CN109354672A - 用疏水低聚物改性的环氧烷氨基甲酸酯缔合增稠剂 - Google Patents

用疏水低聚物改性的环氧烷氨基甲酸酯缔合增稠剂 Download PDF

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CN109354672A
CN109354672A CN201710656288.1A CN201710656288A CN109354672A CN 109354672 A CN109354672 A CN 109354672A CN 201710656288 A CN201710656288 A CN 201710656288A CN 109354672 A CN109354672 A CN 109354672A
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D·R·霍金斯
J·J·拉巴斯克
A·K·范戴克
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Abstract

本发明涉及一种包含缔合增稠剂的水溶液或分散液的组合物，所述缔合增稠剂具有聚(氧化烯‑氨基甲酸酯)主链和包含丙烯酸酯、甲基丙烯酸酯、苯乙烯或其组合的3个到20个结构单元的至少一个末端疏水物。布氏(Brookfield)、ICI和KU粘度分布可用本发明的所述组合物更方便地调谐。

Description

用疏水低聚物改性的环氧烷氨基甲酸酯缔合增稠剂
本发明涉及一种用疏水低聚物改性的环氧烷氨基甲酸酯缔合增稠剂。在过去几十年内疏水改性环氧乙烷氨基甲酸酯(HEUR)缔合增稠剂已经广泛用于涂布应用。这些非离子缔合增稠剂由具有内部、末端和在一些特定情况下侧链疏水物的多种组合的水溶性聚(环氧乙烷)主链(PEO)构成。HEUR一般通过使PEO与化学计量过量的二异氰酸酯反应以形成具有氨基甲酸酯(urethane、carbamate)基团(其表现为弱疏水物)和未反应的异氰酸酯基团的聚合物来制备。还可包括疏水二醇或二胺以引入附加侧链和主链疏水基团。为了完成疏水改性，中间体聚合物通常与直链C6-C24醇或胺反应以产生引起疏水相互作用的末端(和可能侧链)烷基。
即使这些创新和商业成功，HEUR化学性质仍受疏水物的组成限制，限于烷基、烷基-芳基或烷基-胺。虽然这些疏水物通常足够用于增稠，但是配制者想要对特定乳胶组合物的增稠和剪切稀化行为的更多控制，和更高时间依赖性行为，以形成具有优异增稠特性的增稠剂。当前用于制备HEUR的疏水物不足以控制水/疏水物和乳胶/疏水物相互作用的变化。因此，发现提供独立地调谐疏水性和乳胶相互作用的方式的一类疏水物将为HEUR化学性质本领域中的进步。
发明内容
本发明通过提供一种包含缔合增稠剂的水溶液或分散液的组合物来解决本领域中的需要，所述缔合增稠剂具有聚(氧化烯-氨基甲酸酯)主链和包含丙烯酸酯、甲基丙烯酸酯、苯乙烯或其组合的3个到20个结构单元的至少一个末端疏水物。本发明的增稠剂允许布氏(Brookfield)、KU和ICI粘度的便捷优化。
具体实施方式
本发明为一种包含缔合增稠剂的水溶液或分散液的组合物，所述缔合增稠剂具有聚(氧化烯-氨基甲酸酯)主链和包含丙烯酸酯、甲基丙烯酸酯、苯乙烯或其组合的3个到20个结构单元的至少一个末端疏水物。
如本文所用，所述单体的术语“结构单元”是指单体在低聚之后的残余部分。举例来说，甲基丙烯酸甲酯的结构单元如下表示：
其中虚线表示附接到聚合物主链的点。
如本文所用，聚(氧化烯-氨基甲酸酯)主链为含有通过氨基甲酸酯基团共价连接的氧化乙烯、氧化丙烯或氧丁烯基团的聚合物。优选地，聚(氧化烯-氨基甲酸酯)为聚(氧化乙烯-氨基甲酸酯)。
至少一个末端疏水物优选地由式I表示：
其中R为C2-C20二价烃基，优选地C2-C10支链或直链二价亚烷基；R1为H或甲基；并且R2为C1-C18-烷基、C5-C8-环烷基、芳基、C1-C18-烷芳基、C1-C3-二烷基氨基-C1-C18-烷基、C1-C30-烷氧基-(CH2CH2O)z-CH2CH2-、芳氧基-(CH2CH2O)zCH2CH2或缩水甘油基；n为0到20，优选地3到10；m为0到20，优选地0到10；m+n为3到20，优选地3到10，更优选地3到8；并且z为0到50，优选地10到30。
优选的R基团的实例包括-CH2CH2-、-CH2CH2CH2-基团；合适的R2基团的实例包括甲基、乙基、正丁基、2-乙基己基、2-丙基庚基、二甲氨基乙基、叔丁基氨基乙基、环己基、异冰片基和月桂基；合适的R2基团的其它实例包括乙氧基化醇和二烷基胺，如C10H21O(CH2CH2O)zCH2CH2-、C18H35O-(CH2CH2O)z-CH2CH2-、C16H33O(CH2CH2O)zCH2CH2-、C12H25O(CH2CH2O)zCH2CH2-、C22H45O-(CH2CH2O)z-CH2CH2-、三苯乙烯基苯氧基(CH2CH2O)zCH2CH2-、二丁氨基-(CH2CH2O)z-CH2CH2-和双(2-乙基己基)氨基-(CH2CH2O)z-CH2CH2-。
优选地，主链用两个疏水物，更优选地两个结构I的疏水物封端。主链还可包括由存在多异氰酸酯支化剂的结构单元产生的侧链疏水物，或由疏水二醇或二胺产生的并入主链中的疏水物；支化剂，如丙三醇还可用于将支化点引入聚合物主链中。
结构I的疏水物由式II表示的相对应的醇或胺产生：
其中R、R1、R2、m和n为先前定义。
低聚物可在存在羟基烷基硫醇链转移剂的情况下通过丙烯酸酯、甲基丙烯酸酯或苯乙烯单体或其组合的自由基低聚来制备。低聚的程度可通过调节单体与链转移剂的比率来控制。
缔合增稠剂，其为疏水改性的环氧烷氨基甲酸酯缔合增稠剂，优选地疏水改性的环氧乙烷氨基甲酸酯(HEUR)缔合增稠剂，通过在反应条件下使a)醇或胺官能化的丙烯酸酯、甲基丙烯酸酯或苯乙烯低聚物与3个到20个单体单元，优选地式II的醇或胺；b)多异氰酸酯；和c)水溶性聚烷二醇在一起接触方便地制备
多异氰酸酯起始物质为C4-C20脂肪族或芳香族二异氰酸酯或三或四异氰酸酯支化剂。如本文所用，“脂肪族二异氰酸酯”是指饱和或部分不饱和直链、支链或环脂肪族二异氰酸酯，或其组合。合适的二异氰酸酯的实例包括1,4-四亚甲基二异氰酸酯、1,6-六亚甲基二异氰酸酯、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(异氰酸基环己烷)、1,4-亚环己基二异氰酸酯、1-异氰酸基-3-异氰酸基甲基-3,5,5-三甲基环己烷、间亚苯基二异氰酸酯和对亚苯基二异氰酸酯、2,6-甲苯二异氰酸酯和2,4-甲苯二异氰酸酯、二甲苯二异氰酸酯、4-氯-1,3-亚苯基二异氰酸酯、4,4′-亚联苯基二异氰酸酯、4,4′-亚甲基二苯基异氰酸酯、1,5-亚萘基二异氰酸酯和1,5-四氢亚萘基二异氰酸酯。合适的三异氰酸酯包括异氰脲酸酯三聚体和缩二脲三聚体，其特征在于下式：
其中R'为C4-C20亚烷基。如本文所用，“亚烷基”是指双自由基饱和或部分饱和的烃基，其为直链、支链或环脂族或其组合。
合适的异氰脲酸酯三聚体的实例包括六亚甲基二异氰酸酯(HDI)三聚体，以Desmodur N 3600可商购的脂肪族多异氰酸酯，和异佛尔酮二异氰酸酯(IPDI)三聚体，以Demodur X 4470可商购的脂肪族多异氰酸酯。
水溶性聚烷二醇是指水溶性聚环氧乙烷、水溶性聚环氧乙烷/聚环氧丙烷共聚物和水溶性聚环氧乙烷/聚环氧丁烷共聚物。
优选的水溶性聚环氧烷为聚乙二醇，具体地说重均分子量(Mw)在4000、更优选6000并且最优选7000到20,000、更优选到12,000并且最优选到9000道尔顿(Dalton)的范围内的聚乙二醇。合适的聚乙二醇的实例为PEG 8000，其以CARBOWAXTM8000聚乙二醇(陶氏化学公司(The Dow Chemical Company)或其附属公司的商标)购得。
本发明的组合物适用于涂料配方，尤其油漆配方，其可包括以下材料中的任一者或全部：溶剂；填料；无机颜料，如二氧化钛、云母、碳酸钙、二氧化硅、氧化锌、三水合铝、滑石、三氧化锑、飞灰和粘土；有机中空球体颜料；分散剂；表面活性剂；消泡剂；防腐剂，如杀生物剂、防霉剂、杀真菌剂、除藻剂和其组合；助流剂；调平剂；和附加中和试剂，如氢氧化物、胺、氨水和碳酸盐。
本发明的缔合增稠剂的疏水物为配制者提供对特定乳胶组合物的增稠和剪切稀化行为的更多控制以及更高时间依赖性行为。更具体地说，本发明的低聚疏水改性的缔合增稠剂通过提供独立地调谐疏水性和乳胶相互作用的方式克服当前增稠剂的限制。单体组合物和单体的选择容易地改变以调节疏水物在乳胶粒子中的溶解度，同时维持在水或配制物浆液相中的疏水性。
实例
中间体实例1-制备羟基化甲基丙烯酸丁酯低聚物
将甲苯(200g)装入配备有水冷凝器、电动搅拌器、电子热电偶和N2吹扫的1-L的4-颈圆底烧瓶。将反应烧瓶的内容物加热到85℃，此时将甲基丙烯酸丁酯(BMA，284g)、2-羟乙基硫醇(31.2g)和甲苯(160.5g)的单体混合物的一部分(23.8g)添加到烧瓶中，紧接着添加2,2'-偶氮异丁腈(AIBN，1.42g)与甲苯(30g)的混合物的引发剂溶液。混合物搅拌15min，在所述时间之后，以0.29g/min的进料速率添加AIBN(2.84g)和甲苯(50g)的共进料引发剂溶液。在开始共进料引发剂溶液进料之后一分钟，单体混合物的剩余部分以4.0g/min的进料速率进料到反应器中。在两种进料完成之后，将反应混合物在85℃下搅拌16小时。
在反应混合物冷却到室温之后，在真空中去除甲苯。将残余物溶解在乙醚(～600g)中并且放置于分液漏斗中。乙醚溶液用5％水性碳酸钠(500g)洗涤两次并且在真空中去除乙醚。聚合度(dp)为5的羟基封端的BMA低聚物分离为粘稠的可流动产物。
中间体实例2-制备羟基化甲基丙烯酸甲酯低聚物
基本上遵循对于实例1的程序，其中具有以下修改：将甲基丙烯酸甲酯(MMA，200g)、2-羟乙基硫醇(31.2g)和甲苯(50g)的单体混合物的一部分(28.1g)初始地添加到釜中，随后添加具有甲苯(50g)的引发剂溶液(AIBN，1.42g)。然后添加含有AIBN(3.10g)和甲苯(55g)的共进料引发剂溶液，随后添加单体混合物的剩余部分。其中dp＝5的所得羟基化MMA低聚物分离为粘稠的可流动产物。
实例1-制备用羟基化BMA低聚物官能化的HEUR
将CARBOWAXTM8000聚乙二醇(150g)和甲苯(340g)的混合物添加到容器中并且通过共沸蒸馏干燥。混合物冷却到90℃，在所述温度下在搅拌下将Desmodur H脂肪族二异氰酸酯(4.51g)添加到容器中。在容器的内容物搅拌5min之后，将二月桂酸二丁基锡(0.21g)添加到容器中。继续搅拌1h，在所述时间之后，混合物冷却到80℃。然后将来自实例1的BMA低聚物(15.40g)添加到容器中并且再继续搅拌1h。混合物冷却到60℃，添加丁基化羟基甲苯(BHT)(0.05g)，并且在真空中去除溶剂以分离聚合物。
实例2-制备用羟基化MMA低聚物官能化的HEUR
将CARBOWAXTM8000聚乙二醇(150g)和甲苯(360g)的混合物添加到容器中并且通过共沸蒸馏干燥。混合物冷却到90℃，在所述温度下将Desmodur N3600HDI三聚体(0.74g)添加到容器中。在容器的内容物搅拌5min之后，将二月桂酸二丁基锡(0.21g)添加到容器中。继续搅拌1h，在所述时间之后，添加Desmodur H脂肪族二异氰酸酯(3.76g)。继续搅拌1h，在所述时间之后，混合物冷却到80℃。然后将来自实例2的MMA低聚物(8.33g)添加到容器中并且再继续搅拌1h。混合物冷却到60℃，添加BHT(0.05g)，并且在真空中去除溶剂以分离聚合物。
在表1中示出的配方中评估本发明的缔合增稠剂。母料不包括最终水和流变改性剂添加量。
表1-油漆配方
Wt(g)
研磨剂
水 30.00
Kronos 4311 263.38
RHOPLEX<sup>TM</sup>SG-30丙烯酸乳液 421.82
ROPAQUE<sup>TM</sup>超不透明聚合物 49.78
乙二醇 24.30
Texanol聚结剂 19.19
Triton X-405 2.50
研磨剂小计 810.98
调稀剂 810.98
流变改性剂 a
水<sup>b</sup> 200.17
MP-95分散剂
DrewplusL-475泡沫控制剂 4.07
总计 1015.22
RHOPLEX和ROPAQUE为陶氏化学公司或其附属公司的商标
a参见表2
b将水和流变改性剂添加到母料中
含有实例1的缔合增稠剂的油漆配方(油漆1A、1B和1C)以KU和ICI粘度为目标来制备。在相同KU和ICI粘度下测量含有KU增效剂ACRYSOLTMRM825流变改性剂(陶氏化学公司或其附属公司的商标)的比较油漆配方C1A、C1B和C1C的布氏粘度和抗熔垂性(Sagresistances)。此比较研究的结果在表2中示出。2020E是指ICI增效剂，ACRYSOLTMRM2020流变改性剂；Bf4/0.6意指布氏仪器，在0.6rpm下的转子#4。
表2-布氏粘度和抗熔垂性比较研究
具有实例1增稠剂的油漆配方示出了在一系列ICI和KU粘度内显著改善的布氏粘度和抗熔垂性。
还已经发现，KU、ICI和Bf粘度可用本发明的HEUR调谐。在以下表3中，油漆1D和1E使用实例1HEUR制备；油漆2A和2B由实例2HEUR制备；并且比较油漆C2A和C2B使用市售低剪切增稠剂，ACRYSOL RM-12流变改性剂制备。以克计的HEUR的重量是指干重。
表3-ICI、KU和布氏粘度比较
油漆 HEUR(g) KU ICI B<sub>f</sub>
1D 2.83 112 0.3 31100
1E 3.52 111.4 0.3 40100
1F 7 130 0.7 67900
2A 7.5 94.8 0.7 7300
2B 10 104.2 1.0 12000
C2A 3.56 84.5 0.2 32200
C2B 5.34 105 0.1 13500
表3示出在配方中递增量的HEUR的情况下KU、ICI和布氏粘度普遍改善。相比之下，具有市售流变改性剂的油漆配方示出了改善的KU但是较不良KU和ICI分布。

Claims (7)

1.一种组合物，其包含缔合增稠剂的水溶液或分散液，所述缔合增稠剂具有聚(氧化烯-氨基甲酸酯)主链和包含丙烯酸酯、甲基丙烯酸酯、苯乙烯或其组合的3个到20个结构单元的至少一个末端疏水物。
2.根据权利要求1所述的组合物，其中所述疏水物由下式表示：
其中R为C2-C20二价烃基；R1为H或甲基；并且R2为C1-C18-烷基、C5-C8-环烷基、芳基、C1-C18-烷芳基、C1-C3-二烷基氨基-C1-C18-烷基、C1-C30-烷氧基-(CH2CH2O)z-CH2CH2-、芳氧基-(CH2CH2O)zCH2CH2-或缩水甘油基；n为0到20；m为0到20；并且m+n为3到20。
3.根据权利要求1所述的组合物，其中X为O；R为直链或支链C2-C10亚烷基；R2为甲基、乙基、正丁基、2-乙基庚基、二甲氨基乙基、叔丁基氨基乙基、环己基、异冰片基、月桂基、C10H21O(CH2CH2O)zCH2CH2-、C18H35O-(CH2CH2O)z-CH2CH2-、C16H33O(CH2CH2O)zCH2CH2-、C12H25O(CH2CH2O)zCH2CH2-、C22H45O-(CH2CH2O)z-CH2CH2-、三苯乙烯基苯氧基(CH2CH2O)zCH2CH2-、二丁氨基-(CH2CH2O)z-CH2CH2-和双(2-乙基己基)氨基-(CH2CH2O)z-CH2CH2-；其中z＝0到50；m为3到10；n为0到10；并且m+n为3到10。
4.根据权利要求2或3中任一权利要求所述的组合物，其中R为-CH2CH2-；R1为H或CH3；R2为甲基、乙基、正丁基或2-乙基庚基；m为3到10；并且n为0。
5.根据权利要求1到3中任一权利要求所述的组合物，其中所述缔合增稠剂具有聚(氧化乙烯-氨基甲酸酯)主链和两个末端疏水物。
6.根据权利要求5所述的组合物，其中所述聚(氧化乙烯-氨基甲酸酯)主链包含侧链以及末端疏水物。
7.根据权利要求4所述的组合物，其中R为-CH2CH2-；R1为H或CH3并且R2为甲基或丁基，其条件是当R1为甲基时，R2为甲基，并且当R1为H时，R2为丁基；并且m+n为3到8。
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