CN103834221A - 氟烷基膦酸盐/酯组合物 - Google Patents
氟烷基膦酸盐/酯组合物 Download PDFInfo
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- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
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Abstract
本发明是一种组合物，该组合物包含粘合剂和以下氟烷基膦酸的盐的水性分散体：
Description
背景技术
本发明涉及一种包含氟烷基膦酸盐/酯和粘合剂的组合物。
抗粘连性是油漆不自我粘附的能力。例如，良好的抗粘连性能够使门不会粘附于门框或者使窗不会粘附于其框架。水性油漆制剂中的抗粘连性是通过抗粘连添加剂，例如包含高浓度氟的氟化烷基表面活性剂来实现的。建筑涂料组合物中的这些高度氟化的化合物通常比含较低氟含量的化合物具有更好的性能。遗憾的是，这些较好性能的表面活性剂其制备成本高得多，并且往往是环境不友好的。一类流行的此类表面活性剂是氟烷基磷酸盐/酯，其具有以下缺点：氟烷基磷酸盐/酯难以以纯化合物形式制得，其制备是固有非选择性的，得到大量不利的二烷基磷酸盐/酯；其次，磷酸盐/酯通常易于通过水解而降解；第三，法规压力会产生逐渐淘汰的C8或以上全氟化烃类以及具有该取代基的化合物，例如CF3(CF2)7CH2CH2OPO3 -2，这是2015年的粘合剂体系中计划禁止作为添加剂的物质。因此，需要寻找有效的氟化表面活性剂，其能够克服氟化烷基磷酸盐/酯的缺点，同时能够保持或改善粘合剂的抗粘连性能。
发明内容
本发明通过提供一种组合物解决了本领域中的需求，所述组合物包含粘合剂和以下氟烷基膦酸的盐的水性分散体：
其中，R是H或C1-C6-烷基；n是2-6；q是0或1；且p是0-10，前提条件是p和q中的至少一个不是0；并且其中以粘合剂的重量为基准计，所述氟烷基膦酸盐的盐浓度为0.01-3重量％。
本发明的组合物通过包含具有以下性质的表面活性剂而解决了需求，所述表面活性剂易于以高纯度形式制得，并且对水解是稳定的，与其磷酸盐/酯对应物相比更加环境友好。
发明详述
本发明是一种组合物，该组合物包含粘合剂和以下氟烷基膦酸的盐的水性分散体：
其中，R是H或C1-C6-烷基；n是2-6；q是0或1；且p是0-10，前提条件是p和q中的至少一个不是0；并且其中以粘合剂的重量为基准计，所述氟烷基膦酸盐的盐浓度为0.01-3重量％。R优选为H，q优选为0，p优选为1-10。
优选地，所述氟烷基膦酸盐由下式表示：
其中，Y是OH或O-M+，优选O-M+；n优选3-5，更优选3或5；p更优选1-5，更优选1-3，最优选1；其中各M+优选为碱金属阳离子如Na+或K+，或铵阳离子如NH4 +、N-(2-羟乙基)铵、N,N-二(2-羟乙基)铵、N,N,N-三(2-羟乙基)铵、三甲基铵和三乙基铵。
氟烷基膦酸盐可以根据以下方案进行制备：
方案1
其中，X是离去基团，如磺酸盐/酯、正膦、溴或碘；R’是烷基，优选C1-C4-烷基，更优选乙基；p是0或1；q是0-10；当q是0时(即当CnF(2n+1)(CH2)pX在第一步中与P(OR)3直接反应时)，p是1。如U.S.7,815,816中所述，CnF(2n+1)(CH2)p(CH2CHR)qX的制备可以在高温和高压条件下进行。倒数第二个产物是膦酸，使用合适的碱可将其方便地中和成相应的膦酸盐/酯，所述碱可以是无机或有机的。所述碱优选为胺或氨基醇。
粘合剂优选为聚合物颗粒的稳定水性分散体，所述聚合物颗粒的Tg为-60℃至60℃，所述粘合剂可以是适合于涂料组合物的任意粘合剂，包括以下聚合物颗粒的水性分散体：丙烯酸类、苯乙烯-丙烯酸类、乙烯基酯-丙烯酸类、乙烯基酯-乙烯、硅酮、氨基甲酸酯、偏二卤乙烯和乙烯基卤化物。以粘合剂固体的重量为基准计，氟烷基膦酸盐/酯的浓度优选为0.01重量％，更优选0.02重量％，至优选0.5重量％，更优选至0.2重量％，最优选至0.1重量％。
该组合物优选适合于涂料组合物，特别是油漆。正因如此，该组合物可包括多种附加材料，包括溶剂；颜料，如未包封、部分包封或完全包封的TiO2；填料；消泡剂；表面活性剂；分散剂；增稠剂；聚结剂；着色剂；防腐剂；流动剂；流平剂和中和剂。我们发现，含本文所述的氟烷基膦酸盐/酯的组合物表现出优异的抗粘连性，并且不存在氟烷基磷酸盐/酯的缺点。
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。
表1是材料及其缩写的列表。
RHOPLEX、TERGITOL、TAMOL、PRIMAL和ACRYSOL均为陶氏化学公司(The Dow Chemical Company)或其附属公司的商标。
中间体1-全氟己基乙基膦酸盐溶液的制备
将去离子水(8.81克)添加至全氟己基乙基膦酸(2.00克)。再加入乙醇胺(1.00克)，轻轻搅拌该混合物，得到澄清溶液。
中间体2-九氟己基膦酸盐的制备
将纯1,1,1,2,2,3,3,4,4-九氟-6-碘代己烷(10毫摩尔)添加至50毫摩尔磷酸三乙酯。在160℃下将反应混合物加热过夜，得到(3,3,4,4,5,5,6,6,6-九氟己基)膦酸二乙酯，用分馏对其进行分离(产率90-95％)。在0℃条件下将纯溴化三甲基甲硅烷(21毫摩尔)缓慢添加至(3,3,4,4,5,5,6,6,6-九氟己基)膦酸二乙酯(7毫摩尔)的干CH2Cl2(25毫升)溶液中。在室温条件下搅拌该反应混合物过夜，然后向该反应混合物中添加水(30毫摩尔)。在真空条件下除去挥发性物质，得到白色晶体状(3,3,4,4,5,5,6,6,6-九氟己基)膦酸(产率>95%)。制备该膦酸盐的步骤与制备中间体1中所述的步骤类似。
涂料制剂
比较例1–比较例1的组合物示于表2中。该组合物在不含任何抗粘连添加剂的条件下进行制备。该涂料以两段法(研磨阶段和稀释阶段)进行制备。使用考勒斯(Cowls)分散机进行研磨。在1升不锈钢容器中，将水(110.00克)、消泡剂(1.00克)、非离子表面活性剂(2.23克)和分散剂(6.08克)混合1-2分钟。然后，在极高速度搅拌(1000rpm)下，在5分钟内缓慢添加TiO2R-706(322.07)。在1200rpm下再持续分散10-15分钟。使用海格曼规（Hegman gauge）证实均匀的TiO2分散体。研磨后，使用顶挂式搅拌器进行稀释。
在稀释阶段，在缓慢搅拌下在1升塑料容器中将一部分磨料(441.38克)添加至AC-261LF(468.80克)。将消泡剂(2.01克)和Optifilm(11.75克)添加至该混合物中，再持续混合2-3分钟。然后在高速搅拌下添加一部分的RM-5000(20.00克)和水(50.00克)。在持续的高速搅拌下将剩余的RM-5000(21.09克)和水(50.00克)添加至混合物。然后，向混合物中加入RM-895(6.01克)，再加入氨水(0.30克，28％水溶液)和水(37.06克)以调节最终pH和粘度。
表2.比较例1的组成
| 阶段 | 材料 | 重量(克) |
| 磨料 | ||
| TiO2R-706 | 322.07 | |
| 水 | 110.00 | |
| 消泡剂 | 1.00 | |
| 非离子表面活性剂 | 2.23 | |
| 分散剂 | 6.08 | |
| 磨料小计 | 441.38 | |
| 稀释 | ||
| AC-261LF | 468.80 | |
| 消泡剂 | 2.01 | |
| 氨水(28%) | 0.30 | |
| Optifilm | 11.75 | |
| RM-5000 | 41.09 | |
| RM-895 | 6.01 | |
| 水 | 137.06 | |
| 总计 | 1108.39 |
比较例2–比较例2也是在不含任意抗粘连添加剂的条件下制备的(即，没有使用中间体1或2)。该组合物示于表3。
在塑料容器中使用顶挂式搅拌器进行研磨。首先，将丙二醇(32.00克)、水(18.00克)、消泡剂(1.00克)和分散剂(4.00克)混合1-2分钟。接着，在3分钟内缓慢添加TiO2R-746(300.72克)。将分散体再搅拌5分钟。研磨步骤之后，按照与比较例1中所述的基本相同的步骤进行稀释步骤。在加入DR-5500和TT-615之前，添加一部分AMP-95，最后加入余量以调节最终pH。
表3.比较例2的组合物
| 阶段 | 材料 | 重量(克) |
| 磨料 | ||
| TiO2R-746 | 300.72 | |
| 丙二醇 | 32.00 | |
| 水 | 18.00 | |
| 消泡剂 | 1.00 | |
| 分散剂 | 4.00 | |
| 磨料小计 | 355.72 | |
| 稀释 | ||
| AC-337N | 569.47 | |
| 消泡剂 | 2.01 | |
| AMP-95 | 4.10 | |
| Optifilm | 12.96 | |
| DR-5500 | 22.5 | |
| TT-615 | 1.97 |
| 水 | 68.53 | |
| 总计 | 1037.26 |
比较例3–比较例3也是在不含任何抗粘连添加剂的条件下制备的(即，没有使用中间体1或2)。该组合物示于表4。制备比较例3的步骤与制备比较例2所述的步骤基本上相同。
表4.比较例3的组成细节
| 材料 | 重量(克) |
| TiO2R-746 | 274.97 |
| 消泡剂 | 1.35 |
| Byk-348 | 3.20 |
| SF-155 | 546.51 |
| 氨水(28%) | 0.60 |
| Texanol | 7.71 |
| RM-2020NPR | 24.00 |
| RM-8W | 10.60 |
| 水 | 140.71 |
| 总计 | 1009.65 |
实施例1–制备含抗粘连添加剂的油漆组合物
在120毫升塑料容器中，使用Miller GyroMixer将中间体1(0.0626克)与比较例1的组合物(100克)混合9分钟。
实施例2–制备含阻隔添加剂的油漆组合物
制备实施例2的油漆组合物的步骤与制备实施例1所述的步骤基本相同，不同之处在于使用0.1251克中间体1。
对照涂料和实施例涂料的最终pH值约为8.9。在施用前，将涂料在室温下存储48-72小时。
实施例3-6–制备含抗粘连添加剂的油漆组合物
如实施例1中所述，通过将中间体1添加至比较例2的组合物中来制备实施例3-6。
实施例7和8–制备含抗粘连添加剂的油漆组合物
如实施例1中所述，通过将中间体1添加至比较例3的组合物中来制备实施例7和8。
实施例9和10–制备含抗粘连添加剂的油漆组合物
如实施例1中所述，通过将中间体2添加至比较例1的组合物中来制备实施例9和10。
涂料施用
在25℃和50％相对湿度(RH)条件下使用3密耳伯德施涂器(bird applicator)在白色Leneta卡片上制备涂料的刮涂膜。在进行抗粘连性测试之前，在25℃和50％RH条件下将涂层干燥24小时。
测试方法
采用以下测试方法来对涂层进行表征。
进行ASTM D4946-89来表征抗剥落粘连性。对于各涂层，从卡片上切割12个1.5”x1.5”部分，以在室温和热粘连条件下重复三次。将每种切割方块的两块面对面放置，使油漆表面相互接触。对于室温抗粘连测试，对于平坦表面上的每对正方形，将橡皮塞(8号)放置在顶部，并使窄边与试样接触。将1000克砝码放置在塞子顶部。30分钟后，从试样上移除砝码和塞子，然后测试其室温抗粘连性。对于热抗粘连，在50℃下的烘箱中，将试样放置在平坦的金属板上。在烘箱中使橡皮塞(8号)和砝码平衡。在烘箱中将橡皮塞放置(窄边向下)在各试样的顶部。然后，在各塞子上放置1000克砝码。30分钟后，在进行抗热粘连性测试之前，移除砝码和塞子，并从烘箱中取出试样，并使其在室温下冷却30分钟。用缓慢而稳定的力度剥离试样，用标准0至10表示室温抗粘连和热抗粘连结果。表5描述了报告抗剥落粘连性的评级体系。
表5.评价抗粘连性的粘着和密封描述
| 评级 | 粘着和密封描述 |
| 10 | 无粘着，极佳 |
| 9 | 痕量粘着，优秀 |
| 8 | 轻度粘着，非常好 |
| 7 | 轻度粘着，好 |
| 6 | 中度粘着，好 |
| 5 | 中度粘着，中等 |
| 4 | 严重粘着,无密封，中等 |
| 3 | 5-25%密封,差 |
| 2 | 25-50%密封,差 |
| 1 | 50-75%密封,差 |
| 0 | 完全密封，极差 |
表6总结了由比较例1和实施例1和2的制剂所得涂料的抗粘连性。
表6.使用AC-261LF粘合剂的涂料的抗粘连性质
该结果显示，与不含抗粘连添加剂的制剂相比，在室温抗粘连条件和热抗粘连条件下含有全氟己基乙基膦酸盐的制剂所制得的涂料在抗粘连性方面具有显著改善。
表7说明了由比较例2和实施例3至6的制剂所得涂料的抗粘连性。与比较例2相比，在室温和热抗粘连条件下，全氟己基乙基膦酸酯盐溶液作为后添加剂，在抗粘连性方面具有显著改进。
表7.使用粘合剂Rhoplex AC-337N粘合剂的涂料的抗粘连性
表8显示了由比较例3和实施例7和8的制剂所得涂料的抗粘连性。
表8.使用SF-155粘合剂的涂料的抗粘连性
如表8所示，对于苯乙烯-丙烯酸类粘合剂，后添加中间体1相比于比较例3而言，对于室温和热抗粘连条件在抗粘连性方面都显示出显著的改进。
表9显示了由比较例1和实施例9和10的制剂所得涂料的抗粘连性。
表9.使用粘合剂AC-261LF粘合剂的涂料的抗粘连性质
表9显示出，与比较例1相比，使用中间体2作为后添加剂在室温和热抗粘连条件下都在抗粘连性方面具有显著改进。
这表明，氟烷基膦酸盐/酯可用于提供具有优异抗粘连性的涂料制剂。此外，这种添加剂可容易地高产率且高纯度制得，并且对水解稳定。因此，为氟烷基磷酸盐/酯提供了一种可行替代。
Claims (7)
1.一种组合物，该组合物包含粘合剂和以下氟烷基膦酸的盐的水性分散体：
其中，R是H或C1-C6-烷基；n是2-6；q是0或1；且p是0-10，前提条件是p和q中的至少一个不是0；并且其中以粘合剂的重量为基准计，所述氟烷基膦酸盐的盐浓度为0.01-3重量％。
2.如权利要求1所述的组合物，其特征在于，所述氟烷基膦酸盐由以下通式表示：
式中，Y是OH或O-M+；p是1-5；各M+是碱金属或铵阳离子；并且以所述粘合剂的重量为基准计，所述氟烷基膦酸盐的浓度为0.01-0.5重量％。
3.如权利要求2所述的组合物，其特征在于，Y是O-M+；各M+是铵阳离子；并且以所述粘合剂的重量为基准计，所述氟烷基膦酸盐的浓度为0.02-0.2重量％。
4.如权利要求2或3所述的组合物，其特征在于，p是1；n是3-5；各M+选自下组：NH4 +、N-(2-羟乙基)铵、N,N-二(2-羟乙基)铵、N,N,N-三(2-羟乙基)铵、三甲基铵和三乙基铵；并且所述粘合剂是丙烯酸类聚合物粘合剂或苯乙烯-丙烯酸类聚合物粘合剂。
5.如权利要求1-4中任一项所述的组合物，其特征在于，n是3或5。
6.如权利要求1-5中任一项所述的组合物，该组合物还包含一种或多种选自下组的材料：颜料、填料、消泡剂、表面活性剂、分散剂、增稠剂、聚结剂、着色剂、防腐剂、流动剂、流平剂和中和剂，其中所述组合物是涂料组合物。
7.权利要求1-5中任一项所述的组合物，该组合物还包含TiO2、聚结剂、表面活性剂、分散剂、增稠剂、消泡剂和中和剂，其中所述组合物是油漆。
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| US7674928B2 (en) * | 2006-11-13 | 2010-03-09 | E.I. Du Pont De Nemours And Company | Polyfluoroether-based phosphates |
| US20080145552A1 (en) | 2006-12-15 | 2008-06-19 | Mia Genevieve Berrettini | Fluorochemical and polyoxyalkylene siloxane additive for coatings |
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| AU2017203514B2 (en) | 2018-12-06 |
| KR20140048812A (ko) | 2014-04-24 |
| US20140107267A1 (en) | 2014-04-17 |
| EP2722371B1 (en) | 2017-01-11 |
| US9000078B2 (en) | 2015-04-07 |
| EP2722371A1 (en) | 2014-04-23 |
| KR102120156B1 (ko) | 2020-06-08 |
| CN103834221B (zh) | 2019-05-03 |
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| ES2617070T3 (es) | 2017-06-15 |
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