CN117980367A - Ici提高流变改性剂 - Google Patents
Ici提高流变改性剂 Download PDFInfo
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- CN117980367A CN117980367A CN202280063913.0A CN202280063913A CN117980367A CN 117980367 A CN117980367 A CN 117980367A CN 202280063913 A CN202280063913 A CN 202280063913A CN 117980367 A CN117980367 A CN 117980367A
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- C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
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Abstract
本发明涉及一种组合物，该组合物包含支化HEUR的水性溶液和具有在11至19的范围内的HLB的非离子表面活性剂。本发明的组合物提供一种流变改性剂，该流变改性剂向配制者提供跨低剪切速率范围、中剪切速率范围和高剪切速率范围的粘度的独立控制。
Description
背景技术
本发明涉及一种流变改性剂，更具体地涉及一种非离子缔合型增稠剂，该非离子缔合型增稠剂可在宽剪切速率范围内赋予期望的流变特性。
当用于配制水性体系(诸如油漆和涂料)时，非离子缔合型增稠剂(诸如疏水改性的环氧乙烷氨基甲酸酯聚合物(HEUR))需要在宽剪切速率范围内的目标粘度(通常为10-4s-1至104s-1)。粘度通常在三个剪切范围下测量：低剪切范围、中剪切范围和高剪切范围，以快速评估所研究的体系的流变特性。在非离子缔合型增稠剂技术领域中长期存在的挑战是在一个剪切速率范围内调节水性涂料配方的粘度，同时在其他剪切速率范围内保持粘度相对不变。例如，将KU助洗剂添加到油漆配方中将中剪切粘度提高到期望水平，同时将低剪切(Brookfield)和高剪切(ICI)粘度提高到不期望的高水平。类似地，将ICI助洗剂添加到油漆配方将使高剪切粘度提高到目标水平，同时将Brookfield粘度和KU粘度提高到限制油漆配制者在Brookfield粘度、KU粘度和ICI粘度的最佳平衡下实现其目标流变特性的能力的水平。流变特性与应用性能直接相关；因此，在非离子缔合型增稠剂领域中需要发现在低剪切速率状态、中剪切速率状态和高剪切速率状态下提供独立粘度控制的流变改性剂。
发明内容
本发明通过提供包含支化疏水改性的环氧乙烷氨基甲酸酯聚合物(HEUR)的水性溶液和具有在11至19的范围内的HLB的非离子表面活性剂的组合物解决了本领域中的需要；其中：
支化HEUR用具有在3.5至7.0的范围内的cLog P的疏水部分封端；基于组合物的重量，HEUR的浓度在10重量％至25重量％的范围内；其中基于组合物的重量，表面活性剂的浓度在5重量％至25重量％的范围内；并且组合物的至少90重量％包含水、HEUR和表面活性剂。
本发明的组合物为油漆配制者提供了一种独立地控制在低剪切速率状态、中剪切速率状态和高剪切速率状态下的油漆粘度的方法。
具体实施方式
本发明是一种组合物，该组合物包含支化疏水改性的环氧乙烷氨基甲酸酯聚合物(HEUR)的水性溶液和具有在11至19的范围内的HLB的非离子表面活性剂的组合物；其中：
支化HEUR用具有在3.5至7.0的范围内的cLog P的疏水部分封端；基于组合物的重量，HEUR的浓度在10重量％至25重量％的范围内；其中基于组合物的重量，表面活性剂的浓度在5重量％至25重量％的范围内；并且组合物的至少90重量％包含水、HEUR和表面活性剂。
如本文所用，术语“支化疏水改性的环氧乙烷氨基甲酸酯聚合物(HEUR)(支化HEUR)”是指通过多异氰酸酯与以下物质的反应形成的疏水改性的环氧乙烷氨基甲酸酯聚合物：a)醇(或胺)；以及b)聚亚烷基二醇，诸如聚乙二醇，其中“多异氰酸酯”是指用至少3个异氰酸酯基团官能化的化合物。
支化HEUR用封端剂封端以形成具有在3.5至7.0的范围内的cLog P的疏水物。cLogP是使用ChemBioDraw Ultra 13.0(PerkinElmer)确定的，它使用化学片段算法方法来评估基于其组成部分的分子的分配系数。
非离子表面活性剂具有在11或13至19或至18的范围内的疏水-亲脂平衡(HLB)。HLB是根据Griffin，W.C.，非离子表面活性剂HLB值的计算(Calculation of HLB Valuesof Non-ionic surfactants)，Am Perfumer Essend Oil Rev6565，26-29(1954)计算的，更具体地说，是根据以下公式计算的：
其中MW是分子量。
适用于本发明的组合物的非离子表面活性剂包括具有2个至100个C2-C4-环氧烷基团、芳基C2-C4-环氧烷基团或芳烷基C2-C4-环氧烷基团的饱和或部分不饱和的C6-C60-烷基C2-C4-烷氧基化物。优选的环氧烷基团是环氧乙烷(EO)基团；如本文所用，“部分不饱和”允许在表面活性剂的烷基化部分中存在一个或多个双键。非离子表面活性剂的示例包括月桂基-O-(EO)5-17H、十三烷基-O-(EO)5-18H、蓖麻油-(EO)20--81H、十八烷基-O-(EO)6-31H、硬脂基-O-(EO)6-31H、辛基苯基-O-(EO)5-20-H、壬基苯基-O-(EO)5-20H和牛脂胺(EO)6-C25H。
蓖麻油是脂肪甘油三酯的混合物，主要组分具有以下结构：
蓖麻油的乙氧基化可发生在任何或所有羟基基团上。
例如，对于具有下式的非离子表面活性剂：
十二烷基-O-(CH2CH2O)9-H
该表面活性剂的总分子量＝565g/mol；并且9摩尔的环氧乙烷(EO)基团的分子量＝396g/mol。因此，
支化HEUR可如下制备：使多异氰酸酯与化学计量过量的水溶性聚亚烷基二醇反应，随后使所形成的中间体与化学计量过量的二异氰酸酯反应以形成具有异氰酸酯基团的支化聚氨酯聚合物，随后用封端剂将异氰酸酯基团封端。另选地，多异氰酸酯、二异氰酸酯和聚亚烷基二醇可在反应条件下一起接触，随后使形成的中间体与封端剂接触。
水溶性聚亚烷基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。如本文所用，术语环氧丙烷是指具有-(OCH2CH2CH2)-和/或-(OCH(CH3)CH2)-重复基团的聚合物。优选的水溶性聚环氧烷为聚乙二醇，尤其为具有在4000，更优选地6000并且最优选地7000至20,000，更优选地至12,000并且最优选地至9000道尔顿(Dalton)的范围内的重均分子量(Mw)的聚乙二醇。合适的聚乙二醇的示例为PEG 8000，其作为CARBOWAXTM8000聚乙二醇(陶氏化学公司(The Dow ChemicalCompany)(“陶氏(Dow)”)或其附属公司的商标)市售可得。
多异氰酸酯的示例包括氰尿酸酯和缩二脲三聚体，诸如HDI异氰脲酸酯(三聚体)和IPDI异氰脲酸酯(三聚体)，如下所示：
二异氰酸酯的示例包括1,4-四亚甲基二异氰酸酯、1,6-六亚甲基二异氰酸酯(HDI)、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)、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、1-异氰酸酯基-3-异氰酸酯基甲基-3,5,5-三甲基环己烷(IPDI)、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。
由其得到计算的log P(cLog P)的疏水部分由下式表征：
其中氧原子通过饱和碳原子与聚合物主链(虚线)共价键合；其中R1为二价基团并且R2和R3为经选择以实现期望cLog P的单价基团。
优选地，R1为C4-C14-烷基、C5-C8-环烷基或C1-C9-烷基基团和C5-C7-环烷基基团的组合。
优选地，R2为C3-C12-烷基、C5-C8-环烷基或苄基基团；X为O或NR2’，其中R2'为H或为获得期望cLog P而选择的一价基团。优选地，R2’为H、C2-C6烷基或C5-C8环烷基基团。
R3优选地为C9-C16-烷基、二苄基氨基-C2-C5-烷基、二-C4-C8-烷基氨基-C1-C4-烷基、C6-C8-烷基苯基基团、二苄基胺丁基缩水甘油醚醇加成物或二苄基胺2-乙基己基缩水甘油醚醇加成物。
合适的封端剂的示例包括C5-C14直链或支链醇；苄醇；二-C5-C10--胺；C4-C10-胺；二环己基胺；环己胺；苄基甲基胺；以及C10-C16-烷基-(EO)1-40H；以及双(C4-C10-烷基)氨基-(EO)1-40-H。
在表1中示出了在期望cLog P范围的范围内的R1、R2和R2’基团的组合的示例，并且在表2中示出了在期望cLog P范围的范围内的R3基团的示例。
表1-R1、R2和R2’疏水性片段的cLog P值
表2-R3疏水性片段的cLog P值
| O-R3基团 | clogP |
| 1-癸基-O- | 3.89 |
| 1-十一烷基-O- | 4.42 |
| 1-十二烷基-O- | 4.95 |
| 1-十三烷基-O- | 5.48 |
| 1-十四烷基-O- | 6.01 |
| 2-丁基-1-辛基-O- | 4.82 |
| 双(2-乙基己基)N(乙基)-O- | 6.75 |
| DBA-BGE-O- | 4.56 |
| DBA-EHGE-O- | 6.54 |
DBA-BGE-O-和DBA-EHGE-O-分别指二苄基胺丁基缩水甘油醚醇加成物和二苄基胺2-乙基己基缩水甘油醚醇加成物的残余物：
其中残余物由相应的醇产生。
在另一方面，基于组合物的重量，HEUR和表面活性剂的浓度在10重量％至20重量％的范围内，并且至少95重量％或至少99重量％的组合物包含水、HEUR和表面活性剂。已经令人惊讶地发现，本发明的组合物允许显著改善对油漆配方中的低剪切粘度、中剪切粘度和高剪切粘度的控制。
实施例
在表3所示的油漆配方中评价HEUR。TiO2是指Ti-Pure R-746浆料；分散剂是指TAMOLTM731分散剂；消泡剂1是指BYK 348消泡剂；消泡剂是指Tego Foamex 810消泡剂；丙烯酸乳胶是指RHOPLEXTMVSR-2015丙烯酸乳胶；并且HEUR是指实施例HEUR和比较例HEUR。
表3–油漆配方
| 预混物 | 重量(g) |
| TiO2 | 349.8 |
| 分散剂 | 7.5 |
| 消泡剂1 | 1.0 |
| 消泡剂2 | 0.5 |
| 总预混物 | 358.80 |
| 调稀 | |
| 水 | 20.9 |
| 丙烯酸乳胶 | 524.2 |
| 消泡剂1 | 1.0 |
| 消泡剂2 | 0.5 |
| HEUR(15％w/w水性溶液) | 46.7 |
| 水 | 112.2 |
| 总调稀 | 705.5 |
| 总计 | 1064.0 |
HEUR的制备
比较例1-不具有表面活性剂的非支化HEUR
将CARBOWAXTM8000聚乙二醇(PEG 8000，100g，陶氏化学公司或其分支机构的商标)和甲苯(400g)的混合物加热至回流并通过共沸蒸馏干燥2小时。然后将反应器冷却至90℃，随后将六亚甲基二异氰酸酯(HDI，2.69g)加入到反应器中，同时搅拌5分钟。然后加入二月桂酸二丁基锡(0.21g)，并且将反应混合物在90℃下搅拌1小时。将反应混合物冷却至80℃，并将1-癸醇(1.84g)加入反应器中。将所得混合物在80℃下搅拌1小时。在真空中除去溶剂，以得到非支化HEUR聚合物。在甲基-β-环糊精(CD)的存在下将非支化HEUR聚合物溶解在水中以获得由15重量％非支化HEUR聚合物、1重量％CD和79重量％水组成的最终聚合物溶液。
比较例2-具有Ethox CO-81表面活性剂的非支化HEUR
除了在Ethox CO-81表面活性剂(HLB＝15.9)的存在下将非支化HEUR聚合物溶解在水中以获得由15重量％非支化HEUR聚合物、13重量％Ethox CO-81表面活性剂和72重量％水组成的最终聚合物溶液之外，进行比较例1中所述的程序。
比较例3-具有Tergitol 15-S-9表面活性剂的非支化HEUR
除了在Tergitol 15-S-9表面活性剂(HLB＝13.3)的存在下将非支化HEUR聚合物溶解在水中以获得由15重量％非支化HEUR聚合物、13重量％Tergitol 15--S-9表面活性剂和72重量％水组成的最终聚合物溶液之外，进行比较例1中所述的程序。
比较例4-由三元醇制备的不具有表面活性剂的HEUR
将PEG 8000(100g)和Lumulse POE(26)甘油(2.43g)在甲苯(400g)中的混合物加热至回流，并通过共沸蒸馏干燥2小时。然后将反应器冷却至90℃，随后将HDI(3.31g)加入到反应器中，同时搅拌5分钟。然后加入二月桂酸二丁基锡(0.21g)，并且将反应混合物在90℃下搅拌1小时。将反应混合物冷却至80℃，然后将1-癸醇(2.15g)加入反应器中。将所得混合物在80℃下搅拌1小时，在真空中除去溶剂，以得到HEUR聚合物。在CD的存在下将HEUR聚合物溶解在水中以获得由15重量％HEUR聚合物、1重量％CD和79重量％水组成的最终聚合物溶液。
比较例5-由三元醇制备的具有Ethox CO-81表面活性剂的HEUR
除了在Ethox CO-81表面活性剂的存在下将HEUR聚合物溶解在水中以获得由15重量％HEUR聚合物、13重量％Ethox CO-81表面活性剂和72重量％水组成的最终聚合物溶液之外，进行比较例4中所述的程序。
比较例6-由三元醇制备的具有Tergitol 15-S-9表面活性剂的HEUR
除了在Tergitol 15-S-9表面活性剂的存在下将HEUR聚合物溶解在水中以获得由15重量％HEUR聚合物、13重量％Tergitol 15-S-9表面活性剂和72重量％水组成的最终聚合物溶液之外，进行比较例4中所述的步骤。
比较例7-由三异氰酸酯制备的不具有表面活性剂的支化HEUR
在间歇熔融反应器中将PEG 8000(1700g)真空加热至110℃，持续2小时。在N2下将熔体冷却至85℃，随后将丁基化羟基甲苯(0.173g)和1-癸醇(25.67g)的混合物加入到反应器中。将混合物搅拌5分钟，然后将六亚甲基二异氰酸酯(HDI，41.09g)和Desmodur N3600HDI三聚体(8.70g)加入到反应器中。将反应混合物搅拌5分钟，然后将辛酸铋(28％Bi，4.25g)加入到反应器中。将混合物在85℃下搅拌8分钟，然后将所得熔融聚合物从反应器中取出并冷却，以得到支化HEUR聚合物。在CD的存在下将支化HEUR聚合物溶解在水中以获得由15重量％支化HEUR聚合物、1重量％CD和79重量％水组成的最终聚合物溶液。
实施例1-由三异氰酸酯制备的具有Ethox CO-81表面活性剂的支化HEUR
除了在Ethox CO-81表面活性剂的存在下将支化HEUR聚合物溶解在水中以获得由15重量％支化HEUR聚合物、13重量％Ethox CO-81表面活性剂和72重量％水组成的最终聚合物溶液之外，进行比较例7中所述的程序。
实施例2-由三异氰酸酯制备的具有Tergitol 15-S-9表面活性剂的支化HEUR
除了在Tergitol 15-S-9表面活性剂的存在下将支化HEUR聚合物溶解在水中以获得由15重量％支化HEUR聚合物、13重量％Tergitol 15-S-9表面活性剂和72重量％水组成的最终聚合物溶液之外，进行比较例7中所述的程序。
表4示出了由实施例和比较例制备的油漆的ICI、KU和Brookfield粘度数据。ICI粘度以泊(P)为单位报告；KU粘度以克雷布斯单位为单位报告；并且Brookfield粘度以厘泊(cP)为单位报告。
表4-油漆的粘度数据
为了使配制者能够灵活地在最佳低剪切范围、中剪切范围和高剪切范围内配制油漆，最高ICI/KU比以及最低KU粘度和Brookfield粘度是最理想的。仅含有支化HEUR和指定HLB范围内的表面活性剂的配方产生可接受ICI/KU比和KU值，以及较低Brookfield粘度。
Claims (8)
1.一种组合物，所述组合物包含支化HEUR和具有在11至19的范围内的HLB的非离子表面活性剂的水性溶液；其中所述支化HEUR用具有在3.5至7.0的范围内的cLog P的疏水部分封端；基于所述组合物的重量，所述HEUR的浓度在10重量％至25重量％的范围内；基于所述组合物的重量，所述表面活性剂的浓度在5重量％至25重量％的范围内；并且所述组合物的至少90重量％包含水、所述HEUR和所述表面活性剂。
2.根据权利要求1所述的组合物，其中所述非离子表面活性剂是具有2个至100个环氧烷基团的饱和或部分不饱和的C6-C60-烷基烷氧基化物。
3.根据权利要求1所述的组合物，其中所述非离子表面活性剂是具有2个至50个环氧乙烷基团的饱和或部分不饱和的C6-C30-烷基乙氧基化物；其中所述非离子表面活性剂具有在13至18的范围内的HLB。
4.根据权利要求3所述的组合物，其中所述非离子表面活性剂是月桂基-O-(EO)5-17H、十三烷基-O-(EO)5-18H、蓖麻油-(EO)20--81H、十八烷基-O-(EO)6-31H、硬脂基-O-(EO)6-31H、辛基苯基-O-(EO)5-20H、壬基苯基-O-(EO)5-20H或牛油脂肪胺(EO)6-C25H。
5.根据权利要求1所述的组合物，其中所述支化HEUR具有由下式表征的疏水部分：
其中所述氧原子通过饱和碳原子与聚合物主链(虚线)共价键合；其中R1为二价基团并且R2和R3为经选择以实现所述期望cLog P的单价基团。
6.根据权利要求5所述的组合物，其中R1为C4-C14-烷基、C5-C8-环烷基、或C1-C9-烷基和C5-C7-环烷基基团的组合；R2为C3-C12-烷基、C5-C8-环烷基或苄基基团；X为O或NR2’，其中R2'为H或为获得所述期望cLog P而选择的一价基团；并且R3为C9-C16-烷基、二苄基氨基-C2-C5-烷基、二-C4-C8-烷基氨基-C1-C4-烷基、C6-C8-烷基苯基基团、二苄基胺丁基缩水甘油醚醇加成物或二苄基胺2-乙基己基缩水甘油醚醇加成物。
7.根据权利要求4所述的组合物，其中所述支化HEUR具有由下式表征的疏水部分：
其中所述氧原子通过饱和碳原子与所述聚合物主链(虚线)共价键合；R1为C4-C14-烷基、C5-C8-环烷基；R2为C3-C12-烷基、C5-C8-环烷基或苄基基团；R2'为H、C2-C6烷基或C5-C8环烷基基团；并且
R3为C9-C16-烷基、二苄基氨基-C2-C5-烷基、二-C4-C8-烷基氨基-C1-C4-烷基、C6-C8-烷基苯基基团、二苄基胺丁基缩水甘油醚醇加成物或二苄基胺2-乙基己基缩水甘油醚醇加成物。
8.根据权利要求1所述的组合物，其中基于所述组合物的重量，所述非离子表面活性剂的浓度和所述HEUR的浓度在10重量％至20重量％的范围内；并且所述组合物的至少95％包含水、所述HEUR和所述非离子表面活性剂。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202163256672P | 2021-10-18 | 2021-10-18 | |
| US63/256672 | 2021-10-18 | ||
| PCT/US2022/045601 WO2023069249A1 (en) | 2021-10-18 | 2022-10-04 | Ici building rheology modifier |
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| Publication Number | Publication Date |
|---|---|
| CN117980367A true CN117980367A (zh) | 2024-05-03 |
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| CN202280063913.0A Pending CN117980367A (zh) | 2021-10-18 | 2022-10-04 | Ici提高流变改性剂 |
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| CN (1) | CN117980367A (zh) |
| AU (1) | AU2022370211A1 (zh) |
| CA (1) | CA3235274A1 (zh) |
| WO (1) | WO2023069249A1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA2791853C (en) * | 2010-02-12 | 2018-03-06 | Rhodia Operations | Rheology modifier compositions and methods of use |
| FR2976579B1 (fr) * | 2011-06-14 | 2013-07-05 | Coatex Sas | Epaississants non ioniques associatifs contenant des alkyls cyclohexylols, formulations les contenant et leurs utilisations |
| US9260559B2 (en) * | 2012-11-12 | 2016-02-16 | Elementis Specialties, Inc. | Processes for the preparation of rheology modifiers |
| CA2940732C (en) * | 2015-09-17 | 2023-10-03 | Rohm And Haas Company | Pigmented paint formulation with a phosphorus acid functionalized latex binder and an associative thickener |
| EP4229109A1 (en) * | 2020-10-15 | 2023-08-23 | Rohm and Haas Company | Branched rheology modifier with hydrophobic end-capping groups |
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- 2022-10-04 AU AU2022370211A patent/AU2022370211A1/en active Pending
- 2022-10-04 CA CA3235274A patent/CA3235274A1/en active Pending
- 2022-10-04 CN CN202280063913.0A patent/CN117980367A/zh active Pending
- 2022-10-04 WO PCT/US2022/045601 patent/WO2023069249A1/en active Application Filing
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| CA3235274A1 (en) | 2023-04-27 |
| WO2023069249A1 (en) | 2023-04-27 |
| AU2022370211A1 (en) | 2024-05-23 |
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