CN110461913A - 用碱可溶胀聚合物颗粒制备涂料配制物 - Google Patents

用碱可溶胀聚合物颗粒制备涂料配制物 Download PDF

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CN110461913A
CN110461913A CN201880018820.XA CN201880018820A CN110461913A CN 110461913 A CN110461913 A CN 110461913A CN 201880018820 A CN201880018820 A CN 201880018820A CN 110461913 A CN110461913 A CN 110461913A
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swelling
alkali
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J·K·巴德曼
J·德罗契尔
A·海尔
A·K·范戴克
汪琳
K·杨
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Dow Global Technologies LLC
Rohm and Haas Co
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Abstract

本发明涉及一种方法，所述方法包含以下步骤：使溶胀的聚合物颗粒的含水分散体与流变改性剂和粘结剂接触，以形成VOC小于50g/L的涂料组合物。通过具有高酸核含量和低Tg壳的碱可溶胀聚合物颗粒的中和得到所述溶胀的聚合物颗粒。由本发明的所述方法得到的所述组合物可用于增加开放时间，特别是对于低VOC涂料应用。

Description

用碱可溶胀聚合物颗粒制备涂料配制物
背景技术
本发明涉及一种用于用碱可溶胀聚合物颗粒的含水分散体制备涂料配制物的方法。碱可溶胀聚合物颗粒的分散体可用作涂料配制物中的开放时间添加剂。
政府法规和市场运作不断趋向用于涂料配制物的零挥发性有机化合物(VOC)。因此，不含挥发性溶剂和聚结剂的水性配制物已在行业内变得越来越受欢迎。然而，油漆特性已经因为这种巨大的变化而受损；尤其是开放时间，所述开放时间为在其期间新施用的油漆膜可进行二次加工而不留刷痕的时间段。在溶剂型系统中，开放时间是约30分钟至45分钟；在典型的水性配制物中，开放时间是大约3分钟至5分钟。因此，本领域中需要寻找一种用于水性配制物的添加剂，所述添加剂使开放时间延长超过目前可用的添加剂而不降低最终涂料的其它特性，如膜粘合和粘聚强度、硬度、抗粘连性、早期耐起泡性、耐擦洗性、耐污染性以及耐损性。
发明内容
本发明通过提供包含以下步骤的方法解决了本领域中的需要：a)使碱可溶胀聚合物颗粒的含水分散体与碱接触以形成溶胀的聚合物颗粒的含水分散体；和b)使溶胀的聚合物颗粒的含水分散体与流变改性剂和粘结剂接触，以形成VOC小于50g/L的涂料组合物；其中碱可溶胀聚合物颗粒包含Tg不大于25℃的壳和酸官能化核；其中核-壳比率在～1:3.2至～1:6的范围内；并且其中涂料组合物包含按涂料组合物中总固体的重量计1重量％至20重量％的溶胀的聚合物颗粒。
在第二方面，本发明是一种方法，所述方法包含以下步骤：使溶胀的聚合物颗粒的含水分散体与流变改性剂和粘结剂接触，以形成VOC小于50g/L的涂料组合物，其中溶胀的聚合物颗粒具有核-壳形态，其中壳的Tg不大于25℃，并且核包含水和羧酸的盐；并且其中涂料组合物包含按涂料组合物中总固体计1重量％至20重量％的溶胀的聚合物颗粒。
与不含有碱溶胀的颗粒的可比配制物相比，由本发明方法得到的涂料组合物具有明显更长的开放时间。
具体实施方式
在第一方面，本发明是一种方法，所述方法包含以下步骤：a)使碱可溶胀聚合物颗粒的含水分散体与碱接触以形成溶胀的聚合物颗粒的含水分散体；和b)使溶胀的聚合物颗粒的含水分散体与流变改性剂和粘结剂接触，以形成VOC小于50g/L的涂料组合物；其中碱可溶胀聚合物颗粒包含Tg不大于25℃的壳和酸官能化核；其中核-壳比率在～1:3.2至～1:6的范围内；并且其中涂料组合物包含按涂料组合物中总固体的重量计1重量％至20重量％的溶胀的聚合物颗粒。
碱可溶胀聚合物颗粒的特征在于酸官能化的第一阶段部分(核)，优选地羧酸官能化核，和第二阶段部分(壳)，所述第二阶段部分的Tg通过福克斯(Fox)方程式计算不大于25℃。词语“核”和“壳”在本文中便利地用于描述聚合过程的第一阶段和最后阶段(或第一阶段和第二阶段，如果以两个阶段生成聚合物颗粒的话)。因此，最终的碱可溶胀聚合物颗粒可以但不必需具有核-壳形态。碱可溶胀聚合物颗粒可通过许多技术(包括本领域熟知的技术)中的任一种来制备。(参见US 4,468,498；US 5,326,843；和US 9,340,685)。举例来说，核可通过单阶段或多阶段方法来产生，优选地在如正十二烷基硫醇或巯基乙醇的链转移剂的存在下产生。核也可由种子过程来制备。然后核用于在一个或多个附加阶段中制得碱可溶胀聚合物颗粒。
优选地，核包含按核的重量计30重量％、更优选地35重量％并且最优选地38重量％至优选地50重量％、更优选地至45重量％并且最优选地至42重量％的羧酸单体的结构单元。如本文所使用的，术语“结构单元”是指在聚合之后所叙述的单体的剩余部分。举例来说，甲基丙烯酸的结构单元如下所示：
酸官能化核还优选地包含50重量％、更优选地55重量％并且最优选地58重量％至优选地70重量％、更优选地至65重量％并且最优选地至62重量％的非离子烯系不饱和单体的结构单元。
羧酸官能化单体的实例包括甲基丙烯酸、丙烯酸以及衣康酸，其中优选丙烯酸和甲基丙烯酸。非离子烯系不饱和单体的实例包括一种或多种C1-C10丙烯酸烷基酯和甲基丙烯酸酯，如甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯和丙烯酸2-乙基己酯；以及苯乙烯。甲基丙烯酸甲酯和甲基丙烯酸丁酯是优选的非离子烯系不饱和单体。
核还可包含多烯系不饱和单体的结构单元，如乙二醇二(甲基)丙烯酸酯、烯丙基(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯，或二乙烯基苯。如果存在，多烯系不饱和单体的结构单元按核的重量计优选地在0.1重量％、更优选地0.3重量％至10重量％、更优选地至3重量％的范围内。
在与碱接触之前，如通过BI-90Plus Brookhaven颗粒分析仪所测量的，核的平均直径优选地在100nm、更优选地120nm、最优选地150nm至优选地500nm、更优选地至400nm并且最优选地至350nm的范围内。
壳的Tg更优选地不大于20℃并且最优选地不大于15℃。优选地，壳包含Tg>50℃的一种或多种单体(即一种或多种高Tg单体)的结构单元，如甲基丙烯酸甲酯(Tg＝105℃)或苯乙烯(Tg＝100℃)或其组合；和Tg小于10℃的至少一种单体(即一种或多种低Tg单体)的结构单元，如丙烯酸乙酯(Tg＝-23℃)、丙烯酸丁酯(Tg＝-53℃)或丙烯酸2-乙基己酯(Tg＝-52℃)或其组合。壳优选地进一步包含酸单体、优选地羧酸单体、优选地甲基丙烯酸(Tg＝228℃)或丙烯酸(Tg＝101℃)的结构单元。(所叙述的Tg是指由聚合物特性数据库(PolymerProperties Database)报告的对应均聚物的Tg。)
优选地，壳中高Tg单体的结构单元(优选地甲基丙烯酸甲酯或苯乙烯、更优选地甲基丙烯酸甲酯)的浓度按壳的重量计在40重量％、更优选地42重量％并且最优选地44重量％至优选地60重量％、更优选地至55重量％、更优选地至50重量％并且最优选地至48重量％的范围内。
优选地，壳中低Tg单体的结构单元的浓度按壳的重量计在38重量％、更优选地45重量％、更优选地48重量％并且最优选地50重量％至优选地59重量％、更优选至57重量％并且最优选地至54重量％的范围内。低Tg单体优选地为丙烯酸丁酯。
优选地，壳中羧酸单体的结构单元的浓度按壳的重量计在0.2重量％、更优选地0.5重量％至优选地5重量％、更优选地至3重量％并且最优选地至2重量％的范围内。
优选地，在与碱接触之前，碱可溶胀聚合物颗粒的平均直径在150nm、更优选地250nm并且最优选地350nm至优选地900nm、更优选地至750nm并且最优选地至550nm的范围内。
优选地，在碱添加之前，碱可溶胀聚合物颗粒的浓度按水和碱可溶胀聚合物颗粒的重量计在10重量％并且更优选地15重量％至35重量％并且更优选地至30重量％的范围内。类似地，在碱添加之后，按水和碱可溶胀聚合物颗粒的重量计，溶胀的聚合物颗粒的浓度在或被调节成在10重量％、更优选地15重量％至35重量％、更优选地至30重量％的范围内。在碱添加之前，碱可溶胀聚合物颗粒的分散体的粘度在10-100mPa·s的范围内。碱增加了核的pH，从而将其中和并且使其溶胀。碱可以是挥发性碱，如氨、三甲胺、三乙胺或甲基异丙胺；或非挥发性碱，如2-氨基-2-甲基-1-丙醇(可以AMP 95中和剂的形式商购获得)、正丁基二乙醇胺(可以Vantex T中和剂的形式商购获得)、LiOH、NaOH或KOH。如本文所用，非挥发性碱是指沸点高于150℃的碱。
使碱与碱可溶胀聚合物颗粒接触以产生溶胀的聚合物颗粒，所述溶胀的聚合物颗粒的粘度比碱可溶胀颗粒优选地高至少50mPa·s、更优选地高至少100mPa·s并且最优选地高至少200mPa·s。碱的浓度足以中和碱可溶胀聚合物颗粒的核。如本文所用，“中和”意指核的pH升高至比用于制得酸官能化核的酸单体的pKa高至少1.5个单位的pH。举例来说，如果使用甲基丙烯酸(pKa＝4.65)制得酸官能化核，则将碱可溶胀分散体的pH调节至至少6.15、优选地至至少6.5、更优选地至至少7并且最优选地至至少8。优选地，相对于碱可溶胀聚合物颗粒的酸含量，碱的添加量为至少50％化学计量、更优选地至少化学计量并且最优选地大于化学计量。
优选地，使碱与碱可溶胀聚合物颗粒于在15℃、更优选地20℃至60℃、更优选地至50℃、最优选地至40℃范围内的温度下接触。优选地，溶胀的聚合物颗粒的粘度在100mPa·s、更优选地200mPa·s至1500mPa·s的范围内。优选地，在碱添加完成后小于1小时内达到最终粘度的至少90％、更优选地至少95％并且最优选地至少99％。
在将溶胀的聚合物颗粒的含水分散体与粘结剂和流变改性剂的分散体组合之后，所得的配制物优选地表现出小于1000mPa·s、更优选地小于500mPa·s并且最优选地小于200mPa·s的粘度变化。因此，溶胀的聚合物颗粒在本发明的方法中不用作增稠剂，因为大部分(如果不是全部的话)的聚合物颗粒溶胀(和伴随的分散体的增稠)已经在溶胀的聚合物颗粒与构成涂料配制物的其它组分组合之前发生。
如本文所用，术语粘结剂是指当暴露于碱时表现出粒度的增加小于10nm的聚合物颗粒的含水分散体。如通过Brookhaven BI-90Plus颗粒分析仪测定的，这些聚合物颗粒(粘结剂固体)的平均直径优选地在70nm、更优选地100nm至600nm、更优选至500nm的范围内。粘结剂固体的特征还在于包含按粘结剂固体的重量计小于5重量％、优选地小于4重量％并且最优选地小于3重量％的酸单体的结构单元。
粘结剂有利地通过一种或多种烯系不饱和单体的含水乳液聚合来制备，所述一种或多种烯系不饱和单体的实例包括苯乙烯、乙酸乙烯酯、丙烯酰胺、甲基丙烯酰胺、丙烯腈和丙烯酸或甲基丙烯酸的C1-C10烷基酯，包括甲基丙烯酸甲酯、甲基丙烯酸乙酯、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。
如本文所用，术语流变改性剂是指水溶性或水分散性缔合流变改性剂，如疏水改性环氧乙烷氨基甲酸酯聚合物(HEUR)、疏水改性碱可溶胀乳液(HASE)和苯乙烯-马来酸酐三元共聚物(SMAT)，以及非缔合流变改性剂，如碱可溶胀乳液(ASE)。
涂料配制物中与粘结剂(粘结剂固体)相关联的聚合物颗粒的浓度按涂料组合物中固体的重量计优选地在5重量％、更优选地10重量％、至优选地40重量％、更优选地至30重量％的范围内。溶胀的聚合物颗粒的浓度按涂料组合物中固体的重量计在1重量％、优选地2重量％并且更优选地5重量％至20重量％、优选地至15重量％并且更优选地至10重量％的范围内。
优选地，流变改性剂的浓度按涂料组合物中固体的重量计在0.5重量％至5重量％的范围内。溶胀的聚合物颗粒的含水分散体、粘结剂和流变改性剂可以以任何顺序组合。
通过本发明的方法制备的组合物可进一步有利地包括以下组分中的任一种或全部：分散剂、颜料、消泡剂、表面活性剂、溶剂、增量剂、聚结剂、杀生物剂、不透明聚合物和着色剂。所述组合物是VOC小于50g/L的低挥发性有机物含量(VOC)组合物。
实例
碱可溶胀聚合物的制备
A.第1阶段(核)的制备
如下制备第一阶段(核，60MMA/40MAA)：5L的四颈圆底烧瓶(釜)配备有桨式搅拌器、温度计、N2入口和回流冷凝器。将去离子水(1760g)添加到釜中并且在N2下加热至86℃。通过将去离子水(720g)、十二烷基苯磺酸钠(SDS，5.2g，23％活性)、甲基丙烯酸甲酯(780.0g)和甲基丙烯酸(10.0g)混合来制备单体乳液(ME1)。取出一部分ME1(164.0g)并置于单独的容器中、搁置一旁。向剩余的ME1中添加SDS(50.0g，23％活性)和甲基丙烯酸(510.0g)。当釜温度达到86℃时，将去离子水(160.0g)和SDS(5.0g，23％活性)的混合物添加到釜中，然后添加最初取出并放在一边的ME1。接着将过硫酸钠(5.5g)于去离子水(40.0g)中的混合物添加到釜中。釜的温度降至～76℃，接着使其在15分钟的保持期内升至85℃。接着将剩余的ME1在85℃下经2小时进料至釜中。在完成ME1进料之后，将分散体保持在85℃下持续15分钟，之后将分散体冷却到25℃并且过滤以去除任何凝结物。过滤后的分散体具有2.9的pH、31.7％的固体含量和152nm的平均粒度。
B.具有1:5核-壳比率和于核中的40％甲基丙烯酸的碱可溶胀聚合物颗粒的分散体的制备
在N2下向配备有浆式搅拌器、温度计、N2入口和回流冷凝器的5L四颈圆底烧瓶(釜)中添加DI水(500g)并且加热至86℃。通过将DI水193g、SDS(14.3g，23％活性)、丙烯酸丁酯(655.2g)、甲基丙烯酸甲酯(585.9g)和甲基丙烯酸(18.9g)混合来制备单体乳液(ME2)。当釜温度达到86℃时，将部分A(795.0g)的分散体添加到釜中并且将温度调节至60℃。然后将0.1％硫酸铁(II)于水(20g)中的溶液与和DI水(45g)混合的异抗坏血酸(0.6g)溶液一起添加到釜中。将过硫酸钠(3.8g)于DI水(90g)和亚硫酸氢钠(2.5g)于DI水(90g)中的共进料溶液以0.7克/分钟的速率添加到釜中。在开始添加共进料溶液三分钟后，以2克/分钟的速率添加ME2。在开始添加ME2十分钟后，进料速率增加至4g/m。再过十分钟后，ME2进料速率增加至8克/分钟。再过十分钟后，ME进料速率增加至16克/分钟。在整个ME2的添加过程中，釜的温度保持在59-61℃。在完成ME2的添加之后，共进料再过量进料二十分钟。在完成共进料添加后，将釜的内容物冷却至室温并且过滤以去除任何凝结物。过滤后的分散体具有2.1的pH、47.5％的固体含量和275nm的平均粒度，如通过BI-90Plus Brookhaven颗粒分析仪所测量的。
碱可溶胀聚合物在三个单独的实验中用三种不同的碱：NH4OH、2-氨基-2-甲基-1-丙醇和NaOH进行溶胀，如下：将中和碱添加到聚合物分散体中以制备最终固体含量为25％的分散体。在室温下添加中和碱，机械混合10分钟。添加完成一小时后的pH经测量>7。通过将溶胀的颗粒的分散体添加到表1中所述的油漆配制物中来制备油漆配制物。
表1-具有开放时间添加剂的油漆配制物
材料名称 磅 加仑
RHOPLEX<sup>TM</sup>HG-706粘结剂 525.7 59.37
BYK-024消泡剂 1.0 0.1
丙二醇 4.3 0.5
TRITON<sup>TM</sup>X-100表面活性剂 4.4 0.5
水 16.7 2.0
KATHON<sup>TM</sup>LX 1.5％杀生物剂 1.5 0.2
TAMOL<sup>TM</sup>2002分散剂 2.0 0.2
氨(28％) 1.0 0.1
Ti-Pure R-746TiO<sub>2</sub> 285.0 14.7
水 20.0 2.4
TEXANOL聚结剂 7.9 1.0
ACRYSOL<sup>TM</sup>RM-2020E流变改性剂 20.0 2.3
ACRYSOL<sup>TM</sup>RM-725流变改性剂 3.0 0.4
BYK-024消泡剂 2.0 0.2
溶胀的颗粒(25％固体) 95.5 11.4
水 38.7 4.63
总计 1030 100
RHOPLEX、TRITON、KATHON、TAMOL和ACRYSOL都是陶氏化学公司(The Dow ChemicalCompany)或其附属公司的商标。
使用顶置式混合器配制油漆样品。调节流变改性剂和水量以使Stormer粘度为95KU并且ICI粘度为1.3。将样品平衡过夜，然后评估开放时间。
开放时间是根据ASTM-D7488测量的。测试在恒定温度/湿度室(72℉，50％RH)中执行。使用刮涂棒以5密耳间隙将油漆沉积在黑色乙烯基擦洗卡片上。立即通过在湿油漆中使用两个木制施用器制造平行标记来对膜刻痕。随后，使用涂底漆1"尼龙毛刷以定时间隔刷拭膜区部。使膜干燥过夜。由至少三名读者构成的小组以视觉方式检查了面板，并将没有显示刻痕标记迹象的最后一个十字刷区部记录为开放时间。与由相同的油漆配制物制备但不具有开放时间添加剂的涂料的测量开放时间为6分钟相比，对于每种涂料，通过NH4OH、NaOH和2-氨基-2-甲基-1-丙醇中和的样品的测量开放时间为9分钟。

Claims (10)

1.一种方法，所述方法包含以下步骤：a)使碱可溶胀聚合物颗粒的含水分散体与碱接触以形成溶胀的聚合物颗粒的含水分散体；和b)使所述溶胀的聚合物颗粒的含水分散体与流变改性剂和粘结剂接触，以形成VOC小于50g/L的涂料组合物；其中所述碱可溶胀聚合物颗粒包含Tg不大于25℃的壳和酸官能化核；其中核-壳比率在～1:3.2至～1:6的范围内；并且其中涂料组合物包含按所述涂料组合物中总固体的重量计2重量％至20重量％的溶胀的聚合物颗粒。
2.根据权利要求1所述的方法，其中所述碱可溶胀聚合物颗粒的含水分散体的固体含量按所述碱可溶胀聚合物颗粒的含水分散体的重量计在10重量％至35重量％的范围内。
3.根据权利要求2所述的方法，其中在碱添加之前，所述碱可溶胀聚合物颗粒的分散体的粘度在10-100mPa·s的范围内，并且所述溶胀的聚合物颗粒的含水分散体的粘度比所述碱可溶胀颗粒高至少50mPa·s。
4.根据权利要求1至3中任一项所述的方法，其中所述碱可溶胀聚合物颗粒的所述酸官能化核包含按所述核的重量计30重量％至50重量％的羧酸单体的结构单元，和50重量％至70重量％的非离子烯系不饱和单体的结构单元；并且其中所述碱可溶胀聚合物颗粒的所述壳具有不大于20℃的Tg并且包含Tg大于50℃的单体的结构单元、Tg小于10℃的单体的结构单元，和酸单体的结构单元。
5.根据权利要求4所述的方法，其中所述碱可溶胀聚合物颗粒的所述酸官能化核包含按所述核的重量计35重量％至45重量％的甲基丙烯酸或丙烯酸的结构单元；和55重量％至65重量％的非离子烯系不饱和单体的结构单元，其中所述非离子烯系不饱和单体是甲基丙烯酸甲酯或甲基丙烯酸丁酯；其中所述壳包含40重量％至60重量％的苯乙烯或甲基丙烯酸甲酯的结构单元、38重量％至59重量％的丙烯酸丁酯的结构单元，和0.2重量％至5重量％的甲基丙烯酸或丙烯酸的结构单元；并且其中所述碱可溶胀聚合物颗粒的平均直径在150nm至900nm的范围内。
6.根据权利要求3至5中任一项所述的方法，其中所述碱是非挥发性碱，其中所述溶胀的聚合物颗粒的含水分散体的粘度比所述碱可溶胀颗粒的含水分散体高至少100mPa·s，并且其中使所述碱与所述碱可溶胀聚合物颗粒在15℃至60℃范围内的温度下接触。
7.权利要求6所述的方法，其中所述碱是LiOH、NaOH或KOH；其中使所述碱与所述碱可溶胀聚合物颗粒在20℃至40℃范围内的温度下接触；其中所述溶胀的聚合物颗粒的粘度在200mPa·s至1500mPa·s的范围内，并且其中在使所述溶胀的聚合物颗粒的含水分散体与所述粘结剂和所述流变改性剂接触之后，所述组合物表现出小于500mPa·s的粘度变化。
8.根据权利要求1至7中任一项所述的方法，其中所述溶胀的聚合物颗粒的浓度按所述涂料组合物中固体的重量计在5重量％至15重量％的范围内；与所述粘结剂相关联的聚合物颗粒的浓度按所述涂料组合物中固体的重量计在5重量％至40重量％的范围内；并且所述流变改性剂的浓度按所述涂料组合物中固体的重量计在0.5重量％至5重量％的范围内。
9.根据权利要求8所述的方法，其中所述组合物进一步包括选自由以下组成的组的至少一种组分：分散剂、颜料、消泡剂、表面活性剂、溶剂、增量剂、聚结剂、杀生物剂、不透明聚合物和着色剂。
10.一种方法，所述方法包含以下步骤：使溶胀的聚合物颗粒的含水分散体与流变改性剂和粘结剂接触，以形成VOC小于50g/L的涂料组合物，其中所述溶胀的聚合物颗粒具有核-壳形态，其中所述壳的Tg不大于25℃，并且所述核包含水和羧酸的盐；并且其中所述涂料组合物包含按所述涂料组合物中总固体计1重量％至20重量％的所述溶胀的聚合物颗粒。
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