CN109420471B - 用于制备聚合物微球的水性分散体的方法 - Google Patents

用于制备聚合物微球的水性分散体的方法 Download PDF

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CN109420471B
CN109420471B CN201811022016.7A CN201811022016A CN109420471B CN 109420471 B CN109420471 B CN 109420471B CN 201811022016 A CN201811022016 A CN 201811022016A CN 109420471 B CN109420471 B CN 109420471B
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microspheres
weight
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distyryl
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CN109420471A (zh
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J·C·勃林
I·尔雅兹斯
P·R·哈希
P·S·马宗达
E·努吉塞
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Rohm and Haas Co
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Abstract

本发明涉及一种组合物，其包含微球的水性分散体和一类二苯乙烯基或三苯乙烯基苯酚的非离子聚环氧烷或者二苯乙烯基或三苯乙烯基苯酚的阴离子聚环氧烷盐，并且涉及一种用于制备所述组合物的方法。所述微球具有在1μm到25μm范围内的平均粒度以及低变异系数和低凝胶浓度；所述组合物可用于涂料应用，特别是在期望无光饰面的情况下。

Description

用于制备聚合物微球的水性分散体的方法
背景技术
本发明涉及一种用于制备聚合物微球的水性分散体的方法。
粒度在1.1μm到25μm范围内的聚合物微球的水性分散体可用于形成具有无光泽(低光泽度)饰面的涂料的组合物中，例如作为用于触摸感光滑的皮革的透明面漆。US 7,829,626中描述了这种分散体的制备。
制备具有优异的粒度均匀性和在20nm到500nm范围内的最小颗粒形成(细粉)的这些水性聚合物微球仍然是一个挑战。超过阈值水平的细粉的存在导致形成不可接受水平的凝胶，这需要艰难的去除，由此增加了批次时间；在许多情况下，批次必须完全丢弃。
US 2017/0058116(Ando)公开了一种用于通过悬浮聚合来产生微球的方法，其报道具有优异的分散稳定性，但需要额外的制备纤维素官能化小颗粒的步骤，所述纤维素官能化小颗粒吸附到微球的表面以提供这种稳定性。此外，Ando的实例均报道了在32％到50％范围内的变异系数。因此发现一种产生具有可接受的低产量凝胶的单分散微球并且不需要存在吸附到微球表面的小颗粒的方法是有利的。
发明内容
本发明通过在第一方面提供一种方法来解决本领域的需要，所述方法包含以下步骤：在聚合条件下且在二苯乙烯基或三苯乙烯基苯酚的非离子聚环氧烷或者二苯乙烯基或三苯乙烯基苯酚的阴离子聚环氧烷盐存在的情况下，使包含第一单烯属不饱和非离子单体的结构单元的第一微球的水性分散体与第一级单体接触以生长出所述第一微球从而形成第二微球的水性分散体，基于所述第一级单体的重量，所述第一级单体包含70到100重量百分比的第二单烯属不饱和非离子单体，其中所述第一微球的粒度在1μm到15μm范围内并且所述第二微球的粒度在1.1μm到25μm范围内。
在第二方面，本发明是一种组合物，包含a)聚合物微球的水性分散体和基于所述微球的重量0.01到5重量百分比的二苯乙烯基或三苯乙烯基苯酚的非离子聚环氧烷或者二苯乙烯基或三苯乙烯基苯酚的阴离子聚环氧烷盐：
或b)聚合物微球的水性分散体，所述聚合物微球用基于所述微球的重量0.01到5重量百分比的二苯乙烯基或三苯乙烯基苯酚的非离子聚环氧烷或者二苯乙烯基或三苯乙烯基苯酚的阴离子聚环氧烷盐的结构单元而被官能化；
其中所述聚合物微球的固体含量基于所述微球和水的重量在10到60重量百分比范围内；其中所述聚合物微球的粒度在1μm到25μm范围内并且变异系数小于25％；并且其中所述分散体包含基于所述组合物的重量小于1重量百分比的凝胶。
本发明的方法提供了一种用于通过低变异系数和低凝胶形成来控制微球尺寸的方法。
具体实施方式
在第一方面，本发明是一种方法，包含以下步骤：在聚合条件下且在二苯乙烯基或三苯乙烯基苯酚的非离子聚环氧烷或者二苯乙烯基或三苯乙烯基苯酚的阴离子聚环氧烷盐存在的情况下，使包含第一单烯属不饱和非离子单体的结构单元的第一微球的水性分散体与第一级单体接触以生长出所述第一微球从而形成第二微球的水性分散体，基于所述第一级单体的重量，所述第一级单体包含70到100重量百分比的第二单烯属不饱和非离子单体，其中所述第一微球的粒度在1μm到15μm范围内并且所述第二微球的粒度在1.1μm到25μm范围内。
如本文所使用的，术语指定单体的“结构单元”是指单体在聚合之后的剩余部分。例如，甲基丙烯酸甲酯的结构单元通过以下结构来展示：
Figure BDA0001786823400000021
其中点线表示结构单元与微球的连接点。
提及的微球的粒度是指如下文所述通过盘式离心光沉降测量仪测得的中值重均(D50)粒度。提及的乳胶颗粒的粒度是指通过Brookhaven BI 90 Plus粒度分析仪测得的平均粒度。
第一微球优选包含90到100重量百分比的第一单烯属不饱和非离子单体的结构单元，其实例包括：丙烯酸酯，如丙烯酸乙酯、丙烯酸丁酯和丙烯酸2-乙基己酯；甲基丙烯酸酯，如甲基丙烯酸甲酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸乙酰乙酰氧乙酯和甲基丙烯酸脲基酯；丙烯腈；丙烯酰胺类，如丙烯酰胺和双丙酮丙烯酰胺；苯乙烯；和乙烯基酯，如乙酸乙烯酯。尽管第一微球可能包括如甲基丙烯酸或丙烯酸等羧酸单体的结构单元，但优选第一微球包含基本上不存在羧酸单体的结构单元。如本文所使用的，基本上不存在羧酸单体的结构单元意味着基于微球的重量，羧酸单体的结构单元小于5重量百分比、优选小于3重量百分比、更优选小于1重量百分比并且最优选小于0.2重量百分比。
第一微球更优选包含丙烯酸酯或甲基丙烯酸酯或丙烯酸酯和甲基丙烯酸酯的组合的结构单元。
二苯乙烯基或三苯乙烯基苯酚的非离子聚环氧烷或阴离子聚环氧烷盐由具有式I的化合物表示：
Figure BDA0001786823400000031
其中每个R独立地是C1-C4烷基；R1是H、1-苯乙基-(R)p、CH2-CR＝CH2或CH＝CHCH3；每个R2独立地是H、烯丙基、甲基、丙烯酸酯基、甲基丙烯酸酯基或-CH2CHR3OX；每个R3独立地是H、甲基或乙基；m是0到5；n是6到40；p是0、1或2；O-X是羟基、甲氧基、硫酸酯基或磷酸酯基。优选地，R1是1-苯乙基-(R)n；R2优选是H、CH3或烯丙基、m优选是0、1或2；n是10到20；p是0；并且O-X是硫酸酯基或磷酸酯基。更优选的三苯乙烯基苯酚的聚环氧乙烷盐由式II的化合物代表：
Figure BDA0001786823400000041
其中X是-SO3H、-SO3Y、-H2PO3、-HPO3Y或-PO3Y2，其中Y是Li+、Na+、K+或NH4 +。可商购的具有式II的化合物的实例是聚芳基苯基醚硫酸盐的Solvay Soprophor 4D/384铵盐。
二苯乙烯基苯酚或三苯乙烯基苯酚的另一种优选的环氧乙烷盐由具有式III的化合物表示，其中m是非零的。
Figure BDA0001786823400000042
其中n优选是12到18。具有式III的化合物的商业实例是E-Sperse RS-1684反应性表面活性剂。
二苯乙烯基苯酚的聚环氧乙烷盐的另一个实例由具有式IV的化合物表示：
Figure BDA0001786823400000051
具有式IV的化合物的商业实例是Hitenol AR-1025反应性表面活性剂。
结构I(m＝0)的化合物的亚类可以通过使二苯乙烯基或三苯乙烯基苯酚与聚环氧烷(环氧乙烷、1，2-环氧丙烷或1，2-环氧丁烷)在碱金属或碱土金属氢氧化物、碳酸盐或碳酸氢盐，或碱金属氢化物等碱存在的情况下反应来制备；这个中间体然后可以中和成相应的二醇，用卤代甲烷甲氧基化，用磺酰氯磺化或用多磷酸磷酸化。具有式III的化合物可以以相同的方式制备，除了二苯乙烯基或三苯乙烯基苯酚在碱存在的情况下首先与如表氯醇等表卤代醇反应以形成二苯乙烯基或三苯乙烯基苯酚的相应单缩水甘油醚，然后与烯化氧反应。
如本文所描述的，第一微球有利地由重均分子量(Mw)范围为800g/mol、优选1000g/mol到20,000g/mol、优选到10,000g/mol且最优选到5000g/mol的低聚种子的水性分散体制备，所述重均分子量如使用聚苯乙烯标准物通过尺寸排阻色谱法确定的。如本文所描述的，低聚种子的平均直径范围为200nm、更优选400nm、最优选600nm到8000nm、优选到5000nm、更优选到1500nm、最优选到1000nm，如通过盘式离心光沉降测量法(DCP)确定的。低聚种子含有如烷基硫醇等链转移剂的结构单元，其实例包括正十二烷基硫醇、1-己硫醇、1-辛硫醇和2-丁硫醇。
有利地，低聚种子在疏水引发剂存在的情况下以任何顺序与第一单烯属不饱和单体接触，以将引发剂转运到所述种子或用单体溶胀的种子中。如本文所使用的，疏水引发剂是指水溶解度在5ppm、优选10ppm到10,000ppm、优选到1000ppm且更优选到100ppm范围内的引发剂。合适的疏水引发剂的实例包括如过氧基-2-乙基己酸叔戊酯(在20℃时水溶解度＝17.6mg/L)或过氧基-2-乙基己酸叔丁酯(在20℃时水溶解度＝46mg/L)。溶胀程度(种子生长)可以通过单体与种子之比来控制。
从低聚种子形成微球提供了控制微球粒度分布的有效方法。优选地，如通过DCP确定的第一微球和第二微球的变异系数小于25％，更优选小于20％，更优选小于15％且最优选小于10％。优选地，基于水性分散体的重量，在制备第二微球的水性分散体的过程中形成的凝胶的浓度优选小于0.5重量百分比、更优选小于0.2重量百分比、更优选小于0.1重量百分比且最优选小于0.05重量百分比。具有低变异系数的微球的分散体最终导致涂料在最终用途应用中具有可靠且可再现的性能。相反，变异系数大于30％的微球使涂料具有不可靠且不可预测的性能。从质量控制的观点来看，变异系数较少地通过本发明的分散体来实现是有利的。制备具有低凝胶形成的微球分散体以减少用于过滤的时间损失和产品浪费也是有利的。
优选地，第一微球的粒度在2.5μm、更优选3.0μm、优选到12μm、更优选到10μm的范围内。
在本发明的优选方法中，第一微球的水性分散体在聚合条件下且在以下项的存在下接触：1)乳化表面活性剂，如磷酸盐或烷基苯磺酸盐或硫酸盐；以及2)0.05重量百分比、优选0.1重量百分比且更优选0.2重量百分比到5重量％、优选到3重量百分比、更优选到2重量百分比且最优选到1重量百分比的二苯乙烯基或三苯乙烯基苯酚的非离子聚环氧烷或阴离子聚环氧烷盐；以及3)第一级单体，基于所述第一级单体的重量，所述第一级单体包含80重量百分比、优选90重量百分比到100重量百分比、更优选到98重量百分比的第二单烯属不饱和非离子单体。第一微球的体积增加(生长出)以形成粒度在1.1μm且优选2.5μm、优选3.5μm到25μm、更优选到20μm且最优选到15μm范围内的第二微球的水性分散体。
第一级单体优选进一步包含基于第一级单体的重量，优选浓度范围为0.1重量百分比、更优选1重量百分比且最优选2重量百分比到15重量百分比、更优选到10重量百分比且最优选到8重量百分比的多烯属不饱和非离子单体。合适的多烯属不饱和非离子单体的实例包括甲基丙烯酸烯丙酯、丙烯酸烯丙酯、二乙烯基苯、三羟甲基丙烷三甲基丙烯酸酯、三羟甲基丙烷三丙烯酸酯、丁二醇(1，3)二甲基丙烯酸酯、丁二醇(1，3)二丙烯酸酯、乙二醇二甲基丙烯酸酯和乙二醇二丙烯酸酯。在期望对第二微球进行进一步分级的情况下，包含这些多烯属不饱和非离子单体是特别优选的。
第一级单体优选包含基本上不存在羧酸单体的结构单元。
第二微球优选包含90重量百分比到98重量百分比的第二单烯属不饱和非离子单体的结构单元，所述重量百分比可以与第一单烯属不饱和非离子单体相同或不同。应理解，“单体”是指一种或多种单体。
优选第一微球的水性分散体在聚合条件下与具有式II的化合物的盐或过量的具有式III的化合物的盐接触，使得所得的第二微球的分散体优选包含具有式II的化合物盐或未反应的具有式III的化合物的盐。如果期望对第二微球进行进一步分级，则具有式II或式III的化合物的盐的存在是特别有利的。例如，可能期望的是，如通过Fox方程计算的，制备Tg小于25℃的第二微球的分散体，然后在聚合条件下用具有式II或式III的化合物的盐和另外的单烯属不饱和非离子单体(第二级单烯属不饱和非离子单体)对第二微球进行进一步分级以产生具有Tg小于25℃的域和Tg大于50℃的域的第三微球的分散体，所述另外的单烯属不饱和非离子单体可以与第一级单烯属不饱和非离子单体相同或不同。这些域可以形成例如核-壳形态或所谓的“巧克力曲奇饼干”形态。有利地使用可溶于水的引发剂/氧化还原对如叔丁基氢过氧化物和异抗坏血酸(t-BHP/IAA)来形成梯度核-壳形态。
优选地，用于制备第三微球的水性分散体的聚合步骤在至少3、更优选至少4、更优选至少5且最优选至少6到优选12、更优选到10且最优选到8的pH下实施。
另外的具有式I的化合物，特别是具有式I的化合物的盐，可以在第二微球的进一步分级中加入，优选在使用引发剂/偶合剂的情况下在期望的pH范围内。
在第二方面，本发明是一种组合物，包含聚合物微球的水性分散体和基于微球的重量0.01重量百分比、优选0.05重量百分比、更优选0.1重量百分比、最优选0.2重量百分比到5重量百分比、优选到3重量百分比、更优选到2重量百分比且最优选到1重量百分比的二苯乙烯基或三苯乙烯基苯酚的非离子聚环氧烷或二苯乙烯基或三苯乙烯基苯酚的阴离子聚环氧烷盐，优选具有式I的化合物或其盐；或一种组合物，包含聚合物微球的水性分散体，优选具有式I的化合物或其盐，所述聚合物微球用基于微球的重量0.01重量百分比、优选0.05重量百分比、更优选0.1重量百分比且最优选0.2重量百分比到5重量百分比、优选3重量百分比、更优选2重量百分比且最优选1重量百分比的二苯乙烯基或三苯乙烯基苯酚的非离子聚环氧烷或二苯乙烯基或三苯乙烯基苯酚的阴离子聚环氧烷盐而被官能化；
其中聚合物微球的固体含量基于微球和水的重量在10重量百分比、优选20重量百分比、更优选25重量百分比且最优选30重量百分比到60重量百分比、更优选50重量百分比且最优选45重量百分比的范围内；其中聚合物微球的粒度在1μm到25μm范围内并且变异系数小于25％、优选小于15％且更优选小于10％；其中分散体包含基于组合物的重量小于1重量百分比、优选小于0.5重量百分比、更优选小于0.2重量百分比、更优选小于0.1重量百分比且最优选小于0.05重量百分比的凝胶，如实例部分中描述的那样计算的。
微球的水性分散体可用于涂料应用，特别是在期望无光饰面的情况下。这种应用的实例包括皮革、塑料包装、木材、建筑涂料和工业涂料。微球的水性分散体可以任选地包括一种或多种附加组分，如粘合剂、增稠剂、颜料、杀生物剂、溶剂、分散剂和增量剂。
已经发现，可以以低变异系数和低凝胶形成来制备微球的水性分散体。进一步发现，这样的微球有利地包含基本不存在粒度在20nm到500nm范围内的吸附胶乳颗粒，更具体地说，基本不存在用纤维素官能化的吸附胶乳颗粒。如本文所用，“基本上不存在”是指基于微球的重量小于0.3重量百分比、优选小于0.1重量百分比、更优选小于0.05重量百分比且最优选0重量百分比的吸附到微球的胶乳颗粒。
实例
丙烯酸低聚物种子的分子量确定
将丙烯酸低聚物种子(0.1g)的分散体溶解在四氢呋喃(THF，8g，HPLC级)中，然后通过0.45μm PTFE过滤器进行过滤。凝胶渗透色谱法(GPC)分离在配备有安捷伦(Agilent)1100型等度泵、真空脱气机、可变注射体积自动进样器和安捷伦1100HPLC G1362A折射率检测器的液相色谱仪上进行。用安捷伦化学工作站B.04.03版和安捷伦GPC-Addon B.01.01版来处理数据。使用由两根PLgel Mixed D柱(300×7.5mm ID，5μm)和保护柱(50×7.5mm ID，5μm)构成的GPC柱组以1mL/分钟的流速使用THF作为洗脱液来进行GPC分离。用1阶拟合校准曲线来拟合十个聚苯乙烯标准物。标准物的重均分子量(Mw)如下：630；1,370；2,930；4,900；10,190；22,210；50,550；111,400；214,700；和363,600。使用折射率(RI)检测器来收集数据。
用于丙烯酸低聚物种子和微球的DCP粒度设定法
使用经由蔗糖梯度通过离心和沉降来分离模式的盘式离心光沉降测量仪(DCP，路易斯安那州普雷里维尔CPS Instruments公司)来测量粒度和分布。通过将1到2滴低聚物种子分散体加入到10mL含有0.1％月桂基硫酸钠的去离子(DI)水中、然后将0.1mL样本注入填充有15g/mL蔗糖梯度的旋转盘中来制备样本。对于低聚物种子，使用以10,000rpm旋转的0-4％蔗糖梯度盘，并且在注入样本之前注入596-nm聚苯乙烯校准标准物。对于微球，使用以3,000rpm旋转的2-8％蔗糖梯度盘，并且在注入样本之前注入9-μm聚苯乙烯校准标准物。使用仪器的算法来计算中值重均(D50)粒度和变异系数(CV)。
用于测量凝胶形成的方法
将预称重的样本(200g到4,000g)通过20/100/325目堆叠筛网(从顶部到底部按照递减孔径)倒入；每个筛网用大量水进行洗涤并分别收集凝胶并在150℃下干燥30分钟。凝胶数据计算为每个筛网中收集的总干凝胶与总样本尺寸的重量比：
凝胶％＝干凝胶/总样本×100；凝胶ppm＝干凝胶/总样本×106。
实例1-丙烯酸珠的水性分散体的制备
基本上如US 8,686,096实例1和5(第19和20栏)中所描述的制备丙烯酸低聚物种子(33％固体，67丙烯酸丁酯/18正十二烷基硫醇/14.8甲基丙烯酸甲酯/0.2甲基丙烯酸)的水性分散体，其中如通过DCP确定的，中值重均粒度(D50)为885nm且变异系数为5％，并且重均分子量为2532g/mol。此丙烯酸种子用于制备本文所描述的所有实例和比较实例的微球。
通过在单独的小瓶中组合去离子水(4.9g)、Rhodacal DS-4支链烷基苯磺酸盐(DS-4，0.21g，22.5％水溶液)、4-羟基-2，2，6，6-四甲基哌啶(4-羟基TEMPO，0.4g)、过氧基-2-乙基己酸叔戊酯(TAPEH，5.42g，98％活性)，然后用匀质器以15,000rpm乳化10分钟来制备引发剂乳液。然后在单独的小瓶中将引发剂乳液加入到丙烯酸低聚物种子的分散体(4.2g，32％固体)中并混合60分钟。在第一烧瓶中组合去离子水(109.5g)、聚芳基苯基醚硫酸盐的Solvay Soprophor 4D/384铵盐(4D/384，5.25g，25％活性)、DS-4(4.13g，22.5％溶液)、4-羟基TEMPO(0.2g)、丙烯酸正丁酯(BA，252.7g)和甲基丙烯酸烯丙酯(ALMA，10.5g)(一次性ME(shot ME))。在单独的烧瓶中，将去离子水(1575g)加入到装有搅拌器、冷凝器和温度探头的5L圆底烧瓶(反应器)中。将反应器加热到70℃，此后将引发剂和低聚物种子混合物加入到反应器中，并在15分钟内将一次性ME进料到反应器中。在30分钟的诱导期后，所得放热导致反应器温度升到80℃。如通过DCP测得的这个步骤中形成的微球的粒度为4.8μm。
将第一单体乳液(ME1，通过组合去离子水(328.5g)、4D/384(15.75g，25％活性)、DS-4(12.38g，22.5％溶液)、4-羟基TEMPO(0.6g)、BA(758.3g)和ALMA(31.6g)制备)在55分钟内进料到反应器中。保持20分钟后，在3分钟内将NH4OH(0.75g，28％水溶液)加入到反应器中。如通过DCP测得的这个步骤中形成的微球的粒度为8.0μm。
将反应器温度冷却到并保持在75℃，此后将FeSO4·7H2O(11g，0.15％水溶液)和EDTA四钠盐(2g，1％水溶液)混合并加入到反应器中。通过组合去离子水(88g)、DS-4(3.2g，22.5％溶液)、4D/384(5.25g，25％活性)、甲基丙烯酸甲酯(MMA，251g)和丙烯酸乙酯(EA，10.5g)来在单独的烧瓶中制备第二单体乳液(ME2)。在45分钟内将ME2、叔丁基过氧化氢(t-BHP，100g水中1.44g(70％水溶液))和异抗坏血酸(IAA，100g水中1.05g)进料到反应器中。然后通过在20分钟内将t-BHP溶液(40g水中2.54g(70％水溶液))和IAA(40g水中1.28g)进料到反应器中来追踪残余单体。通过45μm筛网来过滤所产生的分散体；收集留在筛网上的凝结物并进行干燥(178ppm)。分析滤液的固体百分比(33.7％)、变异系数(8.4％)和粒度(8.1μm，如通过DCP测得的)。
实例2-用E-Sperse RS-1684反应性表面活性剂来制备丙烯酸珠的水性分散体
除了使用E-Sperse RS-1684反应性表面活性剂(RS-1684)代替一次性ME(RS-1684，13.12g，30％活性)、ME1(RS-1684，4.38g，30％活性)和ME2(RS-1684，4.4g，30％活性)中的4D/384外，基本上如实例1所描述的实施所述方法。如通过DCP测得的，微球的粒度在一次性ME聚合步骤之后为4.7μm、在ME1聚合步骤之后为7.9μm并且在ME2聚合步骤之后为8.2μm。固体百分比为32.7％，ME2结束时形成的微球的变异系数为8.8％，并且凝胶形成为50ppm。
比较实例1-在没有二苯乙烯基或三苯乙烯基苯酚表面活性剂的情况下制备丙烯酸珠的水性分散体
通过组合去离子水(109.5g)、DS-4(4.13g，22.5％溶液)、BA(251.5g)和ALMA(10.5g)在单独的烧瓶中制备一次性单体乳液。向装有搅拌器、冷凝器和温度探头的5L圆底烧瓶(反应器)中加入去离子水(1575g)。将反应器加热到70℃，此后将丙烯酸低聚物种子混合物加入到反应器中，随后在15分钟内加入ME1。保持30分钟后，一次性加入引发剂乳液-通过在单独的小瓶中组合去离子水(4.9g)、DS-4(0.21g，22.5％水溶液)4-羟基TEMPO(0.4g)、TBPEH(5.54g，98％活性)、然后在15,000rpm下用匀质器乳化10分钟制备的。在30分钟的诱导期后，所得放热导致反应器温度升到80℃。存在大量细粉和凝胶(颗粒在50nm到500nm范围内)导致不可靠的微球粒度确定。
然后在55分钟内将第一单体乳液(ME1，通过组合去离子水(328.5g)、DS-4(12.38g，22.5％溶液)、BA(754.5g)和ALMA(31.5g))进料到反应器中。大量细粉和凝胶的存在再次导致不可靠的微球粒度确定。
将反应器温度冷却到并保持在75℃，此后将FeSO4·7H2O(11g，0.15％水溶液)和四乙酸四钠盐(EDTA四钠盐，2g，1％水溶液)混合并加入到反应器中。通过组合去离子水(90g)、DS-4(3.2g，22.5％溶液)、MMA(252g)和EA(10.9g)在单独的烧瓶中制备第二单体乳液(ME2)。在45分钟内将ME2、t-BHP(100g水中1.44g(70％水溶液))和IAA(100g水中1.05g)进料到反应器中。然后通过在20分钟内将t-BHP溶液(40g水中2.54g(70％水溶液))和IAA(40g水中1.28g)进料到反应器中来追踪残余单体。随后的分散体通过45μm筛网进行过滤；收集留在筛网上的凝结物并进行干燥(2.0％)。如通过DCP测得的，分析滤液的固体百分比(32.2％)、变异系数(7.9％)和粒度(5.3μm)。
在用于制备微球的过程中存在4D/384或RS-1684表面活性剂导致形成具有低凝胶形成和低变异系数的组合的8-μm微球。相反，方法描述的不含二苯乙烯基或三苯乙烯基苯酚的比较实例导致高凝胶形成。

Claims (9)

1.一种用于制备聚合物微球的水性分散体的方法，其包含以下步骤：在聚合条件下且在二苯乙烯基或三苯乙烯基苯酚的非离子聚环氧烷或者二苯乙烯基或三苯乙烯基苯酚的阴离子聚环氧烷盐存在的情况下，使包含第一单烯属不饱和非离子单体的结构单元的第一微球的水性分散体与第一级单体接触，以使所述第一微球生长，从而形成第二微球的水性分散体，基于所述第一级单体的重量，所述第一级单体包含70到100重量百分比的第二单烯属不饱和非离子单体，其中所述第一微球的粒度在1 μm到15 μm范围内，并且所述第二微球的粒度在1.1 μm到25 μm范围内。
2.根据权利要求1所述的方法，其中所述第一微球的粒度在2.5 μm到12 μm范围内且所述第二微球的粒度在4.5 μm到20 μm范围内；并且其中所述二苯乙烯基或三苯乙烯基苯酚的非离子聚环氧烷或者二苯乙烯基或三苯乙烯基苯酚的阴离子聚环氧烷盐由具有式I的化合物表示：
Figure DEST_PATH_IMAGE001
其中每个R独立地是C1-C4烷基；R1是H、1-苯乙基-(R)p、CH2CR=CH2或CH=CHCH3；每个R2独立地是H、烯丙基、甲基、丙烯酸酯基、甲基丙烯酸酯基或-CH2CHR3OX；每个R3独立地是H、甲基或乙基；m是0到5；n是6到40；p是0、1或2；O-X是羟基、甲氧基、硫酸酯基或磷酸酯基。
3.根据权利要求2所述的方法，其中所述具有式I的化合物由具有式II、式III或式IV的化合物表示：
Figure 832211DEST_PATH_IMAGE002
其中n是10到20，X是-SO3H、-SO3Y、-H2PO3、-HPO3Y或-PO3Y2，其中Y是Li+、Na+、K+或NH4 +；或者
Figure DEST_PATH_IMAGE003
其中n是12到18；或者
Figure 811668DEST_PATH_IMAGE004
4.根据权利要求3所述的方法，其中所述第一微球的粒度在2.5 μm到12 μm范围内且所述第二微球的粒度在4.5 μm到20 μm范围内；其中基于所述第一级单体的重量，所述二苯乙烯基或三苯乙烯基苯酚的非离子聚环氧烷或二苯乙烯基或三苯乙烯基苯酚的阴离子聚环氧烷盐的浓度在0.2到1重量百分比范围内。
5.根据权利要求4所述的方法，其中所述第一微球的水性分散体在聚合下与另外的第一级单体进一步接触，所述另外的第一级单体是基于所述第一级单体的重量，浓度在0.1到15重量百分比范围内的多烯属不饱和非离子单体，其中所述第二微球的Tg小于25℃。
6.根据权利要求5所述的方法，其中所述第二微球在聚合条件下，用所述具有式II或式III的化合物的盐和第二级单烯属不饱和非离子单体进一步分级以形成具有Tg小于25℃的域和Tg大于50℃的域的第三微球的分散体。
7.根据权利要求1到6中任一项所述的方法，其中所述第一微球通过以下制备：a）在疏水引发剂存在下使低聚物种子的水性分散体与单体接触以将所述引发剂转运到所述种子中；以及b）使所述单体聚合；其中所述低聚物种子具有在800到20,000 g/mol范围内的重均分子量和在200 nm到8000 nm范围内的平均直径。
8.一种组合物，其包含a）聚合物微球的水性分散体和基于所述微球的重量0.01到5重量百分比的二苯乙烯基或三苯乙烯基苯酚的非离子聚环氧烷或者二苯乙烯基或三苯乙烯基苯酚的阴离子聚环氧烷盐，所述二苯乙烯基或三苯乙烯基苯酚的非离子聚环氧烷或者二苯乙烯基或三苯乙烯基苯酚的阴离子聚环氧烷盐由具有式I的化合物表示：
Figure DEST_PATH_IMAGE005
或b）聚合物微球的水性分散体，所述聚合物微球用基于所述微球的重量0.01到5重量百分比的所述具有式I的化合物的结构单元官能化，所述聚合物微球的水性分散体通过包括如下步骤的方法进行制备：在聚合条件下且在二苯乙烯基或三苯乙烯基苯酚的非离子聚环氧烷或者二苯乙烯基或三苯乙烯基苯酚的阴离子聚环氧烷盐存在的情况下，使包含第一单烯属不饱和非离子单体的结构单元的第一微球的水性分散体与第一级单体接触，以使所述第一微球生长，从而形成所述聚合物微球的水性分散体，基于所述第一级单体的重量，所述第一级单体包含70到100重量百分比的第二单烯属不饱和非离子单体；
其中每个R独立地是C1-C4烷基；R1是H、1-苯乙基-(R)p、CH2-CR=CH2或CH=CHCH3；每个R2独立地是H、烯丙基、甲基、丙烯酸酯基、甲基丙烯酸酯基或-CH2CHR3OX；每个R3独立地是H、甲基或乙基；m是0到5；n是6到40；p是0、1或2；O-X是羟基、甲氧基、硫酸酯基或磷酸酯基；
其中所述聚合物微球的固体含量基于所述微球和水的重量在10到60重量百分比范围内；其中所述聚合物微球的粒度在1 μm到25 μm范围内并且变异系数小于25%；并且其中所述分散体包含基于所述组合物的重量小于1重量百分比的凝胶。
9.根据权利要求8所述的组合物，其中所述分散体包含基于所述组合物的重量小于0.2重量百分比的凝胶并且所述微球的变异系数小于15%。
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