CN106916274A - 用于抗粘连性及凝固时间的聚醚‑氨基甲酸酯‑脲添加剂 - Google Patents

用于抗粘连性及凝固时间的聚醚‑氨基甲酸酯‑脲添加剂 Download PDF

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CN106916274A
CN106916274A CN201611176556.1A CN201611176556A CN106916274A CN 106916274 A CN106916274 A CN 106916274A CN 201611176556 A CN201611176556 A CN 201611176556A CN 106916274 A CN106916274 A CN 106916274A
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water
hydrophilic polyurethane
soluble
ethylene oxide
polyethylene glycol
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CN106916274B (zh
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K·耶昂
A·K·范戴克
J·德罗契尔
S·阿图罗
J·J·拉巴斯克
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Dow Global Technologies LLC
Rohm and Haas Co
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Abstract

本发明提供一种亲水性聚氨基甲酸酯，所述聚氨基甲酸酯包含以下聚合单元：(a)具有两个至四个羟基官能团并且重量平均分子量是800至16,000的水溶性多元醇；及(b)具有两个至六个异氰酸酯官能团的脂肪族聚异氰酸酯；其中环氧乙烷聚合单元占所述亲水性聚氨基甲酸酯至少85wt％；并且其中环氧乙烷聚合单元的重量分数与聚氧化乙烯平均分子量的乘积是4,200至16,000。

Description

用于抗粘连性及凝固时间的聚醚-氨基甲酸酯-脲添加剂
技术领域
本发明涉及改善乳胶漆的凝固时间，同时对于抗粘连性无显著负面影响的聚醚-氨基甲酸酯-脲(polyether-urethane-urea，PEUU)添加剂。
背景技术
由聚异氰酸酯和/或二异氰酸酯及二醇制造的疏水性改性的氨基甲酸酯增稠剂(Hydrophobically modified urethane，HEUR)称为含有疏水性基团的水溶性聚合物。其归类为缔合型增稠剂并且常常用于乳胶漆配制物中，其中疏水性基团吸附至乳胶粒子表面上，从而在较宽剪切速率范围内引起粘度增加及所希望的流变学特征。举例来说，US4079028公开了HEUR增稠剂。
然而，在乳胶漆中凝固时间通常是个问题，凝固时间定义为可以再涂布新施加的潮湿漆膜而不会阻碍膜形成或改变物理外观的时间段。
因此，改善凝固时间，同时不会对于抗粘连性产生显著负面影响的乳胶漆配制物将是本领域中的一大进步。
发明内容
本发明是针对一种亲水性聚氨基甲酸酯，所述聚氨基甲酸酯包含以下聚合单元：(a)具有两个至四个羟基官能团的水溶性多元醇；及(b)具有两个至六个异氰酸酯官能团的脂肪族聚异氰酸酯；其中环氧乙烷聚合单元占所述亲水性聚氨基甲酸酯聚合物至少85wt％。
具体实施方式
除非另外说明，否则所有百分含量都是重量百分含量(wt％)，并且所有温度都以℃为单位。除非另外说明，否则所有操作都在室温(20至25℃)下进行。
如本文所使用，术语“水溶性多元醇”是指一或多种聚氧化乙烯、水溶性聚氧化乙烯/聚氧化丙烯共聚物、水溶性聚氧化乙烯/聚氧化丁烯共聚物、水溶性聚氧化乙烯/聚氧化丙烯/聚氧化丁烯三元共聚物，以及包含C3-C8三醇(例如甘油、三羟甲基丙烷)聚合单元及环氧乙烷、环氧丙烷和环氧丁烷中至少一个聚合单元的水溶性多元醇。如本文所使用，术语“水溶性”意思指以溶液的总重量计，可溶于水中至少达到10wt％程度(优选是20wt％)。本文所使用的术语“聚异氰酸酯”是指每分子具有至少两个异氰酸酯基的异氰酸酯源。术语“脂肪族聚异氰酸酯”是指非芳香族聚异氰酸酯，即，非环状脂肪族聚异氰酸酯以及环状脂肪族聚异氰酸酯。
优选水溶性多元醇具有两个至三个，优选两个羟基官能团。优选地，水溶性多元醇的重量平均分子量(Mw)在900至16,000道尔顿，优选1,000至12,000道尔顿，优选1,000至10,000道尔顿范围内。优选水溶性多元醇包括聚乙二醇和乙氧基化甘油。聚乙二醇可以包括至多15wt％，优选不超过10wt％，优选不超过5wt％，优选不超过2wt％的C3-C4环氧烷聚合单元。聚乙二醇可以包括一端经C1-C4烷基，优选甲基封端的环氧乙烷聚合物。优选地，聚乙二醇的重量平均分子量(Mw)在4,000至16,000道尔顿，优选4,000至12,000道尔顿，优选6,000至10,000道尔顿范围内。适合聚乙二醇的实例是PEG 8000，其可以CARBOWAXTM 8000聚乙二醇(The Dow Chemical Company或其附属公司的商标)购得。Mw是通过以下描述的尺寸排阻色谱法(Size Exclusion Chromatography，SEC)测量。优选地，乙氧基化甘油的Mw是800至1600，优选是1000至1400。在一个优选实施例中，所述聚合物另外包含聚合单元聚乙二醇单C1-C4烷基醚以及具有两个至三个羟基官能团的多元醇。
优选地，所述增稠剂的疏水性、末端或连接基团部分的经计算log P(cLogP)是-1.5至4.5；优选是-1.3至4.3。优选地，聚氨基甲酸酯增稠剂还包含脲和/或缩二脲和/或脲基甲酸酯基团。举例来说，当在聚氨基甲酸酯增稠剂制备期间使用如胺或水等反应物时，形成脲基。
优选地，水溶性多元醇具有至少90wt％，优选至少92wt％，优选至少94wt％，优选至少95wt％，；优选不超过99.5wt％，优选不超过99wt％，优选不超过98.5wt％的环氧乙烷聚合单元。环氧乙烷聚合单元的百分含量是基于固体，即，聚合物的干重计算，不考虑非反应性溶剂。
优选地，亲水性聚氨基甲酸酯聚合物包含0.5至5wt％，优选1至4wt％的水溶性多元醇聚合单元，所述水溶性多元醇包含以下聚合单元：C3-C8三醇(例如甘油、三羟甲基丙烷)，以及环氧乙烷、环氧丙烷及环氧丁烷中的至少一种。优选地，水溶性多元醇具有至少75wt％，优选至少85wt％的环氧乙烷单元。
优选地，聚异氰酸酯具有两个至五个，优选两个至四个异氰酸酯官能团。适合二异氰酸酯的实例包括1,4-亚甲基二异氰酸酯、1,6-六亚甲基二异氰酸酯(HDI)及其低聚物(例如1,3,5-三(6-异氰酸酯基己基)1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮(HDI三聚体)及IPDI三聚体)、2,2,4-三甲基-1,6-二异氰酸酯基己烷、1,10-十亚甲基二异氰酸酯、4,4'-亚甲基双(异氰酸酯基环己烷)(H12MDI)、2,4'-亚甲基双(异氰酸酯基环己烷)、1,4-亚环己基二异氰酸酯及1-异氰酸酯基-3-异氰酸酯基甲基-3,5,5-三甲基环己烷(IPDI)。
出乎意料地发现，环氧乙烷聚合单元的百分比与聚氧化乙烯平均分子量的乘积与本发明的聚氨基甲酸酯的凝固时间性能的改善相关。聚氧化乙烯(polyethylene oxide，PEO)平均分子量是聚氨基甲酸酯中聚氧化乙烯单元分子量的加权平均值(Mw)。举例来说，具有相等权重的Mw值是8,000及2,000的聚氧化乙烯的聚氨基甲酸酯具有的聚氧化乙烯平均分子量是5,000。优选地，环氧乙烷聚合单元的百分比与聚氧化乙烯平均分子量的乘积是至少4,400，优选是至少4,500，优选是至少5,000，优选是至少6,000；优选不超过12,000，优选不超过10,000，优选不超过9,000。
亲水性聚氨基甲酸酯可以通过使水溶性多元醇、脂肪族聚异氰酸酯以及任选地，二醇单C1-C4烷基醚(例如经低碳数烷基，优选甲基封端的乙二醇、丙二醇及丁二醇中的一或多种的聚合物)和二胺(优选脂肪族二胺)中的一或多种在反应性条件接触来制备。优选地，二胺和二醇单C1-C4烷基醚中至少一种是水溶性的。优选地，二胺是C2-C6二胺，优选是C2-C4二胺，优选乙二胺。如关于氨基甲酸酯聚合物的合成一般已知的，反应物装载的次序可以变化。举例来说，所有反应物可以在单一合成步骤中一起反应，或反应物可以按任何合成顺序反应以获得所希望的最终聚合物。如本领域中关于逐步聚合反应以制造氨基甲酸酯聚合物所熟知的，使用各成分的摩尔当量比控制如分子量等特性。
优选地，亲水性聚氨基甲酸酯聚合物的Mw是至少10,000，优选是至少16,000，优选是至少20,000，优选是至少30,000；优选不超过2,000,000，优选不超过1,500,000，优选不超过500,000，优选不超过200,000。
如本文中所描述制造的亲水性聚氨基甲酸酯不仅仅是氨基甲酸酯聚合物，而且可以另外包括在所述聚合物主链中的脲基甲酸酯分支点与脲键联的组合。所述聚合物可以另外包括伯胺端基或在聚合物主链中的缩二脲分支点，或其组合。
本发明另外针对包含0.1至5wt％本发明的亲水性聚氨基甲酸酯的乳胶漆。
优选地，乳胶漆包含至少0.2wt％，优选至少0.3wt％，优选至少0.4wt％，优选至少0.5wt％；优选不超过4wt％，优选不超过3wt％的亲水性聚氨基甲酸酯。百分含量是以乳胶漆的总重量计。
本发明另外针对通过添加前述量的亲水性聚氨基甲酸酯来增加乳胶漆的凝固时间，同时对于抗粘连性无显著不良影响的方法。
实例
实例1
通过共沸蒸馏干燥聚乙二醇(8200g/mol，75.4g)于甲苯(220g)中的溶液。将溶液冷却到90℃之后，分别添加DESMODUR N3600(含有70％三聚体及少量更高级低聚物的HDI三聚体，总NCO官能度＝3.1)(1.37g)和乙氧基化甘油(1236g/mol，1.68g)，并且搅拌所述溶液5分钟。将辛酸铋(0.19g)添加至所述溶液中，并搅拌反应混合物1小时。将反应混合物冷却到室温，并经由旋转蒸发去除溶剂。分离出呈白色固体状的聚合物。0.9PEG8000/0.3667N3600/0.2Gly-EO(26)。Mn＝14,000；Mw＝161,000
实例2
通过共沸蒸馏干燥聚乙二醇(8200g/mol，82.2g)于甲苯(202g)中的溶液。将溶液冷却到90℃之后，添加乙二胺(0.075g)，并将溶液搅拌5分钟。分别添加DESMODUR N3600(1.68g)和乙氧基化甘油(1236g/mol，2.07g)，并将反应混合物再搅拌5分钟。添加辛酸铋(0.21g)，并将反应混合物搅拌1小时。将反应混合物冷却到室温，并经由旋转蒸发去除溶剂。分离出呈灰白色固体状的聚合物。0.8PEG8000/0.1乙二胺/0.3667N3600/0.2Gly-EO(26)。Mn＝13,000；Mw＝1,300,000
实例3
通过共沸蒸馏干燥聚乙二醇(8200g/mol，115.8g)于甲苯(216g)中的溶液。将溶液冷却到90℃之后，添加DESMODUR W(H12MDI，11.66g)，并将溶液搅拌5分钟。将辛酸铋(0.19g)添加至溶液中，并将反应混合物搅拌1小时。将CARBOWAX MPEG2000(2000g/mol，129.1g)添加至搅拌的反应混合物中，并将混合物在90℃下再搅拌一小时。将反应混合物冷却到室温，并经由旋转蒸发去除溶剂。分离出呈白色固体状的聚合物。0.35PEG8000/1.1DesW//0.8MePEG2000。Mn＝7,300；Mw＝13,500
实例4
通过共沸蒸馏干燥聚乙二醇(8200g/mol，76.6g)于甲苯(216g)中的溶液。将溶液冷却到90℃之后，添加DESMODUR H(HDI，4.94g)，并将溶液搅拌5分钟。将辛酸铋(0.19g)添加至溶液中，并将反应混合物搅拌1小时。将聚乙二醇(8200g/mol，175.1g)添加至搅拌的反应混合物中，并将混合物在90℃下再搅拌一小时。将反应混合物冷却到室温，并经由旋转蒸发去除溶剂。分离出呈白色固体状的聚合物。0.35E8000/1.1HDI//0.8PEG8000。Mn＝96,000；Mw＝188,000
实例5
在完全室内真空下，在110℃下将聚乙二醇(8200g/mol，1314.8g)混合于Sigma批料熔融反应器中，保持2小时。将反应器冷却到90℃并用氮气净化之后，将丁基化羟基甲苯(0.14g)和乙二胺(1.2g)分别添加至反应器中，并在氮气下，在90℃下将熔融混合物混合5分钟。将DESMODUR N3600(26.9g)和乙氧基化甘油(1236g/mol，33.0g)分别添加至反应器中，并将反应混合物再混合5分钟。将辛酸铋(3.3g)添加至反应器中，并将反应混合物在90℃下混合10分钟。从反应器取出所得熔融聚合物并冷却到室温。0.8PEG8000/0.1乙二胺/0.3667N3600/0.2Gly-EO(26)。Mn＝13,000；Mw＝1,300,000
实例6(比较)
通过共沸蒸馏干燥聚乙二醇(4000g/mol，102.6g)于甲苯(287g)中的溶液。将溶液冷却到90℃之后，添加乙二胺(0.193g)，并将溶液搅拌5分钟。分别添加DESMODUR N3600(4.30g)和乙氧基化甘油(1236g/mol，5.28g)，并将反应混合物再搅拌5分钟。添加辛酸铋(0.26g)，并将反应混合物搅拌1小时。将反应混合物冷却到室温，并经由旋转蒸发去除溶剂。分离出呈白色固体状的聚合物。0.8PEG4000/0.1乙二胺/0.3667N3600/0.2Gly-EO(26)
实例7(比较)
通过共沸蒸馏干燥聚乙二醇(4000g/mol，73.6g)于甲苯(220g)中的溶液。将溶液冷却到90℃之后，分别添加DESMODUR N3600(2.74g)和乙氧基化甘油(1236g/mol，3.36g)，并将溶液搅拌5分钟。将辛酸铋(0.38g)添加至溶液中，并将反应混合物搅拌1小时。将反应混合物冷却到室温，并经由旋转蒸发去除溶剂。分离出呈白色固体状的聚合物。0.9PEG4000/0.3667N3600/0.2Gly-EO(26)
％ OT，mins 1d粘连性，N 1d粘性，N 平整性 应变，DE Tea
实例1 1 9.3 42 32 6.0 11.0
实例2 1 9.1 28 25 5.4 16.8
实例3 1 6.3 85 84 5.9 12.9
对照物 1 5.1 65 87 6.0 9.7
OTE-500 1 9.4 104 125 4.2 18.2
OT是凝固时间；1天粘连性以牛顿表示；1d粘性以牛顿表示；OTE-500是商购的凝固时间添加剂(RHODOLINE OTE-500添加剂，Solvay,Inc.)，其包含非离子型和阴离子型乙氧基化三苯乙烯基苯酚硫酸酯；％添加剂是以乳胶漆的总重量计。
尽管OTE-500具有良好凝固时间，但其降低抗粘连性、抗粘性、平整性及抗污染性，而本发明的聚合物具有良好的凝固时间并且相较于OTE-500，对粘连性、粘性、平整性及污染具有较低或极小影响。意外地发现，相较于对照物，实例2的产物增加抗粘连性和抗粘性。
％ OT，mins
实例1 2 10
实例2 2 11
实例3 2 9.3
实例4 2 12
实例5 2 12.3
实例6 2 5.0
实例7 2 5.7
OTE-500 2 11
OT一般随含量增加而增加。然而，OTE-500由于抗粘连性和抗粘性减弱而通常甚至无法在1％下使用，而相较于OTE-500，PEU和PEUU可以在较高含量下使用，并因此可以实际上增加凝固时间。
实例 ％PEO EO平均Mw PEO分数×EO平均Mw OT(2％)
1 98.25 8200 8057 10
2 97.96 8200 8033 11
3 95.47 4931 4708 9.3
4 98.08 8200 8042 12
5 97.96 8200 8033 12.3
6 96.00 4000 3840 5
7 96.56 4000 3862 5.7
凝固时间是根据ASTM-D7488测量。通过首先用7密耳(0.18 mm)刮浆刀将油漆配制物施加至白色乙烯基衬底来进行抗污染性研究。使膜静置7天，并且使用经过校准的平板扫描仪扫描衬底以获得基线测量值。随后将染色剂施加至干燥膜上，并且使其固化2小时，之后进行去除测试：将Leneta SC-1非研磨介质与水(3:2 v/v)组合以形成溶液。将溶液的薄膜施加至经过染色的涂层上；将非研磨海绵浸渍于溶液中10秒，随后在约5 kPa的压力下使其与经过染色的涂层接触，并且在60个循环/分钟(来回＝1个循环)下振荡100秒。用水冲洗经过擦洗的衬底，并且用扫描仪使经过染色的衬底成像，以在基线与经过擦洗的染色剂之间在实验座标中测量均方根差(ΔE76)。
使用Leneta平整性测试刀片LTB-2的微型类似物制备平整性刮涂膜(drawdown)。在CTR条件下水平地干燥刮涂膜。获取干燥膜的图像并使用经过校准以模拟Leneta刮涂膜平整度标准LS-2的定制软件进行分析。
在22℃和50％RH下使经过涂覆的样品固化24小时。使用定制的自动高通量摩擦计测量粘性。使用1 N的力，将3/8”(9.5 mm)直径的304类型不锈钢球放在涂层表面上。施加此力保持5秒，之后测量将所述球从所述表面移开所需的力。
在22℃和50％RH下使经过涂覆的样品固化24小时。用Epilog Zing激光器将样品精确切割成0.5”×0.5”(12.7×12.7mm)。在50℃下，在施加8kPa压力的重物下将两个经过涂覆的样品彼此接触放置，保持30分钟。接着使用TA-XT Plus物性分析仪测量将其分离所需的力。

Claims (10)

1.一种亲水性聚氨基甲酸酯，所述聚氨基甲酸酯包含以下聚合单元：(a)具有两个至四个羟基官能团并且重量平均分子量是800至16,000的水溶性多元醇；及(b)具有两个至六个异氰酸酯官能团的脂肪族聚异氰酸酯；其中环氧乙烷聚合单元占所述亲水性聚氨基甲酸酯至少85wt％；并且其中环氧乙烷聚合单元的重量分数与聚氧化乙烯平均分子量的乘积是4,200至16,000。
2.根据权利要求1所述的亲水性聚氨基甲酸酯，其中所述亲水性聚氨基甲酸酯的Mw是10,000至2,000,000。
3.根据权利要求2所述的亲水性聚氨基甲酸酯，其中环氧乙烷聚合单元占所述亲水性聚氨基甲酸酯至少90wt％。
4.根据权利要求3所述的亲水性聚氨基甲酸酯，其中所述水溶性多元醇包含：(i)重量平均分子量是4,000至10,000的水溶性聚乙二醇，及(ii)重量平均分子量是800至1,600的乙氧基化甘油。
5.一种亲水性聚氨基甲酸酯，所述聚氨基甲酸酯包含以下聚合单元：(a)具有两个至四个羟基官能团的至少一种水溶性多元醇，所述水溶性多元醇包含重量平均分子量是6,000至10,000的水溶性聚乙二醇；及(b)具有两个至六个异氰酸酯官能团的脂肪族聚异氰酸酯；其中环氧乙烷聚合单元占所述亲水性聚氨基甲酸酯至少85wt％。
6.根据权利要求5所述的亲水性聚氨基甲酸酯，其中所述水溶性多元醇包含：(i)重量平均分子量是6,000至10,000的水溶性聚乙二醇，及(ii)重量平均分子量是800至1,600的乙氧基化甘油。
7.根据权利要求6所述的亲水性聚氨基甲酸酯，其中环氧乙烷聚合单元占所述亲水性聚氨基甲酸酯至少90wt％。
8.一种乳胶漆，所述乳胶漆包含0.1至5wt％的亲水性聚氨基甲酸酯，所述亲水性聚氨基甲酸酯包含以下聚合单元：(a)具有两个至四个羟基官能团并且重量平均分子量是800至16,000的水溶性多元醇；及(b)具有两个至六个异氰酸酯官能团的脂肪族聚异氰酸酯；其中环氧乙烷聚合单元占所述亲水性聚氨基甲酸酯至少85wt％；并且其中环氧乙烷聚合单元的重量分数与聚氧化乙烯平均分子量的乘积是4,200至16,000。
9.根据权利要求8所述的乳胶漆，其中所述水溶性多元醇包含：(i)重量平均分子量是4,000至10,000的水溶性聚烷二醇，及(ii)重量平均分子量是800至1,600的乙氧基化甘油。
10.根据权利要求9所述的乳胶漆，其中所述亲水性聚氨基甲酸酯的Mw是10,000至2,000,000。
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