CN101235117A - A kind of method of styrene/maleic anhydride copolymerization reaction - Google Patents
A kind of method of styrene/maleic anhydride copolymerization reaction Download PDFInfo
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- CN101235117A CN101235117A CNA2008101019480A CN200810101948A CN101235117A CN 101235117 A CN101235117 A CN 101235117A CN A2008101019480 A CNA2008101019480 A CN A2008101019480A CN 200810101948 A CN200810101948 A CN 200810101948A CN 101235117 A CN101235117 A CN 101235117A
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- maleic anhydride
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000007334 copolymerization reaction Methods 0.000 title abstract description 8
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 70
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- 239000003999 initiator Substances 0.000 claims abstract description 40
- 150000002576 ketones Chemical class 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 102
- 238000006243 chemical reaction Methods 0.000 claims description 45
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 31
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 abstract description 33
- 239000002245 particle Substances 0.000 abstract description 23
- 238000002360 preparation method Methods 0.000 abstract description 23
- 238000012674 dispersion polymerization Methods 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 239000003381 stabilizer Substances 0.000 abstract description 5
- -1 azo compound Chemical class 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- 150000001451 organic peroxides Chemical class 0.000 abstract 1
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 40
- 238000006116 polymerization reaction Methods 0.000 description 34
- 239000000126 substance Substances 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 28
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 27
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 27
- 241000237502 Ostreidae Species 0.000 description 25
- 235000020636 oyster Nutrition 0.000 description 25
- 229940117955 isoamyl acetate Drugs 0.000 description 20
- 238000001000 micrograph Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 9
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 8
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 8
- 229920005603 alternating copolymer Polymers 0.000 description 7
- 230000006641 stabilisation Effects 0.000 description 7
- 238000011105 stabilization Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 4
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XINCECQTMHSORG-UHFFFAOYSA-N Isoamyl isovalerate Chemical compound CC(C)CCOC(=O)CC(C)C XINCECQTMHSORG-UHFFFAOYSA-N 0.000 description 2
- CRZQGDNQQAALAY-UHFFFAOYSA-N Methyl benzeneacetate Chemical compound COC(=O)CC1=CC=CC=C1 CRZQGDNQQAALAY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- 238000001246 colloidal dispersion Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- PPXUHEORWJQRHJ-UHFFFAOYSA-N ethyl isovalerate Chemical compound CCOC(=O)CC(C)C PPXUHEORWJQRHJ-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- PQLMXFQTAMDXIZ-UHFFFAOYSA-N isoamyl butyrate Chemical compound CCCC(=O)OCCC(C)C PQLMXFQTAMDXIZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000012673 precipitation polymerization Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- AVMSWPWPYJVYKY-UHFFFAOYSA-N 2-Methylpropyl formate Chemical compound CC(C)COC=O AVMSWPWPYJVYKY-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- MLLAPOCBLWUFAP-UHFFFAOYSA-N 3-Methylbutyl benzoate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1 MLLAPOCBLWUFAP-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- DULCUDSUACXJJC-UHFFFAOYSA-N Ethyl phenylacetate Chemical compound CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- WHKUVVPPKQRRBV-UHFFFAOYSA-N Trasan Chemical compound CC1=CC(Cl)=CC=C1OCC(O)=O WHKUVVPPKQRRBV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000007281 aminoalkylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 229940094941 isoamyl butyrate Drugs 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000003808 methanol extraction Methods 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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Abstract
一种苯乙烯/马来酸酐共聚反应的方法属于聚合物制备领域。本发明的目的在于解决传统分散聚合体系中使用稳定剂带来的弊端。本发明在氮气保护下，将单体Man和St、引发剂有机过氧化物或偶氮化合物，按一定比例溶解在有机酸烷基酯、芳香烃与有机酸烷基酯的混合溶液或酮与烷烃的混合溶液介质中，并于60～90℃反应1/4～12h，得到聚合物微球的分散体系。分散体系中微球的平均粒径为90～1715nm，分散系数为1.04～1.004，数均分子量范围为80000～300000g/mol。本发明具有不使用稳定剂，工艺简单，成本低、所制备的聚合物微球或是粒子表面洁净，而且粒径可控，形貌可控，粒度分布窄等优点。A method for styrene/maleic anhydride copolymerization belongs to the field of polymer preparation. The purpose of the present invention is to solve the drawbacks caused by the use of stabilizers in traditional dispersion polymerization systems. In the present invention, under the protection of nitrogen, the monomer Man and St, the initiator organic peroxide or azo compound are dissolved in the mixed solution of organic acid alkyl ester, aromatic hydrocarbon and organic acid alkyl ester or ketone and organic acid alkyl ester in a certain proportion. in a mixed solution medium of alkanes, and react at 60-90° C. for 1/4-12 hours to obtain a dispersion system of polymer microspheres. The average particle size of the microspheres in the dispersion system is 90-1715nm, the dispersion coefficient is 1.04-1.004, and the number-average molecular weight range is 80000-300000g/mol. The invention has the advantages of no stabilizer, simple process, low cost, clean surface of prepared polymer microspheres or particles, controllable particle size, controllable shape, narrow particle size distribution and the like.
Description
Technical field
The present invention relates to a kind of maleic anhydride (MAn) and the method that vinylbenzene (St) carries out copolyreaction, be specifically related to a kind of MAn and St obtain self stabilization alternating copolymer dispersion system after copolymerization method.
Background technology
Vinylbenzene (St), maleic anhydride (MAn) multipolymer are a kind of excellent property and cheap novel high polymer material, are widely used in the field such as emulsifying agent, curing agent for epoxy resin of emulsifying agent, the agricultural chemicals of properties-correcting agent, dispersing of pigments agent, the floor polishing of water conditioner, latex coating, glue paste.
In addition, preparation and application that a focus of present functional high polymer material field is a polymer microballoon, nano level to micron-sized polymer microballoon because of specific physique such as have that specific surface area is big, adsorptivity is strong, cohesion is big and the surface reaction ability is strong, be widely used for many high-technology fields such as analytical chemistry, biomedicine, standard metering, solid phase carrier, high performance liquid chromatography.
The preparation method of vinylbenzene (St), maleic anhydride (MAn) multipolymer mainly is solution polymerization at present, a spot of mass polymerization, precipitation polymerization, body-suspension polymerization and the letex polymerization of solution phase inversion.
Solution polymerization is the main method for preparing vinylbenzene (St), maleic anhydride (MAn) multipolymer at present, and the emphasis of research is the random multipolymer of preparation.As Tian Yong, Wang Xiufang at " R-SMA synthetic and performance study " (" Chinese leather ", 2007, the 3rd phase, pp.9-11) in the literary composition be with the pimelinketone solvent under higher temperature of reaction (greater than 90 ℃) by the monomeric technology of dropwise reaction, polymerization is finished after methanol extraction obtains pulverous irregular phenylethylene (St), maleic anhydride (MAn) multipolymer of white.Li Xiuqing, Song Yong is strong to be waited at " the synthetic and performance study of styrene-maleic anhydride copolymer " (" Inner Mongol University of Technology's journal ", 2006, the 3rd phase, pp.215-220) in the literary composition, be solvent, by the method for once feeding in raw material with acetone, react 4-5h at a certain temperature, the reaction products therefrom obtains the multipolymer of certain maleic anhydride content through ether sedimentation.And for example Li Huaming, Zhou Disheng etc. are at " solution polymerization process synthesizing styrene-maleic anhydride random copolymer " (" synthetic rubber and plastics ", 1998,15 (3), pp.64-65) in the literary composition, random maleic anhydride, styrol copolymer have been prepared by the method for in acetone solvent, adding polar solvent dimethyl sulfoxide (DMSO) and raising temperature of reaction.As seen a lot of solution polymerization process all concentrate on preparation random maleic anhydride, styrol copolymer with the emphasis of research.
Zhou Wen, multitude Paine are in " the synthetic and characterization research of the body-suspension method of SMA resin " (" modern plastics processed and applied ", 1999, the 4th phase, pp.5-9) in the literary composition, by continuous dropping monomer methods, carry out mass polymerization in 90 ℃, when transformation efficiency reaches 40%～50%, carry out the method for suspension polymerization, prepared random maleic anhydride, styrol copolymer.Because maleic anhydride facile hydrolysis in water medium becomes toxilic acid, reactive behavior reduces greatly, has influenced the composition and the distribution of copolymerization rate and product, must make acid be dehydrated into acid anhydride again during aftertreatment simultaneously, the processing condition complexity.
Li Chunsheng, Zhang Shuxiang etc. are at " supercritical CO
2In maleic anhydride and cinnamic polymerization " (" polymer material science and engineering "; 2006; vol.22; No.5; pp95-97); during greater than 16MPa, do not have polystyrene (PS) generation in reaction pressure, (number-average molecular weight can reach 4.6 * 10 can to obtain very high transformation efficiency and higher molecular weight
4G/mol) pure MAn and St alternating copolymer, product is the fine powdered solid.Reaction will be carried out under higher pressure, and is higher to the device and the processing requirement of polyreaction.
Li Xiaorui, Shen Yiding is in " research of SMA copolymerization and modification " (" polymer material science and engineering ", 2000,16 (3), pp.56-60) mention the mass polymerization of maleic anhydride (MAn) and vinylbenzene (St) in the literary composition, but be difficult to reach reaction in the polymerization process relatively steadily and good heat transfer, mass transfer condition arranged.Therefore the random SMA with the synthetic high molecular weight of substance law and its narrowly distributing has bigger difficulty.
Shen Yiding, Li Xiaorui is in " preparation of styrene-maleic anhydride random copolymers and performance " (" polymer material science and engineering ", 2000,13 (3), pp.32-35) in the literary composition, by solution phase inversion method of emulsion polymerization,, make Zelan 338 with random structure in 90～130 ℃ temperature and using under the condition of polar solvent as medium.Same because maleic anhydride facile hydrolysis in water medium becomes toxilic acid, and reactive behavior reduces greatly, has influenced the composition and the distribution of copolymerization rate and product, must make acid be dehydrated into acid anhydride again during aftertreatment simultaneously, the processing condition complexity.
In the copolymerization process of as seen above-mentioned maleic anhydride (MAn) and vinylbenzene (St), in the preparation that focuses on random copolymers that mostly will study, the purposes of multipolymer also generally concentrates on the chemical property of multipolymer itself and reaches in the follow-up modification.Though the preparation and the application that relate to dispersion system are arranged, also focus on the preparation of polymer material, with focusing on copolymer structure and the molecular weight of reaction control.And all need add some surfactant stabilisers in the preparation of relevant dispersion system and in using, increase difficulty for the purifying of follow-up polymkeric substance, also can increase economically cost and to the pollution of environment.
Nearest Willem Jan Soer etc. are at " Surfactant-free artificiallatexes from modified styrene-maleic anhydride (SMA) copolymers " (Polymer, 2006,47,7621-7627) in the literary composition, under the condition that does not add any stablizer, prepared colloid based on maleic anhydride (MAn) vinylbenzene (St) multipolymer.But the maleic anhydride-styrene polyreaction is the solution polymerization of carrying out in methylethylketone, the preparation of polymeric colloid relates to the amino-alkylation and the conversion of reacting the dispersion system medium of the molecular chain of maleic anhydride (MAn) vinylbenzene (St) multipolymer, no longer be simple maleic anhydride (MAn) vinylbenzene (St) multipolymer, and complex process.
As seen, the oyster white colloid and the colloidal disperse phase that prepare maleic anhydride (MAn) vinylbenzene (St) multipolymer by the self stabilization dispersion polymerization processes that does not add any stablizer are the polymerization process of monodisperse copolymerization thing particle, do not appear in the newspapers up to now.
Summary of the invention
The objective of the invention is to solve the drawback of using stablizer to bring in traditional dispersion polymerization system, and a kind of preparation method of phenylethylene/maleic anhydride copolymer colloidal dispersion system of self stabilization is provided.The colloidal disperse phase is monodispersed polymer microballoon, the monodisperse polymer micro-sphere surface cleaning, and pattern is controlled, and particle diameter is controlled, and narrow particle size distribution, and polymer microballoon is made up of the alternating copolymer of maleic anhydride-styrene.
The method of a kind of phenylethylene/maleic anhydride copolyreaction provided by the present invention, under the condition of nitrogen protection, monomer and initiator joined in the medium dissolve, and in 60～90 ℃ of reaction 1/4～12h, obtain the dispersion system of phenylethylene/maleic anhydride polymer microballoon, obtain the white solid of phenylethylene/maleic anhydride alternate copolymer again through centrifugation; Wherein, described monomer is maleic anhydride Man and vinylbenzene St, and the mol ratio of the two is 6: 1～1: 6, and monomeric mass concentration is 1%～50% in the reaction system; Described initiator is organo-peroxide or azo-compound, and the mass concentration of initiator is 0.01%～1% in the reaction system; Described medium is the mixing solutions of organic acid alkyl ester, aromatic hydrocarbon and organic acid alkyl ester or the mixing solutions of ketone and alkane, and wherein, the volume fraction of ketone is 5%～65% in the mixing solutions of ketone and alkane, preferred 10%～50%.
The mass concentration of described monomer in reaction system preferred 15%～36%.
The initiator that is adopted among the present invention is conventional thermolysis type initiator, comprise for known this compounds of professional and technical personnel: (1) organo-peroxide, for example: dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, dilauroyl peroxide, the special butyl ester of peroxidation phenylformic acid, peroxy dicarbonate diisopropyl ester, di-cyclohexylperoxy dicarbonate etc.; (2) azo-compound, for example: Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.
The mass concentration of initiator in reaction system preferred 0.06%～0.6%.
The present invention is by selecting suitable media implementation MAn and the self stabilization dispersion polymerization of St, its characteristics are: need not to add any stablizer and co-stabilizer in (1) this dispersion polymerization system, can obtain having the colloidal dispersion system of self stabilization effect after polymerization is finished; (2) in the polymerization system be monodisperse polymer micro-sphere or lopsided particle, the microsphere surface cleaning, particle diameter is controlled, the controlled and narrow particle size distribution of pattern.(3) polymer microballoon is made up of the maleic anhydride-styrene alternating copolymer with certain molecular weight.
The selection of reaction medium is crucial unusually for the dispersion polymerization of the self stabilization of MAn and St among realization the present invention, its fundamental principle is: (1) medium all has good solvency action for MAn and two kinds of monomers of St and initiator, to guarantee that before the reaction be homogeneous system; (2) medium can not dissolve for the PMS multipolymer that is generated, after macromolecular chain reaches certain critical length just from medium precipitating come out; (3) polymkeric substance that comes out of precipitating precipitates down with Powdered or block can not be in precipitation polymerization, but stably is suspended in the medium with the microballoon or the form of particle, forms the stable dispersion that is similar to polymer emulsion.The medium that can be used as self stabilization dispersion polymerization system among the present invention has: the mixing solutions of organic acid alkyl ester, aromatic hydrocarbon and organic acid alkyl ester or the mixing solutions of ketone and alkane.
Wherein, the general structure of described organic acid alkyl ester is:
In the formula, R
1For H, C atomicity are 1～8 alkyl, phenyl or benzyl, R
2It for the C atomicity 1～5 alkyl.This type of medium is that its toxicity is lower in the advantage aspect industrial operation and the environmental protection, and mostly has no irritating odor.
The organic acid alkyl ester that the present invention adopts is an ethyl formate, propyl formate, tetryl formate, pentyl formate, ethyl acetate, butylacetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, Isoamyl Acetate FCC, jasmal, methyl propionate, ethyl propionate, butyl propionate, methyl-butyrate, ethyl butyrate, butyl butyrate, isoamyl butyrate, Ethylisovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate or Phenylacetic acid ethylester etc.
Described aromatic hydrocarbon is selected from benzene,toluene,xylene, chlorobenzene or bromobenzene.
Described ketone is selected from acetone, butanone, pimelinketone or hexone.
Described alkane is selected from hexanaphthene, normal hexane, normal heptane, Skellysolve A, octane or octane-iso.
Adopt water-bath or oil bath heating among the present invention, according to technique known, polymeric reaction temperature is determined by the decomposition temperature of initiator, be suitable for 60～90 ℃ as dibenzoyl peroxide, and Diisopropyl azodicarboxylate is suitable for 45～80 ℃; According to the difference that reaction system is formed, the speed of polyreaction is different, approximately reacts 1/4～12h.
From the dispersion system of polymer microballoon, take a sample, observe the form of the prepared polymer microballoon of the present invention with scanning electronic microscope (SEM).The size of microballoon represents that with median size (Dn) size-grade distribution represents that with dispersion coefficient (U) formula is as follows:
U＝D
w/D
n (3)
Wherein, D
iBe the diameter (nm) of i particle, n is a size of a sample, D
wMathematic(al) mean particle diameter for definition.
The median size of the phenylethylene/maleic anhydride copolymer microballoon that the inventive method is prepared is 90～1715nm, and its particle diameter can be controlled by processing parameters such as reaction times, monomer concentration, reaction mediums; Dispersion coefficient is 1.04～1.004, for monodispersity or near monodispersity.Resulting polymers is the alternating copolymer of phenylethylene/maleic anhydride, and the number-average molecular weight scope of alternating copolymer is 80000～300000g/mol.
The present invention has following beneficial effect:
1) the present invention is owing to need not to add any stablizer and co-stabilizer, and reaction system is very simple, and technology controlling and process is easy, saves cost, reduces environmental pollution.
2) prepared polymer microballoon or the particle surface cleaning of the inventive method, and particle diameter is controlled, and pattern is controlled, narrow particle size distribution.
3) phenylethylene/maleic anhydride alternate copolymer of the inventive method preparation has higher molecular weight.
4) technology of the present invention is simple, and speed of reaction is fast, final transformation efficiency height, and the product separate easily, used reaction medium belongs to low toxicity chemical and recyclable utilization.
Description of drawings
The surface sweeping electron micrograph (magnification 10000) of the polymer microballoon of Fig. 1, embodiment 4 preparations.
The surface sweeping electron micrograph (magnification 10000) of the polymer microballoon of Fig. 2, embodiment 6 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 3, embodiment 7 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 4, embodiment 12 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 5, embodiment 15 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 6, embodiment 16 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 7, embodiment 17 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 8, embodiment 18 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 9, embodiment 19 preparations.
Figure 10 is the electron scanning micrograph (magnification 10000) of the polymer microballoon of embodiment 20 preparations.
Below in conjunction with the drawings and the specific embodiments the present invention is further described.
Embodiment
Embodiment 1
MAn and St mole proportioning 1: 1, MAn 0.3065g wherein, St 0.325g; Initiator is Diisopropyl azodicarboxylate AIBN, 0.05g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains maleic anhydride/cinnamic alternating copolymer PMS microballoon.Median size (Dn), dispersion coefficient (U) and polymerization yield (C
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 1.
Embodiment 2
MAn and St mole proportioning 1: 1, MAn 0.613g wherein, St 0.325g; Initiator is AIBN, 0.04g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 1.
Embodiment 3
MAn and St mole proportioning 1: 1, MAn 1.226g wherein, St 1.3g; Initiator is AIBN, 0.04g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 1.
Embodiment 4
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 1, the electron scanning micrograph of polymer microballoon is seen Fig. 1.
Embodiment 5
MAn and St mole proportioning 1: 1, MAn 4.904g wherein, St 5.2g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 1.
Embodiment 6
MAn and St mole proportioning 1: 1, MAn 7.356g wherein, St 7.8g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 1, the electron scanning micrograph of polymer microballoon is seen Fig. 2.
Embodiment 7
MAn and St mole proportioning 4: 1, MAn 9.806g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 1, the electron scanning micrograph of polymer microballoon is seen Fig. 3.
MAn and St mole proportioning 3: 1, MAn 7.356g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 1.
Embodiment 9
MAn and St mole proportioning 2: 1, MAn 4.904g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 1.
Embodiment 10
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 1.
Embodiment 11
MAn and St mole proportioning 1: 2, MAn 2.452g wherein, St 5.2g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 1.
Embodiment 12
MAn and St mole proportioning 1: 3, MAn 2.452g wherein, St 7.8g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 1, the electron scanning micrograph of polymer microballoon is seen Fig. 4.
Embodiment 13
MAn and St mole proportioning 1: 4, MAn 2.452g wherein, St 10.4g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 1.
Embodiment 14
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is a pentyl acetate, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 2.
Embodiment 15
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an ethyl butyrate, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 2, the electron scanning micrograph of polymer microballoon is seen Fig. 5.
Embodiment 16
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an ethyl benzoate, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 2, the electron scanning micrograph of polymer microballoon is seen Fig. 6.
Embodiment 17
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is butanone 4mL, hexanaphthene 41mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 2, the electron scanning micrograph of polymer microballoon is seen Fig. 7.
Embodiment 18
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is butanone 8mL, hexanaphthene 37mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 2, the electron scanning micrograph of polymer microballoon is seen Fig. 8.
Embodiment 19
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is butanone 25mL, hexanaphthene 20mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 2, the electron scanning micrograph of polymer microballoon is seen Fig. 9.
Embodiment 20
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is butanone 33mL, hexanaphthene 12mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 2, the electron scanning micrograph of polymer microballoon is seen Figure 10.
Embodiment 21
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is butanone 37mL, hexanaphthene 8mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance
The results are shown in Table 2.
Embodiment 22
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, under 70 ℃ temperature, react 15min, obtain median size (Dn), dispersion coefficient (U), the polymerization yield (C of PMS copolymer microsphere
p), the number-average molecular weight of polymkeric substance
The results are shown in Table 3.
Embodiment 23
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, under 70 ℃ temperature, react 25min, obtain median size (Dn), dispersion coefficient (U), the polymerization yield (C of PMS copolymer microsphere
p), the number-average molecular weight of polymkeric substance
The results are shown in Table 3.
Embodiment 24
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, under 70 ℃ temperature, react 35min, obtain median size (Dn), dispersion coefficient (U), the polymerization yield (C of PMS copolymer microsphere
p), the number-average molecular weight of polymkeric substance
The results are shown in Table 3.
Embodiment 25
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, under 70 ℃ temperature, react 50min, obtain median size (Dn), dispersion coefficient (U), the polymerization yield (C of PMS copolymer microsphere
p), the number-average molecular weight of polymkeric substance
The results are shown in Table 3.
Embodiment 26
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, under 70 ℃ temperature, react 60min, obtain median size (Dn), dispersion coefficient (U), the polymerization yield (C of PMS copolymer microsphere
p), the number-average molecular weight of polymkeric substance
The results are shown in Table 3.
Embodiment 27
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, under 70 ℃ temperature, react 90min, obtain median size (Dn), dispersion coefficient (U), the polymerization yield (C of PMS copolymer microsphere
p), the number-average molecular weight of polymkeric substance
The results are shown in Table 3.
| Embodiment | The system outward appearance | Polymer particle particle diameter/nm | Dispersion coefficient U | Polymer yield Cp/% | Multipolymer number-average molecular weight/Mn |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 |
The similar oyster white gel of oyster white dispersion system oyster white dispersion system oyster white dispersion system oyster white dispersion system oyster white dispersion system oyster white dispersion system oyster white dispersion system oyster white dispersion system oyster white dispersion system oyster white dispersion system oyster white dispersion system thickness oyster white dispersion system | 324 344 401 538 1081 1715 1076 947 734 538 712 821 950 | 1.031 1.02 1.02 1.009 1.006 1.045 1.03 1.022 1.01 1.009 1.007 1.007 1.008 | 83 85 82 87 88 86 35 44 58 87 57 42 33 | 105361 125578 156789 166786 187893 229567 153476 99785 99995 100567 100235 106732 98765 |
Gained copolymer dispersion system under table 1 different condition
| Implementation example | The system outward appearance | Polymer particle particle diameter/nm | Dispersion coefficient U | Polymer yield | The polymkeric substance pattern | Multipolymer number-average molecular weight/Mn |
| Embodiment 14 embodiment 15 embodiment 16 embodiment 17 embodiment 18 embodiment 19 embodiment 20 embodiment 21 | Oyster white dispersion system oyster white dispersion system oyster white dispersion system system is solidified oyster white dispersion system oyster white dispersion system gelating soln | 782 516 538 / 887 1150 / / | 1.01 1.012 1.013 / 1.01 1.003 / / | 85 84 86 88 86 87 60 53 | The similar liver moss microsphere gel of microballoon microballoon microballoon mass polymer | 105568 100456 100789 111987 109876 99987 54321 20987 |
The copolymer dispersion of diverse microcosmic appearance system under table 2 different condition
| Reaction times/min | The system outward appearance | Polymer particle particle diameter/nm | Polymkeric substance number-average molecular weight g.mol -1 | Polymer yield Cp/% |
| Embodiment 22 embodiment 23 embodiment 24 embodiment 25 embodiment 26 embodiment 27 | Oyster white dispersion system oyster white dispersion system oyster white dispersion system oyster white dispersion system oyster white dispersion system oyster white dispersion system | 292 390 460 507 521 538 | 243333 199110 157166 138060 130202 103761 | 9.64 28.29 47.73 64.51 71.07 80 |
The copolymer dispersion system of table 3 differential responses during the time
Claims (9)
1, a kind of method of phenylethylene/maleic anhydride copolyreaction, it is characterized in that, under the condition of nitrogen protection, monomer and initiator joined in the medium dissolve, and in 60～90 ℃ of reaction 1/4～12h, obtain the dispersion system of phenylethylene/maleic anhydride polymer microballoon, obtain the white solid of phenylethylene/maleic anhydride alternate copolymer again through centrifugation; Wherein, described monomer is maleic anhydride Man and vinylbenzene St, and the mol ratio of the two is 6: 1～1: 6, and monomeric mass concentration is 1%～50% in the reaction system; Described initiator is organo-peroxide or azo-compound, and the mass concentration of initiator is 0.01%～1% in the reaction system; Described medium is the mixing solutions of organic acid alkyl ester, aromatic hydrocarbon and organic acid alkyl ester or the mixing solutions of ketone and alkane, and wherein, the volume fraction of ketone is 5%～65% in the mixing solutions of ketone and alkane.
2, method according to claim 1 is characterized in that, the mass concentration of described monomer in reaction system is 15%～36%.
3, method according to claim 1 is characterized in that, the mass concentration of described initiator in reaction system is 0.06%～0.6%.
4, method according to claim 1 is characterized in that, the general structure of described organic acid alkyl ester is:
In the formula, R
1For H, C atomicity are 1～8 alkyl, phenyl or benzyl, R
2It for the C atomicity 1～5 alkyl.
5, method according to claim 1 is characterized in that, described aromatic hydrocarbon is selected from benzene,toluene,xylene, chlorobenzene or bromobenzene.
6, method according to claim 1 is characterized in that, the volume fraction of ketone is 10%～50% in the mixing solutions of described ketone and alkane.
7, according to claim 1 or 7 described methods, it is characterized in that described ketone is selected from acetone, butanone, pimelinketone or hexone.
8, according to claim 1 or 7 described methods, it is characterized in that described alkane is selected from hexanaphthene, normal hexane, normal heptane, Skellysolve A, octane or octane-iso.
9, method according to claim 1, it is characterized in that, the median size of microballoon is 90～1715nm in the dispersion system of described phenylethylene/maleic anhydride polymer microballoon, dispersion coefficient is 1.04～1.004, and the number-average molecular weight scope of phenylethylene/maleic anhydride alternate copolymer is 80000～300000g/mol.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781387A (en) * | 2010-03-22 | 2010-07-21 | 北京化工大学 | Method for copolymerization of maleic anhydride/conjugated diene |
| CN101979417A (en) * | 2010-10-22 | 2011-02-23 | 北京化工大学 | A new method for preparing alternating copolymers of itaconic anhydride and styrene monomers |
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