CN107857842B - 氧化还原引发的双形态乳胶的现场制备 - Google Patents

氧化还原引发的双形态乳胶的现场制备 Download PDF

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CN107857842B
CN107857842B CN201710826509.5A CN201710826509A CN107857842B CN 107857842 B CN107857842 B CN 107857842B CN 201710826509 A CN201710826509 A CN 201710826509A CN 107857842 B CN107857842 B CN 107857842B
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J·C·勃林
A·S·布朗奈尔
W·高
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Rohm and Haas Co
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Abstract

本发明涉及氧化还原引发的具有凸出磷酸内核的第一聚合物粒子和不具有凸出内核的第二聚合物粒子的双形态水性分散液的现场制备。所述方法提供一种更有效制备用于有色涂料配制物的组合物的方式。

Description

氧化还原引发的双形态乳胶的现场制备
本发明涉及氧化还原引发的具有两种不同形态的聚合物粒子的水性分散液，即双形态乳胶的现场制备。这种乳胶适用作涂料配制品中的粘合剂。
二氧化钛(TiO2)是许多有色涂料配制品中的昂贵组分。当TiO2粒子在膜形成和干燥时彼此靠得太近(它们往往会如此)时，TiO2作为遮盖颜料的功效降低。TiO2的间隔和其所得功效可以使用吸附性乳液聚合物改良。举例来说，美国专利第7,179,531号(布朗(Brown)等人)公开了一种多级聚合物粒子的分散液，所述多级聚合物粒子的特征在于每个粒子的相对较小的内核部分从相对较大的外壳部分中凸出，其中内核部分优先用TiO2吸附基团、通常是磷酸官能化基团官能化。这些所谓的“橡果”粒子被公开为适用于制备提供遮盖力改良的干燥涂层的TiO2-聚合物复合粒子。
最近，US 2015/0005446A1(博林(Bohling)等人)展示了一种将磷酸官能团优先集中于橡果粒子的凸出内核部分的方式，从而减少可能因为无意中磷酸并入外壳部分的表面而发生的絮凝。
US 2015/0011695(博林等人)描述了一种双模态吸附乳胶，其被设计成增加固体含量同时保留用吸附性聚合物粒子技术所实现的遮盖优势。
TiO2吸附性聚合物粒子可改良遮盖功效这一发现代表着涂料技术的重大进展；然而，由于当前方法需要TiO2粒子与远比使粒子间的间隔达到最大所需要更多的吸附性聚合物粒子组合，所以相对较便宜的调漆粘合剂(letdown binder)的使用灵活性受到限制。因此，在涂料组合物领域中有利的是找到一种用于优化颜料粒子间的间隔并且同时提供“拨入(dial in)”所要量的非吸附性调漆粘合剂的方式的方式。
发明内容
本发明通过提供现场制备氧化还原引发的聚合物粒子的双形态水性分散液的方法，提供涂料组合物领域的发展，所述方法包含以下步骤：
a)将具有在40nm到85nm范围内的体积平均粒度的磷酸官能化的丙烯酸类第一种子聚合物粒子的水性分散液与实质上不存在磷酸官能团并且具有在20nm到80nm范围内的体积平均粒度的丙烯酸类第二种子聚合物粒子的水性分散液混合在一起；
b)使单体与所述第一和第二种子聚合物粒子的水性分散液在氧化还原引发的乳液聚合条件下接触，形成1)具有磷酸官能化的凸出内核的聚合物粒子和2)不具有凸出内核的聚合物粒子的分散液；以及
其中具有磷酸官能化的凸出内核的粒子与不具有凸出内核的粒子的重量:重量比在25:75到75:25范围内。
本发明提供一种有效控制有色涂料配制物的TiO2吸附性及非吸附性聚合物粒子的相对量的单步途径。
附图简要说明
为了更完整地理解本发明的内容及其优点，下面结合附图提供以下简要说明和详细说明。
图1是具有磷酸官能化的凸出内核的聚合物粒子和不具有凸出内核的聚合物粒子的示意图。
具体实施方式
本发明提供一种现场制备氧化还原引发的聚合物粒子的双形态水性分散液的方法，其包含以下步骤：
a)将具有在40nm到85nm范围内的体积平均粒度的磷酸官能化的丙烯酸类第一种子聚合物粒子的水性分散液与实质上不存在磷酸官能团并且具有在20nm到80nm范围内的体积平均粒度的丙烯酸类第二种子聚合物粒子的水性分散液混合在一起；
b)使单体与所述第一和第二种子聚合物粒子的水性分散液在氧化还原引发的乳液聚合条件下接触，形成1)具有磷酸官能化的凸出内核的聚合物粒子和2)不具有凸出内核的聚合物粒子的分散液；以及
其中具有磷酸官能化的凸出内核的粒子与不具有凸出内核的粒子的重量:重量比在25:75到75:25范围内。
如本文所用，术语“丙烯酸类”是指以聚合物粒子的重量计，包含至少30重量％的一种或多种甲基丙烯酸酯单体(例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸环己酯和甲基丙烯酸异冰片酯)和/或一种或多种丙烯酸酯单体(例如丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-丙基庚酯和丙烯酸2-乙基己酯)的结构单元的聚合物粒子(包括种子聚合物粒子)。丙烯酸类聚合物还可以包括其它非丙烯酸酯或非甲基丙烯酸酯单体(例如苯乙烯)的结构单元。
如本文所用，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，甲基丙烯酸甲酯的结构单元说明如下：
Figure GDA0001506492780000031
其中虚线表示结构单元附接到聚合物主链的点。
第一种子聚合物粒子的水性分散液宜通过单体的乳液聚合制备，所述单体包含a)甲基丙烯酸甲酯或苯乙烯或其组合，优选地甲基丙烯酸甲酯；b)一种或多种选自由丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-丙基庚酯和丙烯酸2-乙基己酯组成的群组的丙烯酸酯；以及c)磷酸单体或其盐。适合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或经所述基团取代。优选的磷酸二氢酯是丙烯酸羟烷酯或甲基丙烯酸羟烷酯的磷酸酯，包括甲基丙烯酸磷酸乙酯(PEM)和甲基丙烯酸磷酸丙酯。PEM是尤其优选的磷酸单体，由以下结构表示：
Figure GDA0001506492780000041
其中R是H或
Figure GDA0001506492780000042
优选地在第一种子聚合物粒子的乳液聚合中包括羧酸单体或硫酸单体或其盐或其组合。适合的羧酸单体的实例包括丙烯酸、甲基丙烯酸和衣康酸(itaconic acid)和其盐；适合的硫酸单体的实例包括甲基丙烯酸磺乙酯、甲基丙烯酸磺丙酯、苯乙烯磺酸、乙烯基磺酸和2-丙烯酰胺基-2-甲基丙磺酸和其盐。
更优选地，在第一种子聚合物粒子的乳液聚合中包括多烯系不饱和单体，例如甲基丙烯酸烯丙酯或二乙烯基苯。
优选地，以第一种子聚合物粒子的重量计，第一种子聚合物粒子包含：a)2重量％到12重量％的磷酸单体或其盐的结构单元；b)0.5重量％到20重量％的羧酸单体或硫酸单体或其盐或其组合的结构单元；c)0.1重量％到30重量％的多烯系不饱和单体的结构单元；以及d)足够浓度的一种或多种可聚合烯系不饱和本体单体的结构单元，使得如通过福克斯方程式(Fox equation)所计算，预先形成的聚合物粒子的Tg在从-50℃、优选地从-40℃、更优选地从-20℃；到75℃、优选地到30℃、并且更优选地到20℃的范围内。
更优选地，以第一种子聚合物粒子的重量计，第一种子聚合物粒子包含∶a)从3重量％到8重量％的PEM或其盐的结构单元；b)从1重量％到5重量％的丙烯酸或甲基丙烯酸或其盐的结构单元；c)从0.2重量％到5重量％的甲基丙烯酸烯丙酯的结构单元；d)从50重量％到65重量％的丙烯酸丁酯的结构单元；以及e)从25重量％到45重量％的甲基丙烯酸甲酯的结构单元。
如通过BI-90Plus粒度分析仪所测量，第一种子聚合物粒子的体积平均粒度是从40nm、优选地从45nm、更优选地从55nm、并且最优选地从60nm，到85nm、优选地到80nm。
第二种子聚合物粒子的水性分散液宜通过以下各者的乳液聚合，例如通过热或氧化还原引发的乳液聚合，优选通过氧化还原引发的乳液聚合制备：a)甲基丙烯酸甲酯或苯乙烯或其组合，优选地甲基丙烯酸甲酯；b)一种或多种选自由丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-丙基庚酯和丙烯酸2-乙基己酯组成的群组的丙烯酸酯；以及c)实质上不存在磷酸单体。
如本文所用，术语“实质上不存在磷酸单体”是指以第二种子聚合物粒子的重量计，磷酸单体不超过1重量％、优选地不超过0.5重量％、更优选地不超过0.1重量％、并且最优选地0重量％。
优选地，在第二种子聚合物粒子的乳液聚合中包括羧酸单体或硫酸单体或其盐或其组合。
优选地，以单体的重量计，所述单体包含：a)甲基丙烯酸甲酯或苯乙烯或其组合；b)一种或多种选自由丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-丙基庚酯和丙烯酸2-乙基己酯组成的群组的丙烯酸酯单体；以及c)实质上不存在磷酸单体，以单体的重量计。
更优选地，单体包含∶a)从40重量％、更优选地从45重量％，到60重量％、更优选地到55重量％丙烯酸丁酯或丙烯酸2-乙基己酯或其组合；b)从40重量％、更优选地从45重量％，到60重量％、更优选地到55重量％甲基丙烯酸甲酯或苯乙烯或其组合；c)从0.1重量％到5重量％丙烯酸或甲基丙烯酸或4-乙烯基苯磺酸钠或2-丙烯酰胺基-2-甲基丙磺酸或其盐或其组合；e)从0.1重量％到5重量％脲基甲基丙烯酸酯；以及f)0重量％磷酸单体。
如通过BI-90Plus粒度分析仪所测量，第二种子聚合物粒子的体积平均粒度是从20nm、优选地从25nm、更优选地从30nm，到80nm、优选地到70nm、并且更优选地到50nm。
第一和第二种子聚合物粒子的水性分散液以优选地从1:2、更优选地从1:1，到优选地10:1、更优选地5:1、并且最优选地到3:1的第一:第二种子聚合物粒子重量:重量比混合在一起。然后使所述混合物与单体、优选地单体的水性乳液在氧化还原引发的乳液聚合条件下接触，形成具有磷酸官能化的凸出内核的聚合物粒子和不具有凸出内核的聚合物粒子。
优选地，所述单体具有与第二种子聚合物粒子相同的单体概况，这意味着用于制备第二种子聚合物的单体优选地与馈入反应器的单体相同并且比例相同。凸出的聚合物粒子和不具有凸出内核的粒子的随后形成的外壳具有实质上相同的组成：当单体的单体概况与第二种子聚合物相同时，外壳组成是相同的；并且当所述概况不同时，外壳组成大致相同。图1中，附图标记1表示实质上相同的组成，2表示磷酸官能化的凸出内核。
在最优选的制备双形态组合物的方法中，使单体乳液的一部分(单体乳液中总单体的约1重量％到10重量％)在氧化还原引发的乳液聚合条件下聚合，形成第二种子聚合物粒子的水性分散液。优选的氧化还原对包括异抗坏血酸和疏水性有机氢过氧化物，例如叔戊基氢过氧化物或叔丁基氢过氧化物。在现场聚合过程期间反应还优选包括少于0.1重量百分比，更优选少于0.05重量百分比，并且最优选0重量百分比过硫酸盐引发剂。
或者，第一和第二种子聚合物粒子可以在单独的反应器中独立地形成。在任一情况下，第一和第二种子必须具有不同的组成以形成双形态乳胶。然后合并第一和第二种子聚合物粒子的水性分散液，接着添加其余部分的单体乳液，接着进行乳液聚合。第一种子聚合物粒子的浓度以随后添加的单体乳液中全部单体的重量计优选地为2到10重量％。
双形态聚合物粒子(即，具有磷酸官能化的凸出内核和不具有磷酸官能化的凸出内核的聚合物粒子)的所得分散液中具有凸出内核的粒子与不具有凸出内核的粒子的重量:重量比优选地在从30:70并且更优选地从40:60到68:32、更优选地到65:35并且最优选60:40的范围内。具有凸出内核的聚合物粒子的体积平均粒度在从110nm、优选地从120nm到160nm、优选地到150nm的范围内；并且不具有凸出内核的粒子的体积平均粒度在从40nm、更优选地从50nm到130nm，更优选地到120nm的范围内，如通过不对称流场流分离所测定。优选地，凸出内核粒子与非凸出内核粒子的体积平均粒度的比率是从3:1到0.9:1、更优选地到1:1、更优选地到1.1:1。
双形态粒子的水性分散液宜与例如TiO2粒子等颜料粒子组合，形成其中至少一些吸附到TiO2粒子的第一聚合物粒子和其中至少一些不吸附到TiO2粒子的第二聚合物粒子的分散液。因此，本发明提供一种有效制备具有所要含量的吸附和调漆粘合剂的涂料组合物的方式。所述涂料组合物宜进一步包括以下组分中的一种或多种：消泡剂、表面活性剂、分散剂、流变改性剂和中和剂。
实例
使用AFFFF测量粒度和重量比
使用Eclipse 3+(怀亚特技术(Wyatt Technology))控制AFFFF流量调节。采集来自示差折射率(RI)和多角度光散射(道恩海莱士的马尔斯(MALS,DAWN HELEOS))检测器的数据并且通过Astra 6.1.4.25软件(怀亚特技术)处理数据。将乳胶样品用纯化水稀释1000倍并且将100nm和150nm聚苯乙烯NIST可追踪的粒度标准品(来自赛默科技(ThermoScientific)的纳米球标准品)用纯化水稀释100倍。分离通道尺寸就长度来说是15.2cm并且宽度从2.15cm逐渐变窄到0.3cm，含厚度350μm的间隔区和截止值为10kDa的超滤膜再生纤维素(怀亚特技术)。用HPLC级甲苯校准90度MALS检测器；使用球体模型，使用100nm标准的最大峰值，在其它角度下对检测器进行标准化。
分辨率和分离能力量度两个组分之间的分离程度，其可以基于标准品的洗脱曲线，使用申普夫M.E.(Schimpf,M.E.),《分辨率和分离能力》(Resolution andFractionating Power).《场流分离手册》(Field-Flow Fractionation Handbook),申普夫M.；科德威K.(Caldwell,K.)；吉丁士J.C.(Giddings,J.C.)编威利国际科学(WileyInterscience):纽约(New York),2000；第71-94页中所公开的方程式确定。组分的分辨率(Rs)由以下方程式定义：
Figure GDA0001506492780000081
其中δtr是两个组分之间的保留时间差并且
Figure GDA0001506492780000082
是两个组分区域的以时间为单位的平均标准偏差。
基于直径的分离能力(Fd)是平均直径(d)相差相对增量δd/d的粒子之间的分辨率，如通过以下方程式所计算：
Figure GDA0001506492780000083
标准品的分辨率应该≥2并且分离能力应该≥5。关于当前分析中所用的100nm和150nm聚苯乙烯标准品，分辨率和分离能力分别是2.2和5.6。
AFFFF分析所用的流动相是0.1％的飞世尔牌(Fisherbrand)FL-70溶液(飞世尔科技(Fisher Scientific))。所有样品都使用以下流动速率：检测器流率：0.7mL/min；焦点流率：2mL/min；注射流率：0.2mL/min。
注射前的初始维持时间：1min，0错流；聚焦：1min；聚焦和注射：1min；聚焦：1min；洗脱：10min，在1mL/min错流下；洗脱：30min，从1mL/min逐渐下降到0.5mL/min的错流；洗脱6min，0错流。
用纯化水将乳胶样品稀释1000倍，然后注射(20μL)到AFFFF分析仪中进行表征。MALS数据采集速率是1秒/数据点。还将纯化水注射到分析仪中以获得空白，用于RI基线扣除。乳胶粒度通过MALS，使用球体模型获得。粒度的面积:面积比(假定与重量:重量比相同)通过将重叠的RI曲线拟合到两个高斯峰值中来确定。
实例1-制备双形态聚合物粒子
A.内核(预形体)合成
通过混合去离子水(200g)、迪斯邦尼尔(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)与甲基丙烯酸(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四颈圆底烧瓶添加去离子水(600g)和迪斯邦尼尔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℃，并且起始搅拌。然后添加一部分第一单体乳液(70g)，接着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，在40分钟内线性地并且单独地添加第一单体乳液的剩余部分，接着是冲洗液(25g)以及溶解于去离子水(50g)中的过硫酸钠(0.64g)的引发剂溶液。在单体乳液馈料完成之后，使烧瓶的内含物保持在85℃下10分钟，在此时间之后共馈料完成；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，并且用氢氧化铵的稀溶液中和到pH3。使用布鲁克海文(Brookhaven)BI90Plus粒子分析仪测量到的粒度是60-75nm并且固体是40％。
B.橡果核-壳合成
使用去离子水(420g)、十二烷基苯磺酸钠(18.48g，23％活性)、迪斯邦尼尔FES993表面活性剂(56.67g，30％活性)、丙烯酸丁酯(306.85g)、丙烯酸乙酯(484.5g)甲基丙烯酸甲酯(640.05g)、乙酰乙酰氧基甲基丙烯酸酯(143.16g，95％活性)、脲基甲基丙烯酸酯(44.2g，50％活性)、丙烯酸(10.2g)以及4-乙烯基苯磺酸钠(17g，90％活性)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(850g)、迪斯邦尼尔FES 993表面活性剂(22.67g，30％活性)、碳酸钠(2g)以及七水合硫酸亚铁(0.018g)和VERSENETM 100EDTA(陶氏化学公司或其子公司的商标，0.011g)溶解于去离子水(13g)中的溶液。在N2下将烧瓶的内含物加热到80℃，并且起始搅拌。然后添加一部分第二单体乳液(75g，总单体的3.5％)，接着快速将叔戊基氢过氧化物(2g，85％活性)分散于去离子水(15g)中，接着去离子水冲洗(5g)，并添加溶解于去离子水(15g)中的异抗坏血酸(0.85g)的水溶液，接着去离子水冲洗(5g)。搅拌10min后，然后添加来自步骤A的预形体的一部分(212.5g，总单体的5.0％)，接着在90分钟内分开和同时添加以下：a)第二单体溶液的剩余部分；b)含有叔戊基氢过氧化物(5g，85％活性)、迪斯邦尼尔FES 993表面活性剂(3.4g，30％活性)和去离子水(58g)的分散液；以及c)异抗坏血酸(3.4g)于去离子水(65g)中的水溶液，总时间是90分钟。在添加第二单体乳液期间使烧瓶的内含物维持在75℃的温度下。当所有添加都完成时，用随后添加到烧瓶中的去离子水(25g)冲洗含有第二单体乳液的烧瓶。使烧瓶的内含物冷却到65℃，并且向烧瓶添加催化剂/活化剂对以减少残余单体。添加TERGITOLTM 15-S-40表面活性剂(陶氏化学公司或其子公司的商标，12.15g，70％固体)。然后用稀氢氧化铵溶液将聚合物中和到pH 9.3。如通过不对称流场流分离(AFFFF)所测量，非凸出聚合物粒子的粒度是65nm并且凸出内核聚合物粒子的粒度是134nm；固体是48.8％。
实例2-6
用于制备实例2-6的组合物的程序与实例1中所述实质上相同，但第二单体乳液和预形体的部分改为用于实现非凸出粒子与凸出粒子的不同w/w比率、不同粒度。表1展示了预形体和第二单体乳液(ME2)的量，呈占用于制备粒子的总单体的百分比的形式；粒子的粒度(PS)以及非凸出粒子与凸出粒子的w/w比率(NonPro:Pro比率)。必要时，可以通过控制聚合开始时反应器中的表面活性剂浓度来进一步操控粒度和粒度比。
表1-双形态聚合物粒子的量、粒度和w/w比率
实例编号 预形体％ ％ME2 非凸出PS(nm) 凸出PS(nm) NonPro:Pro比率
1 5.0 3.5 65 134 49.2:50.8
2 2.5 3.5 74 145 64.0:36.0
3 7.5 3.5 59 132 38.6:61.4
4 10.0 3.5 51 136 29.1:70.9
5 5.0 2.5 50 139 42.6:57.4
6 5.0 4.5 70 132 55.9:44.1
使用所述双形态乳胶制备油漆配制品，并且发现所述油漆配制品与单独地添加具有不同形态的乳胶所配制的油漆具有几乎相同的性质(例如遮盖力、KU稳定性、光泽度、热老化稳定性以及流变改性剂需求)，证明在本发明组合物的制备中所增加的功效不会对所配制的油漆的最终性质造成不利影响。

Claims (10)

1.一种制备氧化还原引发的聚合物粒子的双形态水性分散液的方法，其包含以下步骤：
a）将具有在40 nm到85 nm范围内的体积平均粒度的磷酸官能化的丙烯酸类第一种子聚合物粒子的水性分散液与具有在20 nm到80 nm范围内的体积平均粒度的丙烯酸类第二种子聚合物粒子的水性分散液混合在一起；
b）使单体与所述第一和第二种子聚合物粒子的水性分散液在氧化还原引发的乳液聚合条件下接触，其中所述单体作为单体乳液添加，形成1）具有磷酸官能化的凸出内核的聚合物粒子和2）不具有凸出内核的聚合物粒子的分散液；以及
其中具有所述磷酸官能化的凸出内核的粒子与不具有凸出内核的粒子的重量:重量比在25:75到75:25范围内，其中所述磷酸官能化的丙烯酸类第一种子聚合物粒子包含以下结构单元：a）甲基丙烯酸甲酯或苯乙烯或其组合；b）一种或多种选自由丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-丙基庚酯和丙烯酸2-乙基己酯组成的群组的丙烯酸酯单体；以及c）甲基丙烯酸磷酸乙酯；所述第二种子聚合物粒子包含以下结构单元：A）甲基丙烯酸甲酯或苯乙烯或其组合；B）一种或多种选自由丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-丙基庚酯和丙烯酸2-乙基己酯组成的群组的丙烯酸酯；以及C）以第二种子聚合物粒子的重量计不超过1重量%的磷酸单体，并且其中所述单体包含：i）甲基丙烯酸甲酯或苯乙烯或其组合；ii）一种或多种选自由丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-丙基庚酯和丙烯酸2-乙基己酯组成的群组的丙烯酸酯；以及iii）以单体的重量计不超过0.5重量%的磷酸单体。
2.根据权利要求1所述的方法，其中所述磷酸官能化的丙烯酸类第一种子聚合物粒子进一步包含：d）羧酸单体或其盐的结构单元；以及e）多烯系不饱和单体的结构单元。
3.根据权利要求1所述的方法，其中所述单体进一步包含羧酸单体或硫酸单体或其盐或其组合。
4.根据权利要求2所述的方法，其中以所述第一种子聚合物粒子的重量计，所述磷酸官能化的丙烯酸类第一种子聚合物粒子包含：a）从3重量%到8重量%的甲基丙烯酸磷酸乙酯或其盐的结构单元；b）从1重量%到5重量%的丙烯酸或甲基丙烯酸或其盐的结构单元；c）从0.2重量%到5重量%的多烯系不饱和单体的结构单元；d）从50重量%到65重量%的丙烯酸丁酯的结构单元；以及e）从25重量%到45重量%的甲基丙烯酸甲酯的结构单元；并且以所述单体的重量计，所述单体包含：i）40重量%到60重量%选自由甲基丙烯酸甲酯和苯乙烯组成的群组的第一单体；ii）从40重量%到60重量%选自由丙烯酸丁酯和丙烯酸2-乙基己酯组成的群组的第二单体；iii）以单体的重量计少于0.5重量%的磷酸单体；以及iv) 从0.1重量%到5重量%酸性单体或其盐，其中所述酸性单体选自由丙烯酸、甲基丙烯酸、4-乙烯基苯磺酸钠和2-丙烯酰胺基-2-甲基丙磺酸组成的群组。
5.根据权利要求4所述的方法，其中所述单体具有与所述第二种子聚合物粒子相同的单体概况。
6.根据权利要求1至5中任一权利要求所述的方法，其中所述第一和第二种子聚合物粒子的水性分散液以从1:2到10:1的第一:第二种子聚合物粒子重量:重量比混合在一起，其中以所述单体乳液的重量计，所述单体乳液包含少于0.1重量的磷酸单体。
7.根据权利要求6所述的方法，其中所述凸出内核聚合物粒子与非凸出内核聚合物粒子的体积平均粒度的比率为3:1到0.9:1。
8.根据权利要求7所述的方法，其中所述凸出内核聚合物粒子的体积平均粒度在从120nm到150 nm的范围内，并且所述非凸出内核聚合物粒子的体积平均粒度在从50 nm到130nm范围。
9.根据权利要求8所述的方法，其中具有所述磷酸官能化的凸出内核的粒子与不具有凸出内核的粒子的重量:重量比在40:60到60:40范围内。
10.根据权利要求1至5中任一权利要求所述的方法，其包含将所述聚合物粒子的双形态水性分散液与TiO2粒子组合以形成吸附到和不吸附到TiO2的聚合物粒子的分散液的进一步步骤。
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