CN1990512B - 生产至少一种水溶性n-乙烯基内酰胺和至少一种疏水性共聚单体的水溶性非浑浊共聚物的方法 - Google Patents
生产至少一种水溶性n-乙烯基内酰胺和至少一种疏水性共聚单体的水溶性非浑浊共聚物的方法 Download PDFInfo
- Publication number
- CN1990512B CN1990512B CN200610169963XA CN200610169963A CN1990512B CN 1990512 B CN1990512 B CN 1990512B CN 200610169963X A CN200610169963X A CN 200610169963XA CN 200610169963 A CN200610169963 A CN 200610169963A CN 1990512 B CN1990512 B CN 1990512B
- Authority
- CN
- China
- Prior art keywords
- vinyl
- methyl
- monomer
- water
- vinyl pyrrolidone
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 34
- 229920001577 copolymer Polymers 0.000 title abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 34
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 6
- -1 vinyl lactam Chemical class 0.000 claims description 41
- 239000000178 monomer Substances 0.000 claims description 34
- 229920002554 vinyl polymer Polymers 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- UBPXWZDJZFZKGH-UHFFFAOYSA-N 1-ethenyl-3-methylpyrrolidin-2-one Chemical compound CC1CCN(C=C)C1=O UBPXWZDJZFZKGH-UHFFFAOYSA-N 0.000 claims description 3
- LWWJIQWIJBMGKE-UHFFFAOYSA-N 1-ethenyl-4-methylpyrrolidin-2-one Chemical compound CC1CN(C=C)C(=O)C1 LWWJIQWIJBMGKE-UHFFFAOYSA-N 0.000 claims description 3
- HQGPZXPTJWUDQR-UHFFFAOYSA-N 1-ethenyl-5-methylpyrrolidin-2-one Chemical compound CC1CCC(=O)N1C=C HQGPZXPTJWUDQR-UHFFFAOYSA-N 0.000 claims description 3
- PBGPBHYPCGDFEZ-UHFFFAOYSA-N 1-ethenylpiperidin-2-one Chemical compound C=CN1CCCCC1=O PBGPBHYPCGDFEZ-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000010992 reflux Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 25
- 239000000243 solution Substances 0.000 description 25
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 13
- 150000002978 peroxides Chemical class 0.000 description 13
- 239000000126 substance Substances 0.000 description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000003750 conditioning effect Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 6
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 6
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000005502 peroxidation Methods 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- XKXIQBVKMABYQJ-UHFFFAOYSA-N tert-butyl hydrogen carbonate Chemical compound CC(C)(C)OC(O)=O XKXIQBVKMABYQJ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- MQFDMZNZEHTLND-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]benzoic acid Chemical compound CC(C)(C)OC1=CC=CC=C1C(O)=O MQFDMZNZEHTLND-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000984082 Amoreuxia Species 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- KMVTVHXTXWKBSQ-UHFFFAOYSA-N tert-butyl 2-ethylbutanoate Chemical compound CCC(CC)C(=O)OC(C)(C)C KMVTVHXTXWKBSQ-UHFFFAOYSA-N 0.000 description 2
- KVWOTUDBCFBGFJ-UHFFFAOYSA-N tert-butyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC(C)(C)C KVWOTUDBCFBGFJ-UHFFFAOYSA-N 0.000 description 2
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- ULPMRIXXHGUZFA-UHFFFAOYSA-N (R)-4-Methyl-3-hexanone Natural products CCC(C)C(=O)CC ULPMRIXXHGUZFA-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- GJPDBURPGLWRPW-UHFFFAOYSA-N 1-(hexyldisulfanyl)hexane Chemical compound CCCCCCSSCCCCCC GJPDBURPGLWRPW-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical class CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- NUTVORGGYDQIDD-UHFFFAOYSA-N 1-ethylsulfanylethanol Chemical compound CCSC(C)O NUTVORGGYDQIDD-UHFFFAOYSA-N 0.000 description 1
- LOXRGHGHQYWXJK-UHFFFAOYSA-N 1-octylsulfanyloctane Chemical compound CCCCCCCCSCCCCCCCC LOXRGHGHQYWXJK-UHFFFAOYSA-N 0.000 description 1
- GOAHRBQLKIZLKG-UHFFFAOYSA-N 1-tert-butylperoxybutane Chemical compound CCCCOOC(C)(C)C GOAHRBQLKIZLKG-UHFFFAOYSA-N 0.000 description 1
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-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
- NYLJHRUQFXQNPN-UHFFFAOYSA-N 2-(tert-butyltrisulfanyl)-2-methylpropane Chemical compound CC(C)(C)SSSC(C)(C)C NYLJHRUQFXQNPN-UHFFFAOYSA-N 0.000 description 1
- WTLNOANVTIKPEE-UHFFFAOYSA-N 2-acetyloxypropanoic acid Chemical compound OC(=O)C(C)OC(C)=O WTLNOANVTIKPEE-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- OPEORUXSPSQRBL-UHFFFAOYSA-N 2-butan-2-yloxybutan-1-ol Chemical class CCC(C)OC(CC)CO OPEORUXSPSQRBL-UHFFFAOYSA-N 0.000 description 1
- HUWFDQSAXOIUNP-UHFFFAOYSA-N 2-butan-2-yloxyethanol Chemical compound CCC(C)OCCO HUWFDQSAXOIUNP-UHFFFAOYSA-N 0.000 description 1
- BJZYYSAMLOBSDY-UHFFFAOYSA-N 2-butoxybutan-1-ol Chemical class CCCCOC(CC)CO BJZYYSAMLOBSDY-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- BRQMAAFGEXNUOL-UHFFFAOYSA-N 2-ethylhexyl (2-methylpropan-2-yl)oxy carbonate Chemical compound CCCCC(CC)COC(=O)OOC(C)(C)C BRQMAAFGEXNUOL-UHFFFAOYSA-N 0.000 description 1
- IPUDBCXGMBSQGH-UHFFFAOYSA-N 2-methoxybutan-1-ol Chemical compound CCC(CO)OC IPUDBCXGMBSQGH-UHFFFAOYSA-N 0.000 description 1
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 1
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 description 1
- XCEFTUZXRMBIES-UHFFFAOYSA-N 2-propan-2-yloxybutan-1-ol Chemical class CCC(CO)OC(C)C XCEFTUZXRMBIES-UHFFFAOYSA-N 0.000 description 1
- RIVJYLGQARVCBI-UHFFFAOYSA-N 2-tert-butylperoxy-2-methylpropane;cumene Chemical compound CC(C)C1=CC=CC=C1.CC(C)(C)OOC(C)(C)C RIVJYLGQARVCBI-UHFFFAOYSA-N 0.000 description 1
- GHSKIQAAGBEVAK-UHFFFAOYSA-N 3-butan-2-yloxybutan-1-ol Chemical class CCC(C)OC(C)CCO GHSKIQAAGBEVAK-UHFFFAOYSA-N 0.000 description 1
- PSGNMTPADMCYFU-UHFFFAOYSA-N 3-butoxybutan-1-ol Chemical class CCCCOC(C)CCO PSGNMTPADMCYFU-UHFFFAOYSA-N 0.000 description 1
- PFCHFHIRKBAQGU-UHFFFAOYSA-N 3-hexanone Chemical compound CCCC(=O)CC PFCHFHIRKBAQGU-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- JDFDHBSESGTDAL-UHFFFAOYSA-N 3-methoxypropan-1-ol Chemical compound COCCCO JDFDHBSESGTDAL-UHFFFAOYSA-N 0.000 description 1
- CBQHQFCHXSBUIW-UHFFFAOYSA-N 3-propan-2-yloxybutan-1-ol Chemical class CC(C)OC(C)CCO CBQHQFCHXSBUIW-UHFFFAOYSA-N 0.000 description 1
- WBXDQCWLCLIVRJ-UHFFFAOYSA-N 4-butan-2-yloxybutan-1-ol Chemical class CCC(C)OCCCCO WBXDQCWLCLIVRJ-UHFFFAOYSA-N 0.000 description 1
- OBXQRJAQMQQZMY-UHFFFAOYSA-N 4-butoxybutan-1-ol Chemical class CCCCOCCCCO OBXQRJAQMQQZMY-UHFFFAOYSA-N 0.000 description 1
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 1
- KOVAQMSVARJMPH-UHFFFAOYSA-N 4-methoxybutan-1-ol Chemical compound COCCCCO KOVAQMSVARJMPH-UHFFFAOYSA-N 0.000 description 1
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 1
- OYVUCQVIHYMROV-UHFFFAOYSA-N 4-propan-2-yloxybutan-1-ol Chemical class CC(C)OCCCCO OYVUCQVIHYMROV-UHFFFAOYSA-N 0.000 description 1
- NEJMTSWXTZREOC-UHFFFAOYSA-N 4-sulfanylbutan-1-ol Chemical compound OCCCCS NEJMTSWXTZREOC-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DZAHXNNEQCZPGJ-UHFFFAOYSA-N CCCCOC(OC)=O.COC(O)=O Chemical class CCCCOC(OC)=O.COC(O)=O DZAHXNNEQCZPGJ-UHFFFAOYSA-N 0.000 description 1
- CUDSBWGCGSUXDB-UHFFFAOYSA-N Dibutyl disulfide Chemical compound CCCCSSCCCC CUDSBWGCGSUXDB-UHFFFAOYSA-N 0.000 description 1
- HTIRHQRTDBPHNZ-UHFFFAOYSA-N Dibutyl sulfide Chemical compound CCCCSCCCC HTIRHQRTDBPHNZ-UHFFFAOYSA-N 0.000 description 1
- LZAZXBXPKRULLB-UHFFFAOYSA-N Diisopropyl disulfide Chemical compound CC(C)SSC(C)C LZAZXBXPKRULLB-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- MUCRYNWJQNHDJH-OADIDDRXSA-N Ursonic acid Chemical compound C1CC(=O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CC[C@@H](C)[C@H](C)[C@H]5C4=CC[C@@H]3[C@]21C MUCRYNWJQNHDJH-OADIDDRXSA-N 0.000 description 1
- FKPKRUSBFSJUPU-UHFFFAOYSA-N [S].C1=CC=CC=C1C1=CC=CC=C1 Chemical compound [S].C1=CC=CC=C1C1=CC=CC=C1 FKPKRUSBFSJUPU-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 229940075933 dithionate Drugs 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical compound CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000008266 hair spray Substances 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- XBUFCZMOAHHGMX-UHFFFAOYSA-N hydroxylamine;phosphoric acid Chemical compound ON.ON.ON.OP(O)(O)=O XBUFCZMOAHHGMX-UHFFFAOYSA-N 0.000 description 1
- NXPHCVPFHOVZBC-UHFFFAOYSA-N hydroxylamine;sulfuric acid Chemical compound ON.OS(O)(=O)=O NXPHCVPFHOVZBC-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000004848 nephelometry Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 150000004978 peroxycarbonates Chemical class 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- KTOYYOQOGAZUHV-UHFFFAOYSA-N s-acetylsulfanyl ethanethioate Chemical compound CC(=O)SSC(C)=O KTOYYOQOGAZUHV-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- PMLRVRLRXOMVHT-UHFFFAOYSA-N tetradecyl hydrogen carbonate Chemical class CCCCCCCCCCCCCCOC(O)=O PMLRVRLRXOMVHT-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
本发明涉及一种通过在引发剂存在下在有机溶剂中在回流条件下自由基聚合至少一种水溶性N-乙烯基内酰胺和至少一种疏水性共聚单体而生产乙烯基内酰胺共聚物的方法，其中在所用乙烯基内酰胺90-99重量％转化后蒸除一些溶剂并继续聚合。
Description
技术领域
本发明涉及一种通过至少一种水溶性N-乙烯基内酰胺和至少一种疏水性共聚单体在有机溶剂中的自由基聚合生产这些单体的水溶性共聚物的方法以及可以通过该方法得到的共聚物及其应用。
背景技术
通过自由基聚合由N-乙烯基内酰胺和疏水性共聚单体生产共聚物是已知的。该类共聚物的生产在有机溶剂如醇类或具有高溶剂含量的水和有机溶剂的混合物中进行。通常而言，聚合在溶剂回流下进行。与N-乙烯基内酰胺相比更易挥发的疏水性单体以此方式进入气相和冷凝液中。
对于许多应用目的而言，需要溶于水中得到清澈溶液，即浓度为5重量％的溶液的FNU值应＜20的共聚物。然而，存在的问题是单体的不同反应性和不同极性可能导致疏水性单体浓度增加，这导致能够由疏水性单体形成不是水溶性的均聚物。甚至在500-1000ppm的少量下，该类均聚物也导致共聚物水溶液浑浊。疏水性单体浓度的增加尤其可能出现在气相和冷凝液中，还可能出现在反应器壁上和聚合介质的表面上。
US 5,395,904描述了通过根据进料方法的受控聚合而聚合乙烯基吡咯烷酮和乙酸乙烯酯。使用可能包含至多50重量％水的醇性溶剂。
US 5,319,041描述了通过根据进料方法的聚合制备乙烯基吡咯烷酮和乙酸乙烯酯的共聚物，其中控制聚合温度。
US 5,502,136描述了一种根据进料方法生产乙烯基吡咯烷酮和乙酸乙烯酯的共聚物的方法，其中经由通过特殊数学式定义的方案控制进料。
US 4,520,179和US 4,554,311描述了以过氧新戊酸叔丁酯作为引发剂在水或水/醇混合物中聚合乙烯基吡咯烷酮和乙酸乙烯酯。其中所用引发剂允许生产具有窄分子量分布的共聚物，这得不到FNU值＜20的水溶性产物。
EP-A 161描述了一种生产乙烯基吡咯烷酮和乙酸乙烯酯的共聚物的方法，其中在聚合之后用特殊引发剂进行后聚合。然而，聚合物具有高残留含量的乙酸乙烯酯且并不足够非浑浊。
EP-A 795 567描述了通过在水溶液中聚合而生产乙烯基内酰胺和疏水性单体的共聚物。
EP-A公开了溶于水中得到清澈溶液的乙烯基吡咯烷酮和乙烯基酯的共聚物的生产，其中在聚合过程中的特定点进行溶剂交换以除去挥发性成分。该方法较复杂。
DE-A 22 18 935描述了N-乙烯基吡咯烷酮与各种水溶性和水不溶性共聚单体的共聚。这里使用水不溶性引发剂，它们以在共聚物的水溶液中的细碎悬浮液形式使用。然而，在水不溶性共聚单体的情况下，这同样不能得到FNU值＜20的所需水溶性共聚物。
发明内容
因此，本发明的目的是提供一种通过在有机溶剂中的自由基共聚来生产至少一种亲水性N-乙烯基内酰胺和至少一种疏水性共聚单体的透明水溶性共聚物的改进方法。
根据本发明，该目的通过在引发剂存在下在有机溶剂中在回流条件下自由基聚合至少一种水溶性N-乙烯基内酰胺和至少一种疏水性共聚单体而实现，其中在所用乙烯基内酰胺90-99重量％转化后蒸除一些溶剂并继续聚合。
具体实施方式
合适的水溶性乙烯基内酰胺为N-乙烯基吡咯烷酮、3-甲基-N-乙烯基吡咯烷酮、4-甲基-N-乙烯基吡咯烷酮、5-甲基-N-乙烯基吡咯烷酮、N-乙烯基吡啶酮、N-乙烯基哌啶酮、N-乙烯基己内酰胺，优选N-乙烯基吡咯烷酮。乙烯基内酰胺的用量为30-90重量％，优选50-90重量％。
本发明方法适于生产其中疏水性单体含量基于单体混合物为10-70重量％，优选10-50重量％的单体混合物的水溶性聚合物。合适的疏水性单体是在水中的溶解度为1-100g/l的那些。合适的疏水性单体例如为乙酸乙烯酯、丙酸乙烯酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙基酯、丙烯酸正丁基酯、丙烯酸叔丁基酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯腈或甲基丙烯腈。疏水性单体尤其为在大气压力下的沸点为60-130℃的聚合温度范围的那些，从而使它们能够在聚合条件下蒸发。甚至在稍低于聚合温度的沸点下，在与溶剂具有足够溶混性且溶剂沸腾的情况下疏水性单体也能随溶剂进入气相中。优选的疏水性单体是乙酸乙烯酯。
可以提到的自由基引发剂例如为过氧化二烷基或二芳基，如过氧化二叔戊基、过氧化二枯基、二(叔丁基过氧异丙基)苯、2，5-二(叔丁基过氧)-2，5-二甲基己烷、过氧化叔丁基枯烯、2，5-二(叔丁基过氧)-2，5-二甲基-3-己烯、1，1-二(叔丁基过氧)-3，3，5-三甲基环己烷、1，1-二(叔丁基过氧)环己烷、2，2-二(叔丁基过氧)丁烷或过氧化二叔丁基，脂族和芳族过氧酯，如过氧新癸酸枯基酯、2-过氧新癸酸2，4，4-三甲基戊基酯、过氧新癸酸叔戊基酯、过氧新癸酸叔丁基酯、过氧新戊酸叔戊基酯、过氧新戊酸叔丁基酯、过氧-2-乙基己酸叔戊基酯、过氧-2-乙基己酸叔丁基酯、过氧二乙基乙酸叔丁基酯、1，4-二(叔丁基过氧)环己烷、过氧异丁酸叔丁基酯、过氧-3，5，5-三甲基己酸叔丁基酯、过氧乙酸叔丁基酯、过氧苯甲酸叔戊基酯或过氧苯甲酸叔丁基酯，过氧化二链烷酰或二苯甲酰，如过氧化二异丁酰、过氧化二(3，5，5-三甲基己酰)、过氧化二月桂酰、过氧化二癸酰、2，5-二(2-乙基己酰过氧)-2，5-二甲基己烷或过氧化二苯甲酰，以及过氧碳酸酯，如过氧二碳酸二(4-叔丁基环己基)酯、过氧二碳酸二(2-乙基己基)酯、过氧二碳酸二叔丁基酯、二乙酰过氧二碳酸酯、过氧二碳酸二肉豆蔻基酯、过氧异丙基碳酸叔丁基酯或过氧-2-乙基己基碳酸叔丁基酯。所用的易溶于油的偶氮引发剂例如为2，2’-偶氮二(异丁腈)、2，2’-偶氮二(2，4-二甲基戊腈)或4，4’-偶氮二(4-氰基戊酸)。
所用自由基引发剂优选为选自如下的化合物：过氧-2-乙基己酸叔丁基酯(Trigonox
21；来自Akzo Nobel的Trigonox牌号)、过氧-2-乙基己酸叔戊基酯(Trigonox
121)、过氧苯甲酸叔丁基酯(TrigonoxC)、过氧苯甲酸叔戊基酯、过氧乙酸叔丁基酯(Trigonox
F)、过氧-3，5，5-三甲基己酸叔丁基酯(Trigonox
42 S)、过氧异丁酸叔丁基酯、过氧二乙基乙酸叔丁基酯(Trigonox
27)、过氧新戊酸叔丁基酯(Trigonox25)、过氧异丙基碳酸叔丁基酯(TrigonoxBPIC)、2，5-二甲基-2，5-二(叔丁基过氧)己烷(Trigonox
101)、过氧化二叔丁基(TrigonoxB)、氢过氧化枯基(Trigonox
K)和过氧-2-乙基己基碳酸叔丁基酯(Trigonox117)。当然还可以使用上述自由基引发剂的混合物。
引发剂基于单体的用量为0.02-15mol％，优选0.05-3mol％。在本发明方法中，引发剂以溶液使用，取决于溶解度，以在有机溶剂中的溶液使用。优选将也用作聚合介质的溶剂用作溶剂。引发剂特别优选以在C1-C4醇中的溶液使用。在这些溶液中，引发剂的浓度基于溶剂为0.02-2mol％，优选0.1-2mol％。优选从下面将引发剂引入聚合混合物中。从下面是指引发剂溶液从聚合混合物的液体表面下引入。这尤其可以在最大混合区发生。本领域熟练技术人员已知最大混合区取决于搅拌器和反应器的几何形状。该引入还可以在反应器底部进行。
合适的聚合介质是极性有机溶剂。该溶剂必须亲水，以使它可以与乙烯基内酰胺在聚合过程中以任何混合比溶混。此外，该溶剂可以在聚合条件下沸腾，从而可以形成回流。合适的例如为脂族或芳族卤代烃类，如氯仿、四氯化碳、六氯乙烷、二氯乙烷、四氯乙烷、氯苯，以及液态C1-或C2-氯氟烃类，脂族C2-C5腈类，如乙腈、丙腈、丁腈或戊腈，线性或环状脂族C3-C7酮类，如丙酮、甲基乙基酮、甲基异丁基酮、2-或3-己酮、2-、3-或4-庚酮、环戊酮、环己酮，线性或环状脂族醚类，如二异丙基醚、1，3-或1，4-二烷、四氢呋喃或乙二醇二甲基醚，碳酸酯，如碳酸二乙酯，以及内酯，如丁内酯、戊内酯或己内酯。合适的一元醇、二元醇或多元醇尤其是C1-C8醇类、C2-C8链烷二醇以及C3-C10三醇或多元醇。其实例是甲醇、乙醇、正丙醇、异丙醇、正丁醇、仲丁醇、叔丁醇、正戊醇、2-戊醇、3-戊醇，以及乙二醇、1，2-丙二醇或1，3-丙二醇。
所用单烷氧基醇尤其为被C1-C6烷氧基取代的上述C1-C8醇、C2-C8链烷二醇和C3-C10三醇。其实例是甲氧基甲醇、2-甲氧基乙醇、2-甲氧基丙醇、3-甲氧基丙醇、2-甲氧基丁醇、3-甲氧基丁醇、4-甲氧基丁醇、2-乙氧基乙醇、2-乙氧基丙醇、3-乙氧基丙醇、2-乙氧基丁醇、3-乙氧基丁醇、4-乙氧基丁醇、2-异丙氧基乙醇、2-异丙氧基丙醇、3-异丙氧基丙醇、2-异丙氧基丁醇、3-异丙氧基丁醇、4-异丙氧基丁醇、2-(正丙氧基)乙醇、2-(正丙氧基)丙醇、3-(正丙氧基)丙醇、2-(正丙氧基)丁醇、3-(正丙氧基)丁醇、4-(正丙氧基)丁醇、2-(正丁氧基)乙醇、2-(正丁氧基)丙醇、3-(正丁氧基)丙醇、2-(正丁氧基)丁醇、3-(正丁氧基)丁醇、4-(正丁氧基)丁醇、2-(仲丁氧基)乙醇、2-(仲丁氧基)丙醇、3-(仲丁氧基)丙醇、2-(仲丁氧基)丁醇、3-(仲丁氧基)丁醇、4-(仲丁氧基)丁醇、2-(叔丁氧基)乙醇、2-(叔丁氧基)丙醇、3-(叔丁氧基)丙醇、2-(叔丁氧基)丁醇、3-(叔丁氧基)丁醇、4-(叔丁氧基)丁醇。
特别合适的是C1-C4醇，优选乙醇或异丙醇。特别优选使用异丙醇作为溶剂。
聚合通常在5-9的中性pH下进行。必要的话，通过加入碱如氨、三乙胺、三乙醇胺、NaOH，或酸如HCl、乳酸、乙酸或甲酸来调节和/或维持该pH。
若需要较低分子量，则可以通过在聚合混合物中加入调节剂来产生。合适的调节剂例如为醛类，如甲醛、乙醛、丙醛、正丁醛和异丁醛，甲酸，甲酸铵，硫酸羟铵和磷酸羟铵。此外，可以使用以有机键合形式包含硫的调节剂。这些调节剂例如为二正丁基硫、二正辛基硫、二苯基硫、二异丙基二硫化物、二正丁基二硫化物、二正己基二硫化物、二乙酰二硫化物和二叔丁基三硫化物。优选调节剂包含SH基团形式的硫。该类调节剂的实例是正丁基硫醇、正己基硫醇或正十二烷基硫醇。特别优选水溶性的含硫聚合调节剂，如亚硫酸氢盐、二亚硫酸盐(disulfite)以及诸如巯基乙酸乙酯、半胱氨酸、2-巯基乙醇、1，3-巯基丙醇、3-巯基-1，2-丙二醇、1，4-巯基丁醇、巯基乙酸、3-巯基丙酸、巯基琥珀酸、硫甘油、二乙醇硫化物、硫二甘醇、乙硫基乙醇、硫脲和二甲亚砜的化合物。其他合适的调节剂是烯丙基化合物，如烯丙醇或烯丙基溴，苄基化合物，如苄基氯，或烷基卤化物，如氯仿或四氯甲烷。在优选实施方案中，将调节剂计量加入反应混合物中，合适的话以在C1-C4醇中的溶液。
在本发明方法中，将单体，合适的话以在C1-C4醇中的溶液，计量加入反应混合物中(进料方法)。在本发明的一个实施方案中，首先引入至多30重量％，优选至多25重量％的水溶性N-乙烯基内酰胺I(基于N-乙烯基内酰胺的总量)和少量引发剂溶液和溶剂，优选乙醇或异丙醇。然后将该混合物升至反应温度并与剩余的引发剂溶液和合适的话调节剂同时连续或分几次计量加入剩余量的单体。通常而言，计量加料在4-14小时，优选5-12小时，理想的是6-10小时内进行。优选乙烯基内酰胺和疏水性共聚单体的加入应使计量加料同时完成。单体在反应混合物中的浓度基于反应混合物为10-80重量％，优选20-70重量％。此时，在反应混合物已经升至所需反应温度之后允许连续或分几次加入引发剂溶液，尤其是在4-16小时内加入。
聚合反应在回流条件下进行。就此而言，回流条件是指液态聚合混合物沸腾且易于挥发的组分如溶剂蒸发并因冷却而再次冷凝。回流通过控制温度和压力而维持。反应温度可以为60-150℃，通常为60-90℃。该反应可以在大气压力下、在自生压力下或在保护性气体表压下进行。在保护性气体表压的情况下，调节压力以使沸腾总是存在。本领域熟练技术人员可以使用相对蒸气压确定合适的压力范围。压力在这里通常不超过2MPa。
聚合在装有搅拌装置的蒸发器中进行。合适的搅拌装置是锚式搅拌器、螺旋桨搅拌器、交叉叶片搅拌器、Mik搅拌器和本领域熟练技术人员已知适于溶液聚合的其他类型搅拌器。此外，还存在一个或多个用于计量加入单体、引发剂溶液和合适的话调节剂(溶液)的进料装置。
此外，该蒸发器在其中不存在液态聚合混合物而是存在气相的反应器上部区域装有冷凝器。
在聚合条件下，考虑到它们的较低沸点，溶剂和疏水性单体部分进入气相中，而较高沸点的N-乙烯基内酰胺保留在液态聚合相中。在冷凝器中，溶剂和疏水性单体的气态混合物冷凝并因此形成所谓的回流。
根据本发明方法，进行溶剂的中间蒸馏以富积疏水性单体。对中间蒸馏所选择的时间点应使得在该时间点已经转化了90-99重量％的乙烯基内酰胺。聚合混合物中乙烯基内酰胺单体含量的测定可以在外部进行，例如通过取样并例如通过气相色谱法(GC)或加溶色谱法(HPLC)等测定未反应单体的残留含量。然而，还可以经由校准的测量探针就地测定，该探针借助红外、UV-Vis或其他光学或光谱方法测定残留含量。该类方法和设备对本领域熟练技术人员而言是已知的。
若乙烯基内酰胺的转化率达到90-99重量％，则借助热蒸馏除去一些比乙烯基内酰胺更易挥发的溶剂和疏水性单体。在这里理想的是选择用于聚合的溶剂以使疏水性单体具有的沸点低于该溶剂，该溶剂具有较高沸点(沸点差低于10℃，优选低于8℃)，和/或该溶剂与疏水性单体形成共沸物。作为蒸馏的结果，从反应混合物中除去一些此时尚未反应的疏水性单体并且疏水性单体和乙烯基内酰胺的浓度因此变得更接近。该蒸馏在乙烯基内酰胺的总计量加料时间的70-130％，优选85-120％之后进行。馏出液的量在此时对应于反应混合物总量的3-20％，优选5-15％。若剩余反应混合物在聚合条件下不能再搅拌或仅能困难地搅拌，则可以用新鲜溶剂同时或随后稀释。然后可以通过添加新鲜溶剂将除去量的溶剂再次送回反应混合物中。同样可以额外计量加入另外5-25重量％，优选8-20重量％的乙烯基内酰胺(基于此时计量加入的乙烯基内酰胺量)。
蒸馏和乙烯基内酰胺的额外计量加料的瞬时重叠也是可能的且缩短了总的循环时间。
然后可以在蒸馏和溶剂的补充加料结束时或在乙烯基内酰胺的额外加料结束时进行后聚合，其中其他引发剂的额外计量加料促进了残留单体的降低。合适的话，在进一步的后聚合时间结束后根据需要进行溶剂的除去和其他溶剂如水的替换。同样可以通过本领域熟练技术人员已知的方法直接干燥通过溶剂交换得到的醇性溶液或水溶液，由此得到粉末产品。
待蒸除的量首先通过蒸馏之后反应混合物的可搅拌性引起，其中溶剂的计量加入将粘度保持为在蒸馏过程中对于粘稠介质中的正常聚合可以处理的幅度(在反应温度下低于50Pas)，其次在蒸馏之后引起：因此，在乙烯基内酰胺的总计量加料时间的70％之后的程序情况下，馏出液的量选择为大于乙烯基内酰胺的总计量加料时间的130％之后的量。
在聚合反应之后，需要的话额外加入一种或多种聚合引发剂并将聚合物溶液加热到例如聚合温度或高于聚合温度的温度，以完成聚合。合适的是上述偶氮引发剂，还有所有其他适于在醇性溶液中的自由基聚合的常规引发剂，例如过氧化物、氢过氧化物、过氧化二硫酸盐、过碳酸盐、过氧酯和过氧化氢。这样将聚合反应进行到转化率为99.9％。在聚合过程中形成的溶液通常包含10-60重量％，优选15-55重量％的聚合物。在聚合之后，还可以将所得溶液进行物理后处理，例如蒸汽蒸馏或用氮气汽提，从而从溶液中除去随蒸汽挥发的溶剂或杂质。此外，还可以进行化学后处理或漂白，例如用过氧化氢或亚硫酸钠/氢过氧化叔丁基进行。
合适的话可以通过对应于现有技术的干燥方法将通过蒸汽蒸馏得到的共聚物的水溶液转化成固体粉末。合适的干燥方法是适合由水溶液进行干燥的那些。优选的方法例如为喷雾干燥、喷雾流化床干燥、转鼓干燥和带式干燥。同样可以使用冻干和冷冻浓缩。
借助本发明方法可以确保共聚单体都总是维持均匀的浓度且不会发生只有一种单体的过浓，从而如前所述防止形成水不溶性均聚物。
所得聚合物通常具有的K值(在浓度为1重量％的水溶液或乙醇溶液中在25℃下测定)为10-100，尤其是15-90，特别优选20-80。K值的测定描述于H.Fikentscher，“Systematik der Cellulosen auf Grund ihrerViskosit
t in Lsung”[基于溶液粘度的纤维素体系]，Cellulose-Chemie13(1932)，58-64和71-74和Encyclopedia of Chemical Technology，第21卷，第2版，427-428(1970)中。
它们的透明溶解性的度量是浊度单位FNU(或NTU)，该单位在浓度为5重量％的聚合物水溶液中在25℃下测量并通过用作为人造不透明剂的福尔马肼(formazin)校准而确定。准确的方法在下列实施例中给出。根据本发明得到的聚合物具有的FNU值＜50，尤其＜20，优选＜7，特别优选＜5。
由本发明方法得到的聚合物尤其用于化妆品和药物制剂中，例如在发蜡添加剂、头发定型添加剂或喷发胶添加剂中作为增稠剂或成膜剂，用于皮肤化妆品制剂、免疫化学品中或在药物制中用作活性成分释放剂。此外，根据本发明生产的聚合物可以用作农业化学的助剂，例如用于种子涂敷或用于缓慢释放肥料配制剂。此外，这些聚合物适用于材料如纸张或塑料的涂敷。这些聚合物还可以用作热熔粘合剂。此外，这些聚合物适合作为转印用粘合剂、润滑添加剂、金属表面防锈剂或除锈剂、防垢剂或除垢剂、从含油的水中回收石油过程中的辅助剂、石油和天然气生产以及石油和天然气运输过程中的辅助剂、废水清洁剂、粘合剂原料、洗涤添加剂和照相工业中的辅助剂。
下列实施例用于说明本发明，但不限制本发明。
实施例
共聚物水溶液的浊度通过浊度法测量(根据DIN 38404的改性方法)测定。在该方法中，以光度法测定由测量溶液所散射的光，光散射由光束与溶液中的颗粒或液滴之间的相互作用引起，这些颗粒或液滴的数目和尺寸构成了浊度。这里所测量的量为浊度单位FNU(或NTU)，其在浓度为5重量％的聚合物水溶液中在25℃下测量并通过用作为人造不透明剂的福尔马肼(formazin)校准而确定。FNU值越高，该溶液越浑浊。通用程序：
进料分配 量 单位
初始进料 进料1 78.4 g
进料2 3.2 g
进料1 异丙醇 300 g
乙烯基吡咯烷酮 333.2 g
乙酸乙烯酯 266.7 g
进料2 异丙醇 50 g
过新戊酸叔丁基酯75％ 2 g
进料3 乙烯基吡咯烷酮 66.6 g
进料4 异丙醇 50 g
过新戊酸叔丁基酯75％ 2 g
过新戊酸叔丁基酯：75％，在矿物油中(Trigonox25)
在体积为2L的搅拌反应器中进行聚合。初始进料用氮气吹扫10分钟，然后加热到聚合温度(内部温度)。在距离聚合温度差10％时开始进料1和2。进料1在v小时内计量加入，进料2在x小时内计量加入。当进料1完成时，在y小时内计量加入进料3。然后将该混合物后聚合1小时，然后蒸除规定量的馏出液。然后必要的话用溶剂稀释该混合物，以赋予可搅拌性，并将其加热到聚合温度加10％的内部温度。一旦达到该温度，在该温度下将进料4在z小时内计量加入。当进料4完成时，将该混合物在该温度下再后聚合2小时。然后蒸馏除去大部分溶剂，并借助蒸汽蒸馏除去残留的量。在该蒸汽蒸馏过程中，根据需要加入水以维持可搅拌性。在冷却之后，合适的话使用水来产生特定固体含量。
固体含量，重量％
K值在浓度为1％的乙醇溶液中测量
GC分析：乙烯基吡咯烷酮，ppm；乙酸乙烯酯，ppm；
外观：颜色、透明度、FNU值
实施例
| 实施例号 | TW％ | K值 | VPppm | Vacppm | 5％水溶液的FTU值 | v[h] | x[h] | y[h] | z[h] | 温度，℃ | 引发剂加料 | 馏出液量[g] |
| V1 | 46.7 | 32.6 | 26 | ＜10 | 173 | 11 | 11 | 2.5 | 4 | 83 | 上 | 0 |
| 1 | 45.3 | 33.1 | 14 | ＜10 | 49 | 11 | 11 | 2.5 | 4 | 83 | 上 | 76 |
| 2 | 47.8 | 31.9 | 31 | ＜10 | 19 | 11 | 11 | 2.5 | 4 | 83 | 上 | 153 |
| 3 | 45.4 | 32.1 | 16 | ＜10 | 45 | 5.5 | 8 | 2 | 2.5 | 83 | 上 | 82 |
| 4 | 44.3 | 32.3 | 11 | ＜10 | 18 | 5.5 | 8 | 2 | 2.5 | 83 | 下 | 79 |
| 5 | 48.6 | 31.8 | ＜10 | ＜10 | 14 | 5.5 | 8 | 2 | 2.5 | 75 | 上 | 164 |
| 6 | 49.4 | 32.4 | ＜10 | ＜10 | 3 | 5.5 | 8 | 2 | 2.5 | 75 | 下 | 171 |
所得聚合物水溶液的外观：
V1：黄色，浑浊
1：黄色，稍显浑浊
2：黄色，清澈
3：黄色，稍显浑浊
4：浅黄色，清澈
5：浅黄色，清澈
6：浅黄色，清澈
Claims (13)
1.一种通过在引发剂存在下在有机溶剂中在回流条件下自由基聚合至少一种水溶性N-乙烯基内酰胺和至少一种疏水性共聚单体而生产乙烯基内酰胺共聚物的方法，其中在所用乙烯基内酰胺90-99重量％转化后借助热蒸馏除去一些比乙烯基内酰胺更易挥发的溶剂和疏水性单体，馏出液的量在此时对应于反应混合物总量的3-20％，并继续聚合。
2.根据权利要求1的方法，其中所用疏水性共聚单体为在水中的溶解度为1-100g/l的单体。
3.根据权利要求1的方法，其中所用疏水性共聚单体为在大气压力下的沸点为60-150℃的单体。
4.根据权利要求2的方法，其中所用疏水性共聚单体为在大气压力下的沸点为60-150℃的单体。
5.根据权利要求1-4中任一项的方法，其中所用疏水性共聚单体为选自由乙酸乙烯酯、丙酸乙烯酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙基酯、丙烯酸正丁基酯、丙烯酸叔丁基酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯腈和甲基丙烯腈组成的组的单体。
6.根据权利要求1-4中任一项的方法，其中所用疏水性共聚单体为乙酸乙烯酯。
7.根据权利要求1-4中任一项的方法，其中所用N-乙烯基内酰胺为选自由N-乙烯基吡咯烷酮、3-甲基-N-乙烯基吡咯烷酮、4-甲基-N-乙烯基吡咯烷酮、5-甲基-N-乙烯基吡咯烷酮、N-乙烯基吡啶酮、N-乙烯基哌啶酮和N-乙烯基己内酰胺组成的组的单体。
8.根据权利要求5的方法，其中所用N-乙烯基内酰胺为选自由N-乙烯基吡咯烷酮、3-甲基-N-乙烯基吡咯烷酮、4-甲基-N-乙烯基吡咯烷酮、5-甲基-N-乙烯基吡咯烷酮、N-乙烯基吡啶酮、N-乙烯基哌啶酮和N-乙烯基己内酰胺组成的组的单体。
9.根据权利要求6的方法，其中所用N-乙烯基内酰胺为N-乙烯基吡咯烷酮。
10.根据权利要求1-4中任一项的方法，其中聚合在60-150℃的温度下进行。
11.根据权利要求9的方法，其中聚合在60-150℃的温度下进行。
12.根据权利要求1-4中任一项的方法，其中所用有机溶剂为醇。
13.根据权利要求11的方法，其中所用有机溶剂为醇。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005062664.5 | 2005-12-23 | ||
| DE102005062664 | 2005-12-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1990512A CN1990512A (zh) | 2007-07-04 |
| CN1990512B true CN1990512B (zh) | 2011-01-19 |
Family
ID=38194805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200610169963XA Active CN1990512B (zh) | 2005-12-23 | 2006-12-25 | 生产至少一种水溶性n-乙烯基内酰胺和至少一种疏水性共聚单体的水溶性非浑浊共聚物的方法 |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US7572870B2 (zh) |
| JP (1) | JP2007169650A (zh) |
| CN (1) | CN1990512B (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7847044B2 (en) * | 2005-12-23 | 2010-12-07 | Basf Se | Method of producing water-soluble nonturbid copolymers of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer by polymerization under increased pressure |
| US7572871B2 (en) * | 2005-12-23 | 2009-08-11 | Basf Se | Method of producing water-soluble nonturbid copolymers of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer |
| DE102007052412A1 (de) * | 2006-11-29 | 2008-06-05 | Basf Se | Verfahren zur Herstellung von wasserlöslichen trübungsfreien Copolymerisaten aus wenigstens einem wasserlöslichen N-Vinyllactam und wenigstens einem hydrophoben Comonomeren |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4554312A (en) * | 1982-09-20 | 1985-11-19 | Gaf Corporation | Method of preparing aqueous solutions of polyvinyl-pyrrolidone homopolymer of various molecular weights using a single initiator system consisting essentially of t-Butylperoxypivalate |
| US5122582A (en) * | 1989-09-22 | 1992-06-16 | Basf Aktiengesellschaft | Preparation of copolymers which form clear aqueous solutions |
| US5319041A (en) * | 1993-03-26 | 1994-06-07 | Isp Investments Inc. | Process for the preparation of vinylpyrrolidone/vinyl acetate copolymers |
| US5395904A (en) * | 1993-12-07 | 1995-03-07 | Isp Investments Inc. | Process for providing homogeneous copolymers of vinylpyrrolidone and vinyl acetate which form clear aqueous solutions having a high cloud point |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3513142A (en) | 1969-03-07 | 1970-05-19 | Du Pont | Production of polyvinyl alcohol of improved color by oxygen purge |
| DE2218935C3 (de) | 1972-04-19 | 1980-01-31 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von wäßrigen Lösungen von N-Vinylpyrrolidonpolymerisaten |
| DE2456807C3 (de) | 1974-11-30 | 1981-04-09 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von Polymerisaten des Vinylpyrrolidons |
| DE2730017A1 (de) | 1977-07-02 | 1979-01-18 | Basf Ag | Verfahren zur reduzierung der restmonomerengehalte bei der polymerisation von vinyllactamen und vinylestern |
| US4520179A (en) | 1982-09-20 | 1985-05-28 | Gaf Corporation | Preparation of vinylpyrrolidone/vinyl acetate copolymers of various molecular weights using a single initiator system consisting essentially of t-Butylperoxypivalate |
| US4554311A (en) | 1982-09-20 | 1985-11-19 | Gaf Corporation | Method of preparing an aqueous solution comprising vinylpyrrolidone/vinyl acetate copolymers of various molecular weights using a single initiator system consisting essentially of t-Butylperoxypivalate |
| DE4020767C1 (zh) | 1990-06-29 | 1992-03-05 | Basf Ag, 6700 Ludwigshafen, De | |
| US5502136A (en) | 1994-12-28 | 1996-03-26 | Isp Investments Inc. | Process for making substantially homogeneous copolymers of vinyl pyrrolidone and vinyl acetate which form clear aqueous solutions |
| DE19609864A1 (de) | 1996-03-13 | 1997-09-18 | Basf Ag | Verfahren zur Herstellung von wasserlöslichen Copolymerisaten aus wenigstens einem wasserlöslichen N-Vinyllactam und wenigstens einem hydrophoben Comonomeren |
| US6369180B1 (en) * | 2000-08-18 | 2002-04-09 | Isp Investments Inc. | Process for making water soluble polyvinylcaprolactam polymers |
| US6512066B1 (en) * | 2002-02-14 | 2003-01-28 | Arco Chemical Technology, L.P. | Process for making crosslinked polyvinylpyrrolidone with low swell volume |
| DE102004022256A1 (de) | 2004-05-04 | 2005-12-01 | Basf Ag | Verfahren zur Herstellung von überwiegend aus Vinylformamid aufgebauten Polymeren |
| US7847044B2 (en) | 2005-12-23 | 2010-12-07 | Basf Se | Method of producing water-soluble nonturbid copolymers of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer by polymerization under increased pressure |
| US20070149737A1 (en) | 2005-12-23 | 2007-06-28 | Basf Aktiengesellschaft | Method of producing water-soluble nonturbid copolymers of at least one water-soluble n-vinyllactam and at least one hydrophobic comonomer |
| US7442751B2 (en) | 2005-12-23 | 2008-10-28 | Basf Se | Method of producing water-soluble nonturbid copolymers of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer |
| US7572871B2 (en) | 2005-12-23 | 2009-08-11 | Basf Se | Method of producing water-soluble nonturbid copolymers of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer |
| US7449531B2 (en) | 2005-12-23 | 2008-11-11 | Basf Se | Method of producing water-soluble nonturbid copolymers of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer |
-
2006
- 2006-12-21 US US11/643,394 patent/US7572870B2/en active Active
- 2006-12-22 JP JP2006345245A patent/JP2007169650A/ja not_active Withdrawn
- 2006-12-25 CN CN200610169963XA patent/CN1990512B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4554312A (en) * | 1982-09-20 | 1985-11-19 | Gaf Corporation | Method of preparing aqueous solutions of polyvinyl-pyrrolidone homopolymer of various molecular weights using a single initiator system consisting essentially of t-Butylperoxypivalate |
| US5122582A (en) * | 1989-09-22 | 1992-06-16 | Basf Aktiengesellschaft | Preparation of copolymers which form clear aqueous solutions |
| US5319041A (en) * | 1993-03-26 | 1994-06-07 | Isp Investments Inc. | Process for the preparation of vinylpyrrolidone/vinyl acetate copolymers |
| US5395904A (en) * | 1993-12-07 | 1995-03-07 | Isp Investments Inc. | Process for providing homogeneous copolymers of vinylpyrrolidone and vinyl acetate which form clear aqueous solutions having a high cloud point |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007169650A (ja) | 2007-07-05 |
| US7572870B2 (en) | 2009-08-11 |
| US20070149736A1 (en) | 2007-06-28 |
| CN1990512A (zh) | 2007-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101190959B (zh) | 制备至少一种水溶性n-乙烯基内酰胺和至少一种疏水性共聚单体的水溶性非混浊共聚物的方法 | |
| CN104204007A (zh) | 聚合物、方法和组合物 | |
| US5626836A (en) | Low VOC hair spray compositions containing terpolymers of vinyl pyrrolidone, vinyl caprolactam and 3-(N-dimethylaminopropyl) methacrylamide | |
| KR20090097933A (ko) | 고분지형 폴리카르보네이트를 함유하는 중합체 분산액 | |
| CN1990513B (zh) | 生产至少一种水溶性n-乙烯基内酰胺和至少一种疏水性共聚单体的水溶性非浑浊共聚物的方法 | |
| US20140037837A1 (en) | Bio-renewable vinyl beads | |
| CN1990512B (zh) | 生产至少一种水溶性n-乙烯基内酰胺和至少一种疏水性共聚单体的水溶性非浑浊共聚物的方法 | |
| CA2199054A1 (en) | Preparation of water-soluble copolymers of at least one water-soluble n-vinyllactam and at least one hydrophobic comonomer | |
| AU733823B2 (en) | Cross-linkable surface coatings and process of preparation | |
| US7442751B2 (en) | Method of producing water-soluble nonturbid copolymers of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer | |
| CN101007857B (zh) | 通过在增加的压力下聚合而生产n-乙烯基内酰胺的水溶性非浑浊共聚物的方法 | |
| US7449531B2 (en) | Method of producing water-soluble nonturbid copolymers of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer | |
| US7572871B2 (en) | Method of producing water-soluble nonturbid copolymers of at least one water-soluble N-vinyllactam and at least one hydrophobic comonomer | |
| US9163102B2 (en) | Soluble branched polymers | |
| DE102006056203B4 (de) | Verfahren zur Herstellung von wasserlöslichen trübungsfreien Copolymerisaten aus wenigstens einem wasserlöslichen N-Vinyllactam und wenigstens einem hydrophoben Comonomeren | |
| DE102006056206A1 (de) | Verfahren zur Herstellung von wasserlöslichen trübungsfreien Copolymerisaten aus wenigstens einem wasserlöslichen N-Vinyllactam und wenigstens einem hydrophoben Comonomeren | |
| DE102006056205A1 (de) | Verfahren zur Herstellung von wasserlöslichen trübungsfreien Copolymerisaten aus wenigstens einem wasserlöslichen N-Vinyllactam und wenigstens einem hydrophoben Comonomeren | |
| FR3104594A1 (fr) | Composition aqueuse thermo-stabilisée | |
| DE102006055851A1 (de) | Verfahren zur Herstellung von wasserlöslichen trübungsfreien Copolymerisaten aus wenigstens einem wasserlöslichen N-Vinyllactam und wenigstens einem hydrophoben Comonomeren | |
| DE102006056204A1 (de) | Verfahren zur Herstellung von wasserlöslichen trübungsfreien Copolymerisaten aus wenigstens einem wasserlöslichen N-Vinyllactam und wenigstens einem hydrophoben Comonomeren durch Polymerisation unter erhöhtem Druck | |
| CA3214139A1 (en) | Aqueous polymer dispersion of voided polymer particles | |
| JP2023109099A (ja) | アクリル共重合体の製造方法、分散剤およびインクジェット用組成物 | |
| DE102006056201A1 (de) | Verfahren zur Herstellung von wasserlöslichen trübungsfreien Copolymerisaten aus wenigstens einem wasserlöslichen N-Vinyllactam und wenigstens einem hydrophoben Comonomeren |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |