CN110387170B - 酮官能化和磷酸单体官能化聚合物颗粒的含水分散液 - Google Patents

酮官能化和磷酸单体官能化聚合物颗粒的含水分散液 Download PDF

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CN110387170B
CN110387170B CN201910211918.3A CN201910211918A CN110387170B CN 110387170 B CN110387170 B CN 110387170B CN 201910211918 A CN201910211918 A CN 201910211918A CN 110387170 B CN110387170 B CN 110387170B
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J·C·勃林
罗璞
张庆
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Dow Global Technologies LLC
Rohm and Haas Co
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Abstract

本发明涉及一种涂料组合物，其包含a)丙烯酸或苯乙烯‑丙烯酸聚合物颗粒的含水分散液，其经具有酮官能团的单体的结构单元和磷酸单体的结构单元官能化；b)包含羧酸单体的结构单元和具有酮官能团的单体的结构单元的分散剂；和c)二酰肼交联剂。本发明的组合物可用于改善由所述组合物形成的涂层中的耐擦洗性。

Description

酮官能化和磷酸单体官能化聚合物颗粒的含水分散液
背景技术
耐擦洗性是漆膜(paint film)抗磨损或擦洗的能力，是水性建筑涂料领域中所重点关注的性质。期望实现可接受耐擦洗性由竞争目标所抵消，即：期望通过用低Tg乳胶聚合物颗粒(即Tg低于25℃的聚合物颗粒)置换高Tg乳胶聚合物颗粒来降低水性建筑涂料制造中的排放水平，以及减少挥发性有机化合物(VOC)暴露于消费者。低Tg乳胶不需要VOC，如溶剂和聚结剂；另一方面，高Tg乳胶具有固有的优良耐擦洗性。
因此，期望研发不含或基本上不含VOC而使涂料具有优异耐擦洗性的水性涂料组合物。
发明内容
本发明通过提供包含以下的涂料组合物满足了所属领域的需要：a)丙烯酸或苯乙烯-丙烯酸聚合物颗粒的含水分散液，以聚合物颗粒的重量计其经0.5到10重量％具有酮官能团的单体的结构单元和0.05到5重量％磷酸单体的结构单元官能化；b)以所述组合物的干重计0.1到5重量％分散剂，并且其具有在500到50,000道尔顿范围内的Mw，并且包含i)5到90重量％羧酸单体的结构单元；和ii)0.5到10重量％具有酮官能团的单体的结构单元；和c)二酰肼交联剂；其中以所述组合物的重量计，聚合物颗粒的固体含量是5到60重量％。
本发明的组合物通过提供具有低VOC和改善耐擦洗性的涂层来满足需要。
具体实施方式
本发明是包含涂料组合物的组合物，所述涂料组合物包含a)丙烯酸或苯乙烯-丙烯酸聚合物颗粒的含水分散液，以聚合物颗粒的重量计其经0.5到10重量％具有酮官能团的单体的结构单元和0.05到5重量％磷酸单体的结构单元官能化；b)以所述组合物的干重计0.1到5重量％分散剂，并且其具有在500到50,000道尔顿范围内的Mw，并且包含i)5到90重量％羧酸单体的结构单元；和ii)0.5到10重量％具有酮官能团的单体的结构单元；和c)二酰肼交联剂；其中以所述组合物的重量计，聚合物颗粒的固体含量是5到60重量％。
聚合物颗粒是丙烯酸或苯乙烯-丙烯酸聚合物颗粒，根据定义，其包含丙烯酸酯单体或苯乙烯单体与丙烯酸酯单体组合的结构单元。如本文所使用，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。优选地，以所述组合物的重量计，聚合物颗粒的固体含量在5到40重量％、更优选到20重量％范围内。如通过动态光散射所测量，聚合物颗粒的平均粒径优选在80nm到500nm范围内。在本发明的一个方面中，如通过Fox方程所计算，聚合物颗粒的Tg低于25℃。
聚合物颗粒包含具有酮官能团的单体(即含有酮基或醛基的单体)的结构单元。具有酮官能团的单体的实例包括以聚合物颗粒的重量计浓度范围优选为1到5重量％的甲基丙烯酸乙酰乙酰氧基乙酯(AAEM)和双丙酮丙烯酰胺(DAAM)。DAAM是优选的具有酮官能团的单体。
合适的磷酸单体的实例包括醇的膦酸酯和磷酸二氢酯，其中醇含有可聚合乙烯基或烯烃基团或经可聚合乙烯基或烯烃基团取代。优选的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：
Figure BDA0002000792890000021
其中R是H或
Figure BDA0002000792890000022
其中虚线表示与氧原子的连接点。
分散剂优选包含以分散剂的重量计10重量％、更优选20重量％、更优选30重量％到80重量％、更优选到60重量％、更优选50到重量％并且最优选到40重量％羧酸单体的结构单元。合适的酸单体的实例包括丙烯酸、甲基丙烯酸和衣康酸。
分散剂优选任选地包含以分散剂的重量计优选在10重量％、更优选30重量％、更优选40重量％并且最优选50重量％到80重量％、更优选到70重量％范围内的一种或多种辅助单体。合适的辅助烯键式不饱和单体的实例包括丙烯酸酯和甲基丙烯酸酯，如甲基丙烯酸甲酯、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、甲基丙烯酸羟乙酯、丙烯酸羟乙酯和丙烯酸2-羟丙酯。甲基丙烯酸丁酯是优选的辅助烯键式不饱和单体的实例。
分散剂优选包含以分散剂的重量计1到5重量％DAAM的结构单元。任选地，分散剂可以包含以分散剂的重量计浓度范围优选为0.05重量％到5重量％、更优选到2重量％的磷酸单体的结构单元，优选PEM。
所述组合物包含二酰肼，其实例包括己二酸二酰肼(ADH)、碳二酰肼(CDH)、癸二酸二酰肼(SDH)、缬氨酸二酰肼(VDH)、间苯二甲酸二酰肼(ISODH)和二十烷二酸酰肼(ICODH)。优选地，交联剂为ADH。二酰肼与存在于分散剂和聚合物颗粒中的具有酮官能团的单体的结构单元的摩尔/摩尔比优选在0.2、更优选0.3并且最优选0.4到优选2、更优选到1.5、更优选到1:1并且最优选到0.6:1范围内。
优选地，如通过相对于聚丙烯酸标准品所测量的凝胶渗透色谱法所测量，分散剂的重均分子量(Mw)在1000道尔顿到优选25,000道尔顿并且更优选到10,000道尔顿范围内。
本发明的组合物可用于所有种类的粘合剂，并且对于低Tg粘合剂(即，具有通过Fox方程所计算<20℃的Tg的乳胶)尤其如此，所述粘合剂需要比乳胶在室温下形成膜所需的浓度更低的聚结剂；减少聚结剂的使用相应地引起不期望VOC水平的降低。因此，在另一个方面中，本发明包含少于50g/L VOC。
本发明的组合物有利地包括选自由以下组成的组的一种或多种材料：增量剂、消泡剂、增稠剂、聚结剂和颜料。
如本文所使用，术语“增量剂”是指用于增加涂料组合物的颜料体积浓度的无机材料。增量剂与颜料的区别通常在于与颜料>2.0的折射率相比，其折射率较低(通常为1.3到1.6)。合适的增量剂的实例包括碳酸钙、粘土、硅酸铝、二氧化硅、硅酸钙、云母、滑石和霞石正长岩。
在本发明组合物的一个优选实施例中，包括足量的增量剂或颜料和增量剂以形成具有超临界颜料体积浓度的组合物。颜料体积浓度(PVC)由下式定义：
Figure BDA0002000792890000041
其中粘合剂固体是指聚合物颗粒的含水分散液中将颜料和增量剂颗粒粘合在一起的聚合物贡献。术语“临界颜料体积浓度”(临界PVC)是指润湿颜料颗粒表面所需的最低聚合物浓度。在临界PVC以下，相对于颜料和增量剂，聚合物颗粒过量存在。因此，在临界PVC处或低于临界PVC的PVC下，相对于颜料和增量剂体积存在足够的相对量的粘合剂体积，引起基本上无孔的干涂层。
在超临界PVC下，粘合剂体积不足以涂布所有颜料和增量剂以形成多孔干涂层，导致后续涂层的性质和性能劣化。因此，与超临界PVC的涂层相比，在临界PVC下或低于临界PVC的涂层的耐磨性和耐污性以及去除性是优良的。然而，超临界PVC涂料的成本优势有时会压过性质降低的劣势。因此，期望研发一种形成具有改善耐擦洗性的涂层的超临界PVC组合物。在另一个实施例中，本发明的组合物具有高于临界值并且在至少55、更优选至少60并且最优选至少65到90范围内的PVC。
使用反射率(包括积分球，分光反射率，10度观测器/D65)测定涂层的临界PVC，如下：比较干燥状态的涂布膜的反射率与已经用渗透溶剂再润湿的相同膜的反射率的差异，所述渗透溶剂的折射率与填充干涂层的空隙的聚合物(如Isopar L溶剂)的折射率类似。当涂层高于临界PVC时，再润湿涂层的Y反射率将从干涂层的初始Y反射率值降低至少2％。
缩写
AA 丙烯酸
MAA 甲基丙烯酸
DAAM 双丙酮丙烯酰胺
MAA 甲基丙烯酸
BA 丙烯酸丁酯
BMA 甲基丙烯酸丁酯
t-BHP 叔丁基过氧化氢
EDTA 乙二胺四乙酸
PEM 甲基丙烯酸磷酸乙酯
IAA D-(-)-异抗坏血酸
APS 过硫酸铵
ADH 己二酸二酰肼
SSS 苯乙烯磺酸钠
NaBS 亚硫酸氢钠
VTS 乙烯基三甲氧基硅烷
HEC CELLOSIZETM QP-4400H羟乙基纤维素
RM-2020 ACRYSOLTM RM-2020NPR
RM-8W ACRYSOLTM RM-8W
MMP 3-巯基丙酸甲酯
实例
中间体比较实例1-制备PEM官能化苯乙烯-丙烯酸乳胶
通过混合DI水(409.1g)、Polystep A16-22表面活性剂(89.65g)、SSS(5.9g)、BA(682.6)、苯乙烯(891.5g)、AA(32.95g)、VTS(5.03g)和PEM(4.03g)来制备单体乳液(ME)。
将配备有机械搅拌器、N2吹扫、温度计、冷凝器、加热套和温度控制器的1-g反应器装有DI水(707.75g)并且加热到85℃。含Polystep A 16-22表面活性剂(8.85g)的水(20g)、一部分ME(54g)、含硫酸铁(0.013g)的水溶液(12g)、含EDTA(0.13g)的水溶液(12g)和含APS(5.8g)的水溶液(20g)。
5分钟后，在将反应温度控制在85℃下的情况下，将含APS(2.34g)的水溶液(64g)和含NaBS(2.45g)的水溶液(64g)以0.74g/min的速率分别进料到反应器中，并且将ME的[剩余部分]以10.4g/min的速率分别进料到反应器中。在加料完成之后，用DI水(30g)冲洗单体乳液容器，并将反应器冷却到55℃。
然后，将含t-BHP(5.88g，70％水溶液)的水溶液(40g)和含IAA(2.37g)的水溶液(40g)各自以1.8g/min的速率添加到反应器中。在完成t-BHP和IAA进料之后，将反应器冷却到室温。当反应器温度达到50℃时，通过添加NH4OH将反应器的内容物的pH调节到8。完成之后，过滤烧瓶内容物以去除凝胶。通过动态光照，发现经过滤分散液的测量粒度是107nm。
中间体比较实例2-制备DAAM官能化苯乙烯-丙烯酸乳胶
DAAM官能化苯乙烯-丙烯酸粘合剂的制备基本上如比较实例1中所描述来进行，不同之处如下：通过混合DI水(409.1g)、Polystep A16-22表面活性剂(89.65g)、SSS(5.9g)、BA(666.46)、苯乙烯(875.36g)、AA(36.98g)、VTS(5.03g)和DAAM(32.28g)来制备ME；另外，当反应器温度达到50℃时，在pH调节步骤之后将含ADH(16g)的水(40g)添加到反应器中。发现经过滤分散液的测量粒度是106nm。
中间体比较实例3-制备PEM官能化乳胶和DAAM官能化乳胶的掺合物
通过混合等比例的如比较实例1和2中所描述制备的乳胶来制备掺合物。
中间体实例1-制备DAAM官能化分散剂
通过混合DI水(574.88g)、Aerosol A-102表面活性剂(87.6g)、乙酸钠(4.67g)、BMA(906.93)、MAA(558.32g)、MMP(38.48g)和DAAM(45.52g)来制备ME。
将配备有机械搅拌器、N2吹扫、温度计、冷凝器、加热套和温度控制器的1-g反应器装有DI水(952.8g)并且加热到85℃。将含Aerosol A-102表面活性剂(9.68g)的水(32g)、一部分ME(54g)和含NaPS(3.04g)的水溶液(24g)添加到反应器中。在添加之后，立即将含NaPS(2.48g)的水溶液(136g)和ME的剩余部分分别以1.57g/min和26.82g/min的速率进料到控制在83℃下的反应器中。在加料完成之后，用DI水(40g)冲洗单体乳液容器，并将反应器冷却到75℃。
然后，将含硫酸铁(0.028g)的水溶液(26g)添加到反应器中，然后均以1.3g/min添加含t-BHP(0.84g，70％水溶液)的水溶液(25g)和含IAA(0.42g)的水溶液(25g)。在所有进料完成之后，将反应器冷却到室温。当反应器温度达到50℃时，添加NH4OH以将乳胶的pH调节到7。在将反应器冷却到室温之后，过滤内容物以去除凝胶。发现经过滤分散液的测量粒度是135nm并且固体含量是21重量％。
中间体比较实例4-制备无DAAM分散剂
基本上如针对中间体实例1所描述制备分散剂，不同之处在于ME不包括DAAM。
中间体实例2-制备PEM官能化和DAAM官能化苯乙烯-丙烯酸乳胶
基本上如比较实例2中所描述制备乳胶，不同之处在于：通过混合DI水(409.1g)、Polystep A16-22表面活性剂(89.65g)、SSS(5.9g)、BA(666.46)、苯乙烯(875.36g)、AA(32.95g)、PEM(4.03g)、VTS(5.03g)和DAAM(32.28g)来制备ME。发现经过滤分散液的测量粒度是116nm。
实例1-制备70PVC涂料配制物
通过首先在低搅动情况下依序将以下成分添加到研磨设备中来制备颜料研磨体：水、中间体1DAAM官能化分散剂(DAAM-分散剂)和Foamstar A-34消泡剂。缓慢添加Omyacarb3增量剂Cellosize QP-4400H增稠剂(HEC)，并且将内容物研磨20分钟，然后添加ADH。
在搅动下将中间体实例2的乳胶添加到研磨体混合物中，然后依序添加Texanol聚结剂、ACRYSOLTM RM-2020NPR增稠剂ACRYSOLTM RM-8W增稠剂。然后将涂料混合10分钟并在测试耐擦洗性之前静置过夜。表1总结了用于制造70PVC涂料(乳胶固体含量42.33％)的成分和量
表1-70PVC涂料配制物
名称 Wt.(lbs)
研磨
水 290.03
DAAM-分散剂 31.73
Foamstar A-34消泡剂 4.11
Omyacarb 3增量剂 667.74
HEC 1.89
ADH 0.20
结束研磨 995.70
调稀
本发明实例2乳胶 228.28
Texanol聚结剂 6.05
RM-2020 22.22
RM-8W 4.73
结束调稀 261.28
总计 1256.78
ISO擦洗测量
耐擦洗性测试是根据ISO 11998执行的。在受控温度和湿度室中用20密耳陶氏(Dow)涂覆器对黑色乙烯基擦洗卡片上进行刮涂，然后干燥7天。在用使用0.25％DS-4作为擦洗介质和Scotch Brite 7448超细手垫作为擦洗垫的Pacific Scientific磨损测试仪进行擦洗测试之前，在分析天平上称重刮涂卡片。在测试之前，用软刷将擦洗介质铺展在涂层表面上，并用擦洗介质将擦洗垫饱和到最终总质量为4g。每次擦洗测试进行200次循环。在200次循环完成之后立即用水冲洗经擦洗面板。使面板干燥过夜，然后测量每个卡片的重量。然后使用重量损失、膜的干密度和擦洗面积来计算膜厚度损失，如：
膜损失＝(重量损失)/[(擦洗面积)×(膜干密度)]。
表2总结了涂料配制物的擦洗膜损失
表2-涂料配制物的擦洗膜损失
Figure BDA0002000792890000091
结果显示，在存在经DAAM官能化的分散剂的情况下，实例1乳胶的耐擦洗性显著改善。出乎意料地，与所测试乳胶中的任一种相比，PEM官能化乳胶和DAAM官能化乳胶(比较实例3)的掺合物给予显著更差的耐擦洗性。

Claims (8)

1.一种涂料组合物，其包含a)丙烯酸或苯乙烯-丙烯酸聚合物颗粒的含水分散液，以所述聚合物颗粒的重量计其经0.5到10重量％的具有酮官能团的单体的结构单元和0.05到5重量％的磷酸单体的结构单元官能化；b)以所述组合物的干重计0.1到5重量％的分散剂，并且其具有在500到50,000道尔顿范围内的Mw，并且包含i)5到90重量％的羧酸单体的结构单元；和ii)0.5到10重量％的具有酮官能团的单体的结构单元；和c)二酰肼交联剂；其中以所述组合物的重量计，聚合物颗粒的固体含量为5到60重量％；
所述涂料组合物进一步包含选自以下组成的组的一种或多种材料：增量剂、消泡剂、增稠剂、聚结剂和颜料；且具有超临界颜料体积浓度。
2.根据权利要求1所述的组合物，其中以所述分散剂的重量计，所述分散剂包含10到80重量％的所述羧酸单体的结构单元，并且进一步包含10到80重量％选自以下组成的组的一种或多种辅助单体的结构单元：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、甲基丙烯酸羟乙酯、丙烯酸羟乙酯和丙烯酸2-羟丙酯。
3.根据权利要求1或2中任一项所述的组合物，其中所述二酰肼与存在于所述分散剂和所述聚合物颗粒中的所述具有酮官能团的单体的所述结构单元的摩尔/摩尔比在0.2:1到2:1范围内。
4.根据权利要求3所述的组合物，其中所述二酰肼为己二酸二酰肼，所述具有酮官能团的单体为双丙酮丙烯酰胺，并且所述磷酸单体为甲基丙烯酸磷酸乙酯，其中己二酸二酰肼与存在于所述分散剂和所述聚合物颗粒中的双丙酮丙烯酰胺的结构单元的摩尔/摩尔比在0.3:1到1.1:1范围内。
5.根据权利要求4所述的组合物，其中所述聚合物颗粒的Tg低于25℃，并且其包含苯乙烯和丙烯酸丁酯的结构单元。
6.根据权利要求5所述的组合物，其中所述分散剂的Mw在1000到25,000道尔顿范围内，其中以所述分散剂的重量计，所述分散剂包含a)30到60重量％羧酸单体的结构单元；b)30到70重量％甲基丙烯酸丁酯的结构单元；和1到5重量％双丙酮丙烯酰胺的结构单元；其中所述羧酸单体为丙烯酸或甲基丙烯酸或其组合。
7.根据权利要求1所述的组合物，其VOC浓度小于50g/L。
8.根据权利要求1所述的组合物，其中所述分散剂进一步包含0.05到5重量％甲基丙烯酸磷酸乙酯的结构单元。
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