CN101007857A - 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 - Google Patents
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 Download PDFInfo
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- CN101007857A CN101007857A CNA2006101699644A CN200610169964A CN101007857A CN 101007857 A CN101007857 A CN 101007857A CN A2006101699644 A CNA2006101699644 A CN A2006101699644A CN 200610169964 A CN200610169964 A CN 200610169964A CN 101007857 A CN101007857 A CN 101007857A
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- Prior art keywords
- vinyl
- water
- lactam
- hydrophobic comonomer
- soluble
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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 25
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- 239000002537 cosmetic Substances 0.000 title description 2
- 239000008194 pharmaceutical composition Substances 0.000 title 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 13
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- 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
- 238000009835 boiling Methods 0.000 claims description 3
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- 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
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- 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 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
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- -1 t-butylperoxy Chemical group 0.000 description 7
- 239000000654 additive Substances 0.000 description 5
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
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- 238000000576 coating method Methods 0.000 description 2
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- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
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- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 229920001519 homopolymer Polymers 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-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
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 2
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical group CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- GJPDBURPGLWRPW-UHFFFAOYSA-N 1-(hexyldisulfanyl)hexane Chemical compound CCCCCCSSCCCCCC GJPDBURPGLWRPW-UHFFFAOYSA-N 0.000 description 1
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- 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
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- LIZVXGBYTGTTTI-UHFFFAOYSA-N 2-[(4-methylphenyl)sulfonylamino]-2-phenylacetic acid Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(C(O)=O)C1=CC=CC=C1 LIZVXGBYTGTTTI-UHFFFAOYSA-N 0.000 description 1
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
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- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 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
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Chemical group CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 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
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- 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
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- 238000007599 discharging Methods 0.000 description 1
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- 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
- PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical compound CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 description 1
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- 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
- 238000002347 injection Methods 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 230000003449 preventive effect Effects 0.000 description 1
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- 150000003254 radicals Chemical class 0.000 description 1
- 230000000630 rising 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
- 150000003839 salts Chemical class 0.000 description 1
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- 159000000000 sodium salts Chemical class 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
- 239000007787 solid Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- 239000000725 suspension Substances 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- XKXIQBVKMABYQJ-UHFFFAOYSA-N tert-butyl hydrogen carbonate Chemical compound CC(C)(C)OC(O)=O XKXIQBVKMABYQJ-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
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-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
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- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明涉及一种通过在引发剂存在下在有机溶剂中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共聚物的方法，其中聚合在避免各组分蒸发的表压下进行。
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的小量下，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，其中聚合在避免组分蒸发的表压下进行。
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、在3、4和5位甲基化的N-乙烯基吡咯烷酮、N-乙烯基己内酰胺、N-乙烯基哌啶酮、N-乙烯基吡啶酮，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的情况下疏水性单体也能随溶剂进入气相中。疏水性单体在这里可以作为与溶剂的共沸混合物或作为与溶剂的物理混合物进入气相中。根据本发明方法，适当选择压力避免了疏水性单体的蒸发。优选的疏水性单体是乙酸乙烯酯。
适于自由基聚合的引发剂例如为偶氮化合物。特别合适的是脂族或环脂族偶氮化合物，如2，2’-偶氮二(异丁腈)，2，2’-偶氮二(2-甲基丁腈)，2，2’-偶氮二(2，4-二甲基戊腈)，1，1′-偶氮二(1-环己烷甲腈)，2-(氨基甲酰基偶氮)异丁腈，4，4’-偶氮二(4-氰基戊酸)及其碱金属和铵盐，例如钠盐，2，2’-偶氮二异丁酸二甲酯，2，2’-偶氮二[2-(2-咪唑啉-2-基)丙烷]，2，2’-偶氮二(2-脒基丙烷)以及后提到的两种化合物的酸加成盐，例如二盐酸盐。过氧引发剂例如为过氧化二苯甲酰、过氧化二乙酰、过氧化二琥珀酰、过新戊酸叔丁基酯、2-乙基己酸叔丁基酯、过马来酸叔丁基酯、二(叔丁基过氧)环己烷、过氧异丙基碳酸叔丁基酯、过乙酸叔丁基酯、2，2-二(叔丁基过氧)丁烷、过氧化二枯基、过氧化二叔戊基、过氧化二叔丁基、氢过氧化对孟烷、氢过氧化蒎烷、氢过氧化枯烯、氢过氧化叔丁基、过氧化氢以及所述引发剂的混合物。所述引发剂还可以与氧化还原组分如抗坏血酸组合使用。优选的引发剂为过氧化二烷基。
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％。
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以任何混合比溶混。特别合适的是C1-C4醇类，优选乙醇或异丙醇。特别优选将异丙醇用作溶剂。适当选择聚合反应过程中的压力防止溶剂蒸发。
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、三乙醇胺或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)和合适的话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2-14小时，优选3-12小时，理想的是4-10小时内进行。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15-70重量％。此时，在反应混合物已经升至所需反应温度之后连续或分几次加入引发剂溶液，尤其是在2.5-16小时内加入。
聚合反应在避免回流的条件下进行。就此而言，这是指液态聚合混合物不沸腾且易于挥发的组分如溶剂和/或疏水性单体不蒸发并且不因冷却而再次冷凝。回流条件的避免通过监测作为温度函数的压力而控制。
反应温度可以为60-150℃，通常为60-90℃。该反应可以在保护性气体表压下进行，其中合适的保护性气体是氮气或氩气，优选氮气。调节压力以使液态聚合混合物不沸腾。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。压力在这里通常为0.05-2MPa，优选0.08-1.2MPa，尤其是0.1-0.8MPa。
聚合在装有搅拌装置的耐压密闭的蒸发器中进行。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。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。
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10-70重量％，优选15-60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，还可以用过氧化氢、亚硫酸钠/氢过氧化叔丁基等对溶液进行化学后处理或漂白。
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。
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 ihrerViskositt 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＜20，尤其＜10，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剂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。这些聚合物还适合作为工业应用的涂料，例如用于涂敷纸张或塑料，或用于热熔粘合剂。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。
实施例：
进料分配 量 单位
初始进料 进料1 78.4
进料2 3.2 g
进料1 异丙醇 299.9 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 50.0 g
过新戊酸叔丁基酯75％ 2.0 g
进料3 烯基吡咯烷酮 66.6 g
进料4 异丙醇 50.0 g
过新戊酸叔丁基酯75％ 2.0 g
过新戊酸叔丁基酯：75％，在矿物油中(Trigonox25)
在体积为2L的耐压密闭的反应器中进行聚合。需要的话通过注入氮气调节所述压力。初始进料用氮气吹扫10分钟并加热。在距离聚合温度(内部温度)差10％时开始进料1和2。进料1在5.5小时内计量加入，进料2在8小时内计量加入。当进料1完成时，在2小时内计量加入进料3。然后将该混合物后聚合1小时。当进料2完成时，将该体系加热到比聚合温度高10％的内部温度。在该温度下将进料4在4小时内加入。当进料4完成时，在该温度下将该混合物再后聚合2小时。
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
| 实施例号 | SC％ | K值 | VPppm | VAcppm | 5％水溶液的FTU值 | 聚合温度，℃ | 压力，MPa | 备注 |
| a) | 48.6 | 32.8 | 89 | ＜10 | 53 | 75 | 0.1 | 浑浊，黄色 |
| 1) | 49.6 | 31.9 | 78 | ＜10 | 19 | 75 | 0.13 | 清澈，黄色 |
| 2) | 48.5 | 32.0 | 11 | ＜10 | ＜1 | 75 | 0.2 | 浅黄色，清澈 |
| b) | 50.2 | 29.8 | 19 | ＜10 | 41 | 70 | 0.1 | 黄色，轻微浑浊 |
| 3) | 49.6 | 30.8 | 23 | ＜10 | ＜1 | 70 | 0.13 | 浅黄色，清澈 |
| 4) | 49.9 | 32.7 | 16 | ＜10 | ＜1 | 70 | 0.2 | 浅黄色，清澈 |
| 5) | 48.9 | 33.1 | 14 | ＜10 | ＜1 | 70 | 0.38 | 浅黄色，清澈 |
| c) | 47.6 | 31.2 | 11 | ＜10 | 105 | 83 | 0.1 | 黄色，浑浊 |
| 6) | 45.3 | 32.2 | ＜10 | ＜10 | 8 | 83 | 0.2 | 浅黄色，清澈 |
| 7) | 49.5 | 33.7 | ＜10 | ＜10 | ＜1 | 83 | 0.38 | 浅黄色，清澈 |
进料时间，进料1(VP/VAc)：5.5小时
进料时间，进料2(引发剂)：8小时
进料时间，进料3(VP)：2小时
对比试验：a)、b)、c)
Claims (10)
1.一种通过在引发剂存在下在有机溶剂中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共聚物的方法，其中聚合在避免各组分蒸发的表压下进行。
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或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。
4.根据权利要求1-3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。
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乙酸乙烯酯。
6.根据权利要求1-5中任一项的方法，其中所用N-乙烯基内酰胺为N-乙烯基吡咯烷酮。
7.根据权利要求1-6中任一项的方法，其中聚合在60-150℃的温度下进行。
8.根据权利要求1-7中任一项的方法，其中所用有机溶剂为醇。
9.根据权利要求1-8中任一项的方法，其中聚合在0.05-2MPa的压力下进行。
10.根据权利要求1-9中任一项的方法，其中聚合在保护性气体下进行。
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| DE102005062355.7 | 2005-12-23 | ||
| DE102005062355 | 2005-12-23 |
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| CN101007857A true CN101007857A (zh) | 2007-08-01 |
| CN101007857B CN101007857B (zh) | 2013-01-02 |
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| 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 |
| US7572870B2 (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 |
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| 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 |
| 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 |
| 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 |
| 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 |
| DE3931681A1 (de) | 1989-09-22 | 1991-04-04 | Basf Ag | Verfahren zur herstellung von in wasser klaren copolymerisaten |
| DE4020767C1 (zh) | 1990-06-29 | 1992-03-05 | Basf Ag, 6700 Ludwigshafen, De | |
| 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 |
| 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 |
| CN1226320C (zh) * | 2003-06-30 | 2005-11-09 | 厦门大学 | N－乙烯基吡咯烷酮和乙酸乙烯酯共聚物的制备方法 |
| CN1635006A (zh) * | 2003-12-31 | 2005-07-06 | 中国科学院广州能源研究所 | 乙烯基吡咯烷酮与乙酸乙烯酯的共聚物作为水合物生长抑制剂的应用 |
| DE102004022256A1 (de) | 2004-05-04 | 2005-12-01 | Basf Ag | Verfahren zur Herstellung von überwiegend aus Vinylformamid aufgebauten Polymeren |
| 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 |
| 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 |
| 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 |
| 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 |
| US7572870B2 (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 |
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- 2006-12-21 US US11/643,222 patent/US7847044B2/en active Active
- 2006-12-22 JP JP2006346234A patent/JP2007169652A/ja not_active Withdrawn
- 2006-12-25 CN CN2006101699644A patent/CN101007857B/zh active Active
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| US20070149735A1 (en) | 2007-06-28 |
| CN101007857B (zh) | 2013-01-02 |
| US7847044B2 (en) | 2010-12-07 |
| JP2007169652A (ja) | 2007-07-05 |
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