CN100451040C - Method for synthesizing latex of heatresistant resin in maleimide class - Google Patents
Method for synthesizing latex of heatresistant resin in maleimide class Download PDFInfo
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- CN100451040C CN100451040C CNB2005100732439A CN200510073243A CN100451040C CN 100451040 C CN100451040 C CN 100451040C CN B2005100732439 A CNB2005100732439 A CN B2005100732439A CN 200510073243 A CN200510073243 A CN 200510073243A CN 100451040 C CN100451040 C CN 100451040C
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- emulsion
- monomer
- latex
- maleimide
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Links
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229920006015 heat resistant resin Polymers 0.000 title claims description 108
- 239000004816 latex Substances 0.000 title claims description 107
- 229920000126 latex Polymers 0.000 title claims description 107
- 230000002194 synthesizing effect Effects 0.000 title abstract description 4
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 title abstract 3
- 239000000839 emulsion Substances 0.000 claims abstract description 248
- 239000000178 monomer Substances 0.000 claims abstract description 186
- 238000003756 stirring Methods 0.000 claims abstract description 110
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims description 140
- 238000004945 emulsification Methods 0.000 claims description 108
- 239000011259 mixed solution Substances 0.000 claims description 57
- 239000003643 water by type Substances 0.000 claims description 54
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 47
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 47
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 46
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 46
- 239000012752 auxiliary agent Substances 0.000 claims description 32
- 230000008569 process Effects 0.000 claims description 31
- 238000005496 tempering Methods 0.000 claims description 29
- 238000012423 maintenance Methods 0.000 claims description 28
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims description 27
- 239000012966 redox initiator Substances 0.000 claims description 27
- 238000010189 synthetic method Methods 0.000 claims description 27
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 26
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 26
- -1 aryl ethylene class Chemical class 0.000 claims description 24
- 229920002554 vinyl polymer Polymers 0.000 claims description 22
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 21
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 7
- 239000004902 Softening Agent Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 239000003795 chemical substances by application 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
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-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 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 239000003999 initiator Substances 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 76
- 239000004159 Potassium persulphate Substances 0.000 description 48
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 48
- 235000019394 potassium persulphate Nutrition 0.000 description 48
- 238000001035 drying Methods 0.000 description 42
- 238000001914 filtration Methods 0.000 description 41
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000000047 product Substances 0.000 description 30
- 230000007704 transition Effects 0.000 description 28
- 239000012071 phase Substances 0.000 description 27
- 238000005070 sampling Methods 0.000 description 26
- 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 25
- 238000005406 washing Methods 0.000 description 25
- 239000000706 filtrate Substances 0.000 description 24
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 20
- 235000014113 dietary fatty acids Nutrition 0.000 description 20
- 239000000194 fatty acid Substances 0.000 description 20
- 229930195729 fatty acid Natural products 0.000 description 20
- 150000004665 fatty acids Chemical class 0.000 description 20
- 229910052700 potassium Inorganic materials 0.000 description 20
- 239000011591 potassium Substances 0.000 description 20
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 230000002950 deficient Effects 0.000 description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 description 8
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 229920001897 terpolymer Polymers 0.000 description 5
- JCJIZBQZPSZIBI-UHFFFAOYSA-N 2-[2,6-di(propan-2-yl)phenyl]benzo[de]isoquinoline-1,3-dione Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N(C1=O)C(=O)C2=C3C1=CC=CC3=CC=C2 JCJIZBQZPSZIBI-UHFFFAOYSA-N 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000344 soap Substances 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
- NBIYKOUEZOEMMC-UHFFFAOYSA-N 1-(2-methylpropyl)pyrrole-2,5-dione Chemical compound CC(C)CN1C(=O)C=CC1=O NBIYKOUEZOEMMC-UHFFFAOYSA-N 0.000 description 1
- XAHCEMQKWSQGLQ-UHFFFAOYSA-N 1-(4-methoxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(OC)=CC=C1N1C(=O)C=CC1=O XAHCEMQKWSQGLQ-UHFFFAOYSA-N 0.000 description 1
- FPDOHAABWLBAKE-UHFFFAOYSA-N 1-bromo-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(Br)C(=O)C=C1C1=CC=CC=C1 FPDOHAABWLBAKE-UHFFFAOYSA-N 0.000 description 1
- SXTILEHINBCKSS-UHFFFAOYSA-N 1-chloro-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(Cl)C(=O)C=C1C1=CC=CC=C1 SXTILEHINBCKSS-UHFFFAOYSA-N 0.000 description 1
- BAWHYOHVWHQWFQ-UHFFFAOYSA-N 1-naphthalen-1-ylpyrrole-2,5-dione Chemical class O=C1C=CC(=O)N1C1=CC=CC2=CC=CC=C12 BAWHYOHVWHQWFQ-UHFFFAOYSA-N 0.000 description 1
- PSKLSRMDQQEEGQ-UHFFFAOYSA-N 1-nitro-3-phenylpyrrole-2,5-dione Chemical compound O=C1N([N+](=O)[O-])C(=O)C=C1C1=CC=CC=C1 PSKLSRMDQQEEGQ-UHFFFAOYSA-N 0.000 description 1
- YEKDUBMGZZTUDY-UHFFFAOYSA-N 1-tert-butylpyrrole-2,5-dione Chemical compound CC(C)(C)N1C(=O)C=CC1=O YEKDUBMGZZTUDY-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical class C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- WAXBZQUSTLNLPU-UHFFFAOYSA-N 2,5-dioxo-3-phenylpyrrole-1-carboxylic acid Chemical compound O=C1N(C(=O)O)C(=O)C=C1C1=CC=CC=C1 WAXBZQUSTLNLPU-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 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
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- KUDZDMBYZGVFJJ-UHFFFAOYSA-N NCN1C(C(=CC1=O)C1=CC=CC=C1)=O Chemical compound NCN1C(C(=CC1=O)C1=CC=CC=C1)=O KUDZDMBYZGVFJJ-UHFFFAOYSA-N 0.000 description 1
- 229920007019 PC/ABS Polymers 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
- JTUOMQJVPHRJHA-UHFFFAOYSA-N [C].C(CCCCCCCCCCC)S Chemical compound [C].C(CCCCCCCCCCC)S JTUOMQJVPHRJHA-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000003945 anionic surfactant 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
- 230000015572 biosynthetic process Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease 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
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920000642 polymer 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
- 229940114930 potassium stearate Drugs 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
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 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
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 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
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a method for synthesizing the emulsion of heat resisting resin in the class of maleimide. The method comprises four parts and operating conditions: an emulsifying agent, part of monomers in the class of arylethylene, monomers in the class of nitrilethylene, initiator, etc. are added in a stirring reactor for emulsifying into primary emulsion (a); monomers in the class of maleimide, the rest of monomers in the class of arylethylene, monomers in the class of nitrilethylene, etc. are added in a mixing tank for forming a monomer mixed liquor (b) of a homogeneous phase; desalted water, initiator, an emulsifying agent and the (b) are added in an emulsifier for emulsifying into monomer emulsion (c); after the (a) is formed, the (c) is added in the reactor and is mixed with the (a) for polyreaction. The obtained emulsion of heat resisting resin has the advantages of good appearance, uniform composition and structure, high heat resisting performance and high yield in a polymerization process; the obtained emulsion can be widely used in heat resisting and modifying aspects of materials such as ABS, PC, PBT, etc. The obtained emulsion can be used for making components and parts with high heat resisting performance of automobiles and household appliances when singly used.
Description
Technical field
The present invention relates to a kind of preparation method's of macromolecule emulsion, particularly a kind of latex of heat-resistant resin in maleimide class synthetic method.
Background technology
The monomeric free-radical polymerized thing of 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, thereby be subjected to extensive concern.Wherein also a lot of about the research of maleimide monomer and the monomeric multipolymer of aryl ethylene class.
The preparation of superelevation heat-resisting 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.Alloyage mainly is meant the PC/ABS alloy.The modification by copolymerization method mainly is made up of two portions technology, what a part was a maleimide (IMID) with the monomeric terpolymer of 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 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 SMIA then can be adopted various polymerization processs such as body, suspension, emulsion and solution polymerization.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 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 oil-soluble initiator, 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, employing be used water soluble starter of typical letex polymerization or redox initiation system.
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 synthetic method of latex of heat-resistant resin in maleimide class, is a kind of maleimide monomer and aryl ethylene class monomer and or synthetic method of the latex of heatresistant resin of itrile group vinyl monomer of preparing specifically.
The synthetic method of latex of heat-resistant resin in maleimide class of the present invention is divided into four parts.Usually the composition and the operational condition of these four parts are as follows: (being 100 mass parts in the polymerization single polymerization monomer total amount, as follows)
(A) preparation of elementary emulsion
In being housed, the reactor of stirring adds 5～100 parts of de-salted waters under 25～35 ℃, 0.05～1.0 parts of emulsifying agents, 0～1.5 part of aryl ethylene class monomer, 0.5～2.5 parts of itrile group vinyl monomers, 0～0.15 part of molecular weight regulator, 0.05 the oxygenant of～0.4 part of persulphate or 0.01～0.07 part of redox initiation system, open to stir and carry out emulsification, after the emulsification 10～75 minutes, make in 20～75 minutes that the water temperature rises to 65～90 ℃ in the reactor, when using redox initiation system, the reduction that adds 0.5～0.75 part of redox initiation system again reaches 10 parts of water mutually, keep constant temperature, kept 5～30 minutes, and promptly formed elementary emulsion (a);
Optimum condition is: add 10～50 parts of de-salted waters under 25～35 ℃ in the reactor of whipping appts is housed, 0.2～0.8 part of emulsifying agent, 0～1.5 part of aryl ethylene class monomer, 0.5～1.0 parts of itrile group vinyl monomers, 0.01～0.05 part of molecular weight regulator, 0.1 the oxygenant of～0.3 part of persulphate or 0.01～0.07 part of redox initiation system, open to stir and carry out emulsification, after the emulsification 20～45 minutes, make in 30～45 minutes that the water temperature rises to 70～80 ℃ in the reactor, the reduction that adds 0.5～0.75 part of redox initiation system when using redox initiation system again reaches 10 parts of water mutually, keep constant temperature, kept 10～20 minutes, and promptly formed elementary emulsion (a).
(B) preparation of monomer mixed solution
Under 25～35 ℃ with 10～45 parts of maleimide monomers, 30～65 parts of aryl ethylene class monomers, 0.5～30 parts of itrile group vinyl monomers, 0.01～0.65 part of molecular weight regulator or and the oxygenant of 0.1～0.4 part of redox initiation system add tempering tank, open to stir and mix, form homogeneous phase monomer mixed solution (b).
Optimum condition is: under 25～35 ℃ with 15～45 parts of maleimide monomers, 35～60 parts of aryl ethylene class monomers, 0.5～25 parts of itrile group vinyl monomers, 0.05～0.45 part of molecular weight regulator or and the oxygenant of 0.15～0.3 part of redox initiation system add tempering tank, open to stir and mix, form homogeneous phase monomer mixed solution (b).
(C) preparation of monomer emulsion
Under 25～35 ℃ with 80～150 parts of de-salted waters, 0～0.65 part of persulphate, 2.0～3.5 parts of emulsifying agents join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 20～75 minutes monomer emulsion (c).
Optimum condition is: under 25～35 ℃ with 100～130 parts of de-salted waters, 0.15～0.45 part of persulphate, 2.5～2.7 parts of emulsifying agents join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).
(D) preparation of latex of heatresistant resin
(a) form good after, within 3～8 hours, (c) joined in batches or continuously in the reactor and to mix also the temperature of maintenance system with (a) and under 55～95 ℃, carry out polyreaction.(c) add after, polyreaction was carried out 0.5～2.0 hour again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.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 and de-salted water in emulsifying tank, and the mode with emulsion after copolyreaction finishes adds.
Optimum condition is: (a) form good after, within 4～6 hours, (c) joined continuously in the reactor and to mix also the temperature of maintenance system with (a) and under 70～85 ℃, carry out polyreaction.(c) add after, polyreaction was carried out 0.5～1.5 hour again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.Can also finish the emulsion that the back adds auxiliary agent in the polymerization of (d), finish all processes of preparation (d).
During preparation (a) in the present invention, must add a spot of itrile group vinyl monomer or and aryl ethylene class monomer, add emulsifying agent, do not add the itrile group vinyl monomer or add the stability decreases that the maleimide monomer can cause the emulsion reaction system, form elementary emulsion, just must add a certain amount of emulsifying agent, initiator, otherwise just can not form the emulsion at initial stage, and, the consumption of these components also must be within certain scope, very little, the active centre of elementary emulsion very little, or the speed of response of the monomer emulsion of its adding is not enough; Too much, it is too big that monomer is formed influence, can produce detrimentally affect to the performance of product.Because persulfate initiator is water miscible, can only add at aqueous phase; Redox initiation system comprises two portions-oxygenant and reduces mutually that oxygenant is an oil soluble, can only add in the monomer, and reduction is water-soluble mutually, can only add when preparation (a).Heat-up rate, thermostat temperature, constant temperature are held time also extremely importantly in the test conditions, will directly have influence on stability of emulsion, if test conditions exceeds suitable scope, even have relatively large polymer formation gel and separate out from emulsion system.
Because the solubleness of NPMI in the ST/AN mixed solution is limited, after the NPMI formula ratio reaches certain umber, temperature is lower than 25 ℃, NPMI 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.
In (D) step, monomer emulsion (c) can be added in 3～8 hours in the reactor in batches and mix with (a) in the present invention, as adding 2%～7% (c) every 5～20 minutes.
Used initiator is the used initiator of general free-radical emulsion polymerization in the synthetic method of latex of heat-resistant resin in maleimide class of the present invention, comprises persulfuric acid salt, redox initiation system.Persulfuric acid salt initiator adds at twice in the present invention, if do not add the part initiator when preparation (a), then can not form enough initiation centers, and polyreaction will can not finished smoothly; If do not add the part initiator when (c) then polymerization rate can reduce in preparation, the monomeric hydrolysis reaction of NPMI can occupy advantage, thereby the stability of the system of destruction influences the color and luster of product; When adopting redox initiation system, must add the partial oxidation agent when preparation (b), reductive agent then once adds when preparation (a), otherwise emulsion polymerization will when preparation (c) abnormal conditions of implode when appearing at preparation (c) take place.The object lesson of initiator has: Potassium Persulphate, and ammonium persulphate, the redox initiation system that organo-peroxide and ferrous salt are formed, owing to be general general type, just no longer for example many.Wherein preferred Potassium Persulphate or isopropyl benzene hydroperoxide-ferrous sulfate redox initiation system.
Normal temperature can carry out the preparation of homogeneous monomer mixed solution, the preparation of monomer emulsion, the preparation of elementary emulsion respectively down among the present invention, can shorten the production cycle like this, remedies the low shortcoming of plant factor.
The maleimide monomer that synthetic method adopted of latex of heat-resistant resin in maleimide class of the present invention has following structure:
(Rn is hydrogen or the alkyl that contains 1-15 carbon in the formula, cycloalkyl, substituted alkyl, aryl, substituted aryl)
Concrete example has: N-methyl maleimide, maleimide, the N-ethyl maleimide, N-tertiary butyl maleimide, N-isobutyl-maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, N-chlorophenyl maleimide, N-aminomethyl phenyl maleimide, N-bromo phenyl maleimide, N-p-methoxy-phenyl maleimide, N-carboxyl phenyl maleimide, N-nitrophenyl maleimide, N-naphthyl maleimides etc., these maleimide monomers can be used alone or in combination.Wherein preferred N-cyclohexyl maleimide and N-phenylmaleimide.
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, 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.
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. one or more.
The emulsifying agent that the present invention uses, mainly contain that anion surfactant is single or composite, 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 OP.
The molecular weight regulator that the present invention uses is not particularly limited, as being general tert-dodecyl mercaptan, dodecyl mercaptan carbon etc.
Among the present invention in emulsion used auxiliary agent can be softening agent, thermo-stabilizer etc., be employed softening agent, thermo-stabilizer in the general plastic working process, different is the present invention can be mixed with softening agent, thermo-stabilizer, emulsifying agent and de-salted water auxiliary agent in emulsifying tank emulsion, mode with emulsion after copolyreaction finishes adds, make their degrees of scatter in polymkeric substance more even, thereby better effects if, so illustrated in greater detail no longer just.
In the synthetic method of latex of heat-resistant resin in maleimide class of the present invention, the amount ranges of each monomer component of recommendation is as follows:
Monomer ratio: the mass ratio of maleimide monomer and aryl ethylene class monomer and itrile group vinyl monomer is adjusted in 10～45/30～66.5/1～32.5, and preferable range is 15～45/35～61.5/1～26.
The consumption of emulsifying agent, initiator, water, softening agent, thermo-stabilizer, molecular weight regulator is identical with general letex polymerization, is conventional amount used, no longer describes in detail.
The characteristics of the synthetic method of latex of heat-resistant resin in maleimide class 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 50～100 ℃, between preferred 60～90 ℃ 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 for 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.
3. feed way: the synthetic method of latex of heat-resistant resin in maleimide class of the present invention, monomer emulsion can add reactor in batches also can add reactor continuously, also can add a part earlier, adds remainder behind the reaction certain hour continuously.Batch charging or add a part of reaction certain hour earlier after during continuous charging, the influence that form multipolymer the pitch time between batch is bigger.Feed way with continuous charging for well.
The synthetic method of latex of heat-resistant resin in maleimide class of the present invention, problems such as the instability, pH that has thoroughly solved emulsion 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.After polymerization finished, latex of heatresistant resin can obtain the heat-resistant resin in maleimide class product through cohesion, washing drying.
Synthetic method with latex of heat-resistant resin in maleimide class of the present invention, it is good that the multipolymer of the maleimide monomer that makes, aryl ethylene class monomer and itrile group vinyl monomer has outward appearance, form and the structure homogeneous, the thermal stability height, the advantage that the polymerization process yield is high, be the good heat resistance modified material of a kind of performance, can be widely used in heat resistance modified aspect materials such as ABS, PC, PBT.As a kind of material of fine heat-resisting performance, its independent use also can be used for preparing automobile, the high heat-stable component of household electrical appliances.
Embodiment
Second-order transition temperature Tg:DSC-differential thermal differential method
Vicat softening temperature: GB/T 1633-2000
The solids that emulsion filtered out after resin emulsion stability finished with reaction and the ratio magnitude of total monomer charging capacity are weighed.
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.
Embodiment 1:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 0.7 part of vinylbenzene, 0.3 part of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 44 parts of vinylbenzene, and 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 (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 2.7 parts of sodium lauryl sulphate join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content, qualified back (〉=37%, as follows) promptly forms latex of heatresistant resin (d).(d) after polymerization finished, measuring its pH was about 8.
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 latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, as the foundation of emulsion reaction system stability (＜1.0% is qualified 〉).Under this condition, the ratio of solids that filters out and monomeric charge amount is 0.75%.
Calculated yield 95.4% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=146 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 152 ℃.
Embodiment 2:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.15 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 44 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.15 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 8, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, as the foundation of emulsion reaction system stability (＜1.0% is qualified 〉).Under this condition, the ratio of solids that filters out and monomeric charge amount is 0.67%.
Calculated yield 96.3% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=145 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 152 ℃.
Embodiment 3:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 0.7 part of vinylbenzene, 2.3 parts of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-cyclohexyl maleimides, 44 parts of vinylbenzene, and 23 parts of vinyl cyanide, 0.12 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 8, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, as the foundation of emulsion reaction system stability (＜1.0% is qualified 〉).Under this condition, the ratio of solids that filters out and monomeric charge amount is 0.88%.
Calculated yield 95.1% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=144 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 150 ℃.
Embodiment 4:
A. the preparation of elementary emulsion
32 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 0.7 part of vinyl toluene, 0.3 part of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
32 ℃ with 30 parts of N-phenylmaleimides, 44 parts of vinyl toluenes, and 25 parts of vinyl cyanide, 0.13 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
32 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 8, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, as the foundation of emulsion reaction system stability (＜1.0% is qualified 〉).Under this condition, the ratio of solids that filters out and monomeric charge amount is 0.68%.
Calculated yield 96.1% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=147 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 153 ℃.
Embodiment 5:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.2 parts of vinylbenzene, 0.8 part of methacrylonitrile, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 80 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 44 parts of vinylbenzene, and 24 parts of methacrylonitriles, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 8, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, as the foundation of emulsion reaction system stability (＜1.0% is qualified 〉)., under this condition, the ratio of solids that filters out and monomeric charge amount is 0.59%.
Calculated yield 96.5% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=149 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 153 ℃.
Embodiment 6:
A. the preparation of elementary emulsion
28 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinylbenzene, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 85 ℃ in the reactor, keep constant temperature, kept 5 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
28 ℃ with 45 parts of N-phenylmaleimides, 54 parts of vinylbenzene, and 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
28 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 8, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, as the foundation of emulsion reaction system stability (＜1.0% is qualified 〉).Under this condition, the ratio of solids that filters out and monomeric charge amount is 0.78%.
Calculated yield 95.1% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=177 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 165 ℃.
Embodiment 7:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-phenylmaleimides, 49 parts of vinylbenzene, and 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 (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 8, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, as the foundation of emulsion reaction system stability (＜1.0% is qualified 〉).Under this condition, the ratio of solids that filters out and monomeric charge amount is 0.95%.
Calculated yield 96.5% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=133 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 137 ℃.
Embodiment 8:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 75 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 10 parts of N-phenylmaleimides, 65 parts of vinylbenzene, and 24 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 (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 8, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, as the foundation of emulsion reaction system stability (＜1.0% is qualified 〉).Under this condition, the ratio of solids that filters out and monomeric charge amount is 0.85%.
Calculated yield 96.5% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=115 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 112 ℃.
Embodiment 9:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 35 parts of N-phenylmaleimides, 40 parts of vinylbenzene, and 24 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 (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 8, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, as the foundation of emulsion reaction system stability (＜1.0% is qualified 〉).Under this condition, the ratio of solids that filters out and monomeric charge amount is 0.67%.
Calculated yield 96.7% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=158 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 155 ℃.
Embodiment 10:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 44 parts of vinylbenzene, and 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 (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined in the reactor in batches and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added 2% of total amount every 5 minutes, and it was added within 4.0～4.5 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 8, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, as the foundation of emulsion reaction system stability (＜1.0% is qualified 〉).Under this condition, the ratio of solids that filters out and monomeric charge amount is 0.65%.
Calculated yield 96.0% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=145 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 151 ℃.
Embodiment 11:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 44 parts of vinylbenzene, and 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 (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined in the reactor in batches and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added 4% of total amount every 10 minutes, and it was added within 4.0～4.5 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 8, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, as the foundation of emulsion reaction system stability (＜1.0% is qualified 〉).Under this condition, the ratio of solids that filters out and monomeric charge amount is 0.58%.
Calculated yield 95.1% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=145 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 151 ℃.
Embodiment 12:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part sodium lauryl sulphate, be dissolved with 1.0 parts of vinyl cyanide of 0.05 part of isopropyl benzene hydroperoxide, after the emulsification 30 minutes, the temperature of heat transferring medium rises to 70 ℃, make in 30 minutes that the water temperature rises to 70 ℃ in the reactor, keep constant temperature, the reduction phase that adds 0.65 part of redox initiation system (comprises 0.05 part of ferrous sulfate, 0.35 part glucose, 0.25 part trisodium phosphate and 10 parts of water), kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 44 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.1 part of tert-dodecyl mercaptan, 0.2 part of isopropyl benzene hydroperoxide adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 75 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 8, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, as the foundation of emulsion reaction system stability (＜1.0% is qualified 〉).Under this condition, the ratio of solids that filters out and monomeric charge amount is 0.65%.
Calculated yield 96.1% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=144 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 150 ℃.
Embodiment 13:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of Sodium dodecylbenzene sulfonate, and 1.0 parts of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 44 parts of vinylbenzene, and 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 (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of Sodium dodecylbenzene sulfonatees and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 8, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, as the foundation of emulsion reaction system stability (＜1.0% is qualified 〉).Under this condition, the ratio of solids that filters out and monomeric charge amount is 0.53%.
Calculated yield 96.5% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=145 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 151 ℃.
Embodiment 14:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 44 parts of vinylbenzene, and 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 (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 2.0 parts of sodium lauryl sulphate and 5.0 parts of OP join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined in the reactor in batches and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added 4% of total amount every 10 minutes, and it was added within 4.0～4.5 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 8, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, as the foundation of emulsion reaction system stability (＜1.0% is qualified 〉).Under this condition, the ratio of solids that filters out and monomeric charge amount is 0.58%.
Calculated yield 96.1% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=143 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 147 ℃.
Embodiment 15:
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 0.7 part of vinylbenzene, 0.3 part of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 44 parts of vinylbenzene, and 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 (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 2.7 parts of sodium lauryl sulphate join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).Measuring its pH is 9～10.
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content, qualified back (〉=37%, as follows) promptly forms latex of heatresistant resin (d).(d) after polymerization finished, measuring its pH was about 8.
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 latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, as the foundation of emulsion reaction system stability (＜1.0% is qualified 〉).Under this condition, the ratio of solids that filters out and monomeric charge amount is 0.65%.
Calculated yield 95.6% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=145 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 151 ℃.
Comparative example 1: on the basis of embodiment 1, remove the configuration section of elementary emulsion, test.
A. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 44 parts of vinylbenzene, and 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 (b).
B. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 3.0 parts of sodium lauryl sulphate join in the emulsor (b) joined carries out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).Measuring its pH is 9～10.
C. the preparation of latex of heatresistant resin
Add 30 parts of water in the reactor, treat that its temperature rises to after 79 ℃, immediately (c) joined continuously equably in the reactor also the temperature of maintenance system and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 7, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, as the foundation of emulsion reaction system stability (＜1.0% is qualified 〉).Under this condition, the ratio of solids that filters out and monomeric charge amount is 3.5%, and is defective.
Calculated yield 90.4% after the pink product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=140 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 147 ℃.
Comparative example 2: on the basis of embodiment 1, remove configuration and monomer mixed solution emulsification two portions of elementary emulsion, test.
A. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 44 parts of vinylbenzene, and 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 (b).
B. the preparation of latex of heatresistant resin
30 ℃ with 160 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 3.0 parts of sodium lauryl sulphate join in the reactor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion.Measuring its pH is 9～10.The temperature of maintenance system is carried out polyreaction under 65 ℃, after reacting 4.5～5.0 hours, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) after polymerization finished, measuring its pH was about 7, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate pink latex of heatresistant resin product.The solids that filters out is weighed after the drying through washing, as the foundation of emulsion reaction system stability (＜1.0% is qualified 〉).Under this condition, the ratio of solids that filters out and monomeric charge amount is 2.8%, and is defective.
Calculated yield 92.1% after the pink product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=147 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 153 ℃.
Comparative example 3: on the basis of embodiment 7, accelerate elementary emulsion heat-up rate, test.
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 10 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-phenylmaleimides, 49 parts of vinylbenzene, and 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 (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, and as the foundation of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 3.5%, and be defective.
Emulsion is calculated yield 92.5% after the product that makes after the cohesion is weighed.Get second-order transition temperature Tg=133 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 137 ℃.
Comparative example 4: on the basis of embodiment 7, the elementary emulsion heat-up rate that slows down is tested.
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 80 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-phenylmaleimides, 49 parts of vinylbenzene, and 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 (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open and stir, about control rotating speed 100rpm.Then (b) joined in the emulsor, improve stirring velocity, carry out emulsification to 400-500rpm.Emulsification 30～45 minutes monomer emulsion (c).
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, and as the foundation of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 2.5%, and be defective.
Emulsion is calculated yield 92.7% after the product that makes after the cohesion is weighed.Get second-order transition temperature Tg=133 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 137 ℃.
Comparative example 5: on the basis of embodiment 7, prolong elementary emulsion constant temperature time, test.
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 60 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-phenylmaleimides, 49 parts of vinylbenzene, and 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 (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, and as the foundation of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 4.3%, and be defective.
Emulsion is calculated yield 91.5% after the product that makes after the cohesion is weighed.Get second-order transition temperature Tg=133 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 137 ℃.
Comparative example 6: on the basis of embodiment 7, shorten elementary emulsion constant temperature time, test.
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 2 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-phenylmaleimides, 49 parts of vinylbenzene, and 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 (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, and as the foundation of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 6.3%, and be defective.
Emulsion is calculated yield 88.5% after the product that makes after the cohesion is weighed.Get second-order transition temperature Tg=133 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 137 ℃.
Comparative example 7: on the basis of embodiment 7, shorten the reinforced time of (c), test.
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 78 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-phenylmaleimides, 49 parts of vinylbenzene, and 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 (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 2.0～2.5 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, and as the foundation of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 3.5%, and be defective.
Emulsion is calculated yield 90.5% after the product that makes after the cohesion is weighed.Get second-order transition temperature Tg=133 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 137 ℃.
Comparative example 8: on the basis of embodiment 7, improve elementary emulsion thermostat temperature, test
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 95 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-phenylmaleimides, 49 parts of vinylbenzene, and 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 (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, and as the foundation of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 3.7% defective.
Emulsion is calculated yield 91.5% after the product that makes after the cohesion is weighed.Get second-order transition temperature Tg=133 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 137 ℃.
Comparative example 9: on the basis of embodiment 7, reduce the thermostat temperature of elementary emulsion, test
A. the preparation of elementary emulsion
30 ℃ add 30 parts of de-salted waters in the reactor of stirring is housed, 0.3 part of sodium lauryl sulphate, and 1.0 parts of vinyl cyanide, 0.1 part of Potassium Persulphate is opened to stir and is carried out emulsification.After the emulsification 30 minutes, make in 30 minutes that the water temperature rises to 60 ℃ in the reactor, keep constant temperature, kept 10 minutes, promptly form elementary emulsion (a).
B. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-phenylmaleimides, 49 parts of vinylbenzene, and 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 (b).
C. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, 0.35 part of Potassium Persulphate, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (c).
D. the preparation of latex of heatresistant resin
(a) form good after, immediately (c) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (c) added it within 4.5～5.0 hours.(c) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (d) after qualified.(d) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (d).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin.The solids that filters out is weighed after the drying through washing, and as the foundation of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 4.7%, and be defective.
Emulsion is calculated yield 91.5% after the product that makes after the cohesion is weighed.Get second-order transition temperature Tg=133 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 137 ℃.
Claims (15)
1. the synthetic method of a latex of heat-resistant resin in maleimide class is divided into four parts, is 100 mass parts in the polymerization single polymerization monomer total amount, and its composition and operational condition are:
(A) preparation of elementary emulsion
In being housed, the reactor of stirring adds 5～100 parts of de-salted waters under 25～35 ℃, 0.05～1.0 parts of emulsifying agents, 0～1.5 part of aryl ethylene class monomer, 0.5～2.5 parts of itrile group vinyl monomers, 0～0.15 part of molecular weight regulator, 0.05 the oxygenant of～0.4 part of persulphate or 0.01～0.07 part of redox initiation system, open to stir and carry out emulsification, after the emulsification 10～75 minutes, make in 20～75 minutes that the water temperature rises to 65～90 ℃ in the reactor, keep constant temperature, when using redox initiation system, the reduction that adds 0.5～0.75 part of redox initiation system again reaches 10 parts of water mutually, kept 5～30 minutes, and promptly formed elementary emulsion (a);
(B) preparation of monomer mixed solution
Under 25～35 ℃ with 10～45 parts of maleimide monomers, 30～65 parts of aryl ethylene class monomers, 0.5～30 parts of itrile group vinyl monomers, 0.01～0.65 part of molecular weight regulator adds tempering tank, the oxygenant that adds 0.1～0.4 part of redox initiation system when using redox initiation system again, open to stir and mix, form homogeneous phase monomer mixed solution (b);
(C) preparation of monomer emulsion
Under 25～35 ℃ with 80～150 parts of de-salted waters, 0～0.65 part of persulphate, 2.0～3.5 parts of emulsifying agents join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor, emulsification 20～75 minutes monomer emulsion (c);
(D) preparation of latex of heatresistant resin
(c) joined in the reactor in batches or continuously, it was added within 3～8 hours, mix with (a) and the temperature of maintenance system is carried out polyreaction under 55～95 ℃ again, polymerase 10 .5～2.0 hour promptly form latex of heatresistant resin (d).
2. the synthetic method of latex of heat-resistant resin in maleimide class according to claim 1, it is characterized in that (A) step condition is: in the reactor of whipping appts is housed, add 10～50 parts of de-salted waters under 25～35 ℃, 0.2～0.8 part of emulsifying agent, 0～1.5 part of aryl ethylene class monomer, 0.5～1.0 parts of itrile group vinyl monomers, 0.01～0.05 part of molecular weight regulator, 0.1 the oxygenant of～0.3 part of persulphate or 0.01～0.07 part of redox initiation system, open to stir and carry out emulsification, after the emulsification 20～45 minutes, make in 30～45 minutes that the water temperature rises to 70～80 ℃ in the reactor, keep constant temperature, when using redox initiation system, the reduction that adds 0.5～0.75 part of redox initiation system again reaches 10 parts of water mutually, kept 10～20 minutes, and promptly formed elementary emulsion (a).
3. the synthetic method of latex of heat-resistant resin in maleimide class according to claim 1 and 2 is characterized in that the reduction of redox initiation system comprises reductive agent mutually, helps reductive agent, complexing agent.
4. the synthetic method of latex of heat-resistant resin in maleimide class according to claim 1, it is characterized in that (B) step condition is: under 25～35 ℃ with 15～45 parts of maleimide monomers, 35～60 parts of aryl ethylene class monomers, 0.5～25 parts of itrile group vinyl monomers, 0.05～0.45 part of molecular weight regulator adds tempering tank, the oxygenant that adds 0.15～0.3 part of redox initiation system when using redox initiation system again, open to stir and mix, form homogeneous phase monomer mixed solution (b).
5. the synthetic method of latex of heat-resistant resin in maleimide class according to claim 1, it is characterized in that (C) step condition is: under 25～35 ℃ with 100～130 parts of de-salted waters, 0.15～0.45 part of persulphate, 2.5～2.7 parts of emulsifying agents join in the emulsor, open to stir (b) joined and carry out emulsification in the emulsor, emulsification 30～45 minutes monomer emulsion (c).
6. the synthetic method of latex of heat-resistant resin in maleimide class according to claim 1, it is characterized in that (D) step condition is: after (a) forming well, join in the reactor continuously with (c), it was added within 4～6 hours, mix with (a) and the temperature of maintenance system is carried out polyreaction under 70～85 ℃, polymerase 10 .5～1.5 hour promptly form latex of heatresistant resin (d) again.
7. the synthetic method of latex of heat-resistant resin in maleimide class according to claim 1 is characterized in that in (D) step, adds the emulsion of auxiliary agent after the polymerization of (d) finishes, and finishes all processes of preparation (d).
8. the synthetic method of latex of heat-resistant resin in maleimide class according to claim 7, it is characterized in that in (D) step, finish the emulsion that the back adds auxiliary agent in the polymerization of (d), be meant softening agent, thermo-stabilizer and emulsifying agent, de-salted water formulated emulsion in emulsifying tank.
9. the synthetic method of latex of heat-resistant resin in maleimide class according to claim 1 is characterized in that maleimide monomer is N-cyclohexyl maleimide, N-phenylmaleimide.
10. the synthetic method of latex of heat-resistant resin in maleimide class according to claim 1 is characterized in that aryl ethylene class monomer is vinylbenzene, Vinyl toluene.
11. the synthetic method of latex of heat-resistant resin in maleimide class according to claim 1 is characterized in that the itrile group vinyl monomer is vinyl cyanide, methacrylonitrile.
12. the synthetic method of latex of heat-resistant resin in maleimide class according to claim 1, it is characterized in that emulsifying agent be among sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, the OP one or more.
13. the synthetic method of latex of heat-resistant resin in maleimide class according to claim 1, the mass ratio that it is characterized in that maleimide monomer and aryl ethylene class monomer and itrile group vinyl monomer is 10～45/30～66.5/1～32.5.
14. the synthetic method of latex of heat-resistant resin in maleimide class according to claim 13, the mass ratio that it is characterized in that maleimide monomer and aryl ethylene class monomer and itrile group vinyl monomer is 15～45/35～61.5/1～26.
15. the synthetic method of latex of heat-resistant resin in maleimide class according to claim 1 is characterized in that monomer emulsion (c) mixed with (a) to reactor every (c) of adding 2%～7% in 5～20 minutes in (D) step in 3～8 hours in batches.
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| CN101503556B (en) * | 2008-02-04 | 2012-03-07 | 中国石油天然气股份有限公司 | Heat resisting flame retardant resin composition with improved glossiness and preparation thereof |
| CN101503549B (en) * | 2008-02-04 | 2012-03-07 | 中国石油天然气股份有限公司 | Maleimide heat resisting flame retardant resin composition containing halogen substituent and preparation |
| CN108264602B (en) * | 2018-01-05 | 2021-03-02 | 长春工业大学 | Terpolymer and preparation method and application thereof |
| CN108285589A (en) * | 2018-01-05 | 2018-07-17 | 长春工业大学 | A kind of high heat-resisting ABS resin and preparation method thereof |
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