CN117843863A - Synthesis method of ultralow molecular weight maleic anhydride-vinyl acetate alternating copolymer - Google Patents
Synthesis method of ultralow molecular weight maleic anhydride-vinyl acetate alternating copolymer Download PDFInfo
- Publication number
- CN117843863A CN117843863A CN202211213603.0A CN202211213603A CN117843863A CN 117843863 A CN117843863 A CN 117843863A CN 202211213603 A CN202211213603 A CN 202211213603A CN 117843863 A CN117843863 A CN 117843863A
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- CN
- China
- Prior art keywords
- vinyl acetate
- maleic anhydride
- molecular weight
- copolymer
- ultra
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- KRWWZDVIEFSIOT-UHFFFAOYSA-N ethenyl acetate;furan-2,5-dione Chemical compound CC(=O)OC=C.O=C1OC(=O)C=C1 KRWWZDVIEFSIOT-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229920005603 alternating copolymer Polymers 0.000 title claims abstract description 65
- 238000001308 synthesis method Methods 0.000 title claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 204
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 198
- 229920001577 copolymer Polymers 0.000 claims abstract description 134
- 239000000178 monomer Substances 0.000 claims abstract description 122
- 238000000034 method Methods 0.000 claims abstract description 79
- 239000003999 initiator Substances 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 239000012429 reaction media Substances 0.000 claims abstract description 50
- 239000006185 dispersion Substances 0.000 claims abstract description 48
- 239000012046 mixed solvent Substances 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 26
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- 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 claims description 268
- 238000003756 stirring Methods 0.000 claims description 51
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 32
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 32
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 31
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- GGBJHURWWWLEQH-UHFFFAOYSA-N Butyl-cyclohexane Natural products CCCCC1CCCCC1 GGBJHURWWWLEQH-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- XINCECQTMHSORG-UHFFFAOYSA-N Isoamyl isovalerate Chemical compound CC(C)CCOC(=O)CC(C)C XINCECQTMHSORG-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- -1 azo compound Chemical class 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 claims description 4
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 claims description 4
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 4
- PPXUHEORWJQRHJ-UHFFFAOYSA-N ethyl isovalerate Chemical compound CCOC(=O)CC(C)C PPXUHEORWJQRHJ-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 4
- PQLMXFQTAMDXIZ-UHFFFAOYSA-N isoamyl butyrate Chemical compound CCCC(=O)OCCC(C)C PQLMXFQTAMDXIZ-UHFFFAOYSA-N 0.000 claims description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001451 organic peroxides Chemical group 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- JLIDRDJNLAWIKT-UHFFFAOYSA-N 1,2-dimethyl-3h-benzo[e]indole Chemical compound C1=CC=CC2=C(C(=C(C)N3)C)C3=CC=C21 JLIDRDJNLAWIKT-UHFFFAOYSA-N 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- AVMSWPWPYJVYKY-UHFFFAOYSA-N 2-Methylpropyl formate Chemical compound CC(C)COC=O AVMSWPWPYJVYKY-UHFFFAOYSA-N 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical group COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- MLLAPOCBLWUFAP-UHFFFAOYSA-N 3-Methylbutyl benzoate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1 MLLAPOCBLWUFAP-UHFFFAOYSA-N 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- DIQMPQMYFZXDAX-UHFFFAOYSA-N Pentyl formate Chemical compound CCCCCOC=O DIQMPQMYFZXDAX-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical group CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229940072049 amyl acetate Drugs 0.000 claims description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 2
- DULCUDSUACXJJC-UHFFFAOYSA-N benzeneacetic acid ethyl ester Natural products CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 claims description 2
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 claims description 2
- 229940007550 benzyl acetate Drugs 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
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 2
- 229940117955 isoamyl acetate Drugs 0.000 claims description 2
- 229940094941 isoamyl butyrate Drugs 0.000 claims description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 2
- 229940095102 methyl benzoate Drugs 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-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
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- FFIUNPRXUCRYFU-UHFFFAOYSA-N tert-butyl pentaneperoxoate Chemical compound CCCCC(=O)OOC(C)(C)C FFIUNPRXUCRYFU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 34
- 238000012673 precipitation polymerization Methods 0.000 abstract description 11
- 239000012986 chain transfer agent Substances 0.000 abstract description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 77
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 48
- 238000006116 polymerization reaction Methods 0.000 description 44
- 230000015572 biosynthetic process Effects 0.000 description 29
- 238000003786 synthesis reaction Methods 0.000 description 29
- 229910052786 argon Inorganic materials 0.000 description 24
- 238000010992 reflux Methods 0.000 description 24
- 238000001035 drying Methods 0.000 description 23
- 238000005516 engineering process Methods 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000004005 microsphere Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229910052595 hematite Inorganic materials 0.000 description 3
- 239000011019 hematite Substances 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
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- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- AOJJSUZBOXZQNB-TZSSRYMLSA-N Doxorubicin Chemical compound O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-TZSSRYMLSA-N 0.000 description 2
- MWWSFMDVAYGXBV-RUELKSSGSA-N Doxorubicin hydrochloride Chemical group Cl.O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 MWWSFMDVAYGXBV-RUELKSSGSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000012648 alternating copolymerization Methods 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
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- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
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- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 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 description 1
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- 231100000053 low toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000002077 nanosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
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- 229920000098 polyolefin Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
The invention provides a method for synthesizing an ultralow molecular weight maleic anhydride-vinyl acetate alternating copolymer, which comprises the following steps: adding monomer maleic anhydride, vinyl acetate and an initiator into a reaction medium, fully dissolving, and reacting the reaction system at 70-95 ℃ for 4 h to obtain a dispersion system of ultra-low molecular weight maleic anhydride-vinyl acetate polymer particles; and centrifugally separating, washing and vacuum drying the dispersion system to obtain the white solid of the ultra-low molecular weight maleic anhydride-vinyl acetate alternating copolymer. The invention uses maleic anhydride and vinyl acetate as monomers, adopts a self-stabilizing precipitation polymerization process with low monomer concentration, high temperature, high maleic anhydride/vinyl acetate ratio, and high proportion of vinyl acetate and poor solvent in mixed solvent to the solution of maleic anhydride and initiator, and can obtain the maleic anhydride-vinyl acetate copolymer with the lowest molecular weight of 2400 g/mol without adding chain transfer agent, thereby solving the odor and cost problems caused by using the chain transfer agent.
Description
Technical Field
The invention belongs to the field of polymer precipitation polymerization, and in particular relates to a method for synthesizing an ultralow molecular weight maleic anhydride-vinyl acetate alternating copolymer.
Background
The polymer having a number average molecular weight of less than 15000g/mol is a low molecular weight polymer, and generally, the polymer having a number average molecular weight of 2400g/mol to 10000g/mol is a more preferable ultra low molecular weight polymer. Low molecular weight polymers are widely used in the practical fields of printing inks, adhesives, processing aids, and the like due to their good solubility, excellent compatibility, low fluid viscosity, and the like. As a low-priced polymer fine chemical, low-molecular-weight maleic anhydride-vinyl acetate alternating copolymer has excellent tissue compatibility and effective fluid diffusion, and thus is often used as an antiscaling agent, an adhesive, a dispersant, a flocculant, a water stabilizer, a slurry thinner, a soil conditioner, a leather retanning agent, a drug carrier, and the like.
At present, the preparation method of the maleic anhydride-vinyl acetate copolymer mainly comprises a solution polymerization method, a precipitation polymerization method, a dispersion polymerization method, an emulsion polymerization method and the like. Wherein, the precipitation polymerization has the advantages of simple post-treatment process, low cost and the like.
Xiao et al in "Synthesis and properties of starch-g-poly (maleic anhydride-co-vinyl acetate)" (Express Polymer Letters,2010,Vol.4 No.1,pp.9-16.) report that a maleic anhydride-vinyl acetate copolymer was prepared by precipitation polymerization using benzene as a dispersion medium and Azobisisobutyronitrile (AIBN) as an initiator, and further esterified with starch to prepare a polyelectrolyte chitosan complex and a pH-responsive polyvinyl alcohol hydrogel. Li et al, "The electrical performance of polyamide/poly (vinylidene fluoride) with vinyl acetate-maleic anhydride copolymer" (International Journal of Polymer Science, vol.2016, article ID 3580820,5 pages.) herein, use toluene as a solvent and Azobisisobutyronitrile (AIBN) as an initiator, and the maleic anhydride-vinyl acetate copolymer was obtained by precipitation polymerization. And then the copolymer is filled in the polyamide 66/polyvinylidene fluoride blend, so that the dielectric property and the piezoelectric property of the blend are improved, and the novel dielectric material is formed. Benzene or toluene in the system is a chemical with strong toxicity, and the benzene or toluene is used as a reaction medium to pollute the environment and does not accord with the development concept of green chemistry.
Karakus et al in "Synthesis, structural characterization, and antiproliferative/cytotoxic effects of a novel modified poly (maleic anhydride-co-vinyl acetate)/doxorubicin conjugate" (Polymer Bulletin,2017, vol.74No.6, pp.2159-2184.) prepared maleic anhydride-vinyl acetate copolymer using solution polymerization with Methyl Ethyl Ketone (MEK) as solvent and Benzoyl Peroxide (BPO) as initiatorIs 3.98X10 5 Da) and modified with doxorubicin hydrochloride (DOX), the modified copolymer was found to be non-toxic and not affecting cell viability. Rezazadeh et al in "Synthesis of a new magnetic nanocomposite hydrogel based on poly (vinyl acetate-co-maleic anhydride)/melamine for efficient dye removal" (Journal of Elastomers and Plastics,2020, vol.52No.1, pp. 70-89.) report the preparation of maleic anhydride-vinyl acetate copolymers using solution polymerization with Azobisisobutyronitrile (AIBN) as the initiator and Tetrahydrofuran (THF) as the reaction medium. After that, melamine (Me) and ferroferric oxide nanoparticles (Fe 3 O 4 NPs) to obtain the magnetic nanocomposite hydrogel capable of efficiently adsorbing Congo Red (CR) dye. Yang Qun et al, "use of polymaleic anhydride-vinyl acetate in the sanding process for the preparation of aqueous nano-hematite pigment dispersions" (printing and dyeing aid, 2014, vol.31no.1, pp.45-49.) in the literature, maleic anhydride-vinyl acetate polymers were prepared in ethyl acetate using solution polymerization with Azobisisobutyronitrile (AIBN) as the initiator, and the polymer solids were first saponified using sodium hydroxide (NaOH) solution. And adding the saponified polymer into hematite pigment, and preparing the nano hematite pigment aqueous dispersion by using a stirring type sanding method. The polymerization system belongs to the field of solution polymerization, but the polymer prepared by the solution polymerization system has high molecular weight, slow reaction rate, difficult recycling of solvent, environmental pollution, and low efficiency because the polymer product can be obtained by secondary treatment in actual operation.
Wei Zheng A series of maleic anhydride-vinyl acetate copolymers were prepared in different pH systems using an emulsion system of polyvinyl alcohol (PVA), nonylphenol polyoxyethylene ether (OP-10) and anionic surfactant, with ammonium persulfate as the initiator, in "study (I) of vinyl acetate homo-emulsion copolymerization modification-emulsion copolymerization of vinyl acetate with five monomers" (university of Beijing forestry, 1994, vol.16No.4, pp.85-91.). However, the presence of water in the above reaction results in the conversion of the maleic anhydride moiety to maleic acid, which reduces the polymerization efficiency and results in a low yield.
Liu Min et al, "synthesis and characterization of vinyl acetate/maleic anhydride copolymers" (colloid and Polymer, 2015, vol.33No.3, pp.119-122.)) are described herein as supercritical carbon dioxide (CO 2 ) As a reaction medium, azo diisobutyronitrile (AIBN) is used as an initiator to synthesize maleic anhydride-vinyl acetate copolymerIn the range of 12400g/mol to 26200 g/mol), the influence of the reaction pressure on the polymerization process and the product morphology is specifically discussed, and the chelating ability and the descaling performance of the copolymer on calcium ions are further studied. The Chinese patent publication No. CN101643526B discloses a method for preparing a maleic anhydride-vinyl acetate copolymer by taking supercritical carbon dioxide as a polymerization medium. The method has the advantages of simple operation, environmental protection, pure product and recyclable medium. Although the maleic anhydride-vinyl acetate copolymer prepared by the method meets the requirement of low molecular weight, a system taking supercritical carbon dioxide as a medium needs to be carried out under higher pressure, so that the safety requirements on a polymerization reaction device, a process flow and equipment are higher.
Self-stabilizing precipitation polymerization is an important polymerization technique of the subject group, and is initially used for preparing maleic anhydride-vinyl acetate copolymer, and is mainly used for preparing copolymer microspheres with uniform and controllable particle size. The system can react under different monomer concentration, monomer proportion, initiator concentration and solvent proportion. Xing Changmin, yang Motai in "A novel, facile method for the preparation of uniform, reactive maleic anhydride/vinyl acetate copolymer micro-and nanospheres" (Macromolecular Rapid Communications,2004,Vol.25 No.17,pp.1568-1574.), "Stabilizer-free dispersion copolymerization of maleic anhydride and vinyl acetate. I.effects of principal factors on microspheres" (Journal of Polymer Science: part A: polymer Chemistry,2005, vol.43No.17, pp. 3760-3770.), and "Stabilizer-free dispersion copolymerization of maleic anhydride and vinyl acetate. II. Polymerization features" (Macromolecular Chemistry and Physics,2006, vol.207No.6, pp. 621-626.) describe such a simple, stabilizer-free process for preparing maleic anhydride-vinyl acetate copolymer microspheres that can be used to prepare copolymer microspheres having a clean surface and uniform and controllable particle size. Meanwhile, yang Motai and Xing Changmin disclose a method for preparing the maleic anhydride-vinyl acetate copolymer microsphere in a 'method for copolymerization of maleic anhydride and vinyl acetate' disclosed in China patent No. ZL 200310115329.4. However, only the morphology of the maleic anhydride-vinyl acetate copolymer microspheres is analyzed in this patent, and the molecular weight of the prepared copolymer is not discussed. Further, the polymers reported in the above three non-patent documents have relatively high molecular weights, and are not suitable for practical fields such as processing aids and adhesives. Our aim is to obtain ultra low molecular weight maleic anhydride-vinyl acetate polymers, so the reaction conditions must be adjusted, for example: low monomer concentration, high temperature, high MAH/VAc ratio, high poor solvent ratio in the mixed solvent, etc.
In recent years, the subject group also discloses a plurality of patents for preparing copolymer microspheres by self-stabilizing precipitation polymerization, wherein the patents related to maleic anhydride-vinyl acetate copolymer are as follows: the Chinese patent publication No. 200810118553.1 discloses a method for preparing a cross-linked maleic anhydride-vinyl acetate copolymer. The Chinese patent publication No. 201911024608.7 discloses a method for preparing composite microspheres containing vinyl acetate-maleic anhydride polymer. The method can be used as an opening agent to remarkably improve the opening performance of the polyolefin film.
In view of the above, there are many disadvantages of the conventional polymerization process for preparing maleic anhydride-vinyl acetate copolymer, and improvement is desired. Also, the maleic anhydride-vinyl acetate copolymer produced by the polymerization method in the above-mentioned document is mostly a polymer having a high molecular weight. It is particularly desirable to address the very few reports in the literature of specific studies on maleic anhydride-vinyl acetate copolymers featuring ultra-low molecular weights.
The self-stabilizing precipitation polymerization method is a special precipitation polymerization method, and the polymer reaches the critical chain length, i.e. precipitates from the solvent, and is particularly suitable for preparing low molecular weight polymers. Thiol chain transfer agents with special odor are often used for preparing low molecular weight polymers in the field of high molecular science, which not only increases the preparation cost, but also causes the products to have bad odor. The Chinese patent publication No. CN101503490B discloses a method for synthesizing a low molecular weight styrene/maleic anhydride alternating copolymer, which discloses a method for preparing a low molecular weight styrene/maleic anhydride copolymer by self-stabilizing precipitation polymerization and adding novel chain transfer agent alpha-methyl styrene, so as to obtain 3000-12000 g/mol low molecular weight polymer and solve the problem that products have bad smell due to the use of thiol chain transfer agents. But the additional cost problems associated with the use of alpha-methylstyrene chain transfer agents remain unsolved.
Disclosure of Invention
The invention aims to provide a synthetic method of an ultralow molecular weight maleic anhydride-vinyl acetate alternating copolymer, which aims to solve the problem that the molecular weight of the maleic anhydride-vinyl acetate copolymer prepared by the conventional polymerization method is relatively high.
The invention is realized in the following way: a synthetic method of an ultralow molecular weight maleic anhydride-vinyl acetate alternating copolymer comprises the following steps:
a. adding monomer maleic anhydride, vinyl acetate and an initiator into a reaction medium, or dripping vinyl acetate monomer into the solution of the maleic anhydride and the initiator to fully dissolve the vinyl acetate monomer, wherein the molar ratio of the maleic anhydride to the vinyl acetate in the reaction system is 1:1-3:1; the sum of mass concentration of maleic anhydride and vinyl acetate is 2% -15%; the initiator is an organic peroxide or azo compound; the reaction medium is a mixed solvent of organic acid alkyl ester and alkane;
b. reacting the reaction system for 4 hours at the temperature of 70-95 ℃ to obtain a dispersion system of ultra-low molecular weight maleic anhydride-vinyl acetate polymer particles;
c. and centrifugally separating, washing and vacuum drying the dispersion system to obtain the white solid of the ultra-low molecular weight maleic anhydride-vinyl acetate alternating copolymer.
Further, the invention can be realized according to the following technical scheme:
in the step a, the volume fraction of alkane in the mixed solvent of the organic acid alkyl ester and alkane in the reaction medium is 10-80%.
In the step a, the volume fraction of alkane in the mixed solvent of the organic acid alkyl ester and alkane in the reaction medium is 60-80%, the proportion of poor solvent is high, and the number average molecular weight of the obtained copolymer is lower.
In the step a, the sum of mass concentration of maleic anhydride and vinyl acetate is 2% -4%.
In the step a, the molar ratio of maleic anhydride to vinyl acetate in the reaction system is 3:1.
In the step b, the reaction system is polymerized at the temperature of 85-95 ℃.
In the step a, the mass concentration of an initiator in a reaction system is 0.1-0.8%; the organic peroxide is cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, ditert-butyl peroxide, dibenzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyvalerate, diisopropyl peroxydicarbonate or dicyclohexyl peroxydicarbonate; the azo compound is azodiisobutyronitrile or azodiisoheptonitrile.
The structural general formula of the organic acid alkyl esterThe method comprises the following steps:
wherein R is 1 Is hydrogen atom, C 1 ～C 8 Alkyl, phenyl or benzyl, R 2 Is C 1 ～C 5 Alkyl of (a);
the organic acid alkyl ester is ethyl formate, propyl formate, isobutyl formate, amyl formate, ethyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isoamyl butyrate, ethyl isovalerate, isoamyl isovalerate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl benzoate or ethyl phenylacetate;
the alkane is cyclohexane, n-hexane, n-heptane, n-pentane, n-octane or isooctane.
The reaction medium is a mixed solvent of butyl acetate and cyclohexane.
In step a, the monomers Maleic Anhydride (MAH), vinyl acetate (VAc) and initiator are fully dissolved in the reaction medium by stirring or ultrasonic wave.
The invention uses maleic anhydride and vinyl acetate as monomers, and adopts the self-stabilization precipitation polymerization process with low monomer concentration, high temperature, high maleic anhydride MAH/vinyl acetate VAc ratio and high ratio of poor solvent in mixed solvent, and the maleic anhydride-vinyl acetate copolymer with the lowest molecular weight of 2400g/mol can be obtained without adding chain transfer agent, thereby perfectly solving the odor and cost problems caused by using the chain transfer agent. The method of dripping vinyl acetate into the solution of maleic anhydride and initiator is also adopted to further reduce the molecular weight of the copolymer. In addition, the high maleic anhydride MAH/vinyl acetate VAc ratio is such that the excessive maleic anhydride MAH does not participate in the polymerization reaction in practice, and thus the supernatant after the polymer separation contains a large amount of maleic anhydride MAH monomer. And vinyl acetate VAc is added into the supernatant again, so that the copolymer can be synthesized by continuing to carry out polymerization reaction, and the ultra-low molecular weight copolymer can be obtained and the high-efficiency recycling of the monomer can be realized.
The selection of a proper reaction medium is very critical for synthesizing the ultra-low molecular weight maleic anhydride-vinyl acetate alternating copolymer, the reaction medium adopted by the invention is a mixed solvent of butyl acetate and cyclohexane, and the reaction medium can fully dissolve maleic anhydride, vinyl acetate monomers and an initiator before the polymerization reaction so as to ensure that the reaction is a homogeneous system. Meanwhile, the copolymer produced by the polymerization reaction cannot be dissolved in the reaction medium, and the copolymer molecular chain is precipitated from the reaction medium when reaching the critical length. The low monomer concentration and the matching of the organic acid alkyl ester and the alkane in the reaction medium have the synergistic effect.
Number average molecular weight of ultra low molecular weight alternating maleic anhydride-vinyl acetate copolymerIn the range 2400-21400 g/mol, and the molecular weight polydispersity index (PDI) is 1.32-1.80.
The polymerization process provided by the invention has the following advantages:
1) The operation is simple, stirring is not needed in the polymerization process, and the energy consumption is saved. After the reaction, the copolymer is precipitated directly from the medium in the form of particles without adding a precipitating agent for secondary treatment.
2) The post-treatment process is simple, and the sediment supernatant can be recycled. The reaction medium is a low-toxicity chemical, so that the environmental pollution is reduced.
3) The reaction system only comprises monomer, initiator and solvent, so that the surface of the obtained product is clean and pollution-free.
4) The invention particularly researches the synthesis process of the ultra-low molecular weight maleic anhydride-vinyl acetate copolymer, and supplements the research gap of the ultra-low molecular weight maleic anhydride-vinyl acetate alternating copolymer in the field.
Drawings
FIG. 1 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 1.
FIG. 2 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 2.
FIG. 3 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 3.
FIG. 4 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 4.
FIG. 5 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 5.
FIG. 6 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 6.
FIG. 7 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 7.
FIG. 8 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 8.
FIG. 9 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 9.
FIG. 10 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 10.
FIG. 11 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 11.
FIG. 12 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 12.
FIG. 13 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 13.
FIG. 14 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 14.
FIG. 15 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 15.
FIG. 16 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 16.
FIG. 17 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 17.
FIG. 18 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared by recycling MAH in the supernatant of example 17.
FIG. 19 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 18.
FIG. 20 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 19.
FIG. 21 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 20.
FIG. 22 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 21.
FIG. 23 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in example 22.
FIG. 24 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in comparative example 1.
FIG. 25 is a Gel Permeation Chromatography (GPC) chart of the copolymer prepared in comparative example 2.
The abscissa in the GPC spectrum of the copolymer gel permeation chromatograph represents the Time of Elution (Time) in minutes (min); the ordinate represents the detector Signal strength (Signal Intensity) in millivolts (mV).
Detailed Description
Number average molecular weight and molecular weight polydispersity index (PDI) test method for ultra low molecular weight maleic anhydride-vinyl acetate copolymer: the ionic effect was suppressed by adding lithium bromide (LiBr, 10 mmol/L) to a Shimadzu LC-20A Gel Permeation Chromatograph (GPC) with N, N-Dimethylformamide (DMF) as the mobile phase at a flow rate of 1.0 mL/min. The temperature was 30℃and the column was Agilent Technologies, PLgel 5 μm MIXED-C.
The invention is further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention in any way.
The procedures and methods not described in detail in the examples of the present invention are conventional methods well known in the art, and reagents used in the examples are all analytically or chemically pure and are all commercially available or prepared by methods well known to those of ordinary skill in the art. The following examples all achieve the object of the invention.
In examples 1 to 7 according to the invention, the butyl acetate and cyclohexane were used in different proportions in the reaction medium and the other reaction parameters were fixed. The volume fraction of cyclohexane in the mixed solvent of butyl acetate and cyclohexane is 10-70%, and the number average molecular weight of the copolymer is 18400-12400 g/mol. In examples 8 to 11, the polymerization temperature was varied and the other reaction parameters were fixed. Wherein, in examples 10 and 11, the polymerization temperatures were 85℃and 95℃respectively (high temperature), and the number average molecular weights of the copolymers were 9100g/mol and 7900g/mol, respectively. Examples 8 and 9, polymerization temperatures of 70℃and 75℃respectively, and copolymer number average molecular weights of 12900g/mol and 12300g/mol, respectively. In examples 6 and 11 to 14, the total mass concentrations of maleic anhydride MAH and vinyl acetate VAc monomers were different, and the other reaction parameters were fixed. Wherein, in example 11, the total mass concentration of the monomers was 4% (low monomer concentration), and the number average molecular weight of the copolymer was 7900g/mol. Examples 6, 12-14, total monomer mass concentrations of 6%, 8%, 10% and 15%, respectively, and copolymer number average molecular weights of 12600g/mol, 13200g/mol, 17000g/mol and 21400g/mol, respectively. In examples 15-17, the molar ratio of maleic anhydride MAH/vinyl acetate VAc monomer was varied and the other reaction parameters were fixed. In example 17, the maleic anhydride MAH/vinyl acetate VAc molar ratio was 3:1 (maleic anhydride/vinyl acetate high ratio), and the number average molecular weight of the copolymer was 2800g/mol. Examples 15 and 16, maleic anhydride MAH/vinyl acetate VAc molar ratios of 1:1 and 2:1, copolymer number average molecular weights of 3900g/mol and 3400g/mol, respectively. In examples 17 to 22, the vinyl acetate VAc was added dropwise at different times, and the other reaction parameters were fixed. Wherein, in examples 18-22, the dripping time of the vinyl acetate VAc is respectively 10min, 20min, 30min, 40min and 50min (dripping monomer), and the number average molecular weight of the copolymer is respectively 3100g/mol, 2700g/mol, 2800g/mol and 2400g/mol. Example 17 vinyl acetate VAc and maleic anhydride MAH, initiator were added to the reaction medium in one portion and the copolymer number average molecular weight was 2800g/mol.
Example 1
According to the formula shown in Table 1, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 1:1, the monomer maleic anhydride MAH is 0.2942g, the vinyl acetate VAc is 0.2583g (the total mass concentration of the monomers is 6%); the initiator is azobisisobutyronitrile AIBN 0.0276g (the initiator accounts for 5 percent of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (9 mL) and cyclohexane (1 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.3%.
Synthesis of the copolymer: placing maleic anhydride MAH, vinyl acetate VAc, azobisisobutyronitrile AIBN and solvent in a round bottom flask equipped with a spherical reflux condenser, stirring at room temperature for 15min, using SchThe lenk line technique (double-exhaust operation technique) provides an inert argon atmosphere for the reactor, then the system is placed in an oil bath at 95 ℃ to react for 4 hours (without stirring) to obtain a dispersion system of the maleic anhydride-vinyl acetate alternating copolymer, the dispersion system is centrifugally separated, washed and dried to obtain a white solid of the maleic anhydride-vinyl acetate alternating copolymer, and the polymerization yield (C) p ) 42% number average molecular weight of copolymer18400g/mol and a molecular weight polydispersity index (PDI) of 1.35, as shown in Table 1. GPC patterns of the obtained copolymer are shown in FIG. 1.
Example 2
According to the formula shown in Table 1, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 1:1, the monomer maleic anhydride MAH is 0.2942g, the vinyl acetate VAc is 0.2583g (the total mass concentration of the monomers is 6%); the initiator is azobisisobutyronitrile AIBN0.0276g (the initiator accounts for 5 percent of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (8 mL) and cyclohexane (2 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.3%.
Synthesis of the copolymer: placing maleic anhydride MAH, vinyl acetate VAc, azodiisobutyronitrile AIBN and solvent in a round bottom flask equipped with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technique (double-discharge operation technique) to provide argon inert environment for the reactor, then placing the system in an oil bath at 95deg.C for reaction for 4h (without stirring) to obtain a dispersion system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the dispersion system, washing, and drying to obtain white solid of maleic anhydride-vinyl acetate alternating copolymer, and the polymerization yield (C p ) 41% of the number average molecular weight of the copolymer16700g/mol and a molecular weight polydispersity index (PDI) of 1.34, as shown in Table 1. GPC patterns of the obtained copolymer are shown in FIG. 2.
Example 3
According to the formula shown in Table 1, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 1:1, the monomer maleic anhydride MAH is 0.2942g, the vinyl acetate VAc is 0.2583g (the total mass concentration of the monomers is 6%); the initiator is azobisisobutyronitrile AIBN0.0276g (the initiator accounts for 5 percent of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (7 mL) and cyclohexane (3 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.3%.
Synthesis of the copolymer: placing maleic anhydride MAH, vinyl acetate VAc, azodiisobutyronitrile AIBN and solvent in a round bottom flask equipped with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technique (double-discharge operation technique) to provide argon inert environment for the reactor, then placing the system in an oil bath at 95deg.C for reaction for 4h (without stirring) to obtain a dispersion system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the dispersion system, washing, and drying to obtain white solid of maleic anhydride-vinyl acetate alternating copolymer, and the polymerization yield (C p ) 52% of the number average molecular weight of the copolymer16200g/mol and a molecular weight polydispersity index (PDI) of 1.37, as shown in Table 1. GPC patterns of the obtained copolymer are shown in FIG. 3.
Example 4
According to the formula shown in Table 1, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 1:1, the monomer maleic anhydride MAH is 0.2942g, the vinyl acetate VAc is 0.2583g (the total mass concentration of the monomers is 6%); the initiator is azobisisobutyronitrile AIBN0.0276g (the initiator accounts for 5 percent of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (6 mL) and cyclohexane (4 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.3%.
Synthesis of the copolymer: maleic anhydride MAH, vinyl acetate VAc, azobisisobutyronitrile AIBN and solvent were placed in a round bottom flask equipped with a spherical reflux condenser, stirred at room temperature for 15min, the reactor was provided with an argon inert atmosphere using Schlenk line technique (double-vent operation technique), after which the system was placed at 95 ℃The reaction was carried out in an oil bath for 4 hours (without stirring) to obtain a dispersion of a maleic anhydride-vinyl acetate alternating copolymer, the dispersion was centrifugally separated, washed and dried to obtain a white solid of the maleic anhydride-vinyl acetate alternating copolymer, and the polymerization yield (C) p ) 56% number average molecular weight of copolymerA polydispersity index (PDI) of 1.37 at 14300g/mol and a molecular weight is shown in Table 1. GPC patterns of the obtained copolymer are shown in FIG. 4.
Example 5
According to the formula shown in Table 1, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 1:1, the monomer maleic anhydride MAH is 0.2942g, the vinyl acetate VAc is 0.2583g (the total mass concentration of the monomers is 6%); the initiator is azobisisobutyronitrile AIBN0.0276g (the initiator accounts for 5 percent of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (5 mL) and cyclohexane (5 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.3%.
Synthesis of the copolymer: placing maleic anhydride MAH, vinyl acetate VAc, azodiisobutyronitrile AIBN and solvent in a round bottom flask equipped with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technique (double-discharge operation technique) to provide argon inert environment for the reactor, then placing the system in an oil bath at 95deg.C for reaction for 4h (without stirring) to obtain a dispersion system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the dispersion system, washing, and drying to obtain white solid of maleic anhydride-vinyl acetate alternating copolymer, and the polymerization yield (C p ) 62% of the number average molecular weight of the copolymer13600g/mol and a molecular weight polydispersity index (PDI) of 1.38 as shown in Table 1. GPC patterns of the obtained copolymer are shown in FIG. 5.
Example 6
According to the formula shown in Table 1, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 1:1, the monomer maleic anhydride MAH is 0.2942g, the vinyl acetate VAc is 0.2583g (the total mass concentration of the monomers is 6%); the initiator is azobisisobutyronitrile AIBN0.0276g (the initiator accounts for 5 percent of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (4 mL) and cyclohexane (6 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.3%.
Synthesis of the copolymer: placing maleic anhydride MAH, vinyl acetate VAc, azodiisobutyronitrile AIBN and solvent in a round bottom flask equipped with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technique (double-discharge operation technique) to provide argon inert environment for the reactor, then placing the system in an oil bath at 95deg.C for reaction for 4h (without stirring) to obtain a dispersion system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the dispersion system, washing, and drying to obtain white solid of maleic anhydride-vinyl acetate alternating copolymer, and the polymerization yield (C p ) 66% of the number average molecular weight of the copolymer12600g/mol and a molecular weight polydispersity index (PDI) of 1.39, as shown in Table 1. GPC patterns of the obtained copolymer are shown in FIG. 6.
Example 7
According to the formula shown in Table 1, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 1:1, the monomer maleic anhydride MAH is 0.2942g, the vinyl acetate VAc is 0.2583g (the total mass concentration of the monomers is 6%); the initiator is azobisisobutyronitrile AIBN0.0276g (the initiator accounts for 5 percent of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (3 mL) and cyclohexane (7 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.3%.
Synthesis of the copolymer: placing maleic anhydride MAH, vinyl acetate VAc, azodiisobutyronitrile AIBN and solvent in a round bottom flask equipped with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technique (double-discharge operation technique) to provide argon inert environment for the reactor, then placing the system in 95 deg.C oil bath to react for 4h (without stirring) to obtain a dispersion system of maleic anhydride-vinyl acetate alternating copolymer, and separatingCentrifugal separation of the dispersion, washing and drying to obtain white solid of maleic anhydride-vinyl acetate alternating copolymer, and polymerization yield (C) p ) 92% number average molecular weight of copolymer12400g/mol and a molecular weight polydispersity index (PDI) of 1.41, as shown in Table 1. GPC patterns of the obtained copolymer are shown in FIG. 7.
Table 1 data comparing the results of the various butyl acetate and cyclohexane ratios in the reaction medium of examples 1 to 7
Example 8
According to the formula shown in Table 2, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 1:1, the monomer maleic anhydride MAH is 0.1961g, the vinyl acetate VAc is 0.1722g (the total mass concentration of the monomers is 4%); the initiator is azobisisobutyronitrile AIBN0.0184g (the initiator accounts for 5% of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (4 mL) and cyclohexane (6 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.2%.
Synthesis of the copolymer: placing maleic anhydride MAH, vinyl acetate VAc, azodiisobutyronitrile AIBN and solvent in a round bottom flask equipped with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technique (double-discharge operation technique) to provide argon inert environment for the reactor, then placing the system in an oil bath at 70deg.C for reaction for 4h (without stirring) to obtain a dispersion system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the dispersion system, washing, and drying to obtain white solid of maleic anhydride-vinyl acetate alternating copolymer, and the polymerization yield (C p ) Number average molecular weight of the copolymer of 7%12900g/mol and a molecular weight polydispersity index (PDI) of 1.42, as shown in Table 2. GPC patterns of the obtained copolymer are shown in FIG. 8.
Example 9
According to the formula shown in Table 2, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 1:1, the monomer maleic anhydride MAH is 0.1961g, the vinyl acetate VAc is 0.1722g (the total mass concentration of the monomers is 4%); the initiator is azobisisobutyronitrile AIBN 0.0184g (the initiator accounts for 5% of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (4 mL) and cyclohexane (6 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.2%.
Synthesis of the copolymer: placing maleic anhydride MAH, vinyl acetate VAc, azodiisobutyronitrile AIBN and solvent in a round bottom flask equipped with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technique (double-discharge operation technique) to provide argon inert environment for the reactor, then placing the system in an oil bath at 75deg.C to react for 4h (without stirring) to obtain a dispersion system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the dispersion system, washing, and drying to obtain white solid of maleic anhydride-vinyl acetate alternating copolymer, and the polymerization yield (C p ) 38% of the number average molecular weight of the copolymer12300g/mol and a molecular weight polydispersity index (PDI) of 1.40, as shown in Table 2. GPC patterns of the obtained copolymer are shown in FIG. 9.
Example 10
According to the formula shown in Table 2, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 1:1, the monomer maleic anhydride MAH is 0.1961g, the vinyl acetate VAc is 0.1722g (the total mass concentration of the monomers is 4%); the initiator is azobisisobutyronitrile AIBN0.0184g (the initiator accounts for 5% of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (4 mL) and cyclohexane (6 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.2%.
Synthesis of the copolymer: placing maleic anhydride MAH, vinyl acetate VAc, azodiisobutyronitrile AIBN and solvent in a round bottom flask equipped with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technique (double-discharge operation technique) to provide argon inert environment for the reactor, then placing the system in an oil bath at 85deg.C for reaction for 4h (without stirring) to obtain a dispersion system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the dispersion system, washing, and drying to obtain white solid of maleic anhydride-vinyl acetate alternating copolymer, and polymerization yield (C p ) 50% of the number average molecular weight of the copolymer9100g/mol and a molecular weight polydispersity index (PDI) of 1.36, as shown in Table 2. GPC patterns of the obtained copolymer are shown in FIG. 10.
Example 11
According to the formula shown in Table 2, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 1:1, the monomer maleic anhydride MAH is 0.1961g, the vinyl acetate VAc is 0.1722g (the total mass concentration of the monomers is 4%); the initiator is azobisisobutyronitrile AIBN0.0184g (the initiator accounts for 5% of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (4 mL) and cyclohexane (6 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.2%.
Synthesis of the copolymer: placing maleic anhydride MAH, vinyl acetate VAc, azodiisobutyronitrile AIBN and solvent in a round bottom flask equipped with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technique (double-discharge operation technique) to provide argon inert environment for the reactor, then placing the system in an oil bath at 95deg.C for reaction for 4h (without stirring) to obtain a dispersion system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the dispersion system, washing, and drying to obtain white solid of maleic anhydride-vinyl acetate alternating copolymer, and the polymerization yield (C p ) Number average molecular weight of 35% of copolymer7900g/mol and a molecular weight polydispersity index (PDI) of 1.33, as shown in Table 2. GPC patterns of the obtained copolymer are shown in FIG. 11.
Table 2 data results comparing examples 8-11 for different polymerization temperatures
Example 12
According to the formula shown in Table 3, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 1:1, the monomer maleic anhydride MAH is 0.3922g, the vinyl acetate VAc is 0.3444g (the total mass concentration of the monomers is 8%); the initiator is azobisisobutyronitrile AIBN0.0368g (the mass percent of the initiator to the total monomer is 5%); the reaction medium was a mixed solvent of butyl acetate (4 mL) and cyclohexane (6 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.4%.
Synthesis of the copolymer: placing maleic anhydride MAH, vinyl acetate VAc, azodiisobutyronitrile AIBN and solvent in a round bottom flask equipped with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technique (double-discharge operation technique) to provide argon inert environment for the reactor, then placing the system in an oil bath at 95deg.C for reaction for 4h (without stirring) to obtain a dispersion system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the dispersion system, washing, and drying to obtain white solid of maleic anhydride-vinyl acetate alternating copolymer, and the polymerization yield (C p ) 77% of the number average molecular weight of the copolymer13200g/mol and a molecular weight polydispersity index (PDI) of 1.48, as shown in Table 3. GPC patterns of the obtained copolymer are shown in FIG. 12.
Example 13
According to the formula shown in Table 3, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 1:1, the monomer maleic anhydride MAH is 0.4903g, the vinyl acetate VAc is 0.4304g (the total mass concentration of the monomers is 10 percent); the initiator is azobisisobutyronitrile AIBN (0.0460 g, the initiator accounts for 5% of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (4 mL) and cyclohexane (6 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.5%.
Synthesis of the copolymer: placing maleic anhydride MAH, vinyl acetate VAc, azodiisobutyronitrile AIBN and solvent in a round bottom flask equipped with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technique (double-discharge operation technique) to provide argon inert environment for the reactor, then placing the system in an oil bath at 95deg.C for reaction for 4h (without stirring) to obtain a dispersion system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the dispersion system, washing, and drying to obtain white solid of maleic anhydride-vinyl acetate alternating copolymer, and the polymerization yield (C p ) 98% of the number average molecular weight of the copolymer17000g/mol and a molecular weight polydispersity index (PDI) of 1.58, as shown in Table 3. GPC patterns of the obtained copolymer are shown in FIG. 13.
Example 14
According to the formula shown in Table 3, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 1:1, the monomer maleic anhydride MAH is 0.7845g, the vinyl acetate VAc is 0.6887g (the total mass concentration of the monomers is 15 percent); the initiator is azobisisobutyronitrile AIBN (0.0737 g, the initiator accounts for 5% of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (4 mL) and cyclohexane (6 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.8%.
Synthesis of the copolymer: placing maleic anhydride MAH, vinyl acetate VAc, azodiisobutyronitrile AIBN and solvent into a round bottom flask equipped with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technology (double-row pipe operation technology) to provide argon inert environment for a reactor, then placing the system into an oil bath at 95 ℃ to react for 4h (without stirring) to obtain a disperse system of maleic anhydride-vinyl acetate alternating copolymer, centrifugally separating, washing and drying the disperse system to obtain white solid of maleic anhydride-vinyl acetate alternating copolymer, and polymerizing the copolymer Yield (C) p ) 98% of the number average molecular weight of the copolymerA polydispersity index (PDI) of 1.74 at 21400g/mol and shown in Table 3. GPC patterns of the obtained copolymer are shown in FIG. 14.
Table 3 comparison of the data results for the different monomer concentrations of example 6, examples 11-14
Example 15
According to the formula shown in Table 4, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 1:1, the monomer maleic anhydride MAH is 0.0981g, the vinyl acetate VAc is 0.0861g (the total mass concentration of the monomers is 2 percent); the initiator is azobisisobutyronitrile AIBN 0.0092g (the initiator accounts for 5 percent of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (2 mL) and cyclohexane (8 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.1%.
Synthesis of the copolymer: placing maleic anhydride MAH, vinyl acetate VAc, azodiisobutyronitrile AIBN and solvent in a round bottom flask equipped with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technique (double-discharge operation technique) to provide argon inert environment for the reactor, then placing the system in an oil bath at 95deg.C for reaction for 4h (without stirring) to obtain a dispersion system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the dispersion system, washing, and drying to obtain white solid of maleic anhydride-vinyl acetate alternating copolymer, and the polymerization yield (C p ) 55% of the number average molecular weight of the copolymer3900g/mol and a molecular weight polydispersity index (PDI) of 1.80, as shown in Table 4. GPC patterns of the obtained copolymer are shown in FIG. 15.
Example 16
According to the formula shown in Table 4, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 2:1, the monomer maleic anhydride MAH is 0.1310g, and the vinyl acetate VAc is 0.0574g (the total mass concentration of the monomers is 2%); the initiator is azobisisobutyronitrile AIBN 0.0094g (the initiator accounts for 5 percent of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (2 mL) and cyclohexane (8 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.1%.
Synthesis of the copolymer: placing maleic anhydride MAH, vinyl acetate VAc, azodiisobutyronitrile AIBN and solvent in a round bottom flask equipped with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technique (double-discharge operation technique) to provide argon inert environment for the reactor, then placing the system in an oil bath at 95deg.C for reaction for 4h (without stirring) to obtain a dispersion system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the dispersion system, washing, and drying to obtain white solid of maleic anhydride-vinyl acetate alternating copolymer, and the polymerization yield (C p ) 45% of the number average molecular weight of the copolymer3400g/mol and a molecular weight polydispersity index (PDI) of 1.57 as shown in Table 4. GPC patterns of the obtained copolymer are shown in FIG. 16.
Example 17
According to the formula shown in Table 4, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 3:1, the monomer maleic anhydride MAH is 0.1471g, and the vinyl acetate VAc is 0.0430g (the total mass concentration of the monomers is 2%); the initiator is azobisisobutyronitrile AIBN 0.0095g (the initiator accounts for 5 percent of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (2 mL) and cyclohexane (8 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.1%.
Synthesis of the copolymer: maleic anhydride MAH, vinyl acetate VAc, azobisisobutyronitrile AIBN and solvent were placed in a round bottom flask equipped with a spherical reflux condenser, stirred at room temperature for 15min, the reactor was provided with an argon inert atmosphere using Schlenk line technique (double-discharge operation technique), and then the system was placed in an oil bath at 95℃for reaction for 4h (without stirring)Stirring) to obtain a dispersion of the maleic anhydride-vinyl acetate alternating copolymer, centrifuging the dispersion, washing the resultant, and drying the resultant to obtain a white solid of the maleic anhydride-vinyl acetate alternating copolymer, and obtaining a polymerization yield (C) p ) 40% of the number average molecular weight of the copolymer2800g/mol and a molecular weight polydispersity index (PDI) of 1.46, as shown in Table 4. GPC patterns of the obtained copolymer are shown in FIG. 17.
Recycling of excess maleic anhydride MAH in the supernatant: adding 0.086g of vinyl acetate VAc into the supernatant after centrifugal separation, stirring for 15min at normal temperature, using Schlenk line technology (double-exhaust operation technology) to provide argon inert environment for a reactor, then placing the system in an oil bath at 95 ℃ for reaction for 4h (without stirring) to obtain a dispersion system of the maleic anhydride-vinyl acetate alternating copolymer, centrifugally separating, washing and drying the dispersion system to obtain white solid of the maleic anhydride-vinyl acetate alternating copolymer. Number average molecular weight of copolymerThe GPC chart of the obtained copolymer is shown in FIG. 18, with a molecular weight polydispersity index (PDI) of 1.91 at 4000 g/mol. />
Table 4 comparison of the results of the data for the different molar ratios of the monomers maleic anhydride MAH and vinyl acetate VAc of examples 15-17
Example 18
According to the formula shown in Table 5, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 3:1, the monomer maleic anhydride MAH is 0.1471g, and the vinyl acetate VAc is 0.0430g (the total mass concentration of the monomers is 2%); the initiator is azobisisobutyronitrile AIBN 0.0095g (the initiator accounts for 5 percent of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (2 mL) and cyclohexane (8 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.1%.
Synthesis of the copolymer: placing maleic anhydride MAH, azodiisobutyronitrile AIBN and solvent into an inclined two-neck round bottom flask with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technology (double-row pipe operation technology) to provide argon inert environment for a reactor, placing the system into an oil bath at 95 ℃, preheating for 10min, beginning to dropwise add vinyl acetate VAc, completing the dropwise addition for 10min, reacting for 4h (without stirring) to obtain a disperse system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the disperse system, washing and drying to obtain reddish brown solid of the maleic anhydride-vinyl acetate alternating copolymer, and obtaining the polymerization yield (C p ) 42% number average molecular weight of copolymerA polydispersity index (PDI) of 1.49 at 3100g/mol is shown in Table 5. GPC patterns of the obtained copolymer are shown in FIG. 19.
Example 19
According to the formula shown in Table 5, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 3:1, the monomer maleic anhydride MAH is 0.1471g, and the vinyl acetate VAc is 0.0430g (the total mass concentration of the monomers is 2%); the initiator is azobisisobutyronitrile AIBN 0.0095g (the initiator accounts for 5 percent of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (2 mL) and cyclohexane (8 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.1%.
Synthesis of the copolymer: placing maleic anhydride MAH, azodiisobutyronitrile AIBN and solvent into an inclined two-neck round bottom flask with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technology (double-row pipe operation technology) to provide argon inert environment for a reactor, placing the system into an oil bath at 95 ℃, preheating for 10min, beginning to dropwise add vinyl acetate VAc, finishing dropwise after 20min, reacting for 4h (without stirring) to obtain a disperse system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the disperse system, washing and drying to obtain reddish brown solid of the maleic anhydride-vinyl acetate alternating copolymer, and obtaining the polymerization yield (C p ) 28%, altogetherNumber average molecular weight of the Polymer2700g/mol and a molecular weight polydispersity index (PDI) of 1.33, as shown in Table 5. GPC patterns of the obtained copolymer are shown in FIG. 20.
Example 20
According to the formula shown in Table 5, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 3:1, the monomer maleic anhydride MAH is 0.1471g, and the vinyl acetate VAc is 0.0430g (the total mass concentration of the monomers is 2%); the initiator is azobisisobutyronitrile AIBN 0.0095g (the initiator accounts for 5 percent of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (2 mL) and cyclohexane (8 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.1%.
Synthesis of the copolymer: placing maleic anhydride MAH, azodiisobutyronitrile AIBN and solvent into an inclined two-neck round bottom flask with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technology (double-row pipe operation technology) to provide argon inert environment for a reactor, placing the system into an oil bath at 95 ℃, preheating for 10min, beginning to dropwise add vinyl acetate VAc, finishing the dropwise addition for 30min, reacting for 4h (without stirring) to obtain a disperse system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the disperse system, washing and drying to obtain reddish brown solid of the maleic anhydride-vinyl acetate alternating copolymer, and obtaining the polymerization yield (C p ) 27% number average molecular weight of copolymer2700g/mol and a molecular weight polydispersity index (PDI) of 1.39, as shown in Table 5. GPC patterns of the obtained copolymer are shown in FIG. 21.
Example 21
According to the formula shown in Table 5, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 3:1, the monomer maleic anhydride MAH is 0.1471g, and the vinyl acetate VAc is 0.0430g (the total mass concentration of the monomers is 2%); the initiator is azobisisobutyronitrile AIBN 0.0095g (the initiator accounts for 5 percent of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (2 mL) and cyclohexane (8 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.1%.
Synthesis of the copolymer: placing maleic anhydride MAH, azodiisobutyronitrile AIBN and solvent into an inclined two-neck round bottom flask with a spherical reflux condenser, stirring at normal temperature for 15min, using Schlenk line technology (double-row pipe operation technology) to provide argon inert environment for a reactor, placing the system into an oil bath at 95 ℃, preheating for 10min, beginning to dropwise add vinyl acetate VAc, completing the dropwise addition for 40min, reacting for 4h (without stirring) to obtain a disperse system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the disperse system, washing and drying to obtain reddish brown solid of the maleic anhydride-vinyl acetate alternating copolymer, and obtaining the polymerization yield (C p ) 30% of the number average molecular weight of the copolymer2800g/mol and a molecular weight polydispersity index (PDI) of 1.42, as shown in Table 5. GPC patterns of the obtained copolymer are shown in FIG. 22.
Example 22
According to the formula shown in Table 5, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 3:1, the monomer maleic anhydride MAH is 0.1471g, and the vinyl acetate VAc is 0.0430g (the total mass concentration of the monomers is 2%); the initiator is azobisisobutyronitrile AIBN 0.0095g (the initiator accounts for 5 percent of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (2 mL) and cyclohexane (8 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.1%.
Synthesis of the copolymer: placing maleic anhydride MAH, azodiisobutyronitrile AIBN and a solvent into an inclined two-mouth round bottom flask with a spherical reflux condenser, stirring at normal temperature for 15min, using a Schlenk line technology (double-row pipe operation technology) to provide an argon inert environment for a reactor, placing the system into an oil bath at 95 ℃, preheating for 10min, beginning to dropwise add vinyl acetate VAc, finishing the dropwise addition for 50min, reacting for 4h (without stirring) to obtain a disperse system of the maleic anhydride-vinyl acetate alternating copolymer, centrifugally separating, washing and drying the disperse system to obtain the reddish brown of the maleic anhydride-vinyl acetate alternating copolymerColored solid, polymerization yield of copolymer (C p ) 23% number average molecular weight of copolymer2400g/mol and a molecular weight polydispersity index (PDI) of 1.45, as shown in Table 5. GPC patterns of the obtained copolymer are shown in FIG. 23.
TABLE 5 comparison of data results for different drop times for vinyl acetate VAc examples 17-22
Comparative example 1
According to the formula shown in Table 6, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 1:1, the monomer maleic anhydride MAH is 0.4903g, and the vinyl acetate VAc is 0.4304g (the total mass concentration of the monomers is 10%); the initiator is azobisisobutyronitrile AIBN (0.0460 g, the initiator accounts for 5% of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (4 mL) and cyclohexane (6 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.5%.
Synthesis of the copolymer: placing maleic anhydride MAH, vinyl acetate VAc, azodiisobutyronitrile AIBN and solvent in a round bottom flask equipped with a spherical reflux condenser, ultrasonically treating at room temperature for 15min, using Schlenk line technique (double-discharge operation technique) to provide argon inert environment for the reactor, then placing the system in 65 ℃ oil bath to react for 5h (without stirring) to obtain a dispersion system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the dispersion system, washing and drying to obtain white solid of maleic anhydride-vinyl acetate alternating copolymer, and obtaining the polymerization yield (C p ) 55% of the number average molecular weight of the copolymer31500g/mol and a molecular weight polydispersity index (PDI) of 1.61, as shown in Table 6. GPC patterns of the obtained copolymer are shown in FIG. 24. As is evident from the comparison of the previous examples, the polymer obtained in comparative example 1 has a larger molecular weight.
Table 6 comparison of data results for comparative example 1 and comparative example 2
Comparative example 2
According to the formula shown in Table 6, the molar ratio of the monomer maleic anhydride MAH to the vinyl acetate VAc is 1:1, the monomer maleic anhydride MAH is 0.7845g, and the vinyl acetate VAc is 0.6887g (the total mass concentration of the monomers is 15%); the initiator is azobisisobutyronitrile AIBN (0.0737 g, the initiator accounts for 5% of the total monomer by mass); the reaction medium was a mixed solvent of butyl acetate (4 mL) and cyclohexane (6 mL). The mass concentration of azobisisobutyronitrile AIBN in the reaction system was 0.8%.
Synthesis of the copolymer: placing maleic anhydride MAH, vinyl acetate VAc, azodiisobutyronitrile AIBN and solvent in a round bottom flask equipped with a spherical reflux condenser, ultrasonically treating at room temperature for 15min, using Schlenk line technique (double-discharge operation technique) to provide argon inert environment for the reactor, then placing the system in 65 ℃ oil bath to react for 6h (without stirring) to obtain a dispersion system of maleic anhydride-vinyl acetate alternating copolymer, centrifuging the dispersion system, washing and drying to obtain white solid of maleic anhydride-vinyl acetate alternating copolymer, and obtaining the polymerization yield (C p ) 60% of the number average molecular weight of the copolymer39200g/mol and a molecular weight polydispersity index (PDI) of 1.78, as shown in Table 6. GPC patterns of the obtained copolymer are shown in FIG. 25. As can be seen from a comparison of the previous examplesThe polymer obtained in comparative example 2 has a larger molecular weight. />
Claims (10)
1. The synthesis method of the ultra-low molecular weight maleic anhydride-vinyl acetate alternating copolymer is characterized by comprising the following steps of:
a. adding monomer maleic anhydride, vinyl acetate and an initiator into a reaction medium, or dripping vinyl acetate monomer into the solution of the maleic anhydride and the initiator to fully dissolve the vinyl acetate monomer, wherein the molar ratio of the maleic anhydride to the vinyl acetate in the reaction system is 1:1-3:1; the sum of mass concentration of maleic anhydride and vinyl acetate is 2% -15%; the initiator is an organic peroxide or azo compound; the reaction medium is a mixed solvent of organic acid alkyl ester and alkane;
b. Reacting the reaction system for 4 hours at the temperature of 70-95 ℃ to obtain a dispersion system of ultra-low molecular weight maleic anhydride-vinyl acetate polymer particles;
c. and centrifugally separating, washing and vacuum drying the dispersion system to obtain the white solid of the ultra-low molecular weight maleic anhydride-vinyl acetate alternating copolymer.
2. The method for synthesizing an ultra-low molecular weight alternating copolymer of maleic anhydride and vinyl acetate according to claim 1, wherein in the step a, the volume fraction of alkane in the mixed solvent of the reaction medium organic acid alkyl ester and alkane is 10% to 80%.
3. The method for synthesizing an ultra-low molecular weight alternating copolymer of maleic anhydride and vinyl acetate according to claim 1, wherein in the step a, the volume fraction of alkane in the mixed solvent of the reaction medium organic acid alkyl ester and alkane is 60% to 80%.
4. The method for synthesizing an ultra-low molecular weight alternating maleic anhydride-vinyl acetate copolymer according to claim 1, wherein in the step a, the sum of mass concentrations of maleic anhydride and vinyl acetate is 2% to 4%.
5. The method for synthesizing an ultra-low molecular weight alternating maleic anhydride-vinyl acetate copolymer according to claim 1, wherein in the step a, the molar ratio of maleic anhydride to vinyl acetate in the reaction system is 3:1.
6. The method for synthesizing an ultra-low molecular weight alternating maleic anhydride-vinyl acetate copolymer according to claim 1, wherein in the step b, the reaction system is polymerized at a temperature of 85 to 95 ℃.
7. The method for synthesizing an ultra-low molecular weight alternating maleic anhydride-vinyl acetate copolymer according to claim 1, wherein in the step a, the mass concentration of the initiator in the reaction system is 0.1% to 0.8%; the organic peroxide is cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, ditert-butyl peroxide, dibenzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyvalerate, diisopropyl peroxydicarbonate or dicyclohexyl peroxydicarbonate; the azo compound is azodiisobutyronitrile or azodiisoheptonitrile.
8. The method for synthesizing an ultra-low molecular weight alternating maleic anhydride-vinyl acetate copolymer according to claim 2, wherein,
the structural general formula of the organic acid alkyl ester is as follows:
wherein R is 1 Is hydrogen atom, C 1 ～C 8 Alkyl, phenyl or benzyl, R 2 Is C 1 ～C 5 Alkyl of (a);
the organic acid alkyl ester is ethyl formate, propyl formate, isobutyl formate, amyl formate, ethyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isoamyl butyrate, ethyl isovalerate, isoamyl isovalerate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl benzoate or ethyl phenylacetate;
The alkane is cyclohexane, n-hexane, n-heptane, n-pentane, n-octane or isooctane.
9. The method for synthesizing an ultra-low molecular weight alternating maleic anhydride-vinyl acetate copolymer according to claim 2, wherein the reaction medium is a mixed solvent of butyl acetate and cyclohexane.
10. The method for synthesizing an ultra-low molecular weight alternating maleic anhydride-vinyl acetate copolymer according to claim 1, wherein in the step a, the monomer maleic anhydride, vinyl acetate and initiator are sufficiently dissolved in the reaction medium by stirring or ultrasonic wave.
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