CN100526347C - Preparation method of halogen substituent maleimide heat-resistant flame-retardant resin emulsion - Google Patents
Preparation method of halogen substituent maleimide heat-resistant flame-retardant resin emulsion Download PDFInfo
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- CN100526347C CN100526347C CNB2006101128417A CN200610112841A CN100526347C CN 100526347 C CN100526347 C CN 100526347C CN B2006101128417 A CNB2006101128417 A CN B2006101128417A CN 200610112841 A CN200610112841 A CN 200610112841A CN 100526347 C CN100526347 C CN 100526347C
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- 239000000839 emulsion Substances 0.000 title claims abstract description 196
- 238000002360 preparation method Methods 0.000 title claims abstract description 100
- 239000011347 resin Substances 0.000 title claims abstract description 93
- 229920005989 resin Polymers 0.000 title claims abstract description 93
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 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 abstract description 28
- 239000003063 flame retardant Substances 0.000 title abstract description 28
- 125000005843 halogen group Chemical group 0.000 title abstract description 4
- 239000000178 monomer Substances 0.000 claims abstract description 111
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 70
- 238000003756 stirring Methods 0.000 claims abstract description 64
- 238000004945 emulsification Methods 0.000 claims abstract description 56
- 239000011259 mixed solution Substances 0.000 claims abstract description 54
- 239000003999 initiator Substances 0.000 claims abstract description 27
- -1 aryl ethylene Chemical compound 0.000 claims abstract description 18
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 150000002367 halogens Chemical group 0.000 claims description 32
- 238000005496 tempering Methods 0.000 claims description 28
- 238000012423 maintenance Methods 0.000 claims description 27
- 239000003643 water by type Substances 0.000 claims description 27
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 25
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 24
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 24
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 24
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 15
- 230000000977 initiatory effect Effects 0.000 claims description 9
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 5
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 4
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 239000012934 organic peroxide initiator Substances 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 150000002825 nitriles Chemical class 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 70
- 239000000047 product Substances 0.000 description 45
- 238000001035 drying Methods 0.000 description 43
- 238000001914 filtration Methods 0.000 description 42
- 238000000034 method Methods 0.000 description 38
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 32
- 239000012752 auxiliary agent Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 29
- 239000012071 phase Substances 0.000 description 27
- 230000008569 process Effects 0.000 description 26
- 238000005070 sampling Methods 0.000 description 25
- 230000007704 transition Effects 0.000 description 25
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 23
- 238000005406 washing Methods 0.000 description 22
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical class O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 21
- 239000000706 filtrate Substances 0.000 description 21
- 239000004159 Potassium persulphate Substances 0.000 description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 12
- 235000019394 potassium persulphate Nutrition 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000008859 change Effects 0.000 description 7
- 239000004902 Softening Agent Substances 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
- 238000007720 emulsion polymerization reaction Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 230000001804 emulsifying effect Effects 0.000 description 5
- 125000001475 halogen functional group Chemical group 0.000 description 5
- 229920001897 terpolymer Polymers 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical group OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229940072033 potash Drugs 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 239000012966 redox initiator Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- JTUOMQJVPHRJHA-UHFFFAOYSA-N [C].C(CCCCCCCCCCC)S Chemical compound [C].C(CCCCCCCCCCC)S JTUOMQJVPHRJHA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 229940114930 potassium stearate Drugs 0.000 description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 2
- 238000010526 radical polymerization reaction Methods 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
- 239000010913 used oil Substances 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical class C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- QRNSUDYQQKOCPW-UHFFFAOYSA-N 3-(2-methylpropyl)pyrrole-2,5-dione Chemical compound CC(C)CC1=CC(=O)NC1=O QRNSUDYQQKOCPW-UHFFFAOYSA-N 0.000 description 1
- USICVVZOKTZACS-UHFFFAOYSA-N 3-butylpyrrole-2,5-dione Chemical group CCCCC1=CC(=O)NC1=O USICVVZOKTZACS-UHFFFAOYSA-N 0.000 description 1
- QUKZJBQJUYHRON-UHFFFAOYSA-N 3-ethylpyrrole-2,5-dione Chemical class CCC1=CC(=O)NC1=O QUKZJBQJUYHRON-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 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 description 1
- ZLPORNPZJNRGCO-UHFFFAOYSA-N 3-methylpyrrole-2,5-dione Chemical class CC1=CC(=O)NC1=O ZLPORNPZJNRGCO-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 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
- 238000012662 bulk polymerization Methods 0.000 description 1
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 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
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- ONQDVAFWWYYXHM-UHFFFAOYSA-M potassium lauryl sulfate Chemical compound [K+].CCCCCCCCCCCCOS([O-])(=O)=O ONQDVAFWWYYXHM-UHFFFAOYSA-M 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- 239000001120 potassium sulphate Substances 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- XNYYNDAEXFUXBD-UHFFFAOYSA-N tert-butylbenzene ethene Chemical compound C=C.C(C)(C)(C)C1=CC=CC=C1 XNYYNDAEXFUXBD-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
A preparation method of halogen substituent maleimide heat-resistant flame-retardant resin emulsion is divided into two parts, and the components and the operation conditions are as follows: adding halogen substituent maleimide monomer, aryl ethylene monomer, nitrile ethylene monomer, initiator and the like into a mixing tank, starting stirring and mixing to form homogeneous monomer mixed solution ; adding an emulsifier into a reactor, starting stirring, adding the (a) into the reactor for emulsification, and heating to polymerize after emulsification to form the heat-resistant flame-retardant resin emulsion . The obtained heat-resistant flame-retardant resin emulsion has the advantages of good appearance, uniform composition and structure, high heat resistance, flame retardance and high yield in the polymerization process, and can be widely used for modifying heat resistance and flame retardance of materials such as ABS, PC, PBT and the like. The single use of the material can also be 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 preparation method's of heat-proof flame-proof resin emulsion, particularly a kind of halogen substituent maleimide heat-proof flame-proof resin emulsion preparation method.
Background technology
The monomeric free-radical polymerized thing of halogen substituent maleimide, because of containing the plane five-membered ring structure on its molecular chain, can effectively suppress the rotation of chain, thereby have very high structure rigidity and thermostability, simultaneously because of containing halogen on its molecular chain, on stable on heating basis, have good flame retardancy again, thereby be subjected to extensive concern.
The preparation of heat-proof combustion-resistant ABS resin comprises two kinds of alloyage and modification by copolymerization methods, and wherein the modification by copolymerization method is a kind of reasonable technological line.The modification by copolymerization method mainly is made up of two portions technology, what a part was a halogen substituent maleimide (XIMID) with the monomeric terpolymer XSMIA of halogen substituent maleimide of aryl ethylene class monomer (AEM) itrile group vinyl monomer (NEM) is synthetic, and another part is the synthetic of ABS graft copolymer.The synthetic of the monomeric terpolymer of halogen substituent maleimide is the stable on heating assurance of superelevation heat-resisting ABS resin, and the ABS graft copolymer is determining the balance of its over-all properties.
The synthetic of XSMIA then can be adopted various polymerization processs such as body, suspension, emulsion and solution polymerization.Halogen substituent maleimide monomer and AEM and or NEM and three's copolyreaction have and the general different characteristics of copolyreaction, polymerization rate is very fast, reaction is difficult to control.Though high temperature suspension polymerization also may address this problem, its to the requirement of equipment than higher.The molecular weight of the monomeric terpolymer of emulsion polymerisation process synthetic halogen substituent maleimide is with respect to various polymerization processs such as body, suspension and solution polymerizations, the molecular weight of polymerisate is bigger, helps improving the physical strength and the resistance toheat (especially heat-drawn wire performance) of product.
GB1026912 has described the multipolymer for preparing maleimide and MMA with the method for mass polymerization, and the initiator of employing is an organo-peroxide.GB1062872 has described the multipolymer for preparing vinylchlorid and maleimide with method of emulsion polymerization, adopts redox initiation system.CA2078337 etc. have reported the method for its solution polymerization, and its solvent generally uses organic solvents such as benzene, and initiator adopts the oil soluble thermal decomposition initiating, as azo-initiator.What GB1086673 and GB1213061 introduced is that what it adopted is water soluble starter with the method for the multipolymer of emulsion polymerization prepared maleimide and vinylbenzene etc.In " polymer material science and engineering " 2001 (17) .1, reported in " second-order transition temperature of St-AN-PMI emulsion copolymers and the rheological " that people such as Liu Guodong deliver and described its general emulsion polymerisation process, promptly adopt emulsifying agent, and be the polymerization process of initiator with the persulphate.
US4757109 has described a kind of technology with emulsion polymerisation process synthesizing styrene, vinyl cyanide, maleimide terpolymer, employing has the anionic emulsifier of well emulsify ability in pH value is 3～9 scopes, initiator adopts redox system or Potassium Persulphate initiator, when this patent is pointed out with the Potassium Persulphate initiator, speed of response is slower, its polymerization technique is fairly simple, does not discuss in view of polymerization process.KR9510550 has also introduced a kind of technology that adopts method of emulsion polymerization synthesizing styrene, vinyl cyanide, maleimide terpolymer, what adopt is used water soluble starter of typical letex polymerization or redox initiation system, does not also discuss in view of polymerization process.
The contriver attempts to seek a kind of under the situation of comparatively convenient, easy handling, synthesizes to obtain forming the relatively emulsion polymerisation process of the SMIA multipolymer of homogeneous that distributes in the monomer ratio scope of broad.
Summary of the invention
At the problems referred to above, the object of the present invention is to provide a kind of preparation method of halogen substituent maleimide heat-proof flame-proof resin emulsion, is a kind of halogen substituent maleimide monomer and aryl ethylene class monomer and or preparation method of the heat-proof flame-proof resin emulsion of itrile group vinyl monomer of preparing specifically.
The preparation method of halogen substituent maleimide heat-proof flame-proof resin emulsion of the present invention is divided into two parts.Usually the composition and the operational condition of these two parts are as follows: (being 100 mass parts in the polymerization single polymerization monomer total amount, as follows)
(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 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).The solids that emulsion filtered out after reaction finished and the ratio of total monomer charging capacity are lower than 3.0%.
Also can add common agent such as softening agent, thermo-stabilizer etc. after polymerization finishes, they can be mixed with the emulsion of auxiliary agent with emulsifying agent, de-salted water in emulsifying tank, and the mode with emulsion after copolyreaction finishes adds.After polymerization finishes, emulsion through cohesion, filter, dry, weigh after calculated yield, yield 〉=90% is qualified.
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 heat-proof flame-proof resin emulsion (b) after qualified.
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.
Used initiator is the used oil soluble thermal decomposition initiating of general radical polymerization in the polymerization process of the present invention, usually oil dissolubility thermal decomposition initiating is meant at 100 ℃ the half life of decomposition initiator less than 4 hours, comprises azo-initiator, organic peroxide initiator.Initiator once adds in the present invention; Oil-soluble conditioning agent also must add in (a), and emulsifying agent then must add aqueous phase; If do not add the part initiator when (b) then polymerization rate can reduce, thereby the stability of the system of destruction in preparation.
The halogen substituent maleimide monomer that the preparation method adopted of halogen substituent maleimide heat-proof flame-proof resin emulsion of the present invention 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 monomer is the compound that contains aryl hydrocarbon or substituted arene in the vinyl monomer.
Aryl ethylene class monomer mainly contains: 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, α-vinyl toluene, α-ethyl styrene, α-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.
The itrile group vinyl monomer is the compound of nitrile group-containing in the vinyl monomer.
The itrile group vinyl monomer mainly contains: vinyl cyanide, methacrylonitrile etc., the combination of one or more in these monomers all can be used.
Used initiator is the used oil soluble thermal decomposition initiating of general radical polymerization among the preparation method of halogen substituent maleimide heat-proof flame-proof resin emulsion of the present invention, 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).
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, peregal, Tween, polyoxyethylene nonionogenic tensides such as Span, wherein preferably sodium dodecyl sulfate, Sodium dodecylbenzene sulfonate or synthetic fatty acid potassium/sodium lauryl sulphate compound system.
The molecular weight regulator that the present invention uses is not particularly limited, as being general tert-dodecyl mercaptan, dodecyl mercaptan carbon etc.
The emulsion of the auxiliary agent described in the present invention, 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 (1～15): (1～15): (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.
Among the preparation method of halogen substituent maleimide heat-proof flame-proof resin emulsion of the present invention, the monomer each component amount ranges of recommendation is as follows:
Monomer ratio: the mass ratio of halogen substituent maleimide monomer and aryl ethylene class monomer and itrile group vinyl monomer is adjusted in 10～45/30～65/0～30, and preferable range is 15～45/30～60/0～25.
Preparation method's characteristics of halogen substituent maleimide heat-proof flame-proof resin emulsion of the present invention are as follows:
1. temperature of reaction can be determined according to the decomposition temperature of the initiator of selecting for use, and temperature of reaction is between 55～100 ℃, between preferred 70～95 ℃ usually.
2. whipped form and rotating speed: for letex polymerization of the present invention, because polymerization system viscosity is not high, just requiring to the shearing action that stirs is not very high, and because method that can be by regulating feed rate reaction speed easily, so this method is less demanding to reactor mixing speed and radiating capacity of equipment, as long as can guarantee to mix.Common whipped form all can, preferably the slurry formula stirs.
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.After polymerization finished, heat-proof flame-proof resin emulsion can obtain the halogen substituent maleimide heat-proof flame-proof resin product through cohesion, washing drying.
Preparation method with halogen substituent maleimide heat-proof flame-proof resin emulsion of the present invention, it is good that the multipolymer of the halogen substituent maleimide monomer that makes, aryl ethylene class monomer and itrile group vinyl monomer has outward appearance, form and the structure homogeneous, fire-retardant, the thermal stability height, the advantage that the polymerization process yield is high is that the good heat-proof combustion-resistant of a kind of performance is material modified, 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 heat-stable component of the high flame retardant of household electrical appliances.
Embodiment
Following examples are to specify of the present invention, and wherein reactor reacts in water-bath for three mouthfuls of glass flask of band stirring, condenser, thermometer; The end opening glass flask that tempering tank stirs for band.Hereinafter " % ", " part " all refers to weight percentage or parts by weight.
Second-order transition temperature Tg:DSC-differential thermal differential method
Vicat softening temperature: GB/T1633-2000
Flame retardant properties test: UL-94
Resin emulsion whether weighed by variable color after certain hour is weighed and placed to the solids that emulsion filtered out after resin emulsion stability finished with reaction and the ratio magnitude of total monomer charging capacity.
The preparation of the emulsion of auxiliary agent:
Under 75 ℃, 5.0% oleic acid potash soap, 10% antioxidant 1076,5% plasticizer phthalic acid dibutylester and 80% de-salted water are mixed with the emulsion of auxiliary agent in emulsifying tank.
Embodiment 1:
A. the 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. the preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.5 parts of sodium lauryl sulphate join in the reactor under 30 ℃, open and stir, and (a) joined carry out emulsification in the reactor.The pH value is surveyed in emulsification after 33 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 5 hours under 75 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (b) after qualified, and surveying the pH value is about 9.
Under 75 ℃, 5.0% oleic acid potash soap, 10% antioxidant 1076,5% plasticizer phthalic acid dibutylester and 80% de-salted water are mixed with the emulsion of auxiliary agent in emulsifying tank.
In (b), add 0.7 part of the emulsion of auxiliary agent at last, be all processes of finishing preparation (b).
Emulsion in the reactor, after filtration, filtrate white heat-proof flame-proof resin emulsion product, placed nondiscoloration 120 hours.The solids that filters out is weighed after the drying, as the criterion (＜3.0% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.8%.
Calculated yield 93.1% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=133 ℃ with the differential calorimeter.Record its vicat softening temperature: 133 ℃, flame retardant properties reaches the V-0 level.
Embodiment 2:
A. the preparation of monomer mixed solution
Under 35 ℃ 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. the preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.2 parts of Sodium dodecylbenzene sulfonatees join in the reactor under 35 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.The pH value is surveyed in emulsification after 42 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 6 hours under 73 ℃.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 through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.Under this condition, the ratio of solids that filters out and monomeric charge amount is 2.5%.
Calculated yield 92.1% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=129 ℃ with the differential calorimeter.Record its vicat softening temperature: 130 ℃, flame retardant properties reaches the V-0 level.
Embodiment 3:
A. the preparation of monomer mixed solution
Under 33 ℃ 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. the preparation of heat-proof flame-proof resin emulsion
Under 30 ℃ with 160 parts of de-salted waters, 2.3 parts of sodium lauryl sulphate, 1.5 parts of synthetic fatty acid potassium join in the reactor, open to stir (a) joined and carry out emulsification in the reactor.The pH value is surveyed in emulsification after 44 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 4.5 hours under 77 ℃.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 through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.Under this condition, the ratio of solids that filters out and monomeric charge amount is 2.3%.
Calculated yield 93.1% after the white 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: 129 ℃, flame retardant properties reaches the V-0 level.
Embodiment 4:
A. the preparation of monomer mixed solution
Under 28 ℃ with 30 parts of N-tribromo cyclohexyl maleimides, 45 parts of vinylbenzene, 25 parts of vinyl cyanide, 0.55 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. the preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.1 parts of sodium lauryl sulphate 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 30 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 6 hours under 71 ℃.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 through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.Under this condition, the ratio of solids that filters out and monomeric charge amount is 2.3%.
Calculated yield 92.1% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=135 ℃ with the differential calorimeter.Record its vicat softening temperature: 137 ℃, flame retardant properties reaches the V-0 level.
Embodiment 5:
A. the preparation of monomer mixed solution
Under 30 ℃ with 30 parts of N-tribromo phenyl maleimides, 45 parts of vinyl toluenes, 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. the preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.5 parts of sodium lauryl sulphate join in the reactor under 30 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.The pH value is surveyed in emulsification after 42 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 5 hours under 75 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (b) after qualified, and surveying the pH value is about 9.(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 through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.Under this condition, the ratio of solids that filters out and monomeric charge amount is 2.2%.
Calculated yield 92.1% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=131 ℃ with the differential calorimeter.Record its vicat softening temperature: 133 ℃, flame retardant properties reaches the V-0 level.
Embodiment 6:
A. the preparation of monomer mixed solution
Under 30 ℃ with 30 parts of N-tribromo phenyl maleimides, 45 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. the preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 4.5 parts of sodium lauryl sulphate join in the reactor under 30 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.The pH value is surveyed in emulsification after 45 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 6 hours under 70 ℃.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 through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.9%.
Calculated yield 94.1% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=130 ℃ with the differential calorimeter.Record its vicat softening temperature: 128 ℃, flame retardant properties reaches the V-0 level.
Embodiment 7:
A. the preparation of monomer mixed solution
Under 32 ℃ with 45 parts of N-tribromo phenyl maleimides, 55 parts of vinylbenzene, 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. the preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.4 parts of sodium lauryl sulphate join in the reactor under 32 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.The pH value is surveyed in emulsification after 32 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 5.5 hours under 78 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (b) after qualified, and surveying the pH value is about 9.(b) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (b).
Emulsion in the reactor, after filtration, filtrate white heat-proof flame-proof resin emulsion product, placed nondiscoloration 120 hours.The solids that filters out is weighed after the drying through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.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.
Embodiment 8:
A. the preparation of monomer mixed solution
Under 25 ℃ with 10 parts of N-tribromo phenyl maleimides, 65 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. the preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 5.5 parts of sodium lauryl sulphate join in the reactor under 25 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.The pH value is surveyed in emulsification after 31 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 5.8 hours under 72 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (b) after qualified, and surveying the pH value is about 9.(b) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (b).
Emulsion in the reactor, after filtration, filtrate white heat-proof flame-proof resin emulsion product, placed nondiscoloration 120 hours.The solids that filters out is weighed after the drying through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.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.
Embodiment 9:
A. the 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. the preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.5 parts of sodium lauryl sulphate join in the reactor under 28 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.The pH value is surveyed in emulsification after 44 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 4.5 hours under 75 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (b) after qualified, and surveying the pH value is about 9.(b) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (b).
Emulsion in the reactor, after filtration, filtrate white heat-proof flame-proof resin emulsion product, placed nondiscoloration 120 hours.The solids that filters out is weighed after the drying through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.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.
Embodiment 10:
A. the preparation of monomer mixed solution
Under 28 ℃ with 25 parts of N-tribromo phenyl maleimides, 50 parts of vinylbenzene, 25 parts of vinyl cyanide, 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. the preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.5 parts of sodium lauryl sulphate join in the reactor under 28 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.The pH value is surveyed in emulsification after 43 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 6 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 (＜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 2.0%.
Calculated yield 92.4% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=119 ℃ with the differential calorimeter.Record its vicat softening temperature: 118 ℃, flame retardant properties reaches the V-1 level.
Embodiment 11:
A. the 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. the preparation of heat-proof flame-proof resin emulsion
Under 30 ℃ with 160 parts of de-salted waters, 2.0 parts of sodium lauryl sulphate, 5.0 parts of OP join in the reactor, open to stir (a) joined and carry out emulsification in the reactor.The pH value is surveyed in emulsification after 45 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 6 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, 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 through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.6%.
Calculated yield 93.1% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=127 ℃ with the differential calorimeter.Record its vicat softening temperature: 126 ℃, flame retardant properties reaches the V-0 level.
Embodiment 12:
A. the preparation of monomer mixed solution
Under 30 ℃ with 25 parts of N-tribromo phenyl maleimides, 50 parts of vinylbenzene, 25 parts of vinyl cyanide, 0.35 part of benzoyl peroxide, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.5 parts of sodium lauryl sulphate join in the reactor under 30 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.The pH value is surveyed in emulsification after 30 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 4 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 through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.5%.
Calculated yield 93.6% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=123 ℃ with the differential calorimeter.Record its vicat softening temperature: 121 ℃ of flame retardant propertiess reach the V-1 level.
Embodiment 13:
A. the preparation of monomer mixed solution
Under 30 ℃ with 30 parts of N-dibromo phenyl maleimides, 45 parts of vinylbenzene, 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of dodecyl mercaptan carbon adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.5 parts of sodium lauryl sulphate join in the reactor under 30 ℃, open and stir, and (a) joined carry out emulsification in the reactor.The pH value is surveyed in emulsification after 35 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 4.6 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 through washing, is qualified as criterion＜3.0% of emulsion reaction system stability 〉.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.9%.
Calculated yield 91.6% 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: 131 ℃ of flame retardant propertiess reach the V-1 level.
Comparative example 1: on the basis of embodiment 1, the change initiator is a Potassium Persulphate, tests.
A. the preparation of monomer mixed solution
Under 30 ℃ with 30 parts of N-tribromo phenyl maleimides, 45 parts of vinylbenzene, 25 parts of vinyl cyanide, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of heat-proof flame-proof resin emulsion
Under 30 ℃ with 160 parts of de-salted waters, 0.35 part of Potassium Persulphate, 3.5 parts of sodium lauryl sulphate join in the reactor, open to stir, about control rotating speed 100rpm.Then (a) joined in the reactor, improve stirring velocity, carry out emulsification to 500-700rpm.The pH value is surveyed in emulsification after 35 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 6 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 7.(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 10 hours, become pink.The solids that filters out is weighed after the drying through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.Under this condition, the ratio of solids that filters out and monomeric charge amount is 3.9%.
Calculated yield 89.7% after the white 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: 125 ℃, flame retardant properties reaches the V-1 level.
Comparative example 2: on the basis of embodiment 2, the change initiator is a Potassium Persulphate, tests.
A. the preparation of monomer mixed solution
Under 30 ℃ with 30 parts of N-tribromo phenyl maleimides, 45 parts of vinylbenzene, 25 parts of vinyl cyanide, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of heat-proof flame-proof resin emulsion
Under 30 ℃ with 160 parts of de-salted waters, 0.35 part of Potassium Persulphate, 3.5 parts of Sodium dodecylbenzene sulfonatees join in the reactor, open to stir, about control rotating speed 100rpm.Then (a) joined in the reactor, improve stirring velocity, carry out emulsification to 500-700rpm.The pH value is surveyed in emulsification after 45 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 4 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 7.(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 10 hours, become pink.The solids that filters out is weighed after the drying through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.Under this condition, the ratio of solids that filters out and monomeric charge amount is 5.1%.
Calculated yield 82.1% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=124 ℃ with the differential calorimeter.Record its vicat softening temperature: 122 ℃, flame retardant properties reaches the V-1 level.
Comparative example 3: on the basis of embodiment 3, the change initiator is a Potassium Persulphate, tests.
A. the preparation of monomer mixed solution
Under 30 ℃ with 30 parts of N-tribromo phenyl maleimides, 45 parts of vinylbenzene, 25 parts of vinyl cyanide, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of heat-proof flame-proof resin emulsion
Under 30 ℃ with 160 parts of de-salted waters, 0.35 part of Potassium Persulphate, 2.0 parts of sodium lauryl sulphate, 1.5 parts of synthetic fatty acid potassium join in the reactor, open to stir, about control rotating speed 100rpm.Then (a) joined in the reactor, improve stirring velocity, carry out emulsification to 500-700rpm.The pH value is surveyed in emulsification after 45 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 6 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 7.(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 10 hours, become pink.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 4.8%.
Calculated yield 82.1% after the white 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: 126 ℃, flame retardant properties reaches the V-2 level.
Comparative example 4: on the basis of embodiment 6, the change initiator is a Potassium Persulphate, tests.
A. the preparation of monomer mixed solution
Under 30 ℃ with 45 parts of N-tribromo phenyl maleimides, 55 parts of vinylbenzene, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of heat-proof flame-proof resin emulsion
Under 30 ℃ with 160 parts of de-salted waters, 0.35 part of Potassium Persulphate, 3.5 parts of sodium lauryl sulphate join in the reactor, open to stir, about control rotating speed 100rpm.Then (a) joined in the reactor, improve stirring velocity, carry out emulsification to 500-700rpm.The pH value is surveyed in emulsification after 34 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 4.6 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 7.(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 10 hours, become pink.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 10.8%.
Calculated yield 81.9% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=124 ℃ with the differential calorimeter.Record its vicat softening temperature: 122 ℃, flame retardant properties reaches the V-1 level.
Comparative example 5: on the basis of embodiment 11, change initiator and add, test at water.
A. the preparation of monomer mixed solution
Under 30 ℃ with 30 parts of N-tribromo phenyl maleimides, 45 parts of vinylbenzene, 25 parts of vinyl cyanide, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of heat-proof flame-proof resin emulsion
Under 30 ℃ with 160 parts of de-salted waters, 2.0 parts of sodium lauryl sulphate, 0.35 part of Diisopropyl azodicarboxylate, 5.0 parts of OP join in the reactor, open to stir (a) joined and carry out emulsification in the reactor.The pH value is surveyed in emulsification after 33 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 5 hours under 75 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (b) after qualified, and surveying the pH value is about 7.(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 10 hours, become pink.The solids that filters out is weighed after the drying through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.Under this condition, the ratio of solids that filters out and monomeric charge amount is 11.8%.
Calculated yield 78.1% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=126 ℃ with the differential calorimeter.Record its vicat softening temperature: 124 ℃, flame retardant properties reaches the V-1 level.
Comparative example 6: on the basis of embodiment 9, emulsifying agent is added oil phase, test.
A. the preparation of monomer mixed solution
Under 30 ℃ with 25 parts of N-tribromo phenyl maleimides, 50 parts of vinylbenzene, 25 parts of vinyl cyanide, 0.35 part benzoyl peroxide, 3.5 parts of sodium lauryl sulphate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, open to stir and mix, form homogeneous phase monomer mixed solution (a).
B. the preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, the unlatching stirring joins (a) carries out emulsification in the reactor under 30 ℃.The pH value is surveyed in emulsification after 42 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 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 7.(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 10 hours, become pink.The solids that filters out is weighed after the drying through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.Under this condition, the ratio of solids that filters out and monomeric charge amount is 9.8%.
Calculated yield 80.6% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=118 ℃ with the differential calorimeter.Record its vicat softening temperature: 116 ℃, flame retardant properties reaches the V-2 level.
Comparative example 7: on the basis of embodiment 9, the change initiator is an isopropyl benzene hydroperoxide, tests.
A. the preparation of monomer mixed solution
Under 30 ℃ with 25 parts of N-tribromo phenyl maleimides, 50 parts of vinylbenzene, 25 parts of vinyl cyanide, 0.35 part of isopropyl benzene hydroperoxide, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of heat-proof flame-proof resin emulsion
With 150 parts of de-salted waters, 3.5 parts of sodium lauryl sulphate join in the reactor under 30 ℃, 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 when temperature rises to 60 ℃, begins to carry out polymerization.The temperature of maintenance system was carried out polyreaction 4.2 hours under 65 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content is 3.7%, and reaction is not carried out substantially.
Comparative example 8: on the basis of embodiment 9, the change initiator is a Potassium Persulphate, tests.
A. the preparation of monomer mixed solution
Under 30 ℃ with 25 parts of N-tribromo phenyl maleimides, 50 parts of vinylbenzene, 25 parts of vinyl cyanide, 0.35 part of Potassium Persulphate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of heat-proof flame-proof resin emulsion
With 150 parts of de-salted waters, 3.5 parts of sodium lauryl sulphate join in the reactor under 30 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.The pH value is surveyed in emulsification after 35 minutes be 9～10, can heat up, and when temperature rises to 60 ℃, begins to carry out polymerization.The temperature of maintenance system was carried out polyreaction 6 hours under 65 ℃.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 7.(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 10 hours, become pink.The solids that filters out is weighed after the drying through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.Under this condition, the ratio of solids that filters out and monomeric charge amount is 7.8%.
Calculated yield 83.0% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=121 ℃ with the differential calorimeter.Record its vicat softening temperature: 119 ℃, flame retardant properties reaches the V-2 level.
Comparative example 9
A. the preparation of monomer mixed solution
Under 30 ℃ with 25 parts of N-tribromo phenyl maleimides, 50 parts of vinylbenzene, 25 parts of vinyl cyanide, 0.35 part of isopropyl benzene hydroperoxide, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of heat-proof flame-proof resin emulsion
With 150 parts of de-salted waters, 3.5 parts of sodium lauryl sulphate join in the reactor under 30 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.After the emulsification 37 minutes, can heat up, when temperature rose to 60 ℃, the reduction phase (comprising 0.05 part of ferrous sulfate, 0.35 part of glucose, 0.25 part of trisodium phosphate) that adds 0.65 part of redox initiation system began to carry out polymerization.The temperature of maintenance system was carried out polyreaction 4.8 hours under 65 ℃.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 120 hours, pink.The solids that filters out is weighed after the drying through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.Under this condition, the ratio of solids that filters out and monomeric charge amount is 3.5%.
Calculated yield 88.5% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=119 ℃ with the differential calorimeter.Record its vicat softening temperature: 116 ℃, flame retardant properties reaches the V-2 level.
Comparative example 10
A. the preparation of monomer mixed solution
Under 30 ℃ with 25 parts of N-tribromo phenyl maleimides, 50 parts of vinylbenzene, 25 parts of vinyl cyanide, 0.35 part of isopropyl benzene hydroperoxide, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of heat-proof flame-proof resin emulsion
With 150 parts of de-salted waters, 3.5 parts of sodium lauryl sulphate join in the reactor under 30 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.After the emulsification 45 minutes, can heat up begins to carry out polymerization.The temperature of maintenance system was carried out polyreaction 6 hours under 65 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content is 4%, and polyreaction is not carried out substantially.
Claims (12)
1. the preparation method of a halogen substituent maleimide heat-proof flame-proof resin emulsion is divided into two parts, is 100 mass parts in the polymerization single polymerization monomer total amount, and its composition and operational condition are:
(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); The halogen substituent maleimide monomer has following structural formula;
Rn contains the halo-alkyl of 1～15 carbon in the formula, cycloalkyl, and substituted alkyl, aryl or substituted aryl, wherein, halogens is bromine or chlorine;
(B) preparation of 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, 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 ℃, and polyreaction carries out promptly forming in 0.5～2.0 hour heat-proof flame-proof resin emulsion (b) again.
2. preparation method according to claim 1, it is characterized in that condition is in (A) step: 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, 0.05～045 part of molecular weight regulator adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
3. preparation method according to claim 1, it is characterized in that condition is in (B) step: in 25～35 ℃ with 140～180 parts of de-salted waters, 2.5～8.5 parts of emulsifying agents join in the reactor, 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, promptly formed heat-proof flame-proof resin emulsion (b).
4. preparation method according to claim 1 is characterized in that the oil soluble thermal decomposition initiating, comprises azo-initiator or organic peroxide initiator.
5. preparation method according to claim 4 is characterized in that azo-initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
6. preparation method according to claim 1 is characterized in that emulsifying agent is anion surfactant, nonionogenic tenside or their compound system.
7. preparation method according to claim 1 is characterized in that emulsifying agent is sodium lauryl sulphate, Sodium dodecylbenzene sulfonate or synthetic fatty acid potassium or their compound system.
8. preparation method according to claim 1 is characterized in that monomer each component usage ratio is: the mass ratio 10～45: 30～65: 0～30 of halogen substituent maleimide monomer and aryl ethylene class monomer and itrile group vinyl monomer.
9. preparation method according to claim 1, it is characterized in that monomer each component usage ratio is: the mass ratio of halogen substituent maleimide monomer and aryl ethylene class monomer and itrile group vinyl monomer is 15～45: 30～60: 0～25.
10. preparation method according to claim 1 is characterized in that the maleimide monomer is N-tribromo cyclohexyl maleimide or N-tribromo phenyl maleimide.
11. preparation method according to claim 1 is characterized in that aryl ethylene class monomer is vinylbenzene or Vinyl toluene.
12. preparation method according to claim 1 is characterized in that the itrile group vinyl monomer is vinyl cyanide or methacrylonitrile.
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