CN111465650B - 多阶段聚合物的水性分散体 - Google Patents
多阶段聚合物的水性分散体 Download PDFInfo
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- CN111465650B CN111465650B CN201780097392.XA CN201780097392A CN111465650B CN 111465650 B CN111465650 B CN 111465650B CN 201780097392 A CN201780097392 A CN 201780097392A CN 111465650 B CN111465650 B CN 111465650B
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- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
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Classifications
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Abstract
用作提供高增稠效率的增稠剂的疏水改性的碱溶性多阶段聚合物的水性分散体和包含这类水性分散体的水性涂料组合物，其示出热老化后良好稳定性，在添加着色剂时不损害稳定性。
Description
技术领域
本发明涉及多阶段聚合物的水性分散体和包含其的水性涂料组合物。
背景技术
疏水改性的碱可溶乳液(HASE)广泛用于被碱中和后增稠水性组合物。这些增稠剂大体上基于通过一个阶段或多阶段聚合将疏水缔合的单体并入聚合主链中。常规的多阶段HASE增稠剂通常在第一阶段包含疏水改性的线性聚合物，并且在第二阶段包含疏水改性的交联聚合物。与一个阶段线性HASE增稠剂相比，这些常规的多阶段HASE增稠剂在颜色漂浮和抗水稀释性方面具有优势，但是包含这些增稠剂的水性涂料组合物在经受热老化时仍然具有粘度增加的问题。为了改善水性涂料组合物的热老化稳定性，EP0444791A1公开一种聚合增稠剂。聚合增稠剂可为包含至少一个碱可溶聚合物阶段和至少一个碱不溶聚合物阶段的多阶段聚合物，其中所述碱可溶聚合物与所述碱不溶聚合物的重量比为约99:1到1:99，并且更优选地约95:5到50:50。通过聚合约1.1重量％到约55重量％的至少一种疏水单体的单体混合物形成离子可溶聚合物。这种聚合增稠剂的增稠效率仍有提高的空间。
因此，期望提供多阶段聚合物的水性分散体，其用作提供高增稠效率的增稠剂，其在经受热老化时为涂料组合物提供改善的粘度稳定性，而不损害添加着色剂时的粘度稳定性。
发明内容
本发明提供新型水性多阶段聚合物分散体和包含其的水性涂料组合物。水性多阶段聚合物分散体可用作提供高增稠效率的增稠剂，例如得到100个克雷布斯单位(KU)的水性涂料组合物的粘度需要小于10克的这类水性多阶段聚合物分散体固体。本发明的水性涂料组合物具有改进的例如在50℃-60℃下热老化后储存稳定性(本文“热老化稳定性”)，如由粘度变化在±10KU内所指示。增稠效率和热老化稳定性根据在下文实例章节中描述的测试方法测量。与包含一个阶段线性HASE增稠剂的水性涂料组合物相比，本发明的水性涂料组合物在添加着色剂时也可具有更好的粘度稳定性。
在第一方面，本发明为多段聚合物的水性分散体，其中多段聚合物包含：
(A)聚合物A，其以聚合物A的重量计，包含
(a1)15重量％或更多的α,β-烯系不饱和羧酸的结构单元，
(a2)单烯系不饱和非离子单体的结构单元，
(a3)小于0.1重量％的疏水缔合的单体的结构单元，和任选地
(a4)选自C3-C20亚烷基二醇二(甲基)丙烯酸酯、聚(亚烷基二醇)二(甲基)丙烯酸酯和其组合的交联剂的结构单元；和
(B)聚合物B，其以聚合物B的重量计，包含
(b1)15重量％或更多的α,β-烯系不饱和羧酸的结构单元，
(b2)单烯系不饱和非离子单体的结构单元，
(b3)0.1重量％到60重量％的疏水缔合的单体的结构单元，和
(b4)选自C3-C20亚烷基二醇二(甲基)丙烯酸酯、聚(亚烷基二醇)二(甲基)丙烯酸酯和其组合的交联剂的结构单元；
其中聚合物A与聚合物B的重量比为95:5到55:45。
在第二方面，本发明为通过多阶段自由基聚合制备多阶段聚合物的水性分散体的方法。方法包含：
(i)通过第一单体混合物的自由基聚合在水性介质中制备聚合物A，以第一单体混合物的总重量计，所述第一单体混合物包含
15重量％或更多的α,β-烯系不饱和羧酸，单烯系不饱和非离子单体，小于0.1重量％的疏水缔合的单体，和任选地选自C3-C20亚烷基二醇二(甲基)丙烯酸酯、聚(亚烷基二醇)二(甲基)丙烯酸酯或其组合的交联剂；和
(ii)在从步骤(i)获得的聚合物A存在下通过第二单体混合物的自由基聚合制备聚合物B，以第二单体混合物的总重量计，所述第二单体混合物包含
15重量％或更多的α,β-烯系不饱和羧酸，单烯系不饱和非离子单体0.1重量％到60重量％的疏水缔合的单体，和选自C3-C20亚烷基二醇二(甲基)丙烯酸酯、聚(亚烷基二醇)二(甲基)丙烯酸酯或其组合的交联剂；
其中聚合物A与聚合物B的重量比为95:5到55:45。
在第三方面，本发明为包含第一方面的水性分散体的水性涂料组合物。
具体实施方式
本发明中的“丙烯酸类”包括(甲基)丙烯酸、丙烯酸(甲基)烷基酯、(甲基)丙烯酰胺、(甲基)丙烯腈及其经改质的形式，例如丙烯酸(甲基)羟基烷基酯。在整篇文件中，词语片段“(甲基)丙烯酰基”是指“甲基丙烯酰基”和“丙烯酰基”。举例来说，(甲基)丙烯酸是指甲基丙烯酸和丙烯酸，并且(甲基)丙烯酸甲酯是指甲基丙烯酸甲酯和丙烯酸甲酯。
在本发明中的“玻璃化转变温度”或“Tg”可通过各种技术包括例如差示扫描量热法(“DSC”)测量或通过使用福克斯方程式计算。本文报告的Tg的特定值为通过使用福克斯方程(T.G.Fox,《美国物理学会公报(Bull.Am.Physics Soc.)》,第1卷,第3期,第123页(1956))计算的那些。举例来说，为了计算单体M1和M2的共聚物的Tg，
其中Tg(calc.)为共聚物的所计算的玻璃化转变温度，w(M1)为在共聚物中的单体M1的重量分数，w(M2)为在共聚物中的单体M2的重量分数，Tg(M1)为单体M1的均聚物的玻璃化转变温度并且Tg(M2)为单体M2的均聚物的玻璃化转变温度；所有温度以K为单位。均聚物的玻璃转化温度可见于例如由J.Brandrup和E.H.Immergut编辑的“《聚合物手册(PolymerHandbook)》”，国际科学出版社(Interscience Publishers)。
如本文所使用，术语指定单体的结构单元(也被称为聚合单元)是指在聚合之后单体的残余物，或呈聚合形式的单体。举例来说，甲基丙烯酸甲酯的结构单元如下所示：
其中虚线表示结构单元与聚合物主链的连接点。
在本文中，“水性”组合物或分散体意指颗粒分散在水性介质中。本文中通过“水性介质”意指水和以介质的重量计，0到30重量％的(一种或多种)水可混溶化合物，例如醇、二元醇、二醇醚、二醇酯等。
在本发明的水性分散体中的多阶段聚合物包含在多阶段自由基聚合的不同阶段中形成的至少一种聚合物A和至少一种与聚合物A不同的聚合物B。
在多阶段聚合物中的聚合物A可包含一种或多种α,β-烯系不饱和羧酸的结构单元(a1)。合适的α,β-烯系不饱和羧酸的实例包括带有酸的单体，如丙烯酸、甲基丙烯酸、马来酸、衣康酸、巴豆酸，或富马酸；带有产生或随后可转化成酸的酸形成基团的单体，如酸基(如酸酐、(甲基)丙烯酸酸酐，或马来酸酸酐)；或其混合物。以聚合物A的重量计，聚合物A可包含15重量％或更多、20重量％或更多、25重量％或更多、30重量％或更多、35重量％或更多、40重量％或更多，或甚至45重量％或更多，并且同时60重量％或更少、55重量％或更少，或甚至50重量％或更少α,β-烯系不饱和羧酸的结构单元。本发明中的“聚合物A的重量”是指聚合物A的干重或固体重量。
在多阶段聚合物中的聚合物A还可包含一种或多种单烯系不饱和非离子单体的结构单元(a2)。如本文所用，术语“非离子单体”是指在pH＝1-14之间不带有离子电荷的单体。合适的单烯系不饱和非离子单体可包括(例如)(甲基)丙烯酸的烷基酯、乙烯基芳香族单体，如苯乙烯和被取代的苯乙烯、羧酸的乙烯基酯、烯系不饱和腈，或其混合物。优选地，单烯系不饱和非离子单体为(甲基)丙烯酸的C1-C18、C2-C10或C3-C6烷基酯，例如，丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸2-乙基己酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸油酯、(甲基)丙烯酸棕榈酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十八烷基酯。更优选地，烯系不饱和非离子单体选自由以下组成的组：甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸丁酯和丙烯酸2-乙基己酯。以聚合物A的重量计，聚合物A可包含40重量％到85重量％、45重量％到80重量％或50重量％到70重量％的单烯系不饱和非离子单体的结构单元。
以聚合物A的重量计，在多阶段聚合物中的聚合物A可任选地包含小于0.1重量％的一种或多种疏水缔合的单体的结构单元(a3)。疏水缔合的单体可具有式I的结构：
H2C＝C(R)CO2(CH2CH2O)n(CH(R1)CH2O)mR2(I)，
其中R为H或CH3、R1为C1-C2烷基，R2为芳烷基苯基或C8-C50直链或支链烷基，n为6到100、10到60或20到40的整数，并且m为0到50的整数，其条件是n≥m并且m+n为6到100。m可为0到20、0到10或0到5的整数。优选地，m为0，并且n为10到60的整数；并且更优选地，m为0，并且n为20到40的整数。优选的R为CH3。R2可为烷基苯取代的苯基团，优选地C1-C4烷基苯取代的苯基团，并且更优选地乙基苯取代的苯基团。合适的疏水缔合的单体可包括(例如)聚乙氧基甲基丙烯酸月桂酯(23个氧化乙烯(EO)单元)、聚乙氧基C13/C15甲基丙烯酸酯(20EO)、聚乙氧基甲基丙烯酸十八硬脂基酯(30EO)、鲸蜡醇聚醚-20甲基丙烯酸酯、二十二烷基聚乙氧基甲基丙烯酸酯(30EO)、聚乙氧基化三苯乙烯基苯酚甲基丙烯酸酯(25EO)、聚乙氧基甲基丙烯酸十八烷基酯(20EO)、聚乙氧基鲸蜡基甲基丙烯酸酯(25EO)、聚乙氧基甲基丙烯酸月桂酯(10EO)、聚乙氧基甲基丙烯酸十八烷基脂(25EO)、聚氧乙烯二十二烷基-甲基丙烯酸二十三基酯、鲸蜡基-十八烷醇的20摩尔乙氧基化物的甲基丙烯酸酯，或其混合物。以聚合物A的重量计，聚合物A可包含小于0.1重量％、小于0.09重量％、小于0.08重量％、小于0.07重量％、小于0.06重量％、小于0.05重量％、小于0.04重量％、小于0.03重量％、小于0.02重量％、小于0.01重量％，或甚至零的疏水缔合的单体的结构单元。在一些实施例中，聚合物A基本上不含疏水缔合的单体的结构单元，例如以聚合物A的重量计，小于0.02％、小于0.01％或甚至零。
在多阶段聚合物中的聚合物A可任选地包含选自C3-C20亚烷基二醇二(甲基)丙烯酸酯、聚(亚烷基二醇)二(甲基)丙烯酸酯或其组合的一种或多种交联剂的结构单元。优选地，亚烷基二醇二(甲基)丙烯酸酯为C3-C15亚烷基二醇二(甲基)丙烯酸酯，并且更优选地C3-C10亚烷基二醇二(甲基)丙烯酸酯。可用于本发明的聚(亚烷基二醇)二(甲基)丙烯酸酯可包括聚(乙二醇)二(甲基)丙烯酸酯、聚(丙二醇)二(甲基)丙烯酸酯、聚(丁二醇)二(甲基)丙烯酸酯或其组合。聚(亚烷基二醇)二(甲基)丙烯酸酯可包含2到20、2到10或2到8个氧化烯单元。合适的交联剂的实例包括1,3-丁二醇二甲基丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、丙三醇1,3-二甲基丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、三丙二醇二甲基丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、丙二醇二丙烯酸酯、1,1,1-三羟甲基丙烷二甲基丙烯酸酯、1,1,1-三羟甲基乙烷二丙烯酸酯或其混合物。以聚合物A的重量计，聚合物A可包含0到2重量％、0.01重量％到1重量％、0.02重量％到0.5重量％，或0.03重量％到0.25重量％的交联剂的结构单元。
在一些实施例中，以聚合物A的重量计，聚合物A包含
(a1)20重量％到60重量％的α,β-烯系不饱和羧酸的结构单元，
(a2)40重量％到80重量％的单烯系不饱和非离子单体的结构单元，
(a3)0到0.05重量％的疏水缔合的单体的结构单元，和
(a4)0到0.25重量％的交联剂的结构单元。
在一些优选实施例中，聚合物A由α,β-烯系不饱和羧酸的结构单元，单烯系不饱和非离子单体，和任选地交联剂组成。
在多阶段聚合物中的聚合物A的Tg可为5℃到80℃、10℃到70℃，或15℃到60℃。
可用于本发明的多阶段聚合物另外包含与聚合物A不同的聚合物B。聚合物B可包含一种或多种α,β-烯系不饱和羧酸的结构单元(b1)，其可选自与上文在聚合物A章节中描述的相同的组(a1)。以聚合物B的重量计，聚合物B可包含15重量％或更多、20重量％或更多、25重量％或更多、30重量％或更多、35重量％或更多、40重量％或更多，或甚至45重量％或更多，并且同时60重量％或更少、55重量％或更少，或甚至50重量％或更少α,β-烯系不饱和羧酸的结构单元。本发明中的“聚合物B的重量”是指聚合物B的干重或固体重量。
在多阶段聚合物中的聚合物B还可包含一种或多种单烯系不饱和非离子单体的结构单元(b2)，其可选自与上文在聚合物A章节中描述的相同组(a2)。以聚合物B的重量计，聚合物B可包含5重量％或更多、10重量％或更多、20重量％或更多、25重量％或更多、30重量％或更多、35重量％或更多，或甚至40重量％或更多，并且同时84重量％或更少、80重量％或更少、75重量％或更少、70重量％或更少，或甚至65重量％或更少的单烯系不饱和非离子单体的结构单元。
在多阶段聚合物中的聚合物B可另外包含一种或多种疏水缔合的单体的结构单元(b3)，其可选自与上文在聚合物A章节中描述的相同组(a3)。以聚合物B的重量计，聚合物B可包含0.1重量％或更多、0.5重量％或更多、1重量％或更多、1.5重量％或更多、2重量％或更多、3重量％或更多、4重量％或更多，或甚至5重量％或更多，并且同时60重量％或更少、50重量％或更少、40重量％或更少、30重量％或更少、20重量％或更少、15重量％或更少、10重量％或更少，或甚至8％或更少的疏水缔合的单体的结构单元。
在多阶段聚合物中的聚合物B可包含一种或多种交联剂的结构单元(b4)其可选自与上文在聚合物A章节中描述的相同组(a4)。以聚合物B的重量计，聚合物B可包含0.01重量％到20重量％、0.02重量％到15重量％、0.03重量％到10重量％、0.05重量％到5重量％或0.1重量％到2重量％的交联剂的结构单元。
在一些实施例中，以聚合物B的重量计，聚合物B包含
(b1)20重量％到60重量％的α,β-烯系不饱和羧酸的结构单元，
(b2)35重量％到75重量％的单烯系不饱和非离子单体的结构单元，
(b3)0.1重量％到30重量％的疏水缔合的单体的结构单元，和
(b4)0.01重量％到2重量％的交联剂的结构单元。
聚合物B的Tg可为5℃到120℃、10℃到100℃，或15℃到80℃。
聚合物A与聚合物B的重量比可在95:5到55:45、94:6到56:44、92:8到58:42、91:9到59:41、90:10到60:40、85:15到65:35或80:20到70:30的范围内。
可用于本发明的多阶段聚合物可在聚合物A中，在聚合物B中，或在聚合物A和聚合物B中另外包含携带选自以下的至少一种官能团的一种或多种单烯系不饱和单体：羰基、磺酸酯、磷酸酯、羟基、酰胺或脲基。携带至少一种官能团的合适的单烯系不饱和单体可包括(例如)双丙酮(甲基)丙烯酰胺(DAAM)、甲基丙烯酸乙酰乙酰氧基乙酯(AAEM)、丙烯酰胺、甲基丙烯酰胺、苯乙烯磺酸钠(SSS)、乙烯基磺酸钠(SVS)、(甲基)丙烯酸2-磷酸乙酯、丙烯酸2-羟乙酯，或其混合物。以多阶段聚合物的重量(例如聚合物A和聚合物B的总重量)计，多阶段聚合物可包含0到20重量％、1重量％到10重量％或2重量％到5重量％的含官能团的单烯系不饱和单体。
在一些优选实施例中，在本发明的水性分散体中的多阶段聚合物包含：
(A)聚合物A，其以聚合物A的重量计，包含
(a1)20重量％到60重量％的α,β-烯系不饱和羧酸的结构单元，
(a2)40重量％到80重量％的(甲基)丙烯酸烷基酯的结构单元，
(a3)小于0.05重量％的疏水缔合的单体的结构单元，和任选地
(a4)0到0.25重量％的交联剂的结构单元；和
(B)聚合物B，其以聚合物B的重量计，包含
(b1)20重量％到60重量％的α,β-烯系不饱和羧酸的结构单元，
(b2)40重量％到80重量％的(甲基)丙烯酸烷基酯的结构单元，
(b3)1重量％到10重量％的疏水缔合的单体的结构单元，和
(b4)0.01重量％到2重量％的交联剂的结构单元；
其中聚合物A与聚合物B的重量比为90:10到60:40。
可用于本发明的多阶段聚合物的重均分子量可为30,000道尔顿或更高、200,000道尔顿或更高、600,000道尔顿或更高、700,000道尔顿或更高、800,000道尔顿或更高、900,000道尔顿或更高，或甚至1,000,000道尔顿或更高，并且同时10,000,000道尔顿或更低、9,200,000道尔顿或更低、9,100,000道尔顿或更低、9,000,000道尔顿或更低、8,000,000道尔顿或更低、7,000,000道尔顿或更低、6,000,000道尔顿或更低、5,000,000道尔顿或更低、4,000,000道尔顿或更低、3,500,000道尔顿或更低，或甚至3,000,000道尔顿或更低。本文的分子量可根据在下文实例章节中描述的测试方法使用具有在线多角度光散射(MALS)和差示折射率检测器的不对称流场流动分级表征。
可选择上文所描述的单体的类型和水平以提供具有适合于不同应用的Tg的多阶段聚合物。多阶段聚合物的Tg可在5℃到100℃、10℃到80℃或15℃到60℃的范围内。多阶段聚合物颗粒的数均粒度可为70纳米(nm)到300nm、80nm到200nm、90nm到150nm，或100nm到120nm的粒度，如通过Brookhaven BI-90粒度分析仪测量。
本发明的多阶段聚合物的水性分散体另外包含水。以水性分散体的总重量计，水的浓度可为30重量％到90重量％或40重量％到80重量％。水多阶段聚合物的水性分散体可适用于许多应用，包括例如木材涂料、建筑涂料和路标漆。多阶段聚合物的水性分散体可用于增稠水性涂料组合物并且可展示令人满意的增稠效率。本文“令人满意的增稠效率”是指在1千克(kg)的水性涂料组合物中为了得到100KU的粘度，在水性涂料组合物中的增稠剂的干燥剂量小于10克(g)，优选地小于5g，如根据在下文实例章节中描述的测试方法所测量。
本发明还涉及制备本发明的多阶段聚合物的水性分散体的方法。这类方法可包括多段自由基聚合，其中依次形成至少两个阶段，其通常导致形成包含至少两种聚合物组合物的多阶段聚合物，如在第一阶段中的聚合物A和在第二阶段中的聚合物B。在制备多阶段聚合物颗粒中，可首先使聚合物A聚合，然后在聚合物A存在下使第二聚合物聚合。多阶段自由基聚合的每个阶段可通过在所属领域众所周知的聚合技术进行，如上文所描述的单体的悬浮聚合或乳液聚合。乳液聚合为优选的方法。聚合物A可又包含以下的第一单体混合物聚合：α,β-烯系不饱和羧酸(a1)，单烯系不饱和非离子单体(a2)，和任选地疏水缔合的单体(a3)和/或多烯系不饱和交联剂(a4)。然后，聚合物B可由包含以下的第二单体混合物聚合：α,β-烯系不饱和羧酸(b1)，单烯系不饱和非离子单体(b2)，疏水缔合的单体(b3)，和交联剂(b4)。以第一单体混合物的重量计，在用于制备聚合物A的第一单体混合物中的每种单体的剂量可与在如上文所描述的聚合物A中的这类单体的结构单元的含量基本上相同。同样适用于在用于制备聚合物B的第二单体混合物中每种单体的剂量。用于制备聚合物A和聚合物B的单体的总重量浓度分别等于100％。第一单体混合物和/或第二单体混合物可作为于水中的乳液添加；或在制备聚合物A或聚合物B的反应时间段内以一次或多次添加或线性或非线性地连续添加，或其组合。适用于乳液聚合方法的温度可低于100℃，例如，在30℃至95℃的范围内或在50℃至90℃的范围内。
在多阶段自由基聚合方法中，自由基引发剂可用于制备聚合物A的阶段，制备聚合物B的阶段，或两个阶段。多阶段自由基聚合方法可为在每个阶段中热引发或氧化还原引发的乳液聚合。合适的自由基引发剂的实例包括过氧化氢、叔丁基过氧化氢、过氧化氢异丙苯、过硫酸铵和/或碱金属过硫酸盐、过硼酸钠、过磷酸和其盐；高锰酸钾，和过二硫酸的铵或碱金属盐。以单体的总重量计，自由基引发剂通常可以0.01重量％到3.0重量％的水平使用。可在多阶段自由基聚合方法中使用包含上文所描述引发剂外加合适的还原剂的氧化还原系统。合适的还原剂的实例包括甲醛次硫酸钠、抗坏血酸、异抗坏血酸、含硫的酸的碱金属盐和铵盐(如亚硫酸钠、亚硫酸氢盐、硫代硫酸盐、次硫酸盐、硫化物、硫氢化物或连二亚硫酸盐)、甲脒亚磺酸、丙酮亚硫酸氢盐、乙醇酸、羟甲基磺酸、乙醛酸水合物、乳酸、甘油酸、苹果酸、酒石酸和前述酸的盐。铁、铜、锰、银、铂、钒、镍、铬、钯或钴的金属盐可用于催化氧化还原反应。可任选地使用金属的螯合剂。
在多阶段自由基聚合方法中，表面活性剂可用于制备聚合物A的阶段，制备聚合物B的阶段，或两个阶段。可在单体的聚合之前或期间或其组合添加表面活性剂。也可在聚合后添加一部分表面活性剂。表面活性剂可用于两个阶段。这些表面活性剂可包括阴离子和/或非离子乳化剂。合适的表面活性剂的实例包括烷基、芳基或烷基芳基硫酸酯、磺酸酯或磷酸酯的碱金属或铵盐；烷基磺酸；磺基琥珀酸盐；脂肪酸；烯系不饱和表面活性剂单体；和乙氧基化醇或酚。在一些优选的实施例中，使用烷基、芳基或烷芳基硫酸酯的碱金属盐或铵盐表面活性剂。以用于制备多阶段聚合物的总单体的重量计，使用的表面活性剂的组合量通常为0.1重量％到10重量％或1重量％到5重量％。
在多阶段自由基聚合方法中，链转移剂可用于制备聚合物A的阶段，制备聚合物B的阶段，或两个阶段。合适的链转移剂的实例包括3-巯基丙酸、十二烷基硫醇、3-巯基丙酸甲酯、3-巯基丙酸丁酯、苯硫酚、壬二酸烷基硫醇，或其混合物。可以有效量使用链转移剂以控制多阶段聚合物的分子量。以用于制备多阶段聚合物的单体的总重量计，链转移剂的存在量可为0到3重量％、0.01重量％到2重量％，或0.05重量％到1重量％。
获得的多阶段聚合物的水性分散体的pH值可为0.5到5.0、1.0到4.5或1.5到4.0。水性多阶段聚合物分散体的粘度可为1到200厘泊(cps)、3到100cps或5到50cps，如在室温(20℃-30℃)下用#2转子以60rpm的剪切速率通过布氏粘度计测量。在中和时，多阶段聚合物可变为水可溶。聚合物A、聚合物B和所得多阶段聚合物可为碱可溶。“碱可溶”意指聚合物在室温下基本上可溶于已用碱将调节到pH约5.0或更高的水性介质中。可通过将一种或多种碱添加到水性分散体中进行中和。合适的碱的实例包括氨水；碱金属或碱土金属化合物，如氢氧化钠、氢氧化钾、氢氧化钙、碳酸钠；伯胺、仲胺和叔胺，如三乙胺、乙胺、丙胺、单异丙胺、单丁胺、己胺、乙醇胺、二乙胺、二甲胺、三丁胺、三乙醇胺、二甲氧基乙胺、2-乙氧基乙胺、3-乙氧基丙胺、二甲基乙醇胺、二异丙醇胺、吗啉、乙二胺、2-二乙氨基乙胺、2,3-二氨基丙烷、1,2-丙二胺、新戊二胺、二甲基氨基丙胺、己二胺、4,9-二氧杂十二烷-1,12-二胺、聚乙烯亚胺或聚乙烯胺；氢氧化铝；或其混合物。
本发明还涉及水性涂料组合物，例如油漆配制物，其包含通常用作增稠剂的上文所描述的水性多阶段聚合物分散体。当在水性涂料组合物中使用时，水性多阶段聚合物分散体通常被中和到高pH值，例如，8或更高，或甚至8.5或更高。以水性涂料组合物的总干重计，水性涂料组合物可包含0.1干重％到5干重％、0.2干重％到2干重％或0.5干重％到1干重％的水性多阶段聚合物分散体。
本发明的水性涂料组合物可另外包含与上文所描述的多阶段聚合物不同的一种或多种粘结剂。以粘结剂的重量计，粘结剂通常包含10％或更少、5％或更少、2％或更少的一种或多种α,β-烯系不饱和羧酸的结构单元。构成粘结剂的结构单元的α,β-烯系不饱和羧酸，即，用于合成粘结剂，可选自与上文在聚合物A章节中所描述的相同的组。粘结剂可为丙烯酸乳液聚合物(例如纯丙烯酸乳液聚合物、苯乙烯丙烯酸乳液聚合物或其混合物)、乙酸乙烯酯-乙烯乳液聚合物、乙酸乙烯酯乳液聚合物，或其混合物。在一个实施例中，使用的粘结剂为丙烯酸乳液聚合物。本文“丙烯酸乳液聚合物”是指包含一种或多种丙烯酸单体或其与包括例如苯乙烯或取代的苯乙烯的其它单体的混合物的结构单元的乳液聚合物粘结剂的重均分子量可为50,000道尔顿或更高，例如50,000到1,000,000道尔顿，或100,000到200,000道尔顿，如通过凝胶渗透色谱法(GPC)分析(柱：PLgel Guard Column(10μm，50mm×7.5mm)和PLgel MIXED GELB(10μm)；柱温：40℃；流动相：THF/FA(5％)；流动速率1.0毫升/分钟；注入体积：100mL；检测器：安捷伦(Agilent)折射率检测器，40℃；和校准曲线：分子量在2,329,000到580g/mol范围内的PL聚苯乙烯窄标准品，使用多项式3拟合)测量。以水性涂料组合物的总干重计，本发明的水性涂料组合物可包含3干重％到75干重％、10干重％到60干重％或20干重％到50干重％的粘结剂。
本发明的水性涂料组合物可另外包含颜料以形成着色涂料组合物(也称为“油漆配制物”)。本文“颜料”是指能够实质上有助于涂料的不透明性或遮盖能力的颗粒无机材料。这类材料的折射率通常大于1.8。无机颜料可包括例如二氧化钛(TiO2)、氧化锌、氧化铁、硫化锌、硫酸钡、碳酸钡或其混合物在优选的实施例中，在本发明中使用的颜料是TiO2。TiO2通常以两种晶体形式存在，即锐钛矿和金红石。TiO2还可以浓缩的分散体形式获得。水性涂料组合物还可包含一种或多种增量剂。本文“增量剂”是指折射率小于或等于1.8并且大于1.3的颗粒无机材料。合适的增量剂的实例包括碳酸钙、粘土、硫酸钙、铝硅酸盐、硅酸盐、沸石、云母、硅藻土、实心或中空玻璃、瓷珠、霞石正长岩、长石、硅藻土、煅烧硅藻土、滑石(水合硅酸镁)、二氧化硅、氧化铝、高岭土、叶蜡石、珍珠岩、重晶石、硅灰石、不透明聚合物(例如可购自陶氏化学公司(The Dow Chemical Company)的ROPAQUETMUltra E(ROPAQUE为陶氏化学公司的商标)或其混合物。水性涂料组合物的颜料体积浓度(PVC)可为10％到98％、15％到90％或20％到80％。PVC可根据以下等式确定：
PVC％＝[体积(颜料+增量剂)/体积(颜料+增量剂+粘结剂)]×100％。
本发明的水性涂料组合物还可包含一种或多种分散剂。分散剂可包括非离子、阴离子和阳离子分散剂，如具有适合分子量的多元酸、2-氨基-2-甲基-1-丙醇(AMP)、二甲基氨基乙醇(DMAE)、三聚磷酸钾(KTPP)、聚磷酸三钠(TSPP)、柠檬酸和其它羧酸。所用的多元酸可包括基于多元羧酸的均聚物和共聚物，包括已经疏水或亲水改性的那些，例如聚丙烯酸或聚甲基丙烯酸或马来酸酐与各种单体如苯乙烯、丙烯酸酯或甲基丙烯酸酯、二异丁烯和其它亲水或疏水共聚单体；其盐；或其混合物。这类多元酸的分子量可在1,000到20,000道尔顿、1,200到10,000道尔顿，或1,500到8,000道尔顿的范围内如通过GPC分析(柱：OnePLgel GUARD柱(10μm，50×7.5mm)和One Mixed B柱(7.8×300mm)串联；和校准：分子量在2329000到580g/mol的范围内的PL聚苯乙烯窄标准品，使用多项式3)测量。合适的商业上可获得的分散剂可包括得自陶氏化学公司在商标名OROTANTM下的那些，如OROTAN 731A、OROTAN 1288；OROTAN 1124；OROTAN 165、OROTAN 2001、OROTAN CA-2500和OROTAN681分散剂。分散剂可用于制备涂料组合物的颜料研磨阶段或调漆阶段。以水性涂料组合物的总重量计，分散剂的存在量可为0到5重量％、0.2重量％到3重量％，或0.3％到2重量％。
本发明的水性涂料组合物可另外包含一种或多种消泡剂。本文“消泡剂”是指减少泡沫并且阻止泡沫形成的化学添加剂。消泡剂可为硅酮基消泡剂、矿物油基消泡剂、环氧乙烷/环氧丙烷基消泡剂、聚丙烯酸烷基酯或其混合物。合适的可商购的消泡剂包括例如均购自迪高(TEGO)的TEGO Airex 902W和TEGO Foamex 1488聚醚硅氧烷共聚物乳液、可购自毕克(BYK)的BYK-024硅酮消泡剂，或其混合物。以水性涂料组合物的总干重计，消泡剂的浓度可大体上为0到1重量％、0.05重量％到0.8重量％，或0.1重量％到0.5重量％。
本发明的水性涂料组合物可另外包含与本发明的水性多阶段聚合物分散体不同的一种或多种额外增稠剂。额外增稠剂可包括纤维素增稠剂，如甲基纤维素醚、羟基甲基纤维素(HMC)、羟基乙基纤维素(HEC)、疏水改性的羟乙基纤维素(HMHEC)、羧甲基纤维素钠(SCMC)、羧基甲基2-羟乙基纤维素钠、2-羟丙基甲基纤维素、2-羟乙基甲基纤维素、2-羟丁基甲基纤维素、2-羟乙基乙基纤维素和2-羟丙基纤维素，以及其它额外增稠剂，例如聚乙烯醇(PVA)、粘土材料、氨酯相关的增稠剂(UAT)、聚醚脲聚氨酯(PEUPU)、聚醚聚氨酯(PEPU)、疏水改性的乙氧基化氨酯(HEUR)，或其混合物。以水性涂料组合物的总干重计，额外增稠剂的存在量大体上可为0到5重量％、0.1重量％到3重量％或0.2重量％到1重量％。
本发明的水性涂料组合物可另外包含一种或多种润湿剂。本文中“润湿剂”是指降低涂料组合物的表面张力，使涂料组合物更容易扩散通过或渗透基材表面的化学添加剂。润湿剂可为阴离子、两性离子或非离子的聚羧酸酯。以水性涂料组合物的总干重计，湿润剂的存在量可为0到2.5重量％、0.5重量％到2重量％，或1重量％到1.5重量％。
本发明的水性涂料组合物可另外包含一种或多种聚结剂。本文“聚结剂”是指在环境条件下使聚合物颗粒融合成连续膜的缓慢蒸发溶剂。合适的聚结剂的实例包括2-正丁氧基乙醇、二丙二醇正丁基醚、丙二醇正丁基醚、二丙二醇甲基醚、丙二醇甲基醚、丙二醇正丙基醚、二乙二醇单丁基醚、乙二醇单丁基醚、乙二醇单己基醚、三乙二醇单丁基醚、二丙二醇正丙基醚、正丁基醚，或其混合物。按水性涂料组合物的总重量计，聚结剂可以以0至5重量％、1重量％至4重量％或2重量％至3重量％的量存在。
除上文所描述的组分以外，本发明的水性涂料组合物可另外包含以下添加剂中的任一种或组合：缓冲剂、中和剂、冻/融添加剂、保湿剂、防霉剂、杀生物剂、防结皮剂、着色剂、流动剂、抗氧化剂、塑化剂、调平剂、触变剂、粘合促进剂和研磨媒剂。以水性涂料组合物的总重量计，这些添加剂可以0到5重量％、1重量％到4重量％或2重量％到3重量％的组合量存在。
本发明的水性涂料组合物可通过掺合水性多阶段聚合物分散体、粘结剂和其它任选组分，例如如上文所描述的颜料和/或增量剂制备。在水性涂料组合物中的组分可以任何顺序混合以提供本发明的水性涂料组合物。任一种上述任选的组分也可在混合期间或之前添加到组合物以形成水性涂料组合物。当水性涂料组合物包含颜料和/或增量剂时，即，颜料配制物，颜料和/或增量剂优选地与分散剂混合，以形成颜料和/或增量剂的浆液。
本发明的水性涂料组合物具有良好热老化稳定性。本文“良好热老化稳定性”是指如水性涂料组合物在50℃下热老化7天或更长、14天或更长、21天或更长、28天或更长，或甚至35天或更长后，粘度变化在±10KU单位内，根据在下文实例章节中描述的测试方法所测量。与包含一个阶段线性HASE增稠剂的水性涂料组合物相比，水性涂料组合物在添加着色剂时也可具有更好的粘度稳定性。
本发明还涉及使用水性涂料组合物的方法，其包含以下：将水性涂料组合物施用到基材，并且干燥施用的水性涂料组合物或使其干燥。
本发明还提供一种制备涂层的方法。方法可包含：形成本发明的水性涂料组合物，将水性涂料组合物施用到基材，并且干燥施用的涂料组合物，或使其干燥，以形成涂层。
本发明的水性涂料组合物可施用到并且粘附到各种基材。合适的基材的实例包括木材、金属、塑料、泡沫、石头、弹性衬底、玻璃、织品、混凝土或水泥衬底。优选地包含颜料的涂料组合物适合于各种应用，如海洋和防护涂料、汽车涂料、交通漆、外墙外保温装饰系统(EIFS)、屋面胶泥、木材涂料、卷材涂料、塑料涂料、粉末涂料、罐头涂料、建筑涂料和土木工程涂料。涂料组合物特别适合于建筑涂料。水性涂料组合物可单独使用或与其它涂料组合使用以形成多层涂层。
本发明的水性涂料组合物可通过包括刷涂、浸涂、辊涂以及喷涂的现有方式施用到基材。水性组合物应用通过喷涂施用。可使用标准喷涂技术和喷涂设备，如空气雾化喷涂、空气喷涂、无空气喷涂、高体积低压喷涂和静电喷涂(如静电钟罩施用)和人工或自动方法。在已将本发明的涂料组合物施用到基材后，可在室温(20℃-25℃)下或在高温，例如35℃至60℃下干燥涂料组合物或使其干燥以形成膜(也就是，涂层)。
实例
现在将在以下实例中描述本发明的一些实施例，除非另外说明，否则其中所有份数和百分比均以重量计。在实例中使用以下材料：
冰甲基丙烯酸(GMAA)、丙烯酸乙酯(EA)、用作引发剂的过硫酸铵(APS)、用作氧化剂的叔丁基过氧化氢(t-BHP)、用作还原剂的异抗坏血酸(IAA)和用作链转移剂的正十二烷基硫醇(nDDM)可购自陶氏化学公司。
SIPOMER BEM聚氧乙烯二十二烷基-二十三基甲基丙烯酸酯(BEM)和SIPOMER SEM-25聚乙氧基化三苯乙烯基苯酚甲基丙烯酸酯(SEM)均可购自苏威公司(Solvay Company)。
具有20EO的聚乙氧基鲸蜡基-甲基丙烯酸十八烷基脂可购自Kal-Gard。
用作促进剂的硫酸亚铁(FeSO4·7H2O)和用作缓冲剂的乙酸钠均来自国药集团化学试剂有限公司(Sinopharm Chemical Reagent Co.,Ltd)。
均可购自陶氏化学公司的甲基丙烯酸烯丙酯(ALMA)和邻苯二甲酸二烯丙酯(DAP)用作交联剂。
均可购自苏威公司的乙二醇二甲基丙烯酸酯(EGDMA)、1,3-丁二醇二甲基丙烯酸酯(BGDMA)、1,4-丁二醇二甲基丙烯酸酯(BDDMA)、丙三醇1,3-二甲基丙烯酸酯(GDMA)、二乙二醇二甲基丙烯酸酯(DEGDMA)和三(乙二醇)二甲基丙烯酸酯(RTGDMA)用作交联剂。
用作冻/融添加剂的丙二醇、AMP-95TM 2-甲基-2-氨基丙醇、OROTAN 1288分散剂、PRIMAL AS-356粘结剂、ROPAQUE Ultra E聚合物、CELLOSIZETMQP30000H增稠剂、ECOSURFTMBD-109湿润剂，和TRITONTMCF-10表面活性剂均可购自陶氏化学公司(AMP-95、PRIMAL、CELLOSIZE、ECOSURF、和TRITON为陶氏化学公司的商标)。
Kathon LXE消泡剂可购自诺普科(Nopco)。
Ti-Pure R-902(TiO2)颜料可购自杜邦(DuPont)。
DISPONIL Fes-32(“Fes-32”)表面活性剂、Foamaster NXZ消泡剂和ASP-170洗涤过的粘土(“ASP-170”)均可购自巴斯夫全球公司(BASF Global Corporation)。
CC-700增量剂可购自广福建材集团(Guangfu Building Materials Group)(中国)。
DB-80增量剂可购自山西晋阳煅烧高岭土有限公司(Shanxi Jinyang CalcinedKaolin Ltd.)(中国)。
可购自伊士曼化学(Eastman Chemical Company)的TEXANOL用作聚结剂。
SR-237TiO2(“SR-237”)可购自山东东佳公司(Shandong Dongjia Company)。
BATF 998A苯乙烯-丙烯酸粘结剂可从BATF公司获得。
在实例中使用以下标准分析设备和方法。
热老化稳定性测试
将油漆配制物(200g)放入塑料瓶中，并且然后在室温下记录油漆配制物的初始粘度(克雷布斯单位(KU)为单位)。然后将油漆配制物分别在50℃下的烘箱中存储7天、14天、21天、28天或35天。测试在储存之后的油漆配制物的所述并且记录为热老化粘度。初始粘度和热老化粘度之间的差被定义为热老化粘度变化(即，在热老化之后的ΔKU)。热老化粘度变化在±10KU内指示可接受的热老化稳定性。热老化粘度变化越小，热老化稳定性越好。
在添加着色剂之后的粘度稳定性
将4g的酞青蓝着色剂添加到200g的油漆配制物中并且充分混合(例如，使用油漆振荡器5分钟)，以得到均匀的有色油漆。通过在添加着色剂之前和在添加着色剂之后的粘度变化(即，在添加着色剂时的ΔKU)确定在添加着色剂之后的粘度稳定性。粘度变化越小，在添加着色剂之后的粘度稳定性越好。
增稠效率
将每种油漆配制物增稠到100KU的目标粘度。增稠效率确定为达到目标KU约100所需要的增稠剂的固体(以每1000克的油漆的克数为单位)，并且记录在表3和4中。
当评估热老化稳定性、在添加着色剂之后的粘度稳定性和增稠效率时，根据ASTM(美国测试与材料协会)D562-10(2014)方法在中等剪切速率(80～100rpm)下通过Stormer粘度计测量油漆配制物的粘度。
多阶段聚合物的分子量测量
短语“分子量”是指如使用具有在线多角度光散射(MALS)和差示折射率检测的不对称流场流动分级(AF4)测量的重均分子量。所用的AF4仪器由EclipseTMDualTecTM分离系统(来自怀雅特技术公司(Wyatt Technology Corp.))组成，所述系统与18角多角度光散射(MALS)检测器(DAWN HELOS II；来自怀雅特技术公司)和差示折光计(RI)(Optilab rEX；来自怀雅特技术公司)串联连接。使用配备有微型真空脱气器的Agilent Technologies 1200系列等度泵提供通过AF4仪器的流量。所有进样均使用自动进样器(AgilentTechnologies1200系列)进行。使用Astra软件版本7.0.1.23(来自怀雅特技术公司)收集和处理来自AF4仪器的数据。在pH为10下在20mM乙酸铵溶液中以1mg/mL的浓度制备样品(用1.2μm多孔尼龙膜过滤)。将样品(25μL)注入标准分离通道系统(25cm长，宽度尺寸从2.15cm开始并且在整个长度上减小到0.3cm)，通道厚度为350μm，并且配备有截留10kDA的再生纤维素超滤膜(怀雅特技术公司)。用于AF4分析的流动相为在pH为10下的20mM乙酸铵溶液。使用1毫升/分钟的施加通道流速进行分离。将样品以1.7毫升/分钟的聚焦流速引入通道3分钟。然后洗脱流以0.5mL/min开始，持续3分钟，并且然后随后线性降低的横流梯度(在12分钟内从0.5毫升/分钟降到0.05mL/min)，然后以0.05mL/min再保持5分钟。平均分子量使用折射率校正散射角度范围为13.0°到70.1°的检测器在空白注射减去0.185mL/g的折射率增量(dn/dc)之后使用Astra软件版本7.0.1.23计算，对于所有计算用Berry模型2阶拟合。本文所报告的分子量以道尔顿为单位。
实例(Ex)1合成HASE
IS-1
为了制备实例1的HASE IS-1，制备两种单体乳液(ME1和ME2)。通过混合去离子(DI)水(289.5g)、32％Fes-32(11.1g)、丙烯酸乙酯(263.11g)和冰甲基丙烯酸(175.4g)制备ME1。通过混合DI水(124.06g)、32％Fes-32(4.75g)、丙烯酸乙酯(100.44g)、冰甲基丙烯酸(71.74g)、PCSM(17.94g)和BGDMA(0.19g)制备ME2。在具有机械搅拌器、冷凝器、温度计和氮气吹扫管线的1加仑反应器中，添加DI水(540g)和32％Fes-32(17.9g)。当反应器温度升高到86℃时，将溶解在DI水(8g)中的APS(0.7g)的引发剂溶液添加到反应器中。在2分钟之后，在86℃下在77分钟内将ME1和0.7％APS溶液(28g)逐渐添加到反应器中。在完成ME1和用于ME1的引发剂进料之后，将ME2和0.7％APS溶液(12g)添加到反应器中。在完成所有ME2和用于ME2的引发剂进料之后，将反应器在86℃下保持15分钟，并且然后添加0.2％FeSO4·7H2O溶液(13.53g)随后4％IAA溶液(15g)和2％t-BHP溶液(15g)两次。最后，冷却反应器并且过滤所得乳液以得到具有30％固体的HASE IS-1。获得的IS-1增稠剂的重均分子量为3,000,000道尔顿。
实例2-11合成HASE
IS-2到IS-11
Ex 2-11的HASE IS-2到IS-11基于与Ex 1描述的相同程序制备，例外为用于M1和M2的单体组成，和/或在第一阶段中的M1的总单体与在第二阶段中的M2的总单体的重量比不同并且在表1中给出。
比较(Comp)Ex 1-9合成HASE CS-1到CS-7、CS-9和CS-10
Comp Ex 1-7和9-10的HASE基于与Ex 1相同的程序制备，例外为用于M1和M2的单体组成，和/或在第一阶段中的M1与在第二阶段中的M2的重量比不同并且在表1中给出。对于HASE CS-5，多阶段聚合物的重均分子量为20,000,000，对于HASE CS-9为9,200,000道尔顿，并且对于HASE CS-10为22,000,000道尔顿。
Comp Ex8合成HASE CS-8
为了制备Comp Ex 8的增稠剂，通过混合DI水(883g)、32％Fes-32(31.55g)、丙烯酸乙酯(572.55g)和GMAA(567.33g)、PCSM(87.01g)和nDDM(1.04g)制备单体乳液(ME)。在具有机械搅拌器、冷凝器、温度计和氮气吹扫管线的1加仑反应器中，添加DI水(707.26g)和32％Fes-32(31.55g)。当反应器温度升高到86℃时，将溶解在DI水(25.31g)中的APS(1.28g)的引发剂溶液添加到反应器中。在2分钟之后，在86℃下在85分钟内将ME和0.5％APS溶液(113g)逐渐添加到反应器中。在完成ME进料之后，APS溶液的其余部分继续进料5分钟过进料。在完成ME和引发剂溶液进料之后，将反应器在86℃下保持15分钟，并且然后添加0.2％FeSO4·7H2O(17.72g)，随后3.5％IAA溶液(23.32g)和8.8％t-BHP溶液(18.5g)两次。最后，冷却反应器并且过滤所得乳液以得到具有30％固体的HASE CS-8的乳液。
上文获得的增稠剂用于制备油漆配制物，并且用于每种油漆配制物的增稠剂的类型和剂量在表3中给出。
表1增稠剂组成
表2增稠剂的特性
| 增稠剂号 | pH | 重量％，重量％ | 粘度*(2#/60rpm) | 粒度(nm) |
| IS-1 | 4.47 | 30.56 | 7.2 | 77 |
| IS-2 | 4.25 | 32.98 | 5.6 | 153 |
| IS-3 | 4.27 | 31.52 | 6.3 | 126 |
| IS-4 | 3.92 | 30.67 | 8.5 | 104 |
| IS-5 | 4.19 | 31.5 | 9 | 108 |
| IS-6 | 4.29 | 32.42 | 9.5 | 110 |
| IS-7 | 4.08 | 31.25 | 8.5 | 98 |
| IS-8 | 4.14 | 31.04 | 8 | 101 |
| IS-9 | 3.96 | 30.93 | 9.5 | 93 |
| IS-10 | 2.83 | 30.1 | 7.5 | 142 |
| IS-11 | 2.92 | 30.17 | 8 | 130 |
| CS-1 | 3.72 | 31.58 | 8.1 | 104 |
| CS-2 | 3.83 | 30.23 | 7.8 | 100 |
| CS-3 | 3.5 | 30.12 | 8.2 | 100 |
| CS-4 | 3.21 | 31.82 | 8.5 | 115 |
| CS-5 | 3.07 | 34.49 | 8.2 | 104 |
| CS-6 | 2.86 | 33.92 | 6.5 | 158 |
| CS-7 | 2.99 | 34.39 | 7.3 | 121 |
| CS-8 | 3.50 | 35％ | 7.5 | 130 |
| CS-9 | 3.41 | 30.4 | 8 | 106 |
| CS-10 | 3.57 | 30.59 | 7 | 120 |
*粘度为在室温下用#2转子以60rpm的剪切速率通过布氏粘度计测量。
油漆配制物IP-1
通过两步涂料制备技术制备IP-1的油漆配制物。
研磨阶段：将水(150g)、AMP-95(1.05g)、丙二醇(20g)、OROTAN 1288(7.88g)、Kathon LXE(1.05g)、TRITON CF-10湿润剂(2.12g)、Foamaster NXZ消泡剂(1.05g)、Ti-Pure R-902TiO2(90.31g)、CC-700增量剂(305.29g)和DB-80增量剂(77.19g)依次添加到罐中并且用高速COWLES混合器搅拌。然后良好地分散研磨阶段组分。
调漆阶段：在研磨阶段之后，用低剪切常规的实验室混合器替换COWLES混合器。然后将PRIMAL AS-356(107g)、Texanol聚结剂(4.82g)、ROPAQUE Ultra E不透明聚合物(30g)、FoamasterNXZ消泡剂(0.5g)、AMP-95(0.6g)和DI水(151.14g)添加到罐并且在低速下搅拌分散体。最后，添加HASE IS-1(11.41g)和DI水(38.59g)以获得KU为约100的油漆配制物。
油漆配制物IP-2到IP-11和CP-1到CP-9
根据与上文在制备IP-1的油漆配制物中描述的相同程序制备IP-2到IP-11的本发明油漆配制物和CP-1到CP-9的比较油漆配制物，例外为增稠剂的类型和剂量(即，增稠效率)不同并且在表3中示出。调节用于每种油漆配制物的水的量以构成1,000g的油漆配制物的总重量。根据上文所描述的测试方法评估获得的漆配制物，并且结果在表3中给出。
表3给出如通过△KU评估的油漆配制物的热老化稳定性结果。如在表3中所示，所有本发明油漆配制物(IP-1到IP-11)示出在50℃下35天热老化之后KU变化小于10个单位，而所有比较涂料(CP-1到CP-9)展示在50℃下热老化35天，或仅7天之后KU变化大于10个单位。通过两阶段乳液聚合制备所有本发明HASE样品(IS-1到IS-11)，其中在第一阶段中获得的碱可溶聚合物包含GMAA和EA的结构单元，但是没有疏水缔合的单体的结构单元，并且在第二阶段中获得的聚合物为包含疏水缔合的单体的结构单元的特定交联的疏水碱可溶聚合物。当在第一阶段中添加疏水缔合的单体时，获得的增稠剂(CS-2和CS-3)提供具有差的热老化稳定性的油漆配制物，如通过在50℃下储存35天之后KU变化大于20指示。当在制备CS-1、CS-3、CS-6和CS-7的比较增稠剂中使用含烯丙基的交联剂(例如ALMA和DAP)时，包含这类增稠剂的油漆配制物示出不稳定的热老化稳定性(在50℃下热老化7天或更长之后KU变化大于10个单位)。当在制备增稠剂的第二阶段中不使用交联剂或EGDMA交联剂(CS-4和CS-5)时，包含这类增稠剂的油漆配制物具有差的热老化稳定性。其中第一阶段聚合物与第二阶段聚合物的重量比分别为50/50和30/70的CS-9和CS-10的增稠剂提供具有差的热老化稳定性的油漆配制物，如通过KU变化大于10个单位指示。
表3油漆配制物的热老化稳定性
油漆配制物IP-12
通过两步涂料制备技术制备IP-12的油漆配制物：
研磨阶段：将水(200g)、AMP-95(1g)、CELLOSIZEQP 30000H(1g)、OROTAN 1288(3.5g)、BD-109润湿剂(1.2g)、SR-237(30g)、Foamaster NXZ消泡剂(1g)、ASP-170(60g)、CC-700增量剂(300g)和DB-80增量剂(110g)依次添加到罐中并且用高速COWLES混合器(约2,000-2,500rpm)搅拌。然后良好地分散研磨阶段组分。
调漆阶段：在研磨阶段之后，COWLES混合器被低剪切常规实验室混合器(<1000rpm)替换。然后将BATF 998A(110g)、Texanol聚结剂(5g)、Kathon LXE(1g)、FoamasterNXZ消泡剂(1g)和DI水(125.3g)添加罐到并且在低速下搅拌分散体。最后，添加上文制备的HASE IS-1增稠剂(14.14g湿重)、AMP-95(1g)和DI水(34.86g)以制备粘度为约100KU的油漆配制物。
Comp油漆配制物CP-10
根据与制备IP-12的油漆配制物相同的程序制备CP-10的油漆配制物，例外为使用以干重计2.34g的CS-8增稠剂，如在表4中示出。调节用于每种油漆配制物的水的量以构成1000g的油漆配制物的总重量。
根据上文所描述的测试方法评估获得的油漆配制物的热老化稳定性特性并且结果在表4中给出。如在表4中所示，包含本发明的IS-1增稠剂的IP-12的油漆配制物在50℃下储存28天之后稳定。相比之下，包含一个阶段线性HASE增稠剂(CS-8)的CP-10的比较油漆配制物在50℃下热老化14天或更长之后示出明显的不稳定性。与CP-10的油漆配制物相比，IP-12的油漆配制物还示出在添加着色剂时KU变化更小。
表4在热老化之后或在添加着色剂时的稳定性
Claims (11)
1.一种多阶段聚合物的水性分散体，其中所述多阶段聚合物包含：
(A)第一阶段的聚合物A，其以所述聚合物A的重量计，包含
(a1)15重量％或更多的α,β-烯系不饱和羧酸的结构单元，
(a2)单烯系不饱和非离子单体的结构单元，
(a3)小于0.1重量％的疏水缔合的单体的结构单元，和任选地
(a4)选自C3-C20亚烷基二醇二(甲基)丙烯酸酯、聚(亚烷基二醇)二(甲基)丙烯酸酯和其组合的交联剂的结构单元；和
(B)第二阶段的聚合物B，其以所述聚合物B的重量计，包含
(b1)15重量％或更多的α,β-烯系不饱和羧酸的结构单元，
(b2)单烯系不饱和非离子单体的结构单元，
(b3)0.1重量％到60重量％的疏水缔合的单体的结构单元，和
(b4)选自C3-C20亚烷基二醇二(甲基)丙烯酸酯、聚(亚烷基二醇)二(甲基)丙烯酸酯和其组合的交联剂的结构单元；
其中所述聚合物A与所述聚合物B的重量比为95:5到55:45；
其中所述疏水缔合的单体(a3)和(b3)各自独立地具有式I的结构，
H2C＝C(R)CO2(CH2CH2O)n(CH(R1)CH2O)mR2 (I)，
其中R为H或CH3，R1为C1-C2烷基，R2为芳烷基苯基或C8-C50直链或支链烷基，n为6到100的整数，并且m为0到50的整数，其条件是n≥m，
并且m+n为6到100；
其中所述单烯系不饱和非离子单体(a2)和(b2)各自独立地选自(甲基)丙烯酸的烷基酯、乙烯基芳香族单体，羧酸的乙烯基酯、烯系不饱和腈或其混合物。
2.根据权利要求1所述的水性分散体，其中所述交联剂(a4)和(b4)各自独立地选自1,3-丁二醇二甲基丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、丙三醇1,3-二甲基丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、三丙二醇二甲基丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、丙二醇二丙烯酸酯、1,1,1-三羟甲基丙烷二甲基丙烯酸酯、1,1,1-三羟甲基乙烷二丙烯酸酯，或其混合物。
3.根据权利要求1所述的水性分散体，其中所述多阶段聚合物的重均分子量为1,000,000到9,000,000道尔顿。
4.根据权利要求1所述的水性分散体，其中所述聚合物A与所述聚合物B的重量比为90:10到60:40。
5.根据权利要求1所述的水性分散体，其中所述聚合物A含有以聚合物A的重量计，小于0.02％的所述疏水缔合的单体的结构单元。
6.根据权利要求1所述的水性分散体，其中所述单烯系不饱和非离子单体(a2)和(b2)各自独立地为(甲基)丙烯酸的烷基酯。
7.根据权利要求1所述的水性分散体，其中以所述聚合物A的重量计，所述聚合物A包含
(a1)20重量％到60重量％的所述α,β-烯系不饱和羧酸的结构单元，
(a2)40重量％到80重量％的所述单烯系不饱和非离子单体的结构单元，
(a3)0到0.05重量％的所述疏水缔合的单体的结构单元，和
(a4)0到0.25重量％的所述交联剂的结构单元。
8.根据权利要求1所述的水性分散体，其中以所述聚合物B的重量计，所述聚合物B包含0.1重量％到30重量％的所述疏水缔合的单体的结构单元。
9.根据权利要求1所述的水性分散体，其中所述多阶段聚合物包含：
(A)所述聚合物A，其以所述聚合物的重量计，包含
(a1)20重量％到60重量％的所述α,β-烯系不饱和羧酸的结构单元，
(a2)40重量％到80重量％的所述单烯系不饱和非离子单体的结构单元，
(a3)0到0.02重量％的所述疏水缔合的单体的结构单元，和
(a4)0到0.25重量％的所述交联剂的结构单元；和
(B)所述聚合物B，其以所述聚合物B的重量计，包含
(b1)20重量％到60重量％的所述α,β-烯系不饱和羧酸的结构单元，
(b2)35重量％到75重量％的所述单烯系不饱和非离子单体的结构单元，
(b3)1重量％到10重量％的所述疏水缔合的单体的结构单元，和
(b4)0.01重量％到2重量％的所述交联剂的结构单元；
其中所述聚合物A与所述聚合物B的重量比为90:10到60:40。
10.一种通过多阶段自由基聚合制备多阶段聚合物的水性分散体的方法，其包含：
(i)通过第一单体混合物的自由基聚合在水性介质中制备聚合物A，以所述第一单体混合物的总重量计，所述第一单体混合物包含
15重量％或更多的α,β-烯系不饱和羧酸，单烯系不饱和非离子单体，小于0.1重量％的疏水缔合的单体，和任选地选自C3-C20亚烷基二醇二(甲基)丙烯酸酯、聚(亚烷基二醇)二(甲基)丙烯酸酯或其组合的交联剂；和
(ii)在从步骤(i)获得的所述聚合物A存在下通过第二单体混合物的自由基聚合制备聚合物B，以所述第二单体混合物的总重量计，所述第二单体混合物包含
15重量％或更多的α,β-烯系不饱和羧酸，单烯系不饱和非离子单体，0.1重量％到60重量％的疏水缔合的单体，和选自C3-C20亚烷基二醇二(甲基)丙烯酸酯、聚(亚烷基二醇)二(甲基)丙烯酸酯或其组合的交联剂；
其中所述聚合物A与所述聚合物B的重量比为95:5到55:45；
其中所述疏水缔合的单体(a3)和(b3)各自独立地具有式I的结构，
H2C＝C(R)CO2(CH2CH2O)n(CH(R1)CH2O)mR2 (I)，
其中R为H或CH3，R1为C1-C2烷基，R2为芳烷基苯基或C8-C50直链或支链烷基，n为6到100的整数，并且m为0到50的整数，其条件是n≥m，并且m+n为6到100；
其中所述单烯系不饱和非离子单体各自独立地选自(甲基)丙烯酸的烷基酯、乙烯基芳香族单体，羧酸的乙烯基酯、烯系不饱和腈或其混合物。
11.一种水性涂料组合物，其包含根据权利要求1到9中任一项所述的水性分散体。
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