CN112239518B - 改善涂层早期耐水性和光泽度的丙烯酸共聚乳液及其应用 - Google Patents
改善涂层早期耐水性和光泽度的丙烯酸共聚乳液及其应用 Download PDFInfo
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- CN112239518B CN112239518B CN202011078933.4A CN202011078933A CN112239518B CN 112239518 B CN112239518 B CN 112239518B CN 202011078933 A CN202011078933 A CN 202011078933A CN 112239518 B CN112239518 B CN 112239518B
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- 239000000839 emulsion Substances 0.000 title claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000011248 coating agent Substances 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 title claims abstract description 31
- 229920006243 acrylic copolymer Polymers 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 75
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000008199 coating composition Substances 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 7
- 230000009477 glass transition Effects 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- -1 polypropylene Polymers 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- 239000010452 phosphate Substances 0.000 claims description 11
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- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
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- 239000000654 additive Substances 0.000 claims description 3
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- 239000003899 bactericide agent Substances 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- QOVCUELHTLHMEN-UHFFFAOYSA-N 1-butyl-4-ethenylbenzene Chemical compound CCCCC1=CC=C(C=C)C=C1 QOVCUELHTLHMEN-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 claims description 2
- ONPJWQSDZCGSQM-UHFFFAOYSA-N 2-phenylprop-2-enoic acid Chemical compound OC(=O)C(=C)C1=CC=CC=C1 ONPJWQSDZCGSQM-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- OIYTYGOUZOARSH-UHFFFAOYSA-N 4-methoxy-2-methylidene-4-oxobutanoic acid Chemical compound COC(=O)CC(=C)C(O)=O OIYTYGOUZOARSH-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
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- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
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- 239000001530 fumaric acid Substances 0.000 claims description 2
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 claims description 2
- YJSSCAJSFIGKSN-UHFFFAOYSA-N hex-1-en-2-ylbenzene Chemical compound CCCCC(=C)C1=CC=CC=C1 YJSSCAJSFIGKSN-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 claims description 2
- 229940005650 monomethyl fumarate Drugs 0.000 claims description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-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
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000518 rheometry Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-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
- 239000002562 thickening agent Substances 0.000 claims description 2
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims 2
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 7
- 125000000129 anionic group Chemical group 0.000 description 7
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- 238000007720 emulsion polymerization reaction Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- WDHYRUBXLGOLKR-UHFFFAOYSA-N phosphoric acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OP(O)(O)=O WDHYRUBXLGOLKR-UHFFFAOYSA-N 0.000 description 5
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- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
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Abstract
改善涂层早期耐水性和光泽度的丙烯酸共聚乳液及其应用。所述丙烯酸共聚乳液的玻璃化转变温度为20℃至50℃，基于固体的酸值为10mg KOH/g至40mgKOH/g，主要由不饱和单体聚合而成，所述不饱和单体包括：（a）一种或多种烯键式不饱和单体、（b）一种或多种芳香族烯键式不饱和单体、（c）一种或多种烯键式不饱和酸单体，其包含一种或多种烯键式不饱和羧酸单体及一种或多种烯键式不饱和强酸单体。本发明丙烯酸共聚物乳液可作为涂料组合物中的成膜物质，在改善涂层光泽度的前提下，还可有效改善涂层的早期耐水性。
Description
技术领域
本发明属于涂料制备技术领域，具体涉及一种改善涂层早期耐水性和光泽度的丙烯酸共聚乳液及其应用。
背景技术
随着涂料行业环保化、可持续发展化转型速度加快，以丙烯酸乳液作为成膜物质的一类水性涂料，以其环保，耐候，经济，不燃不爆，储存运输安全等特性，应用日益广泛。但水性单组分丙烯酸涂料体系依然存在不少性能缺陷，例如光泽度不高，早期耐水性不佳，机械性能不足等。尤其是光泽度及丰满度不如传统的溶剂型醇酸涂料，限制了其应用范围。
另一方面，相当一部分水性单组分丙烯酸涂料用于轻防腐和钢结构体系，施工后的工件需要大量堆积于工厂甚至露天摆放，尤其是针对大型钢结构应用，难以保证施工后的工件均具有良好的遮蔽条件，因此对涂层的早期耐水性尤其是涂层表干一小时后的耐水性有相当高的要求，需要涂层在表干一小时后浸没于水中数天后外观无变化，现如今的丙烯酸乳液往往难以满足这项要求。
CN101405357A公开了一种提升丙烯酸涂层光泽度的方法，采用自由基溶液聚合分别聚合含羧基及含羟基官能团的丙烯酸树脂，然后将二者混合，部分缩聚，将产物中和转相后应用于水性双组分涂层体系。该树脂相较于过往将亲水性羧酸官能团及交联性羟基官能团集中在同一树脂链的方法提升了涂层光泽度。但该树脂仅适用于双组分涂层体系，未公开提升单组分丙烯酸乳液涂层光泽的方案。
CN101903425A公开了采用适宜量的磷酸酯单体、双丙酮丙烯酰胺交联单体复配磷酸酯乳化剂提升单组分水性丙烯酸漆膜早期耐水性的方案，但未公开光泽度改善途径。
CN107207636A公开了改善水性双组分丙烯酸涂料光泽和降低漆膜雾度的方案，但未涉及提升初期耐水性的解决方法。
CN101679801A公开了采用在丙烯酸乳液滴加过程中协同滴加水溶性醇酸溶液的方法来提升漆膜光泽度及降低雾度，但未涉及该方法对于早期耐水性的贡献。
发明内容
本发明所解决的技术问题是，克服以上不足，提供一种可同时改善涂层早期耐水性和光泽度的丙烯酸共聚乳液，其作为涂料组合物中的成膜物质，在改善涂层光泽度的前提下，还可有效改善涂层的早期耐水性。
本发明解决其技术问题所采用的技术方案如下：
一种改善涂层早期耐水性和光泽度的丙烯酸共聚乳液，其玻璃化转变温度为20℃至50℃，基于固体的酸值为10mgKOH/g至40mgKOH/g，主要由以下单体聚合而成：
(a)一种或多种烯键式不饱和单体，其占所有单体质量分数为40-70wt％，优选45-65wt％，最优选50-60wt％；
(b)一种或多种芳香族烯键式不饱和单体，其占所有单体质量分数为30-60wt％，优选35-55wt％，最优选40-50wt％；
(c)一种或多种烯键式不饱和酸单体，包含(c1)一种或多种烯键式不饱和羧酸单体及(c2)一种或多种烯键式不饱和强酸单体。烯键式不饱和酸单体(c)占所有单体质量分数为0.1-10wt％，优选0.5-8wt％，最优选2-6wt％。其中烯键式不饱和强酸单体(c2)占所有单体质量分数为0.1-2wt％，优选0.15-1.5wt％，最优选0.2-1wt％。
单体(a)为(甲基)丙烯酸C1至C20烷基酯，其烷基链优选1-13个碳原子，最优选1-10个碳原子，进而实现漆膜耐水性与成本的平衡。优选的单体包括甲基丙烯酸甲酯、丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、丙烯酸正丁酯、丙烯酸叔丁酯、丙烯酸异辛酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、甲基丙烯酸环己酯、丙烯酸环己酯、丙烯酸异冰片酯、甲基丙烯酸十三酯，甲基丙烯酸十八酯中的一种或几种，特别优选甲基丙烯酸甲酯，丙烯酸丁酯，甲基丙烯酸丁酯及丙烯酸异辛酯的组合。
单体(b)为芳香族烯键式不饱和单体，优选的单体包括苯乙烯、乙烯基甲苯、α-甲基苯乙烯、对甲基苯乙烯、α-丁基苯乙烯、4-正丁基苯乙烯、二乙烯基苯等中的一种或几种，特别优选苯乙烯。
单体(c)为烯键式不饱和酸单体，由烯键式不饱和羧酸单体(c1)及烯键式不饱和强酸单体(c2)组成。单体(c1)选自丙烯酸、甲基丙烯酸、衣康酸、富马酸、马来酸、衣康酸单甲酯、富马酸单甲酯、马来酸酐、乙基丙烯酸、α-苯基丙烯酸等中的一种或几种。单体(c2)选自含磷的烯键式不饱和酸单体，例如乙烯基膦酸、(甲基)丙烯酸乙酯磷酸及其盐、(甲基)丙烯酸丙酯磷酸及其盐、(甲基)丙烯酸丁酯磷酸及其盐、马来酸烷基酯磷酸及其盐、富马酸烷基酯磷酸及其盐、(甲基)丙烯酸二烷基酯磷酸及其盐、磷酸烯丙酯、(甲基)丙烯酸聚氧化烯酯磷酸及其盐等。键式不饱和羧酸单体特别优选丙烯酸和甲基丙烯酸的组合；烯键式不饱和强酸单体特别优选2-甲基-2-丙烯酸-2-羟乙基酯磷酸酯。
上述所有单体的质量分数之和为100wt％。
通过调整每种单体的种类及质量分率来调整共聚物的玻璃化转变温度，可通过Fox公式(T.G.Fox，Bull.Am.Phys.Soc.1956[Ser.II],P.123)进行理论计算。丙烯酸共聚物的玻璃化转变温度根据以下公式给出近似值：
1/Tg＝x1/Tg1+x2/Tg2+x3/Tg3+…+xn/Tgn
其中x1、x2、…xn为单体1、2、…n的质量分数；Tg1、Tg2、…Tgn为由单体1、2、…n构成的均聚物的玻璃化转变温度，单位为开尔文。大部分单体的均聚物的玻璃化转变温度值已收列于Ullmann＇s Encyclopedia of Industrial Chemistry,A21卷，p.169，第五版，VCHWeinheim，1992中。
共聚物乳液组合物还可以包含链转移剂来调整分子量，优选的链转移剂包括卤化物，如四氯化碳，四溴甲烷；或硫醇类，第一类是C2-C22的直链或支链烷基硫醇，如巯基乙醇，正辛硫醇，十二硫醇；第二类是巯基烷酸烷基酯，如巯基乙酸异辛酯，巯基丙酸正辛酯，巯基丙酸异辛酯等。链转移剂可在单体或者预乳液滴加过程中，以连续或者分批次的形式加入。加入量为基于单体质量的0.1-10wt％，优选0.1-5wt％，最优选0.1-1wt％。
可以在乳液聚合过程中使用表面活性剂来降低聚合单体与水相间的界面张力，使乳胶粒以热力学亚稳态或者稳态形式存在。常规的表面活性剂包含阳离子型、阴离子型、非离子型或阴离子/非离子混合型。常用的表面活性剂为阴离子型、非离子型及阴离子/非离子混合型。阴离子型表面活性剂为烷基或芳基硫酸、磺酸或磷酸的碱金属盐或有机胺盐。非离子型表面活性剂为烷基或芳基聚氧乙烯、聚氧丙烯或二者的嵌段共聚物。阴离子/非离子混合型为烷基或芳基聚氧乙烯、聚氧丙烯的硫酸、磺酸、磷酸盐。表面活性剂可以在聚合体系中以基于单体质量的0.1-10wt％，优选0.2-8wt％，最优选0.5-5wt％用。可以在聚合初始的打底物料中或者在滴加物料中加入，亦可以在聚合过程中间歇性的加入。
乳液聚合过程中可以使用自由基引发剂引发聚合反应，包括有机过氧化物及氧化还原体系两类。有机过氧化物的例子包括过硫酸钾、过硫酸铵、过硫酸钠。氧化还原引发体系包含氧化剂和还原剂两组分。合适的氧化剂例子包括叔丁基过氧化物、高锰酸钾、过二硫酸铵或过二硫酸的碱金属盐；合适的还原剂例子为甲醛合次硫酸氢钠、抗坏血酸、异抗坏血酸、亚硫酸钠、亚硫酸氢钠、连二亚硫酸钠、甲脒亚磺酸、羟甲基磺酸、丙酮亚硫酸氢盐等。可以选择含铁、铜、锰、银、铂、钒、镍、铬等的催化剂催化氧化还原反应，使引发温度降低。以上催化剂优选与螯合剂联合使用以提升催化效率。
乳液聚合温度可为30-100℃，优选40-95℃，最优选50-90℃。
乳液聚合可以以间歇法、连续法和半连续法的方式实施。在本发明中，优选使用间歇法和半连续法，意为聚合单体一次性加入或者分批次连续性的滴加入体系。最优选的聚合方式为半连续法，即将表面活性剂水溶液作为初始投料加入反应釜，待反应釜内温度升至设定值时，以纯单体或者以预乳化液的形式将单体滴加入体系，同时滴加的还有引发剂。可以选择核壳、梯度或者多段进料方式进料。得到具有不同几何构型的乳胶粒相形貌，如核壳、壳中多核、多相、橡子型、反转型、壳不完全包封核、梯度或者互穿网络构型。
制备的丙烯酸共聚物乳液可通过加入中和剂将所述共聚物乳液中和至设定pH值，优选的中和剂为有机胺类、无机氨类或碱金属氢氧化物。
通过向乳液中加入一种或多种添加剂来制备涂料组合物，添加剂选自交联剂、，成膜助剂、消泡剂、基材润湿剂、分散剂、流平剂、增稠剂、流变助剂、杀菌剂、防沉剂等；向涂料体系中加入一种或多种颜料、填料，剪切搅拌均匀，直至得到均匀无沉淀的涂料组合物。
本发明涂料组合物可以多种施涂方式涂覆于基材表面，例如空气喷涂、无气喷涂、混合喷涂、刮涂、辊涂、镘涂、浸涂、淋涂、静电喷涂等。干燥方式可为常温干燥或者升温强制干燥。
含有本发明丙烯酸共聚物乳液的涂料组合物涂布于基材(包括金属材料、非金属材料)表面形成的涂膜，既具有高光泽度，又具有良好的早期耐水性。
具体实施方式
以下结合实施例对本发明进行进一步的说明。以下实施例所采用的材料和试剂，
若无特殊说明，均通过常规商业渠道获得。
实施例1：
将去离子水(210.6g)、RS-710(阴离子型磷酸酯乳化剂，3.11g，100％活性物质，索尔维)、SR-1025(阴离子型反应型乳化剂，5.39g，25％活性物质，艾迪科)、氨水(25％含量，0.35g)、丙烯酸(AA，15.69g)、甲基丙烯酸(MAA，24.71)、苯乙烯(St，314.09g)、甲基丙烯酸丁酯(BMA，253.08g)、丙烯酸异辛酯(EHA，136.05g)、2-甲基-2-丙烯酸-2-羟乙基酯磷酸酯(PEM，赢创Visiomer HEMA-phosphate，3.54g)混合，制备单体预乳液，备用；
向设有搅拌器，温度计，加热水浴，回流冷凝管及氮气入口的2L圆底四口烧瓶中加入去离子水(620g)、RS-710(5.06g)、SR-1025(7.7g)和氨水(0.5g)，加热至85℃，加入5wt％的单体预乳液，搅拌混合3min，加入过硫酸铵(APS，1g)溶于去离子水(20g)的种子引发剂溶液进行种子乳液聚合；15min后保持聚合体系温度在85℃，同时滴加剩余的单体预乳液及APS(2.8g)在去离子水(100g)中的溶液，240min滴完；滴加完毕后用去离子水(45g)冲洗预乳液罐及引发剂罐入四口烧瓶，85℃保温60min；
体系降温至65℃，一次性加入氨水(10.92g)中和15min；一次性加入叔丁基过氧化氢(TBHP，0.5g，70％活性物质)溶于去离子水(3g)中的溶液，将FF6M(0.4g，布吕格曼)溶于去离子水(9g)的溶液于15min滴入烧瓶进行单体消除步骤；滴加完毕65℃继续保温30min；降温至40℃加入卡松(7g，陶氏，1.5％活性物质)杀菌剂溶液，氨水调整pH至7.5，100μm滤布过滤出料；得到固含为43.3wt％，pH为7.5，粒径为113nm，旋转粘度为152mPa.s的乳白泛蓝乳液。乳液中St占单体质量分数为42.0wt％，PEM占单体质量分数为0.47wt％。
实施例2及比较例1-5的单体组成比例汇总于表1，聚合方式与实施例1一致。
表1.实施例2级比较例1-5的单体组成和乳液参数
采用表2所列成分分别与实施例1和2制备的丙烯酸共聚物乳液，配制单组分水性丙烯酸白漆，首先将色浆组分高速分散至细度＜15μm，然后按顺序加入乳液，助剂等成分，分散至平滑无缩孔，用去离子水调整成漆至合适粘度。
表2用实施例1制备的丙烯酸共聚物乳液配制单组分水性丙烯酸白漆原料配比
测试方法：
光泽度：以约200μm的湿膜厚度将涂料施涂于Leneta 2A卡纸上，室温(23℃，50％相对湿度)干燥7天后依据DIN EN ISO 2813使用BYK-Gardener反射计测量60°光泽。
铅笔硬度：以约100μm的湿膜厚度将涂料涂覆于玻璃板上，室温干燥7天后采用DINEN ISO 13523-4测试漆膜铅笔硬度，结果以8B(最软)至8H(最硬)中的某一等级表示。
附着力(X切割以及划格)：以约100μm的湿膜厚度将涂料涂覆于打磨过的马口铁板上，室温干燥7天后采用ASTM D3359-93测试漆膜在基材上的附着力，结果以0B(最差)-5B(最优)表示。
早期耐水性：以约100μm的湿膜厚度将涂料涂覆于打磨过的马口铁板上，室温干燥1h后将铁板下半部分放置于去离子水中浸泡3天，评分以1(最差)-5(最优)表示。
评分5：板面无起泡，无起皱，无漆膜溶胀脱落，仅轻微失光。
评分4：仅板面边缘有轻微小泡，无起皱脱落，仅轻微失光
评分3：全部板面有小至中等起泡，无起皱脱落，失光明显
评分2：板面有较多中等至大炮，漆膜受损面积在20％以内
评分1：漆膜大量溶胀脱落，漆膜受损面积在20％以上。
杯突柔韧性：以约100μm的湿膜厚度将涂料涂覆于打磨过的马口铁板上，室温干燥7天后根据GB/T 9753-2007测试，结果以mm表示。
能够较好满足性能需求的丙烯酸共聚物乳液需具备如下性能：
60°光泽：≥85GU
铅笔硬度：≥B
附着力：≥4B
早期耐水：5级
杯突柔韧性：≥8.5mm
各丙烯酸共聚物溶液性能检测结果如表3所示：
表3.丙烯酸共聚物乳液的白漆性能检测结果
实施例1与比较例1的对比清晰地证明了增加St用量对于提升光泽的帮助。比较例2对比实施例1仅仅是将配方中的PEM全部替换为了AA，光泽略有下降，是由于PEM相较于AA对颜料钛白更佳的分散效应所致，早期耐水性也有所降低。相较于实施例1增加了St用量的比较例3显示出较差的早期耐水性及柔韧性，并且漆膜干燥完全后的附着力也呈现一定程度下降。增加了磷酸酯单体PEM用量的比较例4由于漆膜亲水性增加而使得早期耐水性下降。同时增加St及PEM用量的比较例5同样展现出不佳的附着力、柔韧性及早期耐水性。不引入磷酸酯单体PEM而增加疏水性单体EHA用量的比较例6显示出不佳的早期耐水性及略低的附着力，这是由于没有磷酸酯单体对附着力的促进作用所致。
由以上分析可见，本发明通过优化苯乙烯与2-甲基-2-丙烯酸-2-羟乙基酯磷酸酯在乳液聚合中合适的质量分数配比实现了上述漆膜性能，尤其是光泽与早期耐水性的平衡兼顾。
Claims (6)
1.一种改善涂层早期耐水性和光泽度的丙烯酸共聚乳液，其特征在于，所述丙烯酸共聚乳液的玻璃化转变温度为20℃至50℃，基于固体的酸值为10mg KOH/g至40mgKOH/g，由不饱和单体聚合而成，所述不饱和单体包括：
（a）一种或多种烯键式不饱和单体，所述烯键式不饱和单体选自（甲基）丙烯酸C1至C20烷基酯；
（b）一种或多种芳香族烯键式不饱和单体；
（c）一种或多种烯键式不饱和酸单体，其包含一种或多种烯键式不饱和羧酸单体及一种或多种烯键式不饱和强酸单体；
所述芳香族烯键式不饱和单体为苯乙烯、乙烯基甲苯、α-甲基苯乙烯、对甲基苯乙烯、α-丁基苯乙烯、4-正丁基苯乙烯中的一种或几种；
所述烯键式不饱和羧酸单体选自丙烯酸、甲基丙烯酸、衣康酸、富马酸、马来酸、衣康酸单甲酯、富马酸单甲酯、马来酸酐、乙基丙烯酸、α-苯基丙烯酸中的一种；烯键式不饱和强酸单体为2-甲基-2-丙烯酸-2-羟乙基酯磷酸酯；
所述丙烯酸共聚乳液由以下重量配比的不饱和单体聚合而成：40 – 70wt%的烯键式不饱和单体，35-55 wt%的芳香族烯键式不饱和单体，1-10 wt%的烯键式不饱和酸单体，其中烯键式不饱和强酸单体占所有单体质量分数的0.15-1.5 wt%；所有单体质量分数的总和为100wt%。
2.根据权利要求1所述丙烯酸共聚乳液，其特征在于，所述烯键式不饱和单体选自甲基丙烯酸甲酯、丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、丙烯酸正丁酯、丙烯酸叔丁酯、丙烯酸异辛酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、甲基丙烯酸环己酯、丙烯酸环己酯、丙烯酸异冰片酯、甲基丙烯酸十三酯、甲基丙烯酸十八酯中的一种或几种。
3.根据权利要求1或2所述丙烯酸共聚乳液，其特征在于，所述丙烯酸共聚物乳液中，还通过有机碱或无机碱来中和乳液中的酸。
4.根据权利要求3所述丙烯酸共聚乳液，其特征在于，所述有机碱或无机碱为有机胺、氨水或碱金属氢氧化物。
5.如权利1-4任一项所述丙烯酸共聚乳液在涂布金属，木质和混凝土涂层基底中的应用。
6.一种包含权利要求1-4任一项所述聚丙烯共聚乳液的涂料组合物，其特征在于，所述涂料组合物的制备方法为：通过加入中和剂将权利要求1-4任一项所述共聚物乳液中和至设定pH值；加入一种或多种添加剂，所述添加剂选自交联剂、成膜助剂、消泡剂、基材润湿剂、分散剂、流平剂、增稠剂、流变助剂、杀菌剂和防沉剂；再加入一种或多种颜料，填料，剪切搅拌均匀，直至得到均匀无沉淀的涂料组合物。
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| CN111315832A (zh) * | 2017-11-10 | 2020-06-19 | 巴斯夫欧洲公司 | 水性聚合物分散体 |
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| CN102199240A (zh) * | 2011-03-17 | 2011-09-28 | 北京化工大学 | 一种防锈涂料用苯乙烯-丙烯酸酯共聚乳液的制备方法 |
| CN111315832A (zh) * | 2017-11-10 | 2020-06-19 | 巴斯夫欧洲公司 | 水性聚合物分散体 |
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