CN101139417B - Preparation method of maleimide heat-resistant resin emulsion - Google Patents
Preparation method of maleimide heat-resistant resin emulsion Download PDFInfo
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- CN101139417B CN101139417B CN200610112844A CN200610112844A CN101139417B CN 101139417 B CN101139417 B CN 101139417B CN 200610112844 A CN200610112844 A CN 200610112844A CN 200610112844 A CN200610112844 A CN 200610112844A CN 101139417 B CN101139417 B CN 101139417B
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- 239000000839 emulsion Substances 0.000 title claims abstract description 172
- 238000002360 preparation method Methods 0.000 title claims abstract description 111
- 229920006015 heat resistant resin Polymers 0.000 title claims abstract description 83
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 154
- 238000003756 stirring Methods 0.000 claims abstract description 51
- 239000011259 mixed solution Substances 0.000 claims abstract description 47
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 40
- -1 aryl ethylene Chemical compound 0.000 claims abstract description 19
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000004816 latex Substances 0.000 claims description 78
- 229920000126 latex Polymers 0.000 claims description 78
- 238000004945 emulsification Methods 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 37
- 239000012752 auxiliary agent Substances 0.000 claims description 28
- 239000003643 water by type Substances 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 24
- 238000005496 tempering Methods 0.000 claims description 24
- 238000012423 maintenance Methods 0.000 claims description 23
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 21
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 21
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 21
- 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 20
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 20
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 20
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 16
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 16
- 239000000194 fatty acid Substances 0.000 claims description 16
- 229930195729 fatty acid Natural products 0.000 claims description 16
- 150000004665 fatty acids Chemical class 0.000 claims description 16
- 239000011591 potassium Substances 0.000 claims description 16
- 229910052700 potassium Inorganic materials 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 15
- 230000000977 initiatory effect Effects 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 claims description 5
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 4
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 239000012934 organic peroxide initiator 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 28
- 230000001804 emulsifying effect Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 150000002825 nitriles Chemical class 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 59
- 238000001035 drying Methods 0.000 description 33
- 238000001914 filtration Methods 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 29
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 28
- 239000000047 product Substances 0.000 description 23
- 230000007704 transition Effects 0.000 description 22
- 238000005070 sampling Methods 0.000 description 21
- 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 19
- 238000005406 washing Methods 0.000 description 19
- 239000000706 filtrate Substances 0.000 description 18
- 238000007720 emulsion polymerization reaction Methods 0.000 description 7
- 239000004902 Softening Agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 229920001897 terpolymer Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229940072033 potash Drugs 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- JTUOMQJVPHRJHA-UHFFFAOYSA-N [C].C(CCCCCCCCCCC)S Chemical compound [C].C(CCCCCCCCCCC)S JTUOMQJVPHRJHA-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 229940114930 potassium stearate Drugs 0.000 description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000012966 redox initiator 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
- 230000002194 synthesizing effect Effects 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
- BAWHYOHVWHQWFQ-UHFFFAOYSA-N 1-naphthalen-1-ylpyrrole-2,5-dione Chemical compound 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- 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
- 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
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 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
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 235000019359 magnesium stearate Nutrition 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
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 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
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 description 1
- 238000010526 radical polymerization reaction Methods 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
- 230000004044 response Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002002 slurry 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
- 238000010189 synthetic method Methods 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
- 239000010913 used oil Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
A preparation method of maleimide heat-resistant resin emulsion comprises adding maleimide monomer, aryl ethylene monomer, nitrile ethylene monomer, oil-soluble thermal decomposition initiator, etc. into a mixing tank, stirring, and mixing to obtain homogeneous monomer mixed solution ; adding an emulsifier and the like into an emulsifier, stirring, adding the into the emulsifier, and emulsifying to form a monomer emulsion (b); and adding desalted water into the reactor, and adding the desalted water into the reactor to perform polymerization reaction at 60-90 ℃ to form the heat-resistant resin emulsion (c). The obtained heat-resistant resin emulsion has the advantages of good appearance, uniform composition and structure, high heat resistance and high yield in the polymerization process, can be widely used for heat-resistant modification of ABS, PC, PBT and other materials, and can be used alone for preparing high heat-resistant parts of automobiles and household appliances.
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 preparation 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 the oil soluble thermal decomposition initiating, as azo-initiator.What GB1086673 and GB1213061 introduced is that what it adopted is water soluble starter with the method for the multipolymer of emulsion polymerization prepared maleimide and vinylbenzene etc.In " polymer material science and engineering " 2001 (17) .1, reported in " second-order transition temperature of St-AN-PMI emulsion copolymers and the rheological " that people such as Liu Guodong deliver and described its general emulsion polymerisation process, promptly adopt emulsifying agent, and be the polymerization process of initiator with the persulphate.
US4757109 has described a kind of technology with emulsion polymerisation process synthesizing styrene, vinyl cyanide, maleimide terpolymer, employing has the anionic emulsifier of well emulsify ability in pH value is 3～9 scopes, initiator adopts redox system or Diisopropyl azodicarboxylate initiator, when this patent is pointed out with the Diisopropyl azodicarboxylate initiator, speed of response is slower, its polymerization technique is fairly simple, does not discuss in view of polymerization process.KR9510550 has also introduced a kind of technology that adopts method of emulsion polymerization synthesizing styrene, vinyl cyanide, maleimide terpolymer, what adopt is used water soluble starter of typical letex polymerization or redox initiation system, does not also discuss in view of polymerization process.
The contriver attempts to seek a kind of under the situation of comparatively convenient, easy handling, synthesizes to obtain forming the relatively emulsion polymerisation process of the SMIA multipolymer of homogeneous that distributes in the monomer ratio scope of broad.
Summary of the invention
At the problems referred to above, the object of the present invention is to provide a kind of preparation method of latex of heat-resistant resin in maleimide class, is a kind of maleimide monomer and aryl ethylene class monomer and or preparation method of the latex of heat-resistant resin in maleimide class of itrile group vinyl monomer of preparing specifically.This method will have that emulsion system is stable, monomer conversion is high, copolymer structure and the composition setting range is big, the maleimide monomer is easy to disperse, react be easy to control, the characteristics that pH value is stablized, the product thermal stability is high of system.
The preparation process of latex of heat-resistant resin in maleimide class of the present invention is divided into three parts.Usually the composition and the operational condition of these three parts are as follows: (being 100 mass parts in the monomer total amount, as follows)
(A) preparation of monomer mixed solution
25～35 ℃ with 10～45 parts of maleimide monomers, 30～65 parts of aryl ethylene class monomers, 0～30 part of itrile group vinyl monomer, 0.1～0.6 part of oil soluble thermal decomposition initiating, 0.01～0.65 part of molecular weight regulator adds tempering tank, open to stir and mix, form homogeneous phase monomer mixed solution (a).
Optimum condition is: 25～35 ℃ with 15～45 parts of maleimide monomers, 35～60 parts of aryl ethylene class monomers, 0.2～0.5 part of oil soluble thermal decomposition initiating, 0～25 part of itrile group vinyl monomer, 0.05～0.45 part of molecular weight regulator adds tempering tank, open to stir and mix, form homogeneous phase monomer mixed solution (a).
(B) preparation of monomer emulsion
25～35 ℃ with 80～150 parts of de-salted waters, and 2.0～8.5 parts of emulsifying agents join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor.Emulsification 20～75 minutes monomer emulsion (b).
Optimum condition is: 25～35 ℃ with 100～130 parts of de-salted waters, and 2.5～2.7 parts of emulsifying agents join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).
(C) preparation of latex of heatresistant resin
Add 10～50 parts of de-salted waters in the reactor of whipping appts is housed, temperature is raised to after 60～80 ℃, within 3～8 hours (b) joined in the reactor in batches or continuously, and the temperature of maintenance system is carried out polyreaction under 60～90 ℃.(b) 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 (c) after qualified.Also can add common agent such as softening agent and 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: add 20～40 parts of de-salted waters in the reactor of whipping appts is housed, temperature is raised to after 65～80 ℃, within 4～6 hours (b) joined in the reactor continuously, and the temperature of maintenance system is carried out polyreaction under 70～85 ℃.(b) 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 (c) after qualified.Can also finish the emulsion that the back adds auxiliary agent in the polymerization of (c), finish all processes of preparation (c).
Used initiator among the preparation method of latex of heat-resistant resin in maleimide class of the present invention, it is the used oil soluble thermal decomposition initiating of general radical polymerization, usually oil dissolubility thermal decomposition initiating is meant at the initiator of the half life of decomposition below 100 ℃ less than 4 hours, comprises azo class, organo-peroxide class.The object lesson of initiator has: Diisopropyl azodicarboxylate, and 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide etc., owing to be general general type, just no longer for example many.Wherein preferred Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
In (B) step, monomer emulsion (b) can be added in 3～8 hours in the reactor in batches and mix with (a) in the present invention, as adding 2%～7% (b) every 5～20 minutes.
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.Normal temperature can carry out the preparation of homogeneous monomer mixed solution, the preparation of monomer 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 the preparation method adopted of latex of heat-resistant resin in maleimide class of the present invention has following structural formula:
(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, N-ethyl maleimide, N-tertiary butyl maleimide, N-isobutyl-maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, N-aminomethyl phenyl maleimide N-p-methoxy-phenyl maleimide, N-carboxyl phenyl maleimide, N-nitrophenyl maleimide, N-naphthyl maleimide 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.
The emulsifying agent that the present invention uses, mainly contain anion surfactant, nonionogenic tenside or their compound system, for example: sodium lauryl sulphate, dodecyl sulphate potassium, Sodium dodecylbenzene sulfonate, Potassium dodecylbenzenesulfonate, potassium stearate, synthetic fatty acid potassium, anion surfactants such as sodium oleate, OP, peregal, Tween, polyoxyethylene nonionogenic tensides such as Span, wherein preferably sodium dodecyl sulfate, Sodium dodecylbenzene sulfonate or synthetic fatty acid potassium or their compound system.
The molecular weight regulator that the present invention uses is not particularly limited, as being general tert-dodecyl mercaptan, dodecyl mercaptan carbon etc.
The emulsion of the auxiliary agent described in the present invention, be meant softening agent, thermo-stabilizer, emulsifying agent and de-salted water are mixed with the emulsion of auxiliary agent in emulsifying tank, mode that can emulsion after copolyreaction finishes adds, make their degrees of scatter in polymkeric substance more even, thereby better effects if. used auxiliary agent can be a softening agent in emulsion, thermo-stabilizer etc., be employed softening agent such as DOP in the general plastic working process, DCP, Magnesium Stearate etc., thermo-stabilizer is as 1076,1010,2246, emulsifying agent such as potassium stearate, potassium oleate, synthetic fatty acid potassium etc., proportioning also is to adopt general proportioning in the prior art, as softening agent: thermo-stabilizer: the weight ratio of emulsifying agent is (1～15): (1～15): (3～10), emulsifying agent, initiator, water, softening agent, the consumption of thermo-stabilizer is identical with general letex polymerization, be conventional amount used, no longer describing in detail. the present invention also can not add the emulsion of auxiliary agent certainly, and use directly is provided after the polymerization.
Heat-up rate, thermostat temperature, constant temperature are held time also extremely importantly in each condition in the present invention, also will directly have influence on stability of emulsion, exceed the related scope of this patent, also have relatively large polymer formation gel and separate out from emulsion system.
Among the preparation 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 10～45/30～65/0～30, and preferable range is 15～45/35～60/0～25.
Preparation method's characteristics 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 60～90 ℃, between preferred 70～85 ℃ usually.
2. whipped form and rotating speed: for letex polymerization of the present invention, because polymerization system viscosity is not high, just requiring to the shearing action that stirs is not very high, and because method that can be by regulating feed rate reaction speed easily, so this method is less demanding to reactor mixing speed and radiating capacity of equipment, as long as can guarantee to mix.Common whipped form all can, preferably the slurry formula stirs.
3. feed way: the preparation 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 resin emulsion whether weighed by variable color after certain hour is weighed and placed to the solids that emulsion filtered out after resin emulsion stability finished with reaction and ratio (the being not more than 1.5%) size of total monomer charging capacity.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.
Emulsion polymerization 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
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.
Second-order transition temperature Tg:DSC-differential thermal differential method
Vicat softening temperature: GB/T 1633-2000
Resin emulsion whether weigh by variable color behind the solids that emulsion filtered out after resin emulsion stability finished with reaction and the ratio magnitude (≤1.5%) of total monomer charging capacity and the placement certain hour.
The emulsion of auxiliary agent is: the emulsion that 5.0% oleic acid potash soap, 10% antioxidant 1076,5% plasticizer phthalic acid dibutylester and 80% de-salted water is mixed with auxiliary agent under 75 ℃ in emulsifying tank.
Embodiment 1:
A. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 45 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 3.0 parts of sodium lauryl sulphate join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).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 (b) joined continuously equably in the reactor also the temperature of maintenance system and under 80 ℃, carry out polyreaction.The feed rate of control (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9.
Under 75 ℃, 5.0% oleic acid potash soap, 10% antioxidant 1076,5% plasticizer phthalic acid dibutylester and 80% de-salted water are mixed with the emulsion of auxiliary agent in emulsifying tank.
In (c), add 0.7 part of the emulsion of auxiliary agent at last, be all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying, as the criterion (≤1.5% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.2%, and is qualified.
Calculated yield 95.3% after the white 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 ℃.
Embodiment 2:
A. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 45 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.15 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 2.2 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).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 (b) 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 (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours. and the solids that filters out is through washing, weigh after the drying, criterion (≤1.5% is qualified) as emulsion reaction system stability. under this condition, the ratio of solids that filters out and monomeric charge amount is 1.1%, and is qualified.
Calculated yield 95.3% 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: 150 ℃.
Embodiment 3:
A. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-cyclohexyl maleimides, 45 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of 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 (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).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 (b) 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 (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying, as the criterion (≤1.5% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.3%.
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 monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 45 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.2 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 3.0 parts of Sodium dodecylbenzene sulfonatees join in the emulsor (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).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 75 ℃, immediately (b) joined continuously equably in the reactor also the temperature of maintenance system and under 85 ℃, carry out polyreaction.The feed rate of control (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying, as the criterion (≤1.5% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.1%, and is qualified.
Calculated yield 95.2%. got second-order transition temperature Tg=140 ℃ with differential differential thermal instrumentation after the white product that emulsion makes after cohesion, filtration, drying was weighed. record its vicat softening temperature: 147 ℃.
Embodiment 5:
A. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 45 parts of vinyl toluenes, and 25 parts of vinyl cyanide, 0.45 part of Diisopropyl azodicarboxylate, 0.12 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of 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 (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).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 (b) 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 (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying, as the criterion (≤1.5% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.4%, and is qualified.
Calculated yield 95.3% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=141 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 148 ℃.
Embodiment 6:
A. the preparation of monomer mixed solution
28 ℃ with 30 parts of N-cyclohexyl maleimides, 45 parts of vinylbenzene, and 25 parts of methacrylonitriles, 0.25 part of Diisopropyl azodicarboxylate, 0.13 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of monomer emulsion
28 ℃ 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 (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).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 60 ℃, immediately (b) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 60 ℃, carry out polyreaction.The feed rate of control (b) added it within 7.5～8.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying, as the criterion (≤1.5% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.2%.
Calculated yield 95.1% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=148 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 155 ℃.
Embodiment 7:
A. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 45 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.45 part of 2,2'-Azobis(2,4-dimethylvaleronitrile), 0.21 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 3.0 parts of sodium lauryl sulphate join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).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 75 ℃, immediately (b) joined continuously equably in the reactor also the temperature of maintenance system and under 80 ℃, carry out polyreaction.The feed rate of control (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying, as the criterion (≤1.5% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.2%, and is qualified.
Calculated yield 94.8% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=142 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 147 ℃.
Embodiment 8:
A. the preparation of monomer mixed solution
32 ℃ with 10 parts of N-phenylmaleimides, 65 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of monomer emulsion
32 ℃ 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 (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).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 73 ℃, immediately (b) 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 (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying, as the criterion (≤1.5% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.1%, and is qualified.
Calculated yield 95.3% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=117 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 108 ℃.
Embodiment 9:
A. the preparation of monomer mixed solution
30 ℃ with 45 parts of N-phenylmaleimides, 55 parts of vinylbenzene, and 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 3.0 parts of sodium lauryl sulphate join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).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 80 ℃, immediately (b) joined continuously equably in the reactor also the temperature of maintenance system and under 90 ℃, carry out polyreaction.The feed rate of control (b) added it within 3.5～4.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying, as the criterion (≤1.5% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.2%, and is qualified.
Calculated yield 95.1% after the white 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: 157 ℃.
Embodiment 10:
A. the preparation of monomer mixed solution
25 ℃ with 25 parts of N-phenylmaleimides, 50 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of monomer emulsion
25 ℃ with 130 parts of de-salted waters, and 2.3 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).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 (b) 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 (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying, as the criterion (≤1.5% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.3%, and is qualified.
Calculated yield 95.3% 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: 124 ℃.
Embodiment 11:
A. the preparation of monomer mixed solution
34 ℃ with 30 parts of N-phenylmaleimides, 45 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of benzoyl peroxide, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of monomer emulsion
33 ℃ with 130 parts of de-salted waters, and 2.5 parts of sodium lauryl sulphate and 5.0 parts of OP join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).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 (b) joined continuously equably in the reactor also the temperature of maintenance system and under 80 ℃, carry out polyreaction.The feed rate of control (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying, as the criterion (≤1.5% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.5%, and is qualified.
Calculated yield 95.3% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=141 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 148 ℃.
Embodiment 12:
A. the preparation of monomer mixed solution
27 ℃ with 25 parts of N-phenylmaleimides, 50 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.45 part of benzoyl peroxide, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of monomer emulsion
27 ℃ 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 (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).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 (b) 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 (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9.
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying, as the criterion (≤1.5% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.2%, and is qualified.
Calculated yield 95.6% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=130 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 125 ℃.
Embodiment 13:
A. the preparation of monomer mixed solution
34 ℃ with 30 parts of N-phenylmaleimides, 45 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of dodecyl mercaptan carbon adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of monomer emulsion
34 ℃ with 130 parts of de-salted waters, and 3.0 parts of sodium lauryl sulphate join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor. emulsification 30～45 minutes monomer emulsion (b). 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 (b) joined continuously equably in the reactor also the temperature of maintenance system and under 80 ℃, carry out polyreaction.The feed rate of control (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9.
Under 75 ℃, 5.0% oleic acid potash soap, 10% antioxidant 1076,5% plasticizer phthalic acid dibutylester and 80% de-salted water are mixed with the emulsion of auxiliary agent in emulsifying tank.
In (c), add 0.7 part of the emulsion of auxiliary agent at last, be all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying, as the criterion (≤1.5% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.1%, and is qualified.
Calculated yield 95.3% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=169 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 146 ℃.
Comparative example 1: on the basis of embodiment 1, remove the monomer emulsifying part, test.
A. the preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 45 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 (a).
B. the preparation of latex of heatresistant resin
30 ℃ with 160 parts of de-salted waters, 0.35 part of Diisopropyl azodicarboxylate, and 3.0 parts of sodium lauryl sulphate join in the reactor, open to stir (a) 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 (c) after qualified.(c) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate white latex of heatresistant resin product.The solids that filters out is weighed after the drying, as the criterion (≤1.5% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 4.7%.
Calculated yield 89.1% after the white 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 2: on the basis of embodiment 10, shorten the reinforced time of monomer emulsion, test.
A. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-phenylmaleimides, 50 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of 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 (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).
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 (b) joined continuously equably in the reactor and to mix with (a) and the temperature of maintenance system is carried out polyreaction under 80 ℃. the feed rate of control (b), it was added within 1.0～1.5 hours. after (b) adding, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content, promptly forming latex of heatresistant resin (c) after qualified. polymerization (c) finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying through washing, and as the criterion of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 3.5%.
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 3: on the basis of embodiment 10, shorten the emulsification times of monomer emulsion, test.
A. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-phenylmaleimides, 50 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of 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 (a) joined and carry out emulsification in the emulsor.Emulsification 5～10 minutes monomer emulsion (b).
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 (b) 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 (b) added it within 1.0～1.5 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying through washing, and as the criterion of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 6.5%.
Emulsion is calculated yield 88.5% after the product that makes after the cohesion is weighed.Get second-order transition temperature Tg=134 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 137 ℃.
Comparative example 4: on the basis of embodiment 10, improve polymeric reaction temperature, test.
A. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-phenylmaleimides, 50 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of 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 and stir, and (a) joined emulsor carry out emulsification.Emulsification 30～45 minutes monomer emulsion (b).
C. the preparation of latex of heatresistant resin
Add 30 parts of water in the reactor, treat that its temperature rises to after 85 ℃, immediately (b) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 95 ℃, carry out polyreaction.The feed rate of control (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying through washing, and as the criterion of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 2.5%.
Emulsion is calculated yield 92.5% after the product that makes after the cohesion is weighed.Get second-order transition temperature Tg=135 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 135 ℃.
Comparative example 5: on the basis of embodiment 10, reduce polymerization temperature, test.
A. the preparation of monomer mixed solution
30 ℃ with 25 parts of N-phenylmaleimides, 50 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of 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 and stir, and (a) joined carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).
C. the preparation of latex of heatresistant resin
Add 30 parts of water in the reactor, treat that its temperature rises to after 55 ℃, immediately (b) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 55 ℃, carry out polyreaction.The feed rate of control (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying through washing, and as the criterion of emulsion reaction system stability, under this condition, the solids that filters out and the ratio of charging capacity are 6.3%.
Emulsion is calculated yield 87.5% after the product that makes after the cohesion is weighed.Get second-order transition temperature Tg=136 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 138 ℃.
Comparative example 6:
A. the preparation of monomer mixed solution
30 ℃ with 10 parts of N-phenylmaleimides, 65 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of isopropyl benzene hydroperoxide, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B. the preparation of 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 (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).Measuring its pH is 9～10.
C. the preparation of latex of heatresistant resin
Add 20 parts of water in the reactor, treat that its temperature rises to after 65 ℃.Immediately (b) joined continuously equably after 15 minutes in the reactor and the temperature of maintenance system is carried out polyreaction under 75 ℃.The feed rate of control (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content is 3%, the reaction do not carry out substantially.
Claims (14)
1. the preparation method of a latex of heat-resistant resin in maleimide class is divided into three parts, is 100 mass parts in the monomer total amount, and its composition and operational condition are:
(A) preparation of monomer mixed solution
25～35 ℃ with 10～45 parts of maleimide monomers, 30～65 parts of aryl ethylene class monomers, 0～30 part of itrile group vinyl monomer, 0.1～0.6 part of oil soluble thermal decomposition initiating, 0.01～0.65 part of molecular weight regulator adds tempering tank, open to stir and mix, form homogeneous phase monomer mixed solution (a);
(B) preparation of monomer emulsion
25～35 ℃ with 80～150 parts of de-salted waters, and 2.0～8.5 parts of emulsifying agents join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor, emulsification 20～75 minutes monomer emulsion (b);
(C) preparation of latex of heatresistant resin
Add 10～50 parts of de-salted waters in the reactor of whipping appts is housed, temperature is raised to after 60～85 ℃, within 3～8 hours (b) joined in the reactor in batches or continuously, and the temperature of maintenance system is carried out polyreaction under 60～90 ℃; (b) add after, polyreaction was carried out 0.5～2.0 hour again, promptly formed latex of heatresistant resin (c).
2. preparation method according to claim 1, the condition that it is characterized in that (A) step is: 25～35 ℃ with 15～45 parts of maleimide monomers, 35～60 parts of aryl ethylene class monomers, 0.2～0.5 part of oil soluble thermal decomposition initiating, 0～25 part of itrile group vinyl monomer, 0.05～0.45 part of molecular weight regulator adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
3. preparation method according to claim 1, the condition that it is characterized in that (B) step is: 25～35 ℃ with 100～130 parts of de-salted waters, 2.5～2.7 parts of emulsifying agents join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor, emulsification 30～45 minutes monomer emulsion (b).
4. preparation method according to claim 1, the condition that it is characterized in that (C) step is: add 20～40 parts of de-salted waters in the reactor of whipping appts is housed, temperature is raised to after 65～80 ℃, within 4～6 hours, join in the reactor continuously with (b), and the temperature of maintenance system is carried out polyreaction under 70～85 ℃, (b) add after, polyreaction was carried out 0.5～1.5 hour again, promptly formed latex of heatresistant resin (c).
5. the preparation method of latex of heat-resistant resin in maleimide class according to claim 1 is characterized in that in (C) step, adds the emulsion of auxiliary agent after the polymerization of (c) finishes, and finishes all processes of preparation (c).
6. the preparation method of latex of heat-resistant resin in maleimide class according to claim 1 is characterized in that the maleimide monomer is N-cyclohexyl maleimide, N-phenylmaleimide.
7. the preparation 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.
8. the preparation 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.
9. preparation method according to claim 1 is characterized in that the oil soluble thermal decomposition initiating is meant at the initiator of the half life of decomposition below 100 ℃ less than 4 hours, comprises azo class or organic peroxide initiator.
10. preparation method according to claim 9 is characterized in that azo-initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
11. preparation method according to claim 1 is characterized in that emulsifying agent is anion surfactant, nonionogenic tenside or their compound system.
12. preparation method according to claim 1 is characterized in that emulsifying agent is sodium lauryl sulphate, Sodium dodecylbenzene sulfonate or synthetic fatty acid potassium or their compound system.
13. preparation method according to claim 1 is characterized in that monomer ratio: the mass ratio of maleimide monomer and aryl ethylene class monomer and itrile group vinyl monomer is 10～45: 30～65: 0～30.
14. preparation method according to claim 1 is characterized in that monomer ratio: the mass ratio of maleimide monomer and aryl ethylene class monomer and itrile group vinyl monomer is 15～45: 35～60: 0～25.
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| US4757109A (en) * | 1985-05-16 | 1988-07-12 | Mitsubishi Rayon Co., Ltd. | Process for the preparation of maleimide copolymers and thermoplastic resin composition using the same |
| CN1555398A (en) * | 2001-09-17 | 2004-12-15 | Abs compositions with improved characteristic combinations | |
| CN1765945A (en) * | 2005-10-31 | 2006-05-03 | 浙江大学 | Preparation method of heat-proof modifier for uniform copolymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4757109A (en) * | 1985-05-16 | 1988-07-12 | Mitsubishi Rayon Co., Ltd. | Process for the preparation of maleimide copolymers and thermoplastic resin composition using the same |
| CN1555398A (en) * | 2001-09-17 | 2004-12-15 | Abs compositions with improved characteristic combinations | |
| CN1765945A (en) * | 2005-10-31 | 2006-05-03 | 浙江大学 | Preparation method of heat-proof modifier for uniform copolymerization |
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