituent maleimide monomeric unit accounts for 10～45 quality % in the halogen substituent maleimide heat-proof flame-proof resin, the aryl ethylene monomeric unit accounts for 30～65 quality %, and the itrile group ethylene monomer unit accounts for 0～30 quality %; But B. conjugated diene rubber grafting aryl ethylene monomer, itrile group vinyl monomer or and 30～55 parts of the graftomer of the acrylate monomer of copolymerization, conjugated diene rubber accounts for 35～60 quality % in the graftomer, the aryl ethylene monomeric unit accounts for 20～45.5 quality %, the itrile group ethylene monomer unit accounts for 5.5～22 quality %, but the acrylate monomeric units of copolymerization accounts for 0～10 quality %; C. the copolymer of aryl ethylene monomer and itrile group vinyl monomer is 5～35 parts, and the aryl ethylene monomeric unit accounts for 65～78 quality % in the copolymer, and the itrile group ethylene monomer unit accounts for 22～35 quality %; The emulsion that wherein is used to prepare described halogen substituent maleimide heat-proof flame-proof resin obtains 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 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, the temperature of maintenance system was carried out polyreaction 3～8 hours under 55～95 ℃, system temperature is risen to 90～100 ℃ then, and polyreaction was carried out 0.5～2.0 hour again, the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (b).
2. composition according to claim 1, it is characterized in that the aryl ethylene monomer be selected from vinylbenzene, Vinyl toluene, 1.3-dimethyl styrene, 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. composition 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. composition according to claim 1, but it is characterized in that the acrylate monomer of copolymerization is selected from ethyl propenoate, methyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl acrylate, one or more in the butyl methacrylate.
5. composition 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.
6. composition according to claim 1 is characterized in that emulsifying agent is anion surfactant, nonionogenic tenside or their compound system.
7. composition according to claim 6, 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.
8. composition according to claim 1 is characterized in that molecular weight regulator is tert-dodecyl mercaptan or dodecyl mercaptan carbon.
9. composition according to claim 1 is characterized in that the oil soluble thermal decomposition initiating is azo-initiator or organic peroxide initiator.
10. composition according to claim 1, the copolymer molecular weight that it is characterized in that aryl ethylene monomer and itrile group vinyl monomer is 60000～120000.
11. composition according to claim 1 is characterized in that conjugated diene rubber comes from polybutadiene latex, polyisoprene latex, polychloroprene latex, butadiene-styrene copolymer latex, perbutan latex or butadiene-acrylic acid butyl ester copolymer emulsion.
12. the preparation of compositions method of the described halogen substituent-containing maleimide heat-proof flame-proof resin of claim 1, it is characterized in that halogen substituent maleimide heat-proof flame-proof resin emulsion and conjugated diene rubber grafting aryl ethylene monomer, but the itrile group vinyl monomer or and the graft copolymer emulsion of the acrylate monomer of copolymerization and the emulsion of 0.8～1.2 part of auxiliary agent mix, 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, added in 30～45 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; Condense the slurry that and wash after drying with de-salted water after filtration, finally obtain the mixture of the graftomer of halogen substituent maleimide heat-proof resin and conjugated diene rubber; Mixture with the graftomer of above-mentioned 65～95 parts halogen substituent maleimide heat-proof resin that obtains and conjugated diene rubber, with the copolymer blend of 5～35 parts aryl ethylene monomer and itrile group vinyl monomer, blend obtains heat resisting flame retardant resin composition after forcing machine is extruded.
13. preparation of compositions method according to claim 12, it is characterized in that conjugated diene rubber grafting aryl ethylene monomer, but the itrile group vinyl monomer or and the emulsion preparation method of the graft copolymer of the acrylate monomer of copolymerization: use the redox system initiator, with conjugated diene rubber, but the summation of the acrylate monomer of aryl ethylene monomer and itrile group vinyl monomer and copolymerization is 100 mass parts meters: under 25～35 ℃ with 35～60 parts particle diameter conjugated diene rubber 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 2.0～6.5 parts then, 0.1～0.3 part oxygenant, 6～16 parts aryl ethylene 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 3.5～15.5 parts of itrile group vinyl monomers after～2.5 hours, 14～39 parts aryl ethylene monomer, but the oxygenant of 0～8 part of the acrylate monomer of copolymerization and 0.1～0.3 part, graft latex transformation efficiency 95% finishes reaction when above.
14. preparation of compositions method 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 claim 13 or 14 described preparation of compositions methods.
16. preparation of compositions method 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. preparation of compositions method according to claim 13 is characterized in that the pH buffer reagent is yellow soda ash or sodium bicarbonate.
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