CN103373929B - 二苄基胺疏水物 - Google Patents

二苄基胺疏水物 Download PDF

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CN103373929B
CN103373929B CN201310134240.6A CN201310134240A CN103373929B CN 103373929 B CN103373929 B CN 103373929B CN 201310134240 A CN201310134240 A CN 201310134240A CN 103373929 B CN103373929 B CN 103373929B
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J·J·拉巴斯科
B·R·博布辛
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Abstract

本发明涉及由下式表示的化合物：式中各R1独立地是甲基或乙基，n是1-10。所述化合物可以在制备疏水改性的环氧烷氨基甲酸酯聚合物中使用，它用于涂料制剂用作流变改性剂。

Description

二苄基胺疏水物
背景技术
本发明涉及可用于制备疏水改性的环氧烷氨基甲酸酯聚合物的基于胺的疏水物，所述聚合物可用于涂料制剂用作流变改性剂。
流变改性剂通常被设计用来在较宽的剪切速率范围内赋予涂料制剂所需的流变性质。美国专利第7,741,402号揭示了用疏水物改性的环氧乙烷氨基甲酸酯聚合物，其包含有机碱如仲胺或叔胺(胺改性的HEUR)，该部分的存在使得可以通过调节pH来控制粘度。当HEUR组合物的pH相对于结合的碱的pKa而言足够低时，碱基被质子化，粘度较低；当pH足够高时，发生缔合性增稠。因此，将碱性疏水物结合到HEUR聚合物中，可以使得在低pH下有较高浓度的聚合物溶解在水中；一旦该溶液加入高pH的漆涂料环境中，碱脱质子化，缔合性增稠机理被激活。
胺改性的HEUR对它所加入的漆制剂的pH敏感。例如，制剂的pH在长时间和热老化后可能降低到有助于缔合性增稠的临界pH以下的水平，由此产生较差的制剂；因此，希望发现一种疏水物，尤其是基于胺的疏水物，能够在面对pH降低机理时将制剂保持在所需的粘度。
发明内容
在一个方面，本发明通过提供由下式表示的化合物解决了该需求：
式中各R1独立地是甲基或乙基，n是1-10。
在第二个方面，本发明提供一种包含疏水改性的环氧烷氨基甲酸酯聚合物的稳定水性分散体的组合物，所述环氧烷氨基甲酸酯聚合物具有由以下结构表示的叔胺基封端：
其中R1和n如上文定义。
本发明的聚合物可用作在宽pH范围内配制的漆制剂的流变改性剂。
发明详述
在第一个方面，本发明提供一种由下式I表示的化合物：
其中R1和n如上文定义。优选地，R1是乙基，n优选为3-5。
本发明的化合物可以根据以下方案进行制备：
在第二个方面，本发明提供一种包含疏水改性的环氧烷氨基甲酸酯聚合物的稳定水性分散体的组合物，所述环氧烷氨基甲酸酯聚合物具有由下式Ia表示的叔胺基封端：
其中R1和n如上文定义。R1优选是乙基，n基本上优选为3-6。
较佳地，所述疏水改性的环氧烷氨基甲酸酯聚合物通过在反应条件下，将a)式I化合物，b)二异氰酸酯和c)水溶性聚亚烷基二醇接触来制备。
二异氰酸酯原料是C4-C20脂族或芳族二异氰酸酯。本文所用的“脂族”表示饱和或部分饱和的直链、支链、脂环族或它们的组合。合适的二异氰酸酯的例子包括1,4-丁二异氰酸酯、1,6-己二异氰酸酯、2,2,4-三甲基-1,6-二异氰酸根合己烷、1,10-癸二异氰酸酯、4,4’-亚甲基二(异氰酸根合环己烷)、1,4-环己二异氰酸酯、1-异氰酸根合-3-异氰酸甲酯基-3,5,5-三甲基环己烷、间苯二异氰酸酯和对苯二异氰酸酯、2,6-甲苯二异氰酸酯和2,4-甲苯二异氰酸酯、苯二亚甲基二异氰酸酯、4-氯-1,3-苯二异氰酸酯、4,4’-联苯二异氰酸酯、4,4’-亚甲基二苯基异氰酸酯、1,5-萘二异氰酸酯和1,5-四氢萘二异氰酸酯。
水溶性聚亚烷基二醇涉及水溶性聚环氧乙烷、水溶性聚环氧乙烷/聚环氧丙烷共聚物、水溶性聚环氧乙烷/聚环氧丁烷共聚物。本文所用的术语“环氧丙烷”指的是具有-(OCH2CH2CH2)-和/或-(OCH(CH3)CH2)-重复基团的聚合物。
优选的水溶性聚环氧烷是聚乙二醇，特别是重均分子量在从4000、更优选从6000、最优选从7000到20,000、更优选到12,000、最优选到9000道尔顿的范围内的聚乙二醇。合适的聚乙二醇的例子是PEG8000，可作为CARBOWAXTM8000聚乙二醇(美国密歇根州米德兰的陶氏化学公司或其附属公司的商标)购得。
或者，水溶性聚环氧烷可与多异氰酸酯以外的多官能基团连接，形成能受益于本发明中所述的叔胺改性的非氨基甲酸酯组合物。合适的备选连接基的例子包括表卤醇、偕二卤化物(gem dihalides)和氨基塑料。
本发明的组合物可以在涂料制剂，特别是漆制剂中使用，它可以包括以下材料中的任一种或全部：溶剂；填料；颜料，例如二氧化钛、云母、碳酸钙、二氧化硅、氧化锌、研磨玻璃、三水合铝、滑石、三氧化锑、飞灰和粘土；聚合物包封的颜料，例如聚合物包封或部分包封的遮光颜料颗粒，包括二氧化钛、氧化锌或锌钡白聚合物；吸附或结合在颜料如二氧化钛表面的聚合物或聚合物乳液；空心颜料，包括具有一个或多个空穴的颜料；分散剂，例如氨基醇和聚羧酸盐(酯)；表面活性剂；消泡剂；防腐剂，例如杀生物剂、防霉剂、杀真菌剂、除藻剂和它们的组合；流动剂；均化剂；额外的中和剂，例如氢氧化物、胺、氨和碳酸盐(酯)。
例如，涂料制剂可包括聚合物包封的遮光颜料颗粒，其包含i)遮光颜料颗粒，例如二氧化钛颗粒，直径为100nm-500nm，折射率至少为1.8；ii)包封聚合物；和iii)用于包封的遮光颜料颗粒和所述聚合物的聚合物分散剂。这些聚合物包封的遮光颜料颗粒的描述参见例如美国专利公开US2010/0298483A1。在另一个例子中，涂料组合物可包含如WO2007/112503A1中所述的聚合物包封的遮光颜料颗粒。
实施例
下面的实施例仅是为了阐述，而不是用来限制本发明的范围。
中间体1
将二苄基胺(7627 g)加入24L N2吹扫的压力容器中。对反应器用N2加压并排空数次，然后用N2加压并加热至130℃。将环氧乙烷(1880 g)以保持压力低于60psia的速率进料至反应器（约4h）。环氧乙烷加料完成之后，在130℃搅拌反应混合物14小时。温度降至60℃并释放压力之后，将45％氢氧化钾(70 g)加入容器中，在110℃搅拌反应混合物以去除水。将温度升至130℃，将环氧丁烷(11,277g)以保持压力低于60 psia的速率进料至反应器（约31h）。加料完成之后，在130℃搅拌反应混合物4小时。将反应混合物冷却至室温，用乙酸中和该反应混合物。
中间体2
在配有冷凝器、加料漏斗和机械搅拌器的圆底烧瓶中，将二(2-乙基己基)胺(2010.0克)在氮气气氛下加热到110℃。在剧烈搅拌下，在2小时内向反应器中滴加缩水甘油(685克)。在缩水甘油加料完成后，继续搅拌1小时。通过真空蒸馏(165-175°C;1.0毫米汞柱)纯化产物。
中间体3
在配有冷凝器和机械搅拌器的圆底烧瓶中，将二戊基胺(372.4克)、丁基缩水甘油醚(346.2克)和水(27克)在氮气气氛下加热到回流(105-115℃)。5小时后，将混合物冷却到30°C。在30-150°的温度范围内通过真空蒸馏(14毫米汞柱)除去水和残留的丁基缩水甘油醚之后，分离产物。
实施例1–基于中间体1制备HEUR聚合物
在间歇式熔融反应器中将CARBOWAXTM8000聚乙二醇(陶氏化学公司及其附属公司的商标，分子量为8200;1539.1克)在真空下加热至110℃并保持2小时。然后加入丁基化羟基甲苯(BHT,0.191g)并混合5分钟。再向反应器中加入Desmodur W H12-MDI(108.19g)，并混合5分钟。然后向反应器中加入辛酸铋溶液(28%,3.85克)，在搅拌下将混合物的温度在110°C保持10分钟。再向反应器中加入中间体1(258.16g)，在搅拌下将温度在110°C保持10分钟。从反应器中移出所得的熔融的聚合物并冷却。
对比例1–基于二(2-乙基己基)氨基乙醇制备HEUR聚合物
在间歇式熔融反应器中将CARBOWAXTM8000聚乙二醇(分子量为8200;1709.8克)在真空下加热至110℃并保持2小时。然后，将反应混合物冷却到85°C，然后加入二(2-乙基己基)氨基乙醇(91.58克)，继续搅拌5分钟。然后向反应器中加入IPDI(78.44克)，继续混合5分钟。然后，向反应器中加入辛酸铋溶液(28%,4.27克)。然后该混合物在搅拌条件下在85℃保持20分钟。从反应器中移出所得的熔融的聚合物并冷却。
对比例2–基于二(2-乙基己基)氨基乙醇制备HEUR聚合物
在间歇式熔融反应器中将CARBOWAXTM8000聚乙二醇(分子量为8200;1844.0克)在真空下加热至110℃并保持2小时。将中间体2(31.54克)和中间体3(19.74克)加入反应器中，混合5分钟。然后向反应器中加入IPDI(76.38克)，继续混合5分钟。然后，向反应器中加入辛酸铋溶液(28%,4.40克)。然后该混合物在搅拌条件下在110℃保持12分钟。从反应器中移出所得的熔融的聚合物并冷却。
热老化稳定性研究
在颜料体积浓度为40.5％，总固体浓度为38.0体积％的缎光白制剂中评价增稠的漆的热老化稳定性。以湿漆制剂的重量为基准计，所述制剂包含30.3重量％的湿ROVACETM661乙烯基丙烯酸类粘结剂（陶氏化学公司或其附属公司的商标），以及4.1重量％的湿RHOPLEXTMSG-10M丙烯酸类共聚物（陶氏化学公司或其附属公司的商标）。已经知道，初始pH约为9的包含聚(乙酸乙烯酯)粘结剂的漆在老化后由于乙酸酯基的水解而发生pH降低。初始漆pH约为9，有助于漆的胶体稳定性和杀生物稳定性。老化后漆的pH通常降低到约pH=7，此时水解速率明显减慢。在实验室研究中常采用热老化来加快显现漆老化的效果。如果老化后出现大幅粘度下降，则是不利的。表1示出热老化稳定性的研究结果。
表1
增稠剂 使用水平(%) pH1 斯托默1 pH2 斯托默2 Δ斯托默
实施例1 0.32 9.0 99 8.8 102 +3
对比例1 0.51 9.1 95 8.1 73 -22
对比例2 0.40 9.0 111 8.2 81 -30
SCT-275 0.41 9.0 109 8.1 96 -12
使用水平(%)是漆中使用的增稠剂的浓度。该浓度表示为每单位最终漆湿重量的干燥活性增稠剂的重量百分数。实施例1-3的增稠剂和对比例的增稠剂以16重量％活性增稠剂水分散体的形式加入。这些水性增稠剂分散体还包含3％(湿重)的乳酸(以供货形式提供)。乳酸以85％固体的形式提供。增稠剂分散体通过以下方式制备：将干燥的增稠剂固体、水和乳酸在50毫升密封塑料离心管中混合，缓慢旋转混合物两天，以完全均化增稠剂固体。
pH1是各漆配制后1小时测量的漆的初始pH。用氨将pH调节到所示的值。
斯托默1是在半品脱金属罐中在25°C测量的漆的初始斯托默粘度，为克雷布斯单位。斯托默1是在漆配制后24小时测量的。在此平衡期间，将漆保持在25°C。在测量斯托默粘度之前，才将漆倒入半品脱金属罐中，用压舌板搅拌20秒。克雷布斯粘度计是符合ASTM-D562的旋转桨叶粘度计。KU粘度在购自布鲁克菲尔德工程实验室(Brookfield Engineering Labs)(美国麻萨诸塞州米德博罗(Middleboro,MA,USA))的布鲁克菲尔德克雷布斯单位粘度计KU-1+上测量。
pH2是在60℃烘箱储存2周后漆的pH值。在热老化过程中，将漆储存在密封金属罐中。
斯托默2是在半品脱金属罐中在25℃测量的经过热老化的漆的最终斯托默粘度，为克雷布斯单位。在测量斯托默粘度之前，才用压舌板剧烈搅拌漆20秒。
Δ斯托默(克雷布斯单位)等于斯托默2减斯托默1。Δ斯托默的值接近零是理想的。
SCT-275表示ACRYSOLTMSCT-275流变改性剂（陶氏化学公司的商标），它是可购自陶氏化学公司的非酸抑制性聚氨酯缔合性增稠剂。使用丁基卡必醇-水共溶剂混合物抑制产品的出厂粘度。
用实施例1中增稠剂增稠的漆与用对比例增稠的漆相比在老化后的粘度下降要小得多。用实施例1增稠的漆老化后的粘度下降与用市售流变改性剂增稠的漆的粘度下降类似，或前者优于后者，但与本发明的增稠剂不同，市售流变改性剂增加了所述漆的VOC。

Claims (1)

1.一种包含疏水改性的环氧烷氨基甲酸酯聚合物的稳定水性分散体的组合物，所述环氧烷氨基甲酸酯聚合物具有由以下结构表示的叔胺基封端：
式中各R1独立地是甲基或乙基，n是1-10。
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