CN113557250A - 含水共聚物分散体和它们在涂料组合物中的用途 - Google Patents
含水共聚物分散体和它们在涂料组合物中的用途 Download PDFInfo
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- CN113557250A CN113557250A CN202080018889.XA CN202080018889A CN113557250A CN 113557250 A CN113557250 A CN 113557250A CN 202080018889 A CN202080018889 A CN 202080018889A CN 113557250 A CN113557250 A CN 113557250A
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- GOPSAMYJSPYXPL-UHFFFAOYSA-N prop-2-enyl n-(hydroxymethyl)carbamate Chemical compound OCNC(=O)OCC=C GOPSAMYJSPYXPL-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
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- AYBFZRTVERSNMY-UHFFFAOYSA-M sodium;18-hydroxyoctadecane-1-sulfonate Chemical compound [Na+].OCCCCCCCCCCCCCCCCCCS([O-])(=O)=O AYBFZRTVERSNMY-UHFFFAOYSA-M 0.000 description 1
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- 239000011975 tartaric acid Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- KWXLCDNSEHTOCB-UHFFFAOYSA-J tetrasodium;1,1-diphosphonatoethanol Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P(=O)([O-])C(O)(C)P([O-])([O-])=O KWXLCDNSEHTOCB-UHFFFAOYSA-J 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
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Abstract
一种含水共聚物分散体通过多级乳液聚合方法来获得,该方法包括:在第一聚合级的反应区中,使包含至少88wt%的C1‑C18羧酸的乙烯酯和至多12wt%乙烯的第一单体组合物聚合,以产生Tg>20℃的第一级聚合物;和在第二聚合级的反应区中并且在该第一级聚合物存在下,使包含C1‑C18羧酸的乙烯酯和(甲基)丙烯酸的C2‑C8烷基酯的第二单体组合物聚合,以产生Tg≤20℃的第二级聚合物。每个聚合级在包含至少0.1wt%的保护性胶体和至少0.05wt%的离子表面活性剂的稳定化体系存在下进行。
Description
领域
本发明涉及含水共聚物分散体和它们在涂料组合物如高光泽门窗漆、大漆、染色剂和清漆中的用途。
背景
由于安全和健康原因二者,现今对于不含挥发性有机含量(VOC)的建筑涂覆材料的需求是公知的。转换到水性或高固体漆、尤其是基于乙烯酯共聚物粘结剂的那些已经回答了这种需求,但是在表面光泽是重要的情况下如在缎面漆、半光泽漆和高光泽漆的情况下仍然存在与漆相关的问题。这样的漆需要具有良好的抗结块性以防止涂漆的表面如门窗上结块。这个问题先前是通过引入有机溶剂来解决的,但是这种方案部分地抵消了使用水基漆的主要优点。虽然结块问题可以通过将“硬”聚合物(即,具有相对高的玻璃化转变温度(Tg)的聚合物)引入配制物中来缓解,但是这个步骤往往导致完成的涂层光泽值下降。同样重要的是完成的涂层具有优异的耐沾污性。
在试图解决结块问题方面,美国专利号6656998提出了一种利用含水乳液共混物的光泽的水性漆配制物,该共混物基本上由以下组成:干Tg高于室温但湿Tg低于室温的乙酸乙烯酯聚合物的第一乳液,所述第一乳液在室温下成膜;和乙酸乙烯酯、乙烯和任选的第三单体的共聚物或乙酸乙烯酯、丙烯酸烷基酯和任选的第三单体的共聚物的第二乳液,所述第二乳液的所述共聚物的干Tg低于20℃,其中所述光泽的水性漆当作为涂料施加并干燥时,具有至少20的ASTM 60°光泽度。
针对结块问题提出的另一种解决方案在美国专利申请公开号2009/0203814中提供,其公开了一种多级含水共聚物分散体,该分散体得自重量比为95/5至5/95的至少一种均聚物或共聚物A和至少一种均聚物或共聚物B,其中该共聚物A得自将产生具有0-20℃的第一玻璃化转变温度的软共聚物的单体组合物A,该均聚物或共聚物B得自将产生具有20-50℃的第二玻璃化转变温度的硬均聚物或共聚物的单体组合物B,和其中该第一和第二玻璃化转变温度的差值是至少10°K。每个单体组合物A和B包含50-100重量%的至少一种具有1-18个碳原子的羧酸的乙烯酯,和单体组合物A或B中的至少之一包含0.05-10重量%的至少一种不饱和的可共聚有机硅化合物。该含水共聚物分散体包含至少0.5重量%的非离子乳化剂,并且用于生产分散体的离子组分的总质量与非离子组分的总量的比率小于1。类似的但主要通过离子乳化剂稳定的共聚物分散体公开在美国专利号7078455中。
美国专利申请公开号2005/0107527公开了一种可用于涂料组合物的含水聚合物分散体,其表现出改进的抗结块性,并且包括通过如下方法制造的多级乳液聚合物,该方法包括第一聚合级和第二聚合级,在第一聚合级中,具有至少约50℃的计算的玻璃化转变温度的第一单体混合物经由自由基乳液聚合进行聚合,以获得第一级乳液聚合物,在第二聚合级中,具有约-30℃至约10℃的计算的玻璃化转变温度的第二单体混合物在该第一级乳液聚合物存在下经由自由基乳液聚合进行聚合。
虽然有这些进展,但是仍然有兴趣开发新的聚合物分散体,其适合于生产表现出改进的抗结块性和耐沾污性的光泽涂料。
概述
根据本发明,提供一种含水共聚物分散体,其通过自由基引发的多级乳液聚合方法来获得,该聚合方法包括:
(a)在第一聚合级的反应区中,使包含至少88重量%的至少一种C1-C18羧酸的乙烯酯和至多12重量%乙烯的第一单体组合物聚合,以产生玻璃化转变温度Tg大于20℃的第一级聚合物;和
(b)在第二聚合级的反应区中并且在该第一级聚合物存在下,使包含至少一种C1-C18羧酸的乙烯酯和至少一种丙烯酸或甲基丙烯酸的C2-C8烷基酯的不同的第二单体组合物聚合,以产生玻璃化转变温度Tg小于或等于20℃的第二级聚合物,该至少一种丙烯酸或甲基丙烯酸的C2-C8烷基酯的量至多为该第二单体组合物中总单体的30重量%,
其中该第一单体组合物基本上不含丙烯酸或甲基丙烯酸的C2-C8烷基酯;
其中该第二单体组合物在至少部分的该第二聚合级期间计量入该反应区中,和
其中每个聚合级(a)和(b)在稳定化体系存在下进行,该稳定化体系包含至少0.1重量%的至少一种保护性胶体、至少0.05重量%的至少一种离子表面活性剂和小于2重量%的非离子表面活性剂,该稳定化体系中的所有百分比基于该第一和第二单体组合物中单体的总重量计。
本发明还涉及由本文所述含水共聚物分散体生产的涂料组合物,其具有改进的抗结块性和耐沾污性。
详述
本发明涉及含水的基于乙烯酯的共聚物分散体和它们在生产具有良好的抗结块性和耐沾污性的独特组合的光泽的涂料组合物中的用途。特别地,本发明提供一种涂料组合物,其包含通过自由基引发的多级乳液聚合方法获得的含水共聚物分散体,在该方法中,包含至少88重量%的至少一种C1-C18羧酸的乙烯酯和至多12重量%乙烯的第一单体组合物在第一聚合级的反应区中聚合,以产生玻璃化转变温度Tg大于20℃、优选至少26℃的第一级聚合物。包含至少一种C1-C18羧酸的乙烯酯和至多为该第二单体组合物中总单体的30重量%量的至少一种丙烯酸或甲基丙烯酸的C2-C8烷基酯的不同的第二单体组合物然后在第二聚合级的反应区中并且在该第一级聚合物存在下聚合,以产生玻璃化转变温度Tg小于或等于20℃、例如0℃-20℃、优选5℃-20℃、更优选7-20℃的第二级聚合物。
在至少部分的该第二聚合级期间,该第二单体组合物以变化的速率或更优选以恒定速率逐渐计量入该反应区中。相反,在大多数实施方案中,该第一单体组合物中存在的所有C1-C18羧酸的乙烯酯和任何乙烯是在该第一聚合级开始之前加入该反应区的。
每个该第一和第二聚合级在稳定化体系存在下进行,该稳定化体系包含至少0.1wt%的至少一种保护性胶体、至少0.05wt%的至少一种离子表面活性剂和小于2wt%的非离子表面活性剂,该稳定化体系中的所有百分比基于该第一和第二单体组合物中单体的总重量计。
要理解的是本文提及的聚合物的所有玻璃化转变温度使用Fox等式(T.G.Fox,Bull.Am.Ph.Soc.(Ser.11)1,123[1956]和Ullmann'sEnzyklopadie der technischenChemie[Ullmann's Encyclopedia of Industrial Chemistry],Weinheim(1980),第19卷,第1-7-18页)计算,根据Fox,以下等式是在高摩尔质量的情况下共聚物的玻璃化转变温度Tg的良好近似:
1/Tg=X1/Tg 1+X2/Tg 2+…Xn/Tg n
X1、X2、…Xn是质量分数1、2、…n,和Tg 1、Tg 2、…Tg n是在每种情况下仅由单体1、2…n中的一种组成的聚合物的玻璃化转变温度(以度开尔文计)。后者公开在例如Polymerdatabase.com(2015)或在Brandrup,E.H.Immergut,Polymer Handbook,第3版,J.Wiley,纽约1989中,例如乙烯均聚物的玻璃化转变温度是193°K(参见Polymerdatabase.com),和乙酸乙烯酯均聚物的玻璃化转变温度是315°K(参见Ullmann'sEncyclopedia of Industrial Chemistry,VCH Weinheim,第A21卷(1992)第169页)。在玻璃化转变温度的简化计算中,可以仅考虑主要为相形成做出贡献的主要单体,和忽略任何由小于2重量%的质量分数形成的另外单体的贡献,前提是这些单体的质量分数的总和不超过4重量%。
第一和第二单体组合物
第一和第二单体组合物各自包含一种或多种C1-C18羧酸的乙烯酯。在第一单体组合物的情况下,这些一种或多种乙烯酯占第一单体组合物中总单体的至少约88重量%、例如至少约90重量%和至多约92重量%、例如至多约95重量%、例如至多约100重量%。在第二单体组合物的情况下,这些一种或多种乙烯酯可以占第二单体组合物的至少约50重量%、例如至少约70重量%、例如至少约80重量%,基于该第二单体组合物中单体的总重量。
合适的乙烯酯包括具有1-18个碳原子的直链和/或支化脂族羧酸的乙烯酯。另外,还可以使用芳族羧酸的乙烯酯。还可以使用不同的乙烯酯的混合物。
优选的乙烯酯单体包括甲酸乙烯酯,乙酸乙烯酯,丙酸乙烯酯,丁酸乙烯酯,异丁酸乙烯酯,戊酸乙烯酯,2-乙基己酸乙烯酯,酸基中具有9-11个碳原子饱和支化单羧酸的乙烯酯如VeoVaTM 9、VeoVaTM 10和VeoVaTM 11,相对长链的饱和或不饱和脂肪酸的乙烯酯如月桂酸乙烯酯或硬脂酸乙烯酯,以及苯甲酸和取代的苯甲酸衍生物的乙烯酯如对叔丁基苯甲酸乙烯酯。乙酸乙烯酯对于第一和第二单体组合物的每者而言是特别优选的。
除了上述乙烯酯之外,第一单体组合物还可以包含至多12重量%、例如至多8.5重量%量的乙烯,基于第一单体组合物的总单体。在一些实施方案中,第一单体组合物不包含乙烯。
除了上述乙烯酯之外,第二单体组合物还包含至少一种丙烯酸或甲基丙烯酸的C2-C8烷基酯,其量为至多30重量%、例如至多约15重量%、例如至多约10重量%,基于第二单体组合物中的总单体。典型地,第二单体组合物中(甲基)丙烯酸酯的最小量是至少2重量%、例如至少5重量%,基于该第二单体组合物中的总单体。通常,第一单体组合物基本上不含丙烯酸或甲基丙烯酸的C2-C8烷基酯。在本上下文中,“基本上不含”意指包含小于0.05%重量的丙烯酸或甲基丙烯酸的C2-C8烷基酯。
用于本发明涂料组合物中的优选的丙烯酸或甲基丙烯酸的C2-C8烷基酯是均聚物的Tg小于0℃的那些,例如丙烯酸乙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸仲丁酯、丙烯酸2-乙基己基酯和甲基丙烯酸2-乙基己基酯,其中丙烯酸正丁酯是特别优选的。
除了上述乙烯酯和(甲基)丙烯酸酯之外,第二单体组合物还可以包含至多25重量%、例如至多20重量%、例如2-15重量%量的乙烯,基于第二单体组合物中的总单体。
在一些实施方案中,第一和第二单体组合物各自可以进一步包含0.05重量%至约5重量%的至少一种选自烯属不饱和磺酸、烯属不饱和磷酸、烯属不饱和膦酸及其盐的稳定化单体,基于各自单体组合物中的总单体。合适的烯属不饱和磺酸的实例包括具有2-8个碳原子的那些,例如乙烯基磺酸、2-丙烯酰氨基-2-甲基丙烷磺酸、2-丙烯酰氧基乙烷磺酸和2-甲基丙烯酰氧基乙烷磺酸、2-丙烯酰氧基丙烷磺酸和3-甲基丙烯酰氧基丙烷磺酸和乙烯基苯磺酸。合适的烯属不饱和膦酸的实例还包括具有2-8个碳原子的那些如乙烯基膦酸。除了或代替所述酸,可以使用它的盐、优选碱金属盐或铵盐、特别优选钠盐,例如乙烯基磺酸的钠盐和2-丙烯酰氨基丙烷磺酸的钠盐。在大多数实施方案中,至少部分的稳定化单体在第一聚合级期间逐渐计量入聚合反应器中。类似的计量可以用于将稳定化单体加入至第二单体组合物中。
任选地,第一和第二单体组合物中的之一或二者可以进一步包含至多5重量%、例如0.05重量%至约5重量%的至少一种烯属不饱和单羧酸和/或二羧酸和/或其酰胺,基于各自单体组合物中的总单体。合适的单体包括烯属不饱和C3-C8单羧酸和烯属不饱和C4-C8二羧酸,以及其酸酐或酰胺和烯属不饱和C4-C8二羧酸的单酯。烯属不饱和C3-C8单羧酸的实例包括丙烯酸、甲基丙烯酸和巴豆酸及其酸酐和酰胺。烯属不饱和C4-C8二羧酸包括马来酸、富马酸、衣康酸和柠康酸及其单酰胺或双酰胺和它们与C1-C12、优选C1-C4烷醇的单酯如马来酸单甲酯和马来酸单正丁酯。
用于第一和第二单体组合物中的之一或二者的另外的任选的共聚单体是环氧官能的烯属不饱和化合物,例如甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯和/或乙烯基环氧环己烷。这些共聚单体的存在量可以为各自单体组合物中总单体的至多10重量%、优选至多5重量%。
用于第一和第二单体组合物中之一或二者,尤其是用于第二单体组合物的另外的任选的共聚单体是硅氧烷官能的烯属不饱和化合物如丙烯酰氧基烷基三(烷氧基)硅烷和甲基丙烯酰氧基烷基三(烷氧基)硅烷、乙烯基三烷氧基硅烷和/或乙烯基烷基二烷氧基硅烷。这些共聚单体的存在量可以为各自单体组合物中总单体的至多5重量%、优选至多3重量%、优选至多1重量%。
用于第一和第二单体组合物中之一或二者的另外的任选的共聚单体是多烯属不饱和的和因此交联的共聚单体,例如邻苯二甲酸二烯丙基酯、马来酸二烯丙基酯、氰尿酸三烯丙基酯、四烯丙基氧乙烷、二乙烯基苯、丁二醇1,4-二甲基丙烯酸酯、三甘醇二甲基丙烯酸酯、己二酸二乙烯酯、(甲基)丙烯酸烯丙基酯、巴豆酸乙烯酯、亚甲基双丙烯酰胺、己二醇二丙烯酸酯、季戊四醇二丙烯酸酯和三羟甲基丙烷三丙烯酸酯或来自这个组的两种或更多种化合物的混合物。这些共聚单体的存在量可以是各自单体组合物中总单体的至多10重量%、优选至多2重量%。
用于第一和第二单体组合物中之一或二者的另外的任选的共聚单体是不饱和羧酸的羟基官能酯如(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯及其与环氧乙烷或环氧丙烷的加合物。这些共聚单体的存在量可以为各自的单体组合物中总单体的至多10重量%、优选至多5重量%。
用于第一和第二单体组合物中之一或二者的另外的任选的共聚单体是含有可交联基团如羰基或N-羟甲基的烯属不饱和化合物。其实例是双丙酮丙烯酰胺,乙酰乙酸烯丙基酯,乙酰乙酸乙烯酯,(甲基)丙烯酸乙酰乙酰氧基乙基酯,N-乙醇(甲基)丙烯酰胺,N-丙醇(甲基)丙烯酰胺,(甲基)丙烯酰胺,氨基甲酸烯丙基酯,丙烯腈,N-羟甲基(甲基)丙烯酰胺或N-羟甲基烯丙基氨基甲酸酯的N-羟甲基酯、N-羟甲基烷基醚或曼尼希碱,丙烯酰氨基乙醇酸和/或其盐,丙烯酰氨基甲氧基乙酸甲酯,N-(2,2-二甲氧基-1-羟乙基)丙烯酰胺,N-二甲基氨基丙基(甲基)丙烯酰胺,N-甲基(甲基)丙烯酰胺,N-丁基(甲基)丙烯酰胺,N-环己基(甲基)丙烯酰胺,N-十二烷基(甲基)丙烯酰胺,N-苄基(甲基)丙烯酰胺,对羟基苯基(甲基)丙烯酰胺,N-(3-羟基-2,2-二甲基丙基)甲基丙烯酰胺,乙基咪唑啉酮甲基丙烯酸酯或N-乙烯基甲酰胺,N-乙烯基吡咯烷酮。这些共聚单体的存在量可以为各自单体组合物中总单体的至多5重量%、优选至多3重量%。
用于第一和第二单体组合物中之一或二者的另一任选的共聚单体是至少一种湿粘合改进单体,优选选自(甲基)丙烯酸乙酰乙酰氧基乙基酯,乙酰乙酸烯丙基酯,N-乙烯基脲,N-烯丙基脲,N-乙烯基咪唑啉-2-酮-和N-烯丙基咪唑啉-2-酮,N-乙烯基氧乙基咪唑啉-2-酮,N-(2-(甲基)丙烯酰氨基乙基)咪唑啉-2-酮,N-(2-(甲基)丙烯酰氧乙基)咪唑啉-2-酮,N-(2-(甲基)丙烯酰氧基乙酰氨基乙基)咪唑啉-2-酮和N-2-(烯丙基氨基甲酸酯)氨基乙基咪唑啉酮。粘合改进单体优选在单体混合物中的存在量为至多10%重量、优选至多5%重量,基于各自单体混合物中所用的可自由基聚合单体的总重量。
优选地,第一单体组合物与第二单体组合物的重量比的范围为5:95至95:5,例如范围为20:80至40:60。
分散体稳定化体系
在聚合期间和之后二者中,本文所述的多级聚合物以含水共聚物分散体或胶乳的形式来稳定。共聚物分散体因此在稳定化体系存在下制备并且随后包含该稳定化体系,该稳定化体系通常包含至少一种保护性胶体和至少一种离子表面活性剂、特别是阴离子表面活性剂。非离子表面活性剂也可以存在,但是通常不优选。
合适的保护性胶体(即聚合物稳定剂)包括乙烯醇聚合物和共聚物,甲基纤维素,羟乙基和丙基纤维素,以及羧甲基纤维素钠,明胶,酪蛋白,淀粉,阿拉伯胶,羟乙基淀粉和藻酸钠。优选的保护性胶体是乙烯醇聚合物和共聚物、尤其是乙烯醇和乙烯基吡咯烷酮的共聚物。还可以使用保护性胶体的混合物。典型地,基于所用单体的总量,保护性胶体的量是至少0.1重量%、例如0.1-5重量%、优选0.3-3重量%。
合适的离子表面活性剂的实例包括链长为C12-C20的线性脂族羧酸的钠、钾和铵盐,羟基十八烷基磺酸钠,链长为C12-C20的羟基脂肪酸的钠、钾和铵盐及它们的磺化和/或硫酸化和/或乙酰化产物,烷基硫酸盐,包括处于三乙醇胺盐形式的那些,烷基(C10-C20)磺酸盐,烷基(C10-C20)芳基磺酸盐和它们的磺化产物,木质素磺酸及其钙、镁、钠和铵盐,树脂酸,氢化和脱氢的树脂酸和它们的碱金属盐,十二烷基化二苯基醚二磺酸钠,烷基硫酸钠或钾,硫酸化的烷基或芳基乙氧基化物(EO度是1-30),例如乙氧基化的月桂基醚硫酸钠或具有4-8个碳原子的磺化二羧酸的二酯的盐,优选双-C4-C18烷基酯的盐或这些盐的混合物,优选琥珀酸酯的磺化盐,更优选磺化琥珀酸的双-C4-C18烷基酯的盐如碱金属盐,或聚乙氧基化烷醇的磷酸盐。特别合适的是烷基(C10-C20)芳基磺酸盐如烷基苯磺酸盐,烷基硫酸钠或钾如月桂基硫酸钠,和硫酸化的C10-C16烷基乙氧基化物的钠、钾或铵盐(EO度是1-30)。
当使用离子乳化剂时,其量基于所用单体的总量典型地是至少0.05重量%、例如0.05-10重量%、优选0.05-5.0重量%、更优选0.05-3重量%和最优选0.1-2重量%。
虽然它们的使用不是优选的,但是合适的非离子乳化剂的实例包括酰基、烷基、油基和烷基芳基乙氧基化物。这些产品是可商购的,例如在名称或下可商购。它们包括例如乙氧基化的单烷基酚、二烷基酚和三烷基酚(EO度:3-50,烷基取代基:C4-C12)以及乙氧基化的脂肪醇(EO度:3-80;烷基:C8-C36),尤其是C10-C14脂肪醇(3-40)乙氧基化物,C11-C15羰基合成醇(3-40)乙氧基化物,C16-C18脂肪醇(11-80)乙氧基化物,C11羰基合成醇(3-40)乙氧基化物,C13羰基合成醇(3-40)乙氧基化物,具有20个环氧乙烷基团的聚氧乙烯失水山梨糖醇单油酸酯,最小环氧乙烷含量是10重量%的环氧乙烷和环氧丙烷的共聚物,油醇的聚环氧乙烷(4-40)醚,和壬基酚的聚环氧乙烷(4-40)醚。
用于制备本文的共聚物分散体的非离子乳化剂的量典型地小于2重量%、优选小于1.5重量%、更优选小于0.75重量%,基于总单体量。
多级聚合方法
本发明涂料组合物中所用的共聚物分散体通过在含水介质中并且在一种或多种自由基引发剂存在下通过上述单体和稳定化体系的多级乳液聚合产生。合适的自由基引发剂包括过氧化氢、过氧化苯甲酰、过氧化环己酮、异丙基枯基过氧氢、过硫酸钾、过硫酸钠和过硫酸铵、具有偶数个碳原子和C8-C12链长的饱和单碱式脂族羧酸的过氧化物、叔丁基氢过氧化物、二叔丁基过氧化物、过碳酸二异丙酯、偶氮二异丁腈、过氧化乙酰基环己烷磺酰、过氧化苯甲酸叔丁酯、过辛酸叔丁酯、过氧化双(3,5,5-三甲基)己酰、过新戊酸叔丁酯、氢过氧化蒎烷、氢过氧化对甲烷。上述化合物也可以用于使用过渡金属盐如铁(II)盐或其他还原剂的氧化还原体系中。氧甲烷亚磺酸的碱金属盐、羟基胺盐、二烷基二硫代氨基甲酸钠、亚硫酸氢钠、亚硫酸氢铵、连二亚硫酸钠、二异丙基黄原二硫化物、抗坏血酸、酒石酸和异抗坏血酸也可以用作还原剂。在氧化还原对用于引发的情况下,氧化剂和还原剂通常在每个聚合级期间计量入聚合混合物中。
多级乳液聚合可以根据常规的乳液聚合技术进行。优选地,该方法通过如下进行:在第一级中,在水相中在一种或多种表面活性剂、保护性胶体和引发剂存在下在合适的温度如20-120℃、优选40-110℃和最优选50-95℃下聚合第一单体组合物以产生第一聚合物相。反应温度也可以在聚合期间上升,如美国专利申请2017/029544中所述。在一些实施方案中,将至少主要单体(即一种或多种C1-C18羧酸的乙烯酯和当存在时的乙烯)在第一聚合级开始之前预加入至聚合反应器中。至少部分的稳定化单体(即烯属不饱和磺酸、膦酸和/或磷酸或其盐)然后可以在至少部分的第一聚合级期间计量入反应区中。
在至少80%、例如至少85%、例如至少90%、优选至少95%重量的第一级单体完全或几乎完全转化后,第二单体组合物在第二级中,在含水相中在第一聚合物相以及表面活性剂、保护性胶体引发剂存在下在合适的温度如20-120℃、优选40-110℃、更优选50-95℃进行聚合,以产生第二聚合物相和由此获得包含第一和第二聚合物相的聚合物颗粒。第二单体组合物的单体优选在第二聚合级期间任选地与另外量的稳定化单体一起计量入聚合反应器中。
在一些实施方案中,可以令人期望的是预聚少量(小于10重量%)的第一单体组合物以原位产生种子,然后将其余量的第一和第二单体组合物顺序加入至反应器以形成最终的聚合物分散体。
在第二级中的聚合完成后,为了脱单体,随后可以是另外的优选的化学后处理、尤其是利用氧化还原催化剂如上述氧化剂和还原剂的组合的化学后处理。另外,存在的残留单体可以以已知方式除去,例如通过物理脱单体,即蒸馏除去,尤其是借助于蒸汽蒸馏或通过用惰性气体汽提来进行。特别有效的组合是物理和化学方法之一,其允许将残留单体降低到非常低的含量(<1000ppm、优选<100ppm)。
聚合物分散体
通过本发明的方法生产的含水多级分散体典型的固含量是20-70重量%、优选30-65重量%和更优选40-60重量%,并且pH是2-7、优选3.5-6。
在一些实施方案中,另外的保护性胶体或乳化剂是后加入到上述的多级聚合方法的产物中。优选的后加入的保护性胶体是乙烯醇聚合物和共聚物、尤其是乙烯醇和乙烯基吡咯烷酮的共聚物。还可以使用保护性胶体的混合物。典型地,后加入的保护性胶体的量是0.1-3重量份、优选0.2-2重量份,基于该聚合物分散体的固含量。
本文所述的含水多级聚乙烯酯组合物是稳定的分散体,其可以用于生产适合于涂覆多种基底的涂料组合物。合适的基底例如木材,混凝土,金属,玻璃,陶瓷,塑料,灰泥,壁纸,其他纸,或涂漆的、涂底漆的或风化的基底。涂料组合物以取决于涂料组合物构成的方式施加到待涂覆的基底上。施加可以借助于辊涂、刷涂、刀涂、浸涂或作为喷涂来进行,这取决于配制物的粘度和颜料含量以及基底。
这样的涂料组合物优选的用途是用于半光泽或高光泽漆、大漆、染色剂和清漆,特别是不含溶剂和不含增塑剂的漆。当用于这样的应用时,通过本发明方法生产的含水多级分散体典型地与一种或多种常规填料和/或颜料组合。在本上下文中,颜料被理解为意指折射率大于或等于1.75的固体,而填料被理解为意指折射率小于1.75的固体。
矿物填料的实例是碱土金属氧化物,碱土金属碳酸盐和/或硅酸盐填料,特别是碳酸钙、云母、长石、高岭土、石英粉和/或颗粒状石英级分和大理石粉和/或颗粒状大理石级分。当用于灰泥和底灰时,该填料通常粒度是至少40μm,而当用于漆时,填料典型的粒度是1-40μm。
颜料可以是任何无机或有机的并且可以是赋色或不透明的细分散固体。优选的颜料具有小于或等于1μm、优选0.1-0.5μm的初级颗粒的中值直径,其通过沉降分析根据DIN66115测定。无机颜料的实例是金属氧化物,例如二氧化钛、氧化铁或氧化锌,特别是二氧化钛。有机颜料的实例是酞菁,特别是酞菁蓝或二芳基颜料、偶氮颜料或喹吖啶酮颜料。
为了在水中分散填料和颜料,可以加入基于阴离子或非离子润湿剂的辅助剂,例如优选焦磷酸钠、聚磷酸钠、萘磺酸盐、聚丙烯酸钠、聚马来酸钠和聚膦酸盐如1-羟基乙烷-1,1-二膦酸钠和腈基三(亚甲基膦酸)钠。
也可以将增稠剂加入至本文所述的涂料组合物。可以使用的增稠剂尤其包括纤维素衍生物如甲基纤维素(MC)、羟乙基纤维素(HEC)和羧甲基纤维素。可以使用的其他增稠剂包括酪蛋白、阿拉伯胶、黄芪胶、淀粉、藻酸钠、聚乙烯醇、聚乙烯基吡咯烷酮、聚丙烯酸钠和基于丙烯酸和甲基丙烯酸的水溶性共聚物如丙烯酸/丙烯酰胺和甲基丙烯酸/丙烯酸酯共聚物。疏水改性的碱溶性(丙烯酸)乳液(HASE)、疏水改性的乙氧基化(聚)氨酯(HEUR)和聚醚多元醇(PEPO)也是可用的。还可以使用无机增稠剂例如膨润土或锂蒙脱石。
对于各种应用来说,有时候还期望包括引入本文的胶乳漆组合物中的少量其他添加剂如杀菌剂、pH调节剂和消泡剂。这可以以常规方式和在制备胶乳的任何方便点进行。
涂料组合物还可以包含交联添加剂。这样的添加剂可以是:芳族酮如烷基苯基酮,其可以在苯环上具有一个或多个取代基,或二苯甲酮和取代的二苯甲酮作为光引发剂。适合于此目的的光引发剂公开在例如DE-A-3827975和EP-A-0417568中。当乙烯酯共聚物包含处于共聚形式的含羰基的单体时,合适的交联化合物还是具有至少两个氨基的水溶性化合物如脂族二羧酸的二酰肼,如DE-A-3901073中公开的。
此外,在涂料组合物中可以使用基于链烷烃和聚乙烯的蜡,和消光剂、消泡剂、防腐剂或疏水剂、UV稳定剂、杀生物剂、纤维、增塑剂和本领域技术人员已知的另外的添加剂作为另外的添加剂。增塑剂的实例是邻苯二甲酸二甲酯、邻苯二甲酸二异丁酯、己二酸二异丁酯、Coasol 和Plastilit 优选不使用聚结剂和增塑剂。消泡剂的实例是矿物油消泡剂或硅酮消泡剂。UV稳定剂的实例是空间受阻哌啶化合物(HALS)或二苯甲酮衍生物。
由本文所述聚合物分散体生产的涂料组合物表现出抗结块性、耐擦洗性和耐沾污性的优异组合,这使得它们能够用作具有较高的光彩和较低颜料体积浓度的漆中的唯一粘结剂。
下面的非限定性实施例用于说明本发明。实施例中报告的份数和百分比基于重量,除非另有指示。
对比例C1
将由以下成分组成的水溶液引入到配备有搅拌器、夹套加热和计量泵的30L压力反应器中:8566g的去离子(DI)水,35g乙酸钠,142g的88%皂化聚乙烯醇(PVOH)的20%活性溶液(在4%固含量下的粘度是4mPas),327g的具有30个环氧乙烷单元的乙氧基化脂肪醇的65%活性水溶液,322g的烷基苯磺酸钠(支化)的22%活性水溶液,284g的乙烯基磺酸钠(SVS)的25%活性水溶液。反应器内部的气氛用氮气充满。将3929g的乙酸乙烯酯和213g的乙烯装入反应器,并且将反应混合物加热到55℃。
为了确保聚合,制备了下面的缓慢添加溶液:a)单体:8304g的乙酸乙烯酯,1076g的丙烯酸丁酯和56.7g乙烯基三甲氧基硅烷(VTMS),b)氧化剂:处于580gDI水中的40g的过硫酸钠(NaPS),c)还原剂:25g的FF6M和640gDI水,d)稳定剂溶液:处于244gDI水中的327g的具有30个环氧乙烷单元的乙氧基化脂肪醇的65%活性水溶液。
在聚合开始之前,将10%的还原剂溶液加入至反应器。随后通过并行添加氧化剂(192g/h)和还原剂(184g/h)来开始聚合。在聚合开始后通过升温来观察,反应器温度升高到70℃,并且稳定剂溶液的添加以245g/h的速率开始。使反应混合物在没有添加单体混合物(a)的情形下在70℃下聚合30min。30min的等待时间段后,以4530g/h的速率开始添加单体混合物(a),并且将另外的640g乙烯计量入反应器中。在单体混合物(a)添加结束前30min,将温度进一步升高到87℃。在所有添加完成后,在87℃下保温另外10分钟,然后冷却反应器。
为了减少残留单体的量,在脱气后,将所形成的产物用经280gDI水稀释的20g的叔丁基氢过氧化物(TBHP)的70%活性溶液和处于280gDI水中的12.5g的FF6M进行处理,并且在真空下物理脱单体。
对比例C2
将由以下成分组成的水溶液引入到配备有搅拌器、夹套加热和计量泵的30L压力反应器中:7422g的DI水,49g乙酸钠,1419g的88%皂化聚乙烯醇(PVOH)的10%活性溶液(在4%固含量下的粘度是4mPas),645g的烷基苯磺酸钠(支化)的22%活性水溶液,284g的乙烯基磺酸钠(SVS)的25%活性水溶液和2.8g的FF6M(Brüggemann Chemical)。反应器内部的气氛用氮气充满。将4726g的乙酸乙烯酯和127g的乙烯装入反应器,并且将反应混合物加热到55℃。
为了确保聚合,制备下面的缓慢添加溶液:a)单体:8196g的乙酸乙烯酯,b)氧化剂:处于580gDI水中的40g的过硫酸钠(NaPS),c)还原剂:25g的FF6M和640gDI水,d)稳定剂:199g的25%活性SVS和245g的DI水。聚合是通过并行添加氧化剂(249g/h)和还原剂(265g/h)来开始。在聚合开始后通过升温来观察,反应器温度设定点升高到70℃,并且将引发剂速率降低到对于氧化剂为185g/h和对于还原剂为200g/h,并且稳定剂溶液的添加以190g/h的速率开始。使反应混合物在不添加单体混合物(a)的情形下在70℃下聚合40min。40min的等待时间段后,以4275g/h的速率开始添加单体混合物(a),并且将另外的1140g乙烯计量入反应器中。在乙酸乙烯酯添加结束前30min,将温度进一步升高到87℃。在所有添加完成后,在87℃下保温另外10分钟,然后冷却反应器。
为了减少残留单体的量,在脱气后,将所形成的产物用经280gDI水稀释的20g的叔丁基氢过氧化物(TBHP)的70%活性溶液和处于280gDI水中的12.5g的FF6M进行处理,并且在真空下物理脱单体。
对比例C3
将由以下成分组成的水溶液引入到配备有搅拌器、夹套加热和计量泵的10L压力反应器中:2632g的DI水,17g乙酸钠,508g的EA45的10%活性溶液,231g的烷基苯磺酸钠(支化)的22%活性水溶液,102g的乙烯基磺酸钠(SVS)的25%活性水溶液和1g的FF6M(Brüggemann Chemical)。反应器内部的气氛用氮气充满。将1118g的乙酸乙烯酯和46g的乙烯装入反应器,并且将该反应混合物加热到55℃。
为了确保聚合,制备下面的缓慢添加溶液:a)单体:3307g的乙酸乙烯酯和254g的丙烯酸丁酯(BA),b)氧化剂:处于208gDI水中的15g的过硫酸钠(NaPS),c)还原剂:9g的FF6M和228gDI水,d)稳定剂:71g的25%活性SVS和87g的DI水。
聚合通过并行添加氧化剂(34g/h)和还原剂(36g/h)来开始。在聚合开始后通过升温来观察,反应器温度设定点升高到70℃,稳定剂溶液的添加以87g/h的速率开始并且单体混合物(a)的添加以1379g/h开始。使反应混合物在70℃下聚合40min,此时将另外348g的乙烯计量入反应器中(开始第2相)和将引发剂添加速率升高到71g/h(氧化剂)和75g/h(还原剂),同时将单体混合物(a)的添加保持在1379g/h的速率。在单体混合物(a)添加结束前30min,将温度进一步升高到87℃。在所有添加完成后,在87℃下保温另外10分钟,然后冷却反应器。
本发明实施例E1
将由以下成分组成的水溶液引入到配备有搅拌器、夹套加热和计量泵的30L压力反应器中:8057g的DI水,52g的乙酸钠,529g的88%皂化聚乙烯醇(PVOH)的20%活性溶液(在4%固含量下的粘度是4mPas),962g的烷基苯磺酸钠(支化)的22%活性水溶液,302g的乙烯基磺酸钠(SVS)的25%活性水溶液和144g的具有30个环氧乙烷单元的乙氧基化脂肪醇的65%活性水溶液。反应器内部的气氛用氮气充满。将5033g的乙酸乙烯酯和136g的乙烯装入反应器,并且将反应混合物加热到55℃。
为了确保聚合,制备下面的缓慢添加溶液:a)单体:8132g的乙酸乙烯酯和756g的丙烯酸丁酯(BA),b)氧化剂:处于620gDI水中的44g的过硫酸钠(NaPS),c)还原剂:26g的FF6M和680g的DI水,d)稳定剂:363g的25%活性SVS和260g的DI水。
在聚合开始前,将10%的还原剂溶液加入至反应器中。随后通过并行添加氧化剂(204g/h)和还原剂(196g/h)来开始聚合。在聚合开始后通过升温来观察,反应器温度设定点升高到70℃,并且稳定剂溶液的添加以267g/h的速率开始。使反应混合物在不添加单体混合物(a)的情形下在70℃下聚合40min。40min的等待时间段后,以4635g/h的速率开始添加单体混合物(a),并且将另外1058g的乙烯计量入反应器中。在单体混合物(a)添加结束前30min,将温度进一步升高到87℃。在所有添加完成后,在87℃下保温另外10分钟,然后冷却反应器。
本发明实施例E2
将由以下成分组成的水溶液引入到配备有搅拌器、夹套加热和计量泵的10L压力反应器中:3080g的DI水,17g的乙酸钠,57g的羟乙基纤维素(HEC,5%活性水溶液的粘度为100-180mPas),317g的烷基苯磺酸钠(支化)的22%活性水溶液,121g的乙烯基磺酸钠(SVS)的25%活性水溶液和1g的FF6M(Brüggemann Chemical)。反应器内部的气氛用氮气充满。将1655g的乙酸乙烯酯和45g的乙烯装入反应器,并且将反应混合物加热到55℃。
为了确保聚合,制备下面的缓慢添加溶液:a)单体:2674g的乙酸乙烯酯和248g的丙烯酸丁酯(BA),b)氧化剂:处于204gDI水中的14g的过硫酸钠(NaPS),c)还原剂:9g的FF6M和224g的DI水,d)稳定剂:116g的25%活性SVS和86g的DI水。聚合通过并行添加氧化剂(67g/h)和还原剂(71g/h)来开始。在聚合开始后通过升温来观察,反应器温度设定点升高到70℃,并且稳定剂溶液的添加以86g/h的速率开始。使反应混合物在不添加单体混合物(a)的情形下在70℃下聚合40min。40min的等待时间段后,以1525g/h的速率开始添加单体混合物(a),并且将另外348g的乙烯计量入反应器中。在单体混合物(a)添加结束前30min,将温度进一步升高到87℃。在所有添加完成后,在87℃下保温另外10分钟,然后冷却反应器。
本发明实施例E3
将由以下成分组成的水溶液引入到配备有搅拌器、夹套加热和计量泵的10L压力反应器中:2750g的DI水,17g的乙酸钠,177g的88%皂化聚乙烯醇(PVOH)的10%活性溶液(在4%固含量下的粘度是4mPas),321g的烷基苯磺酸钠(支化)的22%活性水溶液,116g的具有30个EO的乙氧基化仲脂肪醇的65%活性水溶液和101g的乙烯基磺酸钠(SVS)的25%活性水溶液。反应器内部的气氛用氮气充满。将1400g的乙酸乙烯酯和76g的乙烯装入反应器,并且将反应混合物加热到55℃。
为了确保聚合,制备下面的缓慢添加溶液:a)单体:2960g的乙酸乙烯酯,384g的丙烯酸丁酯(BA)和20g的乙烯基三甲氧基硅烷(VTMS),b)氧化剂:处于207gDI水中的14g的过硫酸钠(NaPS),c)还原剂:9g的FF6M和228gDI水和0.1g的FeSO4(7H2O),d)稳定剂:处于87gDI水中的121g的乙烯基磺酸钠(SVS)的25%活性水溶液。
在聚合开始前,将10%的还原剂溶液加入反应器中。随后通过并行添加氧化剂(68g/h)和还原剂(65g/h)来开始聚合。在聚合开始后通过升温来观察,反应器温度设定点升高到70℃,并且稳定剂溶液的添加以89g/h的速率开始。使反应混合物在不添加单体混合物(a)的情形下在70℃下聚合30min。30min的等待时间段后,以1615g/h的速率开始添加单体混合物(a),并且将另外228g的乙烯计量入反应器中。在单体混合物(a)添加结束前30min,将温度进一步升高到87℃。在所有添加完成后,在87℃下保温另外10分钟,然后冷却反应器。
本发明实施例E4
将由以下成分组成的水溶液引入到配备有搅拌器,夹套加热和计量泵的10L压力反应器中:2750g的DI水,17g的乙酸钠,177g的88%皂化聚乙烯醇(PVOH)的10%活性溶液(在4%固含量下的粘度是4mPas),321g的烷基苯磺酸钠(支化)的22%活性水溶液和101g的乙烯基磺酸钠(SVS)的25%活性水溶液。反应器内部的气氛用氮气充满。将1400g的乙酸乙烯酯和76g的乙烯装入反应器,并且将反应混合物加热到55℃。
为了确保聚合,制备下面的缓慢添加溶液:a)单体:2960g的乙酸乙烯酯,384g的丙烯酸丁酯(BA)和20g的乙烯基三甲氧基硅烷(VTMS),b)氧化剂:处于207gDI水中的14g的过硫酸钠(NaPS),c)还原剂:9g的FF6M和228g的DI水和0.1g的FeSO4(7H2O),d)稳定剂:121g的乙烯基磺酸钠(SVS)的25%活性水溶液和处于87gDI水中的116g的具有30个EO的乙氧基化仲脂肪醇的65%活性水溶液。
在聚合开始前,将10%的还原剂溶液加入反应器中。随后通过并行添加氧化剂(68g/h)和还原剂(65g/h)来开始聚合。在聚合开始后通过升温来观察,反应器温度设定点升高到70℃,并且稳定剂溶液的添加以89g/h的速率开始。使反应混合物在不添加单体混合物(a)的情形下在70℃下聚合30min。30min的等待时间段后,以1615g/h的速率开始添加单体混合物(a),并且将另外228g的乙烯计量入反应器中。在单体混合物(a)添加结束前30min,将温度进一步升高到87℃。在所有添加完成后,在87℃下保温另外10分钟,然后冷却反应器。
对比例C1-C3和本发明实施例E1-E4的主要组成特性汇总在表1中,其中值以基于所有单体的总重量计的重量%表示。
表1
对比例C1-C3和本发明实施例E1-E4中生产的聚合物分散体的物理性能汇总在表2中。
表2
C1 | C2 | C3 | E1 | E2 | E3 | E4 | |
固体 | 56% | 54.5% | 54.5% | 56.3% | 54% | 55.5% | 56.5% |
固体<sup>1</sup>,1级 | 28% | 27.5% | 29% | 33.5% | 30% | 29% | 29.5% |
Tg<sup>1</sup>,1级 | 22℃ | 38℃ | 36.5℃ | 32℃ | 38℃ | 25.5℃ | 35℃ |
Tg 1级最终 | 未检出 | 未检出 | 未检出 | 29℃ | 未检出 | 27.5℃ | 26℃ |
Tg 2级最终 | 20.5℃ | 19℃ | 18.5℃ | 15℃ | 17℃ | 19℃ | 19℃ |
粒度[nm]<sup>2</sup> | 270 | 209 | 214 | 260 | 439 | 180 | 230 |
粘度[mPa s]<sup>3</sup> | 374 | 1370 | 1090 | 1120 | 1870 | 990 | 1040 |
pH | 5 | 5.1 | 5.2 | 5.1 | 5 | 5 | 4.9 |
n.d.=未检出
1针对添加乙烯之前所获得的样品进行测量。Tg通过差示扫描量热法(DSC)根据ISO 16805测量。
2重均粒径,其通过Beckman Coulter LS 13320粒度分析仪测定。
3Brookfield粘度测量条件:20℃,20rpm,转子3
漆配制物
漆配制物由使用表3中所列成分在对比例C1-C3和本发明实施例E1-E4中产生的聚合物分散体来产生。实验VAE胶乳在25PVC半光泽漆配制物中测试。该配制物使用Coalescent CLX,一种可获自Celanese的零VOC聚结剂。
表3
Natrosol Plus 330是羟乙基纤维素增稠剂,可获自Ashland,Inc.
AMP-95是2-氨基-2-甲基-1-丙醇pH调节剂/缓冲剂,可获自ANGUS ChemicalCompany。
Acticide BW 20是水基苯并异噻唑啉酮防腐剂,可获自Thor Specialties,Inc.
Foamaster MO 2185是100%活性消泡剂,可获自BASF,Inc.
Acrymal L 216和PSL RM 45分别是氟表面活性剂和阴离子表面活性剂,由PeachState Labs销售。
Tronox CR-826是经二氧化硅/氧化铝处理的金红石钛颜料,可获自Tronox,Inc.
Burgess 28是水合硅酸铝颜料,可获自Burgess Pigment Company。
Minex 10是霞石正长岩增量剂颜料,可获自Unimin Specialty Minerals,Inc.
Acrysol RM-2020NPR和Acrysol RM-825是非离子疏水改性的聚环氧乙烷氨基甲酸酯增稠剂,可获自Dow Inc.
Coalescent CLX是基于三甘醇双(2-乙基己酸酯)的零VOC聚结剂,可获自Celanese Corporation
Aquaklean 403是微粉化聚乙烯蜡,可获自Micro Powders,Inc.
所形成的漆配制物的特性汇总在表4中。
表4
密度(lbs/gal) | 10.60 |
PVC(%) | 25% |
重量固体(%) | 50.41% |
体积固体(%) | 37.13% |
漆配制物的光学性能在恒定的温度(23℃)和湿度(50%)室中干燥7天的BYK不透明图上的3密耳刮涂件(6”Bird棒)上测量。结果以及不同的漆配制物的粘度值一起汇总在表5中。
表5
可以看出表5中汇总的所有漆的一般性能落入半光泽漆的预期的光泽和光彩范围内。
漆测试程序
使用下面的测试程序来评价上述胶乳漆配制物。
抗结块性测试
使用ASTM D4946来评价漆配制物的结块。抗结块性方法程序如下:
所需材料
1.(6”)6密耳间隙Bird棒。
2.真空板。
3.密封的测试图。
4.漆样品。
5.裁纸刀。
6.1Kg砝码。
7.50℃烘箱。
8.秒表或计时器。
程序
刮涂件的制备
1.打开真空泵和将测试图在真空板上居中和相应地标记
2.将清洁的6密耳刮涂棒置于所述图的标记部分之下
3.首先搅拌漆样品来确保均匀性,并且将足够的漆轻覆在刀片边缘附近来沿着板长度形成连续膜
4.将6密耳棒缓慢和均匀地刮涂到图的长度
5.立即清洁和干燥棒
6.将图移出到水平表面
对于每个样品重复该程序。
一旦所述图已经调理了最小16小时,则可以进行结块测试
1.使用裁纸刀,切割完全涂漆的覆盖的1.5”(4cm)宽的正方形。每个测试周期需要6个正方形。
2.将正方形面对面配对,并且每个用适当的信息、样品号、环境(RT)或烘箱(OV)标记。
3.将三对正方形置于恒温室中的连续平坦表面上,并且将1个#8橡胶塞(窄端向下)居中和将1Kg砝码置于正方形上。
4.第二天从这对正方形上移除塞子和砝码。
5.请将另外三对正方形置于50℃烘箱中,并且重复步骤4
6.在30分钟后,从烘箱中移出第二对正方形,并且冷却
测试样品评价
样品的评价在板干燥24小时或7天之后进行。记录结果。
1.撕开正方形,寻找声音、粘连和寻找膜损坏或破裂的迹象。
2.根据表6中给出的数字评级来对正方形评级。
表6
耐擦洗性测试
耐擦洗性测试根据ASTM D2486进行。测试漆和对照漆通过将7密耳漆膜刮涂在Leneta黑塑料片上来制备。将刮涂件在恒定的温度(23℃)和湿度(50%)室中干燥7天。将干燥的图贴到玻璃板上,并且放入配备有擦洗刷和用于保持擦洗板的盆的擦洗机中。所述刷通过将它浸没入水中一整夜来准备。在即将运行擦洗测试之前,将所述刷通过在未涂覆的Leneta片上运行400个周期来调理。将所述刷置于刷架中,并且将测试板放在刷子下,并且夹到玻璃板上。用10g研磨介质(BYK Gardner)将刷毛均匀铺展。然后将所述板用5ml水沿着刷子路径润湿。启动擦洗机,并且在每400个周期之后直到膜穿透,停止机器,并且将10g研磨介质均匀铺展到刷毛上,和将所述板沿着刷子路径用5ml水润湿。记录当在垫片上擦洗时,引起膜穿透的擦洗周期数。耐擦洗性测试在同一刮涂件上使用具有不同的尼龙刷的两种不同的机器进行两次。相关的擦洗指数以相对于对照漆样品的%来表达。结果汇总在表6中。
根据Master Painters Institute(MPI)法的擦洗能力
指示性擦洗能力测试根据MPI 147性能标准进行。使用刮涂棒(具有7密耳间隙)将漆刮涂到黑色Leneta塑料片的整个长度上,这类似于ASTM D2486程序。将刮涂件在恒定的温度(23℃)和湿度(50%)室中干燥7天。使用壬基酚乙氧基化物表面活性剂的2%溶液(IGEPAL CO-630,可获自Sigma-Aldrich)作为擦洗介质。溶液使用蠕动泵(可获自Cole-Parmer)以8-10滴/分钟的速率加入至处于测试中的擦洗板。将擦洗板连续擦洗4000个周期,在自来水下洗涤,并且干燥24小时。检查刮涂件的膜穿透和60°光泽度改变。如果漆没有表现出膜穿透和表现出小于20%的60°光泽度改变,则它们被认为对于进一步的评价而言是可接受的。结果汇总在表7中。
根据Master Painters Institute(MPI)法的耐沾污性
耐沾污性的指示性测试根据MPI147性能标准进行。根据ASTM D2486使用7密耳间隙的刮涂棒将漆刮涂到白色Leneta塑料片的整个长度上。将刮涂件在恒定的温度(23℃)和湿度(50%)室中干燥7天。将测试试样用石墨(可获自Sigma Aldrich,20微米粒度)、热咖啡(Kirtland Dark French Roast)和2%苯胺黑(nigrosin)染料溶液(可获自Sigma-Aldrich)依照MPI 147标准(可获自Master Painters Institute,www.specifypaint.com/MPIStore_us.asp)中所述程序进行沾污。使用1%的壬基酚乙氧基化物表面活性剂溶液(IGEPAL CO-630)和0.5%磷酸三钠(可获自Sigma-Aldrich)作为清洁介质。使用蠕动泵以8-10滴/分钟的速率将溶液加入至测试中的擦洗板。将沾污的板用纤维素海绵连续洗涤1000个周期。在用海绵洗涤后,将所述板根据MPI 147标准中的说明用自来水洗涤,并且干燥24小时。使用BYK Gardner分光光度计测量未沾污的经洗涤部分和沾污的经洗涤部分之间的颜色差异。对于每个污点,颜色差异作为ΔE*表达。结果汇总在表7中。
表7:
结果讨论
从表7中可看出,与由对比例C1-C4的聚合物分散体生产的漆相比,由本发明实施例E1-E4的聚合物分散体生产的漆表现出改进的抗结块性(尤其是7天干燥后)而没有耐擦洗性的显著下降和改进的抗石墨沾污性的组合。实施例E3和E4的含硅烷分散体还产生了良好的耐咖啡和苯胺黑沾污性。
虽然已经通过参考具体实施方案描述和示例了本发明,但是本领域技术人员将理解本发明本身可以进行无需在本文示出的变化。为此原因,为了确定本发明真正范围的目的,应当仅参考附加的权利要求。
Claims (16)
1.一种含水共聚物分散体,其通过自由基引发的多级乳液聚合方法来获得,该聚合方法包括:
(a)在第一聚合级的反应区中,使包含至少88重量%的至少一种C1-C18羧酸的乙烯酯和至多12重量%乙烯的第一单体组合物聚合,以产生玻璃化转变温度Tg大于20℃的第一级聚合物;和
(b)在第二聚合级的反应区中并且在该第一级聚合物存在下,使包含至少一种C1-C18羧酸的乙烯酯和至少一种丙烯酸或甲基丙烯酸的C2-C8烷基酯的不同的第二单体组合物聚合,以产生玻璃化转变温度Tg小于或等于20℃的第二级聚合物,该至少一种丙烯酸或甲基丙烯酸的C2-C8烷基酯的量为该第二单体组合物中总单体的至多30重量%,
其中该第一单体组合物基本上不含丙烯酸或甲基丙烯酸的C2-C8烷基酯;
其中该第二单体组合物在至少部分的该第二聚合级期间计量入该反应区中,和
其中每个聚合级(a)和(b)在稳定化体系存在下进行,该稳定化体系包含至少0.1重量%的至少一种保护性胶体、至少0.05重量%的至少一种离子表面活性剂和小于2重量%的非离子表面活性剂,该稳定化体系中的所有百分比基于该第一和第二单体组合物中单体的总重量计。
2.根据权利要求1所述的分散体,其中第一单体组合物包含至少90重量%的该至少一种C1-C18羧酸的乙烯酯。
3.根据权利要求1或权利要求2所述的分散体,其中该第一单体组合物的该至少一种C1-C18羧酸的乙烯酯包括乙酸乙烯酯。
4.根据前述权利要求中任一项所述的分散体,其中该第一级聚合物的玻璃化转变温度Tg是至少26℃。
5.根据前述权利要求中任一项所述的分散体,其中该第一单体组合物中存在的该至少一种C1-C18羧酸的乙烯酯和任何乙烯在该第一聚合级开始之前加入至该反应区。
6.根据前述权利要求中任一项所述的分散体,其中在至少部分的聚合级(a)期间,将选自烯属不饱和磺酸、烯属不饱和膦酸和烯属不饱和磷酸及其盐的另外的单体计量入该反应区中。
7.根据权利要求6所述的分散体,其中该另外的单体包括乙烯基磺酸或其盐。
8.根据前述权利要求中任一项所述的分散体,其中该第二单体组合物包含至少50重量%的该至少一种C1-C18羧酸的乙烯酯。
9.根据前述权利要求中任一项所述的分散体,其中该第二单体组合物的该至少一种C1-C18羧酸的乙烯酯包括乙酸乙烯酯。
10.根据前述权利要求中任一项所述的分散体,其中该第二单体组合物包含5-15重量%的至少一种丙烯酸或甲基丙烯酸的C2-C8烷基酯。
11.根据前述权利要求中任一项所述的分散体,其中该第二单体组合物的该至少一种丙烯酸或甲基丙烯酸的C2-C8烷基酯包括丙烯酸正丁酯。
12.根据前述权利要求中任一项所述的分散体,其中该第二级聚合物的玻璃化转变温度Tg是0-20℃、优选5-20℃。
13.根据前述权利要求中任一项所述的分散体,其中该第一单体组合物占该第一和第二单体组合物中单体总量的5-95重量%、优选20-40重量%。
14.一种涂料组合物,其包含前述权利要求中任一项所述的含水共聚物分散体。
15.一种漆配制物,其包含权利要求14的涂料组合物。
16.一种漆涂层,其由权利要求15的漆配制物生产,并且当在23℃下干燥7天后经受根据ASTM D4946的测试时表现出抗结块性为至少6,和当在23℃和50%湿度下干燥7天后经受根据MPI 147的抗石墨沾污测试时表现出变色(ΔE)小于2。
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US6656998B1 (en) | 2000-05-01 | 2003-12-02 | Air Products Polymers, L.P. | Glossy paints containing emulsion polymers of vinyl acetate |
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US7285590B2 (en) | 2003-11-13 | 2007-10-23 | Hexion Specialty Chemicals, Inc. | Aqueous dispersions containing multi-stage emulsion polymers |
DE102005032194B4 (de) | 2005-07-09 | 2008-11-27 | Celanese Emulsions Gmbh | Wässrige Kunststoff-Dispersionen, Verfahren zu deren Herstellung sowie deren Verwendung |
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US12071496B2 (en) | 2024-08-27 |
WO2020180617A1 (en) | 2020-09-10 |
CN113557250B (zh) | 2024-03-15 |
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