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CN108219075A - 具有橡实形态的氟烷基化聚合物粒子的水性分散液 - Google Patents

具有橡实形态的氟烷基化聚合物粒子的水性分散液 Download PDF

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CN108219075A
CN108219075A CN201711160860.1A CN201711160860A CN108219075A CN 108219075 A CN108219075 A CN 108219075A CN 201711160860 A CN201711160860 A CN 201711160860A CN 108219075 A CN108219075 A CN 108219075A
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CN108219075B (zh
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J·C·勃林
A·S·布朗奈尔
A·斯沃茨
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Rohm and Haas Co
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Abstract

本发明提供一种组合物，其包含1)具有核‑壳形态的聚合物粒子的水性分散液，其中核心从壳层凸出；其中核心包含5到90重量百分比的氟烷基化单体结构单元，和2)小于0.09重量百分比的磷酸单体结构单元；并且其中以壳层的重量计，壳层包含0.1到5重量百分比的衣康酸或磷酸单体。本发明通过提供使氟烷基官能团选择性浓缩成具有橡实形态的聚合物粒子的方法来解决所属领域中的需求，从而提供后续涂层的耐沾污性的改良。

Description

具有橡实形态的氟烷基化聚合物粒子的水性分散液
背景技术
本发明涉及具有橡实形态的氟烷基化聚合物粒子的水性分散液。
用氟烷基官能化的聚合物粒子(氟烷基化乳胶)的水性分散液由于其与传统的未经氟化的烃类聚合物不同的性能而用于涂料配制物中。在性能特性之后寻求防污性、抗污染性、耐久性和/或耐候性的涂料应用中通常需要包含氟化官能团。使用氟烷基化乳胶的一项主要缺陷是与其烃对应部分有关的显著成本费用。相应地，在涂料领域中寻找能够更高效地传递经改良的抗污染性的聚合物将是有利的。
发明内容
本发明通过提供一种组合物来解决所属领域中的需求，所述组合物包含1)聚合物粒子的水性分散液，所述聚合物粒子具有如通过动态光散射所测量在40nm到300nm范围内的粒度，其中聚合物粒子具有其中核心从壳层凸出的核-壳形态；其中以核心的重量计，核心包含5到90重量百分比的氟烷基化单体结构单元，和2)小于0.09重量百分比的磷酸单体结构单元；并且其中以壳层的重量计，壳层包含0.1到5重量百分比的衣康酸或磷酸单体；其中壳层与核心的重量:重量比在3:1到50:1范围内。本发明通过提供使氟烷基官能团选择性浓缩成具有橡实形态的聚合物粒子的方法来解决所属领域中的需求。
具体实施方式
本发明是涉及组合物，其包含1)聚合物粒子的水性分散液，所述聚合物粒子具有如通过动态光散射所测量在40nm到300nm范围内的粒度，其中所述聚合物粒子具有其中核心从壳层凸出的核-壳形态；其中以核心的重量计，核心包含5到90重量百分比的氟烷基化单体结构单元，和2)小于0.09重量百分比的磷酸单体结构单元；并且其中以壳层的重量计，壳层包含0.1到5重量百分比的衣康酸或磷酸单体；其中壳层与核心的重量:重量比在3:1到50:1范围内。
聚合物粒子的特征在于具有橡实形态，由此核心从壳层凸出。
聚合物粒子的核心部分包含氟烷基化单体结构单元。优选地，以核心的重量计，核心包含20，更优选25重量百分比到70，更优选50重量百分比的氟烷基化单体结构单元。
氟烷基化单体是烯系不饱和的并且优选包含至少一个全氟甲基和一个亚甲基。优选氟烷基单体种类由下式说明：
其中R1是H或甲基；R2是O、S或NR4；R3是H或F；并且x是1或2；并且y是从0、优选1到10、优选到5，并且更优选是2，其中R4是H或甲基。R2优选是O；R3优选是F。
聚合物粒子优选是丙烯酸、苯乙烯-丙烯酸，或乙烯基酯-丙烯酸聚合物(包括乙酸乙烯酯-丙烯酸和叔碳酸乙烯酯-丙烯酸聚合物)。
聚合物粒子的凸出核心部分优选包含10到90重量百分比的苯乙烯或丙烯酸酯单体结构单元或其组合。如本文中所使用，丙烯酸酯单体是指丙烯酸酯，如丙烯酸乙酯、丙烯酸丁酯和丙烯酸2-乙基己酯，以及甲基丙烯酸酯，如甲基丙烯酸甲酯和甲基丙烯酸丁酯。如本文中所使用，指定单体的术语“结构单元”是指单体在聚合之后的残余物。举例来说，优选类别的氟烷基化单体的结构单元如下文所说明：
其中点线表示结构单元与聚合物主链的连接点并且y优选是0、1或2。
聚合物粒子的核心部分优选包含小于0.05，更优选小于0.01并且最优选0重量百分比的磷酸单体。核心部分优选包含组合浓度在以核心的重量计0.1到10重量百分比范围内的羧酸单体和/或硫酸单体和/或其盐的结构单元。当存在时，羧酸单体或其盐的结构单元的浓度优选在以核心的重量计0.1、更优选地在0.5重量百分比到5、更优选地到3重量百分比范围内；类似地，当存在时，硫酸单体或其盐的结构单元的浓度优选在以核心的重量计0.1、更优选在0.5重量百分比到5、更优选到3重量百分比范围内。
适合的羧酸单体包括丙烯酸、甲基丙烯酸、衣康酸和其盐；适合的硫酸包括甲基丙烯酸磺乙酯、甲基丙烯酸磺丙酯、苯乙烯磺酸、乙烯磺酸和2-(甲基)丙烯酰胺基-2-甲基丙磺酸以及其盐。优选地，核心包含羧酸单体或其盐的结构单元以及硫酸单体或其盐的结构单元；更优选地，核心包含组合浓度以核心的重量计在1到10重量百分比范围内的甲基丙烯酸或其盐以及苯乙烯磺酸的盐，更确切地说，4-乙烯基苯磺酸钠。
核心进一步优选包含以核心的重量计0.1、更优选0.3并且最优选0.5重量百分比到优选5并且更优选到3重量百分比的多烯系不饱和单体结构单元。优选多烯系不饱和单体的实例是二烯系不饱和单体，如甲基丙烯酸烯丙酯或二乙烯基苯。
核心优选具有在30、更优选40nm到90、更优选到80nm范围内的体积平均直径(如通过BI-90动态光散射粒子分析仪测量)和优选地如通过福克斯方程式(Fox equation)所计算的在-30℃、更优选-20℃到优选60℃、更优选到40℃并且最优选到20℃范围内的Tg。
聚合物粒子的壳层优选进一步包含1)以壳层的重量计，总浓度优选在20、更优选30并且最优选40重量百分比到70、更优选60并且最优选55重量％范围内的甲基丙烯酸甲酯或苯乙烯或其组合；和2)以壳层的重量计，总浓度在20、更优选30并且最优选40重量百分比到优选70、更优选65并且最优选60重量百分比范围内的丙烯酸丁酯、丙烯酸2-乙基己酯或丙烯酸乙酯或其组合的结构单元，更优选是丙烯酸丁酯结构单元。
以壳层的重量计，壳层包含0.1、优选0.2、更优选0.5重量百分比到5并且优选地3重量百分比的衣康酸或磷酸单体结构单元，优选是磷酸单体。合适的磷酸单体的实例包括醇的膦酸酯和磷酸二氢酯，其中所述醇含有可聚合乙烯基或烯烃基团或经所述基团取代。优选磷酸二氢酯是羟基烷基甲基丙烯酸酯和羟基烷基丙烯酸酯的磷酸酯，包括甲基丙烯酸磷酸乙酯和甲基丙烯酸磷酸丙酯，其中甲基丙烯酸磷酸乙酯是尤其优选的。“甲基丙烯酸磷酸乙酯”(PEM)在本文中用于指以下结构：
其中R是H或
其中点线表示与氧原子的连接点。
以壳层的重量计，壳层还优选包含0.1，更优选0.5并且最优选1重量百分比到10，更优选8重量百分比的酸单体或其盐的结构单元，所述酸单体或其盐选自硫酸单体、羧酸单体以及硫酸单体和羧酸单体的盐。更优选地，以壳层的重量计，壳层包含组合浓度在0.5到8重量百分比范围内的甲基丙烯酸或其盐和4-乙烯基苯磺酸盐的结构单元。
壳层与核心的重量:重量比在3:1、优选5:1到50:1、优选到35:1范围内。聚合物粒子具有如通过动态光散射所测量的在40nm、优选50nm并且更优选70nm到300nm、优选到200nm并且更优选到180nm范围内的粒度。
在制造聚合物粒子的水性分散液的优选方法中，第一单体乳液宜通过在乳液聚合条件下接触水、丙烯酸丁酯、甲基丙烯酸甲酯或苯乙烯、甲基丙烯酸烯丙酯、甲基丙烯酸2,2,2,-三氟乙酯、4-乙烯基苯磺酸钠以及甲基丙烯酸以形成凸出核心的前驱体来制备。分离和表征凸出核心的前驱体(预成型体)。接着，水、前驱体和丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸、4-乙烯基苯磺酸钠以及任选的磷酸单体的单体乳液在乳液聚合条件下，在与前驱体聚合分开和不同的步骤中反应，以形成具有橡实形态的聚合物粒子的稳定水性分散液。
在另一种制造水性分散液的优选方法中，经由二步骤方法制得聚合物粒子，其中第一单体乳液宜通过在乳液聚合条件下接触水、丙烯酸丁酯、甲基丙烯酸甲酯或苯乙烯、甲基丙烯酸烯丙酯、甲基丙烯酸2,2,2,-三氟乙酯、4-乙烯基苯磺酸钠和甲基丙烯酸以形成聚合物粒子的分散液来制备。在同一个反应器中，聚合物粒子的分散液接着在乳液聚合条件下与丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸、4-乙烯基苯磺酸钠和任选的磷酸单体的第二单体乳液反应，以形成具有橡实形态的聚合物粒子的稳定水性分散液。
组合物可包括选自以下组成的组的其它成分：分散剂、颜料、消泡剂、表面活性剂、溶剂、其它结合剂、延长剂、聚结剂、杀生物剂、不透光聚合物以及着色剂。已发现来自使用在橡实核心中具有氟化烷基官能团的橡实型胶乳粒子配制的油漆的涂层与未经这样官能化的橡实乳胶相比显示抗压粘性的显著改良。
实例
实例1-具有氟烷基化核心的橡实聚合物粒子的水性分散液
A.核心(预成型体)合成
通过混合去离子水(200g)、Disponil FES 993表面活性剂(64g，30％活性)、丙烯酸丁酯(203.2g)、苯乙烯(203.2g)、甲基丙烯酸2,2,2,-三氟乙酯(192g)、甲基丙烯酸烯丙酯(9.6g)、4-乙烯基苯磺酸钠(17.78g，90％活性)和甲基丙烯酸(16g)制备第一单体乳液。
向配备有桨式搅拌器、温度计、氮气入口以及回流冷凝器的5L四颈圆底烧瓶中添加去离子水(600g)和Disponil FES 32表面活性剂(21.3g，30％活性)。在N2下将烧瓶的内含物加热到85℃，并且开始搅拌。接着添加一部分第一单体乳液(70g)，随后快速添加溶解于去离子水(30g)中的过硫酸铵(2.56g)溶液，随后添加去离子水冲洗液(5g)。在搅拌10分钟之后，分别在40分钟和50分钟内以线性方式并且分开地添加第一单体乳液的剩余部分，随后添加冲洗液(25g)，以及溶解于去离子水(24g)中的过硫酸铵(0.64g)和氢氧化铵(1g，29％活性)的引发剂溶液。在单体乳液进料完成之后，使烧瓶的内含物保持在85℃下10分钟，在此时间之后共进料完成；并且接着使烧瓶的内含物再保持在85℃下10分钟。
使烧瓶的内含物冷却到70℃，并且向烧瓶添加催化剂/活化剂对以减少残余单体。接着用稀的氢氧化铵溶液将聚合物中和到pH 4.5。使用Brookhaven BI 90Plus粒子分析仪测量的粒度是59nm并且固体是40.2％。
B.橡实核-壳合成
使用去离子水(400g)、十二烷基苯磺酸钠(55.4g，23％活性)、Disponil FES 993表面活性剂(42.5g，30％活性)、丙烯酸丁酯(749.7g)、甲基丙烯酸甲酯(759.9g)、甲基丙烯酸(10.2g)和4-乙烯基苯磺酸钠(11.33g，90％活性)来制备第二单体乳液。
向配备有桨式搅拌器、温度计、N2入口以及回流冷凝器的5L四颈圆底烧瓶中添加去离子水(975g)。在N2下将烧瓶的内含物加热到84℃，并且开始搅拌。
接着添加一部分来自步骤A的预成型体(425g，以最终聚合物计总单体的10％)，随后添加溶解于去离子水(20g)中的过硫酸铵(5.1g)溶液和去离子水冲洗液(5g)。在搅拌5分钟之后，在80分钟的总时段内将第二单体乳液和含有溶解于去离子水(60g)中的过硫酸铵(1.7g)和氢氧化铵(2g，29％活性)的溶液各自以线性方式并且分开地添加到烧瓶中。在第二单体乳液进料30分钟内向第二单体乳液中添加PEM(25.5g，60％活性)，接着添加去离子水冲洗液(25g)。
在添加第二单体乳液期间使烧瓶的内含物维持在84℃的温度下。当所有添加完成时，用去离子水(25g)冲洗含有第二单体乳液的容器，接着将其添加到烧瓶中。
使烧瓶的内含物冷却到65℃，并且向烧瓶中添加催化剂/活化剂对以减少残余单体。接着用稀的氢氧化铵溶液将聚合物中和到pH＝8.8。使用Brookhaven BI 90Plus粒子分析仪测量的粒度是129nm并且固体是46.5％。
比较实例1-具有PEM官能化核心的橡实聚合物粒子的水性分散液
A.核心(预成型体)合成
通过混合去离子水(200g)、Disponil FES 993表面活性剂(43g，30％活性)、丙烯酸丁酯(371.2g)、甲基丙烯酸甲酯(195.2g)、甲基丙烯酸烯丙酯(9.6g)、甲基丙烯酸磷酸乙酯(51.2g，60％活性)和甲基丙烯酸(12.8g)来制备第一单体乳液。
向配备有桨式搅拌器、温度计、氮气入口以及回流冷凝器的5L四颈圆底烧瓶中添加去离子水(600g)和Disponil FES 32表面活性剂(43g，30％活性)。在N2下将烧瓶的内含物加热到85℃，并且开始搅拌。接着添加一部分第一单体乳液(70g)，随后快速添加溶解于去离子水(30g)中的过硫酸钠(2.56g)溶液，接着添加去离子水冲洗液(5g)。在搅拌10分钟之后，分别在40分钟和50分钟内以线性方式并且分开地添加第一单体乳液的剩余部分，随后添加冲洗液(25g)，以及溶解于去离子水(50g)中的过硫酸钠(0.64g)引发剂溶液。在单体乳液进料完成之后，使烧瓶的内含物保持在85℃下10分钟，在此时间之后共进料完成；并且接着使烧瓶的内含物再保持在85℃下10分钟。使烧瓶的内含物冷却到室温并且用稀的氢氧化铵溶液中和到pH 3。使用Brookhaven BI 90Plus粒子分析议测量的粒度是60-75nm并且固体是40％。
B.橡实核-壳合成
使用去离子水(400g)、十二烷基苯磺酸钠(55.4g，23％活性)、Disponil FES 993表面活性剂(42.5g，30％活性)、丙烯酸丁酯(749.7g)、甲基丙烯酸甲酯(759.9g)、甲基丙烯酸(10.2g)和4-乙烯基苯磺酸钠(11.33g，90％活性)来制备第二单体乳液。
向配备有桨式搅拌器、温度计、N2入口以及回流冷凝器的5L四颈圆底烧瓶中添加去离子水(975g)。在N2下将烧瓶的内含物加热到84℃，并且开始搅拌。接着添加一部分来自步骤A的预成型体(425g，以最终聚合物计的总单体的10％)，随后添加溶解于20g去离子水中的过硫酸铵(5.1g)溶液和5g去离子水冲洗液。在搅拌5分钟之后，在80分钟的总时段内将第二单体乳液和含有溶解于去离子水(60g)中的过硫酸铵(1.7g)和氢氧化铵(2g，29％活性)的溶液各自以线性方式并且分开地添加到烧瓶中。在添加第二单体乳液期间使烧瓶的内含物维持在84℃的温度下。当所有添加完成时，用去离子水(25g)冲洗含有第二单体乳液的容器，接着将其添加到烧瓶中。
使烧瓶的内含物冷却到65℃，并且向烧瓶中添加催化剂/活化剂对以减少残余单体。接着用稀的氢氧化铵溶液将聚合物中和到pH 8.8。使用Brookhaven BI 90Plus粒子分析仪测量的粒度是136nm并且固体是46.7％。
比较实例2-具有PEM官能化壳层和核心的橡实物
基本上如比较实例1中所描述进行聚合，但具有以下修改：历时30分钟将甲基丙烯酸磷酸乙酯(25.5g，60％活性)添加到第二单体乳液进料中，随后将去离子水冲洗液(25g)添加到第二单体乳液中。
使用Brookhaven BI 90Plus粒子分析仪测量的粒度是142nm并且固体是46.6％。
比较实例3-具有氟烷基化核心的橡实聚合物粒子的水性分散液
除了在步骤B中不添加PEM以外，基本上如实例1中所描述进行聚合。使用Brookhaven BI 90Plus粒子分析仪测量的粒度是125nm并且固体是46.7％。
油漆配制物展示于表1中。TAMOL和ACRYSOL是The Dow Chemical Company或其附属公司的商标。
表1-油漆配制物
材料名称 镑 加仑
光泽配制物
研磨物
水 40.0 4.8
BYK-022消泡剂 1.0 0.1
Surfynol CT-111研磨助剂 3.3 0.4
TAMOLTM2011分散剂 8.8 1.0
Ti-Pure R-746TiO2 314.2 16.2
研磨物小计 367.3 22.5
稀释物
乳胶 538.9 60.7
水 - -
BYK-024消泡剂 5.0 0.6
十二醇酯聚结剂 27.3 3.4
氨(28％) 0.0 0.0
ACRYSOLTMRM-2020NPR流变改性剂 26.2 3.0
ACRYSOLTMRM-8W流变改性剂 2.7 0.3
水 79.0 9.5
总计 1046.3 100.0
耐沾污性
在经处理的铝板上使用7mil塑料涂覆器抽取油漆并且在CTR(25℃，50％R.H.)中干燥过夜。随后，将面板向南以45°倾角(南45)置放在室外6天，随后测量油漆的初始(暴露前)Y反射率。随后，使用覆盖一半面板的1英寸(2.5cm)毛刷涂覆氧化铁污物浆料。通过在存在0.1gTAMOLTM731A分散剂情况下使125g Mapico 422氧化铁分散于250g水中来制备氧化铁污物浆料。具有浆料的面板在罩盖中干燥4小时。在水流下去除经干燥的浆料，同时用干净的粗棉布片轻轻地擦拭。将面板风干至少2小时。通过下式在经浆料处理的区域内测量Y反射率值：
表2显示每种油漆的耐沾污性。
表2-耐沾污性测量值
实例乳胶 耐沾污性％(Y-污染/Y-未污染)
比较实例1 81.62
比较实例2 83.22
比较实例3 81.04
本发明实例1 88.57
结果表明将氟烷基并入橡实物的凸出核心部分并且将PEM并入壳层部分可显著改良具有橡实形态的粒子的耐沾污性，所述粒子包括核心中的PEM(比较实例1)，或核心和壳层中的PEM(比较实例2)，或核心中的氟烷基而非壳层中的PEM(比较实例3)。

Claims (9)

1.一种组合物，其包含1)聚合物粒子的水性分散液，所述聚合物粒子具有如通过动态光散射所测量的在40nm到300nm范围内的粒度，其中所述聚合物粒子具有核-壳形态，其中所述核心从所述壳层凸出；其中以所述核心的重量计，所述核心包含5到90重量百分比的氟烷基化单体结构单元，和2)小于0.09重量百分比的磷酸单体结构单元；并且其中以所述壳层的重量计，所述壳层包含0.1到5重量百分比的衣康酸或磷酸单体；其中所述壳层与所述核心的重量:重量比在3:1到50:1范围内。
2.根据权利要求1所述的组合物，其中所述氟烷基化单体是由任一个下式表示：
其中R1是H或甲基；R2是O、S或NR4；R3是H或F；并且x是1或2；并且y是0到10，其中R4是H或甲基。
3.根据权利要求2所述的组合物，其中所述氟烷基化单体是由任一个下式表示：
其中x是1并且y是0、1或2。
4.根据权利要求2所述的组合物，其中所述壳层与所述核心的重量:重量比在5:1到35:1范围内，并且其中所述聚合物粒子具有如通过动态光散射所测量的在70nm到200nm范围内的粒度。
5.根据权利要求4所述的组合物，其中以所述壳层的重量计，所述壳层包含0.5到5重量百分比的磷酸单体，并且其中所述磷酸单体是甲基丙烯酸磷酸乙酯；其中以所述壳层的重量计，所述壳层进一步包含0.1到10重量百分比的选自以下组成的组的酸单体结构单元：硫酸单体、羧酸单体以及羧酸单体和硫酸单体的盐。
6.根据权利要求5所述的组合物，其中以所述壳层的重量计，所述酸单体是组合浓度在0.5到8重量百分比范围内的甲基丙烯酸或其盐和4-乙烯基苯磺酸盐。
7.根据权利要求5所述的组合物，其中以所述核心的重量计，所述核心进一步包含0.1到5重量百分比的硫酸单体或其盐的结构单元；和以所述核心的重量计，0.1到5重量百分比的羧酸单体或其盐的结构单元；并且其中以所述核心的重量计，核心包含小于0.05重量百分比的甲基丙烯酸磷酸乙酯结构单元。
8.根据权利要求5所述的组合物，其中以所述核心的重量计，所述核心进一步包含浓度在0.1到5重量百分比范围内的甲基丙烯酸或其盐的结构单元；和以所述核心的重量计，在0.1到5重量百分比范围内的4-乙烯基苯磺酸结构单元；并且其中以所述核心的重量计，所述核心包含小于0.01重量百分比的甲基丙烯酸磷酸乙酯结构单元。
9.根据权利要求8所述的组合物，其中以所述壳层的重量计，所述壳层进一步包含组合浓度在20到60重量百分比范围内的甲基丙烯酸甲酯或苯乙烯或其组合的结构单元；和组合浓度在20到60重量百分比范围内的丙烯酸丁酯或丙烯酸2-乙基己酯或其组合的结构单元。
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