CN100369938C - 乳液聚合物 - Google Patents
乳液聚合物 Download PDFInfo
- Publication number
- CN100369938C CN100369938C CNB001329286A CN00132928A CN100369938C CN 100369938 C CN100369938 C CN 100369938C CN B001329286 A CNB001329286 A CN B001329286A CN 00132928 A CN00132928 A CN 00132928A CN 100369938 C CN100369938 C CN 100369938C
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- Prior art keywords
- emulsion polymer
- weight
- monomer
- deflocculant
- emulsion
- Prior art date
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- 239000004908 Emulsion polymer Substances 0.000 title claims abstract description 122
- 239000000178 monomer Substances 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 18
- 239000008199 coating composition Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 4
- 235000006491 Acacia senegal Nutrition 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 241000978776 Senegalia senegal Species 0.000 claims description 3
- 230000021736 acetylation Effects 0.000 claims description 3
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- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
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- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 2
- 239000003381 stabilizer Substances 0.000 abstract 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 22
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 18
- 235000019395 ammonium persulphate Nutrition 0.000 description 17
- -1 2-EHA Chemical compound 0.000 description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
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- 239000003795 chemical substances by application Substances 0.000 description 7
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- 239000003999 initiator Substances 0.000 description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 5
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- 239000003973 paint Substances 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
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- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 2
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical class ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical compound OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- QXIQCNFSNJEMOD-UHFFFAOYSA-N 3-hydroxybutan-2-yl prop-2-enoate Chemical compound CC(O)C(C)OC(=O)C=C QXIQCNFSNJEMOD-UHFFFAOYSA-N 0.000 description 1
- OIYTYGOUZOARSH-UHFFFAOYSA-N 4-methoxy-2-methylidene-4-oxobutanoic acid Chemical compound COC(=O)CC(=C)C(O)=O OIYTYGOUZOARSH-UHFFFAOYSA-N 0.000 description 1
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- 150000003818 basic metals Chemical class 0.000 description 1
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- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
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- 238000005034 decoration Methods 0.000 description 1
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- 238000005530 etching Methods 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
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- XNCMOUSLNOHBKY-UHFFFAOYSA-H iron(3+);trisulfate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XNCMOUSLNOHBKY-UHFFFAOYSA-H 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- MOOYVEVEDVVKGD-UHFFFAOYSA-N oxaldehydic acid;hydrate Chemical compound O.OC(=O)C=O MOOYVEVEDVVKGD-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
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- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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Abstract
本发明提供了一种乳液聚合物以及提供了通过至少一种第一种烯属不饱和单体的自由基聚合形成第一种乳液聚合物,以及随后用胶体稳定剂、至少一种第二种烯属不饱和单体以及氧化还原体系在20-85℃处理第一种乳液聚合物以制备这种乳液聚合物的方法。
Description
本发明涉及乳液聚合物及其制法。更具体地说,本发明涉及能够向含有此种乳液聚合物的含水涂料组合物提供改进流变性质的乳液聚合物。这种乳液聚合物通过用胶体稳定剂、单体和氧化还原体系在20-85℃对第一种乳液聚合物进行后聚合处理制得的。
美国专利5,665,816中公开了由醋酸乙烯酯、乙烯和各种烯属不饱和共聚单体在不饱和羧酸和1.5-20%重量的纤维素醚存在下进行聚合生成玻璃化转变温度-40℃-0℃的并包括至少部分接技形式的纤维素醚的共聚物而制备的含水分散体。在整个聚合反应中不饱和羧酸和纤维素醚都存在。
本发明人面临的问题是提供改性的乳液聚合物。本发明人发现,在第一种乳液聚合物生成后,用胶体稳定剂、单体和氧化还原体系在20-85℃对第一种乳液聚合物进行后聚合处理,可以有效地改进乳液聚合物并可在聚合反应中免除反应混合物发生凝胶化的担心。而且,后聚合过程可以在不同的时间和地方以及在比原来的聚合反应更低的温度下进行,从而有效地免除了用于随后聚合反应的反应釜。
本发明的第一方面是提供一种乳液聚合物,其制法包括,通过至少一种第一种烯属不饱和单体的自由基聚合直到至少95%重量的第一种单体转变成第一种乳液聚合物,随后用为第一种乳液聚合物重量的0.01-6%重量的胶体稳定剂、0.01-10%重量的至少一种第二种烯属不饱和单体和0.05-0.35%重量的氧化还原体系在20-85℃对生成的第一种乳液聚合物进行后处理,直到第一种乳液聚合的残余单体和第二种单体的总和的至少90%已经转变成聚合物。
本发明的第二方面是提供制备乳液聚合物的方法,此法包括通过至少一种第一种烯属不饱和单体的自由基聚合,直到至少95%重量的第一种单体转变成第一种乳液聚合物,以制成第一种乳液聚合物,随后用为第一种乳液聚合物0.01-6%重量的胶体稳定剂、为第一种乳液聚合物0.01-10%重量的至少一种第二种烯属不饱和单体和为第一种乳液聚合物0.05-0.35%重量的氧化还原体系在20-85℃处理第一种乳液聚合物,直到第一种乳液聚合物的残余单体和第二种单体的总和的至少90%已经转化成聚合物。
本发明涉及由至少一种第一种烯属不饱和单体的自由基聚合直到至少95%重量的第一种单体已经转化成第一种乳液聚合物,随后用本发明的方法进行处得到的乳液聚合物。第一种乳液聚合物含至少一种共聚的烯属不饱和单体。烯属不饱和单体包括,例如(甲基)丙烯酸酯各单体,包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、丙烯酸癸酯、丙烯酸月桂酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸异癸酯、甲基丙烯酸月桂酯;(甲基)丙烯酸羟乙酯和(甲基)丙烯酸羟丙酯;(甲基)丙烯酰胺;(甲基)丙烯腈;苯乙烯和取代的苯乙烯;丁二烯;醋酸乙烯酯、丁酸乙烯酯和其它的乙烯酯;以及诸如乙烯、氯乙烯、偏氯乙烯等乙烯基单体。在本文中使用“甲基”随后有另一词如丙烯酸酯或丙烯酰胺是指丙烯酸酯或丙烯酰胺也包括甲基丙烯酸酯和甲基丙烯酰胺。
第一种乳液聚合物可以含为聚合物重量0.5-5%重量,优选0.5-2%重量的含共聚的单烯属不饱和酸基团的单体,如丙烯酸、甲基丙烯酸、巴豆酸、衣康酸、富马酸、马来酸、衣康酸单甲酯、富马酸单乙酯、富马酸单丁酯、马来酸酐、甲基丙烯酸磺乙酯和甲基丙烯酸磷乙酯。第一种乳液聚合物可以含为聚合物重量0-5%,优选0-2%重量的含共聚的单烯属不饱和氨基的单体,如(甲基)丙烯酸二乙基氨基乙酯和(甲基)丙烯酸叔丁基氨基乙酯。第一种乳液聚合物可以含为聚合物重量0-1%重量的共聚的多烯属不饱和单体,例如甲基丙烯酸烯丙酯、邻苯二甲酸二烯丙酯、二甲基丙烯酸1,4-丁二醇酯、二甲基丙烯酸1,2-乙二醇酯、二丙烯酸1,6-己二醇酯和二乙烯苯。优选的第一种乳液聚合物含主要量的共聚的丙烯酸、苯乙烯+丙烯酸或醋酸乙烯酯+丙烯酸单体。更优选的第一种乳液聚合物含共聚的丙烯酸乙酯或丙烯酸丁酯。最优选的第一种乳液聚合物含主要量的甲基丙烯酸甲酯和丙烯酸乙酯或甲基丙烯酸甲酯和丙烯酸丁酯。
第一种乳液聚合物的玻璃化转变温度(“Tg”)优选为-40℃-85℃,更优选为-10℃-40℃,玻璃化转变温度的测定是用差示扫描量热仪(DSC)在热流与温度转变图取中点作为Tg值。要达到所要求的聚合物Tg范围选择单体和单体的量在该领域是众所周知的。
用于制备第一种乳液聚合物的聚合方法在该领域也是众所周知的。在该乳液聚合方法中,可以使用传统的表面活性剂,如阴离子和/或非离子乳化剂,如烷基、芳基或烷芳基硫酸、磺酸或磷酸的碱金属或铵盐、烷基磺酸、磺基琥珀酸盐、脂肪酸、烯属不饱和表面活性剂单体以及乙氧基化醇或酚。表面活性剂用量一般为单体重量的0.1-6%重量。单体的加入可以是纯态或作为在水中的乳液。在反应时期,单体可以一次或多次添加或连续地、线形或非线形地,或以这些形式的混合形式加入。
在第一种乳液聚合物的制备中可以使用热也可以使用氧化还原引发方法。可以使用传统的热自由基引发剂,如过氧化氢、过氧化钠、过氧化钾、过氧化氢叔丁基、氢过氧化枯烯、过硫酸铵和/或碱金属盐、过硼酸钠、过磷酸及其盐、高锰酸钾和过硫酸的铵盐或碱金属盐,一般为单体总重量的0.01%-3.0%重量。这里的“氧化还原体系”是氧化剂+还原剂的结合,可以有效地产生自由基,包括上面列举的自由基引发剂作为适宜的氧化剂和适宜的还原剂,例如甲醛次硫酸钠、抗坏血酸、异抗坏血酸、含硫酸的碱金属盐和铵盐,如亚硫酸钠、亚硫酸氢盐、硫代硫酸盐、亚硫酸氢盐、硫化物、氢硫化物、连二亚硫酸盐、Formadine亚磺酸、羟基甲磺酸、丙酮亚硫酸氢盐、胺如乙醇胺、乙二醇酸、水合二羟乙酸、乳酸、甘油酸、马来酸、酒石酸以及上述各酸的盐可以使用。催化铁、铜、锰、银、铂、钒、镍、铬、钯或钴的金属盐的氧化还原反应可以任选使用。在反应时期,引发剂或引发剂系统可以一次或多次或连续地、线形地或非线形地加入或以上述混合方式加入。
链转移剂例如氢化合物如四溴甲烷、烯丙基化合物或硫醇如硫代甘醇酸烷基酯、巯基链烷醇酸烷基酯以及C4-C22直链或支链烷基硫醇可以使用以降低所生成的聚合物的分子量和/或提供和用任何产生由自由基引发剂得到的都不同的分子量分布。优选是直链或支链C4-C22烷基硫醇如正-十二烷基硫醇和叔-十二烷基硫醇。在大多数或全部整个反应期间或在反应期间的有限的部分,链转移剂可以一次或多次或连续地、线形地或非线形地、同单体配合地或非配合地加入。
在整个反应过程中聚合反应的温度一般保持在低于100℃,以生成第一种乳液聚合物。优选的反应温度为30-95℃,更优选为40-90℃。在第一种乳液聚合物进行后处理之前,制备第一种乳液聚合物的第一种单体的乳液聚合的进行要使得第一种单体转化成第一种乳液聚合物至少达95%重量,测定方法是重力法或气体色谱法。未转化成第一种乳液聚合物的第一种单体被称为“第一种乳液聚合物的残余单体”。
第一种乳液聚合物粒子的平均粒径优选为10-5000毫微米,更优选为50-1000毫微米,是用BI-90粒度分级器测定的。
第一种乳液聚合物随后用为第一种乳液聚合物重量的0.01-6%重量,优选为0.25-3%重量的胶体稳定剂、为第一种乳液聚合物的0.01-10%重量,优选为1-10%重量,更优选为2.4-6%重量的至少一种第二种烯属不饱和单体以及为第一种乳液聚合物重量0.05-0.35%重量的氧化还原体系在20-85℃,优选为55-75℃进行处理,直到第一种乳液聚合物的残余单体和第二种单体总和的至少90%已经转化成聚合物,例如用重力法或气相色谱法测定的。不受任何理论约束,据认为,第一种乳液聚合物的处理效果是将某些或全部的胶体稳定剂连接或接枝到第一种乳液聚合物粒子的表面,从而有效地改进所形成的乳液聚合物,增强了含该乳液聚合物的含水涂料组合物的粘度和流变性能。本发明乳液聚合物的形成以在12,000秒-1测定的含该乳液聚合物的含水涂料组合物高粘度,如ICI粘度作为标志,这和未处理过的第一种乳液聚合物和相同量的相同胶体稳定剂的共混物是不同的。
这里的“胶体稳定剂”是指可以有效地在含水介质中保护带电荷的胶体粒子抗聚结的非离子分子。在保护胶体领域众所周知的是,胶体稳定剂的重均分子量为1000-300,000,并且如通过重均溶解度参数测定的,一般比第一种乳液聚合物的组成更亲水。 在该领域熟知的胶体稳定剂包括,例如羟乙基纤维素(优选的重均分子量为50,000-150,000)、N-乙烯基吡咯烷酮、聚乙烯醇(优选的重均分子量为10,000-200,000)、部分乙酰化的聚乙烯醇、羧甲基纤维素、树胶如阿拉伯树胶、淀粉、蛋白质以及它们的混合物。优选的胶体稳定剂是羟乙基纤维素或聚乙烯醇。
第二种烯属不饱和单体是单烯属不饱和单体,如作为第一种烯属不饱和单体在上面公开的的那些单烯属不饱和单体。优选的第二种烯属不饱和单体是丙烯酸乙酯和丙烯酸丁酯、它们的混合物和含大于30%重量的丙烯酸乙酯或丙烯酸丁酯的单体混合物。
处理第一种乳液聚合物所用的氧化还原体系包括氧化剂和还原剂,如上面公开的适用于第一种乳液聚合物聚合的那些氧化剂和还原剂。
在20-85℃进行对第一种乳液聚合物的处理,直到第一种乳液聚合物的残余单体和第二种单体的总和的至少90%已经转化为聚合物。胶体稳定剂、第二种烯属不饱和单体和氧化还原体系可以用各种方法以各种混合加入。优选是以两种分开的溶液加入氧化还原体系,一种含氧化剂,第二种为还原剂在水中的溶液,胶体稳定剂和乳化的第二种单体作为第二种在水中的混合物加入。无论那种溶液可以作为单一的或作为逐步进料、顺流或顺序地加入。优选是两者顺流地在一定时间,如5-20分钟内加入。
第一种乳液聚合物的处理可以在间歇、半连续地或连续反应器或容器中进行。这些反应器或容器包括但不限于形成第一种乳液聚合物的反应器或容器。 优选是在第二种反应器、排液槽、储槽等中处理第一种乳液聚合物,这样可以腾空第一种聚合反应器或容器用于再生产。处理本发明的第一种乳液聚合物的场所与选择第一种乳液聚合物聚合的反应器比较限制较少,因为包括氧化还原体系的处理所要求的温度一般低于单体主要部分聚合最需要的温度,因为在处理步骤产生的热量远低于在单体主要部分聚合时产生的热量。
本发明的含水组合物是由在涂料领域众所周知的方法制造的。首先,如果涂料组合物需要加有颜料,在高切变力下(如在COWLES混合器中进行的)将至少一种颜料充分分散在含水介质中,或可以使用至少一种预分散的颜料。然后在低切变力搅拌下将乳液聚合物同所需要的其它涂料助剂一起加入。或者,将乳液聚合物包括在颜料分散步骤中。含水组合物可含传统的涂料助剂,如增粘剂、颜料、乳化剂、聚结剂、缓冲剂、中和剂、增稠剂或流变改进剂、保湿剂、润湿剂、杀虫剂、增塑剂、防沫剂、着色剂、蜡和抗氧化剂。
含水涂料组合物中的固体含量可以为约10%-70%体积。含水组合物的粘度用布鲁克非尔德粘度计测定为0.05-10帕.秒(50厘泊-10,000厘泊),对于适用于不同的应用方法的粘度可以大不相同。
含水涂料组合物可以用传统的涂施方法涂布,例如用刷子或辊涂机涂布、辊涂、刮涂法、印刷法、空气雾化喷涂、空气辅助喷涂、无空气喷涂、高容量低压喷涂以及空气辅助的无空气喷涂。
含水涂料组合物可以涂于用于产生装饰、保护、粘结等效果的底材, 如用或不用如酸蚀、电晕放电或底漆前处理过的塑料、木材、金属、前曾涂过的表面、耐侯表面、聚合物薄膜、再建造的木制品、粘结性底材、沥青底材等。
涂在底材上的含水组合物一般经干燥,或在温度20-95℃干燥。
下面的实施例用来说明本发明以及由试验方法得到的结果。
缩写
AA=丙烯酸
BA=丙烯酸丁酯
MMA=甲基丙烯酸甲酯
AN=丙烯腈
HEC=羟乙基纤维素
APS=过硫酸铵
t-BHP=过氧化氢叔丁基
SSF=甲醛次硫酸钠
实施例1 乳液聚合物1的制备
在三升烧瓶中装入340克加热到85℃的去离子水(“DI”),然后加入用5克去离子水漂洗过的11.0克45%固体100毫微米的丙烯酸乳液、溶解在10克去离子水中的3.6克过硫酸铵以及溶解在10克去离子水中0.5克(29%)氢氧化铵水溶液,制成由310克去离子水、2.4克(23%活性)十二烷基苯磺酸钠、416克丙烯酸丁酯、523.8克甲基丙烯酸甲酯以及12.3克甲基丙烯酸组成的单体乳液。然后将94%重量部分的单体乳液在2小时中加到烧瓶中。在85℃进行制备第一种乳液聚合物的反应。然后将烧瓶内容物在1小时内逐步冷却到60℃(“EOFHold”)。在65℃,将15克的0.1%硫酸铁七水合物溶液同1.5克的1.0%Versene溶液混合,并加入到烧瓶中。随后同时开始将三种分别的混合物送入。第一种混合物是为第一种乳液聚合物1.9%重量的混合有6.0%单体乳液(上述的)羟乙基纤维素(作为CellosizeHydroxyethyl Cellulose QP3L(Union Carbide)的7.4%溶液),在7分钟内送入(“Stab Feed”)。第二种混合物是溶解在25克去离子水中的1.4克的过硫酸铵溶液。第三种混合物是0.3克甲醛次硫酸钠溶解于25克去离子水中的溶液,在20分钟内加入(“Oxid Red进料”)。将反应混合物保持在60℃(“处理温度”)20分钟(“End of TreatHold”),然后加入溶解于10克去离子水中的9.7克(29%)氢氧化铵水溶液。加入溶解于5克去离子水中的0.35克(70%)过氧化氢叔丁基的溶液和溶解于7.5克去离子水中的0.17克异抗坏血酸溶液。乳液聚合物1的粒径为550毫微米,固体总合量为49.3%,布鲁克非尔德粘度为1710毫帕秒(1710厘泊)。
实施例2 乳液聚合物2-17和对比乳液聚合物A的制备
用本发明实施例1的方法和在表4.1所指出的变化制备了乳液聚合物2-17。对比乳液聚合物A是在室温下加入为第一种乳液聚合物重量1.9%重量的HEC的第一种乳液聚合物。
实施例3 含水涂料组合物的制备
通过用COWLES分散机形成含72克丙二醇、13.6克TAMOL 731(25.0%)颜料分散剂、1.48克FOAMSTER VL(消泡剂)和267.64克二氧化钛(Ti-Pure R-900)的分散体,随后加入在表4.1中指出的乳液聚合物、TEXANOL聚结剂和NATROSOL 250 MR增稠剂溶液和水,得到具有PVC(颜料体积浓度)=23.65和VS(体积固体)=34的含水涂料,制成白漆。
实施例4 含乳液聚合物的含水涂料组合物的性能评价
含乳液聚合物的含水涂料组合物的ICI(高切变力)粘度列举在表4.1中。ICI粘度的测定是按照ASTM试验D4287-94用ICI锥板式粘度计在切变率12,000秒-1下测定的。
表4.1乳液聚合物和涂料评价
乳液聚合物 | PSnm | EOFHold | SecMon | SecMon | %Stab | Stab | SecMon+Stab进料 | ppmOxid | Oxid | ppmRed | Red | Oxid+Red进料 | TreatTemp | EndofTreatHold | 乳液聚合物固体 | 乳液聚合物粘度 | AqCtgICI |
1 | 550 | 60 | 6.0 | ME | 1.90 | HEC | 17 | 1500 | APS | 300 | SSF | 20 | 60 | 15 | 49.3 | 1710 | 1.20 |
2 | 540 | 15 | 6.0 | ME | 1.90 | HEC | 13 | 无 | 无 | 无 | 无 | 无 | 78-85 | 15 | 0.95 | ||
3 | 476 | 15 | 10.0 | ME | 1.90 | HEC | 17 | 无 | 无 | 无 | 无 | 无 | 77-85 | 15 | 49.9 | 1480 | 0.95 |
Comp A | 550 | 20 | 无 | 无 | 无 | HEC | 无 | 无 | 无 | 无 | 无 | 无 | 无 | 无 | |||
1.90 | HEC | 室温 | 0.65 | ||||||||||||||
4 | 550 | 16 | 6.0 | ME | 1.90 | HEC | 17 | 500 | tBHP | 350 | IAA | shot | 70 | 10 | 50.1 | 760 | 0.80 |
5 | 550 | 27 | 6.0 | ME | 1.90 | HEC | 20 | 500 | tBHP | 350 | IAA | shot | 55 | 10 | 51.0 | 500 | 0.75 |
6 | 550 | 14 | 6.0 | ME | 1.90 | HEC | 17 | 700 | APS | 160 | SSF | 17 | 70 | 3 | 1.45 | ||
7 | 550 | 35 | 6.0 | ME | 1.90 | HEC | 15 | 700 | APS | 160 | SSF | 20 | 70 | 10 | 47.9 | 610 | 0.90 |
8 | 505 | 60 | 6.0 | ME | 1.30 | HEC | 15 | 1500 | APS | 300 | SSF | 15 | 64 | 15 | 49.3 | 1440 | 1.50 |
9 | 513 | 60 | 7.0 | ME | 1.00 | HEC | 15 | 1500 | APS | 300 | SSF | 15 | 64 | 15 | 49.6 | 590 | 1.30 |
10 | 508 | 60 | 6.0 | ME | 1.30 | HEC | 15 | 1500 | APS | 300 | SSF | 15 | 62 | 15 | 47.6 | 480 | 0.90 |
11 | 383 | 60 | 4.5 | ME | 0.75 | HEC | 10 | 1500 | APS | 300 | SSF | 10 | 65 | 15 | 49.5 | 280 | 0.70 |
12 | 385 | 60 | 6.0 | ME | 0.75 | HEC | 10 | 1500 | APS | 300 | SSF | 15 | 63 | 18 | 49.7 | 790 | 1.20 |
13 | 402 | 60 | 6.0 | ME | 0.75 | HEC | 10 | 1500 | APS | 300 | SSF | 10 | 63 | 11 | 49.4 | 440 | 1.60 |
14 | 380 | 60 | 6.0 | ME | 1.50 | HEC | 17 | 1500 | APS | 300 | SSF | 17 | 63 | 15 | 46.9 | 560 | 1.85 |
15 | 399 | 60 | 6.0 | ME | 1.50 | HEC | 20 | 1500 | APS | 300 | SSF | 20 | 63 | 15 | 47.3 | 1160 | 1.70 |
16 | 400 | 60 | 6.0 | ME | 1.50 | HEC | 15 | 1500 | APS | 300 | SSF | 15 | 64 | 15 | 49.2 | 880 | 0.90 |
17 | 400 | 60 | 6.0 | ME | 0.75 | HEC | 8 | 1500 | APS | 300 | SSF | 13 | 64 | 15 | 50.6 | 1180 | 0.90 |
註:
PS nm=以毫微米表示的聚合物乳液的粒径
EOF Hold=以秒计的在制备第一种聚合物的单体进料结束和第一种乳液聚合物处理开始之间的时间。
%Sec Mon,Sec Mon=在处理第一种乳液聚合物中加入的第二种单体和为第一种乳液聚合物重量的单体的%重量。
ME=单体乳液,即使用和第一种乳液聚合物的单体组成相同的组成。%Stab,Stab=处理第一种乳液聚合物中加入的胶体稳定剂和为第一种乳液聚合物的胶体稳定剂的%重量。
Sec Mon+Stab feed=在处理第一种乳液聚合物中加入的第二种单体和胶体稳定剂进料所用的以分钟计的时间。
ppm Oxid,Oxid,ppm Red,Red,Init+Red feed==在处理第一种乳液聚合物中加入的氧化剂(Oxid)和还原剂(Red)的组成和量以及加入经过的时间,shot=单一加入。
Treat Temp=在处理第一种乳液聚合物时的温度以及其后保持的时间。Treat Hold=在处理第一种乳液聚合物中在加入氨/水之前所有的进料结束后以分钟计的时间。
含本发明的实施例1-7的乳液聚合物的涂料组合物与含对比实施例A的乳液聚合物相比显示出更高的高切变力(ICI)粘度,所有的含相同量的稳定剂,表示生成本发明的乳液聚合物以及含它们的含水涂料组合物的流变性能有改进。含本发明实施例8-17的乳液聚合物的涂料组合物与含对比实施例A的相比显示出更高的高切变力(ICI)粘度,尽管它们含较少的胶体稳定剂,表示本发明的乳液聚合物的生成和表示含其的含水涂料组合物的流变性质的改进。
Claims (6)
1.一种乳液聚合物,其具有10-5000毫微米的粒径和-40℃至85℃的玻璃化转变温度,该乳液聚合物通过如下方法制备而成:至少一种第一种烯属不饱和单体的自由基聚合直到所说的第一种单体的至少95%重量已经转化为第一种乳液聚合物,随后用为所说的第一种乳液聚合物重量的0.01-6%重量的胶体稳定剂、为所说的第一种乳液聚合物重量1-10%重量的至少一种第二种烯属不饱和单体以及为所说的第一种乳液聚合物重量的0.05-0.35%重量的氧化还原体系在20-85℃处理所说的第一种乳液聚合物,直到所说的第一种乳液聚合物的残余单体和所说的第二种单体的总量的至少90%已经转化为聚合物。
2.权利要求1的乳液聚合物,其中所说的胶体稳定剂选自羟乙基纤维素、N-乙烯基吡咯烷酮、聚乙烯醇、部分乙酰化的聚乙烯醇、羧甲基纤维素、阿拉伯树胶以及它们的混合物,所说的胶体稳定剂的重均分子量为1000-300,000。
3.制备乳液聚合物的方法,包括通过至少一种第一种烯属不饱和单体的自由基聚合直到至少95%重量的单体已经转化成所说的第一种乳液聚合物以制成第一种乳液聚合物,随后用为所说的第一种乳液聚合物重量0.01-6%重量的胶体稳定剂、为所说的第一种乳液聚合物重量1-10%重量的至少一种第二种烯属不饱和单体以及为所说的第一种乳液聚合物重量的0.05-0.35%重量的氧化还原体系在20-85℃处理所说的第一种乳液聚合物,直到所说的第一种乳液聚合物的残余单体和所说的第二种单体的总量的至少90%已经转化为聚合物。
4.权利要求3的方法,其中形成所说的第一种乳液聚合物以及所说的处理所说的第一种乳液聚合物在不同的反应器中进行。
5.权利要求3的方法,其中所说的胶体稳定剂选自羟乙基纤维素、N-乙烯基吡咯烷酮、聚乙烯醇、部分乙酰化的聚乙烯醇、羧甲基纤维素、阿拉伯树胶以及它们的混合物,所说的胶体稳定剂的重均分子量为1000-300,000。
6.包括权利要求1的乳液聚合物的含水涂料组合物。
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AU2006201172B2 (en) * | 2005-04-04 | 2010-11-25 | Rohm And Haas Company | Aqueous polymer dispersions |
DE602006019249D1 (de) * | 2005-06-28 | 2011-02-10 | Nuplex Resins Bv | Polyharnstoffprodukt als thixotropes rheologiemodifizierendes mittel |
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CN103946323B (zh) | 2011-09-19 | 2017-09-22 | 本杰明·摩尔公司 | 羟乙基纤维素接枝的丙烯酸胶乳 |
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US9914797B2 (en) * | 2013-11-13 | 2018-03-13 | Rohm And Haas Chemicals Llc | Alkali-swellable crosslinked acrylate copolymer, methods of manufacture thereof, and composition comprising the same |
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CN106752963A (zh) * | 2017-01-19 | 2017-05-31 | 四川省四亨实业有限公司 | 一种除醛净化全效墙面漆 |
KR102323951B1 (ko) * | 2017-12-22 | 2021-11-09 | 주식회사 엘지화학 | 그라프트 공중합체의 제조방법 및 열가소성 수지 조성물 |
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