CN103992680B - 烷氧基化的氟烷基磷酸盐组合物 - Google Patents
烷氧基化的氟烷基磷酸盐组合物 Download PDFInfo
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Abstract
本发明涉及一种组合物，该组合物包含粘合剂和以下氟烷基磷酸酯的盐的水性分散体：其中n、p、q、R1和R2如本文所定义。本发明的组合物可用作漆制剂的抗粘连添加剂。
Description
技术背景
本发明涉及一种水性组合物，该组合物包含粘合剂和烷氧基化的烷基氟代磷酸盐，该组合物可用作涂料制剂中的抗粘连添加剂。
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。
一类市售的氟烷基抗粘连添加剂的例子是C8和以上的全氟化烃类以及具有该取代基的化合物，例如CF3(CF2)7CH2CH2OPO3 -2；这类抗粘连添加剂尽管有效，但是在2015年的粘合剂体系中计划禁止将它们作为添加剂。因此，需要寻找有效的氟化表面活性剂，其能够克服C8和以上的氟烷基磷酸盐/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化合物的磷酸盐的水性分散体：
其中，n是2-6；p是1、2或3；q是1-5；R1和R2中的一个是H、CH3或CH2CH3，并且R1和R2中的另一个是H；其中，以所述粘合剂的重量为基准计，所述磷酸盐的浓度为0.01-0.5重量％。本发明通过提供一种包含氟烷基磷酸盐的组合物解决了一种需求，所述氟烷基磷酸盐能有效作为抗粘连添加剂并且预期能够符合监管标准。
具体实施方式
本发明是一种组合物，该组合物包含粘合剂和以下化合物的磷酸酯的盐的水性分散体：
其中，n是2-6；p是1、2或3；q是1-5；R1和R2中的一个是H、CH3或CH2CH3，并且R1和R2中的另一个是H；其中，以所述粘合剂的重量为基准计，所述磷酸盐的浓度为0.01-0.5重量％。所述磷酸盐通常以磷酸盐的混合物形式制备，因此，q优选表示烷氧基化链的摩尔平均长度。因此，包含等摩尔量的CF3(CF2)5CH2CH2O(CH2CH2O)2P(O)(OH)2的盐和CF3(CF2)5CH2CH2O(CH2CH2O)3P(O)(OH)2的盐的混合物的q值为2.5。
优选的磷酸盐是下式表示的氟烷基磷酸盐的混合物：
其中，n是3-5，优选3或5；q是2-4，更优选2-3；Y是OH或O-M+；其中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。
所述氟烷基磷酸盐通常可分两步制备。在第一步中，CnF(2n+1)(CH2)pOH可以与化学计量过量的环氧乙烷、环氧丙烷或环氧丁烷反应，较好的是在升高的温度和压力条件下进行以实现烷氧基化，然后可以与POCl3反应，用水猝灭该反应，用碱进行中和，以形成所需的氟烷基磷酸盐。方案1显示了该制备过程：
方案1-氟烷基磷酸盐的制备
应理解，也可形成一些量的区域异构体：CnF(2n+1)(CH2)pO-(CHR1CH2O)q-P(O)(OH)2。
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。以所述粘合剂固体的重量为基准计，所述氟烷基磷酸盐的浓度优选为0.02-0.2重量％，更优选为0.02-0.1重量％。
该组合物优选适合于涂料组合物，特别是漆。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，包含本文所述的氟烷基磷酸盐的组合物在低浓度且不使用任何辅助抗粘连添加剂的条件下表现出优异的抗粘连性。
实施例
中间体1A：1H,1H,2H,2H-全氟辛-1-醇的乙氧基化
将1H,1H,2H,2H-全氟辛-1-醇(3毫摩尔)、二金属氰化物(DMC,～0.1-0.2重量%)、THF(1毫升)加入玻璃PPR小瓶中。反应在Symyx平行压力反应器(PPR)中进行。通过Isco注射泵输送环氧乙烷（EO，9毫摩尔），所述Isco注射泵在PPR手套箱内装配有自动控制的针以及压缩气体微型阀，其与Cavro机器臂相连。将玻璃插入件与用于小室的可移动的PEEK搅拌桨叶一起在真空、125℃条件下干燥过夜。将装有醇、THF和DMC的插入件加入各PPR孔中，用N2加压至50psi。在90℃下引入EO，在该温度条件下将反应搅拌3小时。所得乙氧基化物无需另外纯化即可用于下一步骤。
中间体2A-4A：1H,1H,2H,2H-全氟辛-1-醇的丙氧基化
按照中间体1的步骤进行，不同之处在于，使用环氧丙烷（中间体2，12毫摩尔；中间体3，15毫摩尔；中间体4，18毫摩尔）作为烷氧化试剂，并用N2对装有醇、环氧丙烷和DMC的插入件加压至50psi，并加热至110℃保持18小时。所得丙氧基化物无需另外纯化即可用于下一步骤。
中间体5A-8A：1H,1H,2H,2H-全氟辛-1-醇的丁氧基化
按照中间体1的步骤进行，不同之处在于，使用环氧丁烷（中间体5，9毫摩尔；中间体6，12毫摩尔；中间体7，15毫摩尔；中间体8，18毫摩尔）作为烷氧化试剂，并用N2对装有醇、环氧丁烷和DMC的插入件加压至50psi，并加热至110℃保持18小时。所得丁氧基化物无需另外纯化即可用于下一步骤。
中间体1B-8B：由烷氧基化的1H,1H,2H,2H-全氟辛-1-醇制备磷酸
用THF（约10倍）分别稀释中间体1-8，然后在0℃下将其缓慢加入预混合的POCl3(对于乙氧基化物为2.2当量；对于丙氧基化物或丁氧基化物为1.2当量，Et3N(1.2当量)和THF(100毫升))中。在N2、室温条件下搅拌过夜后，小心地用约200毫升冰水猝灭该反应混合物。用NaCl饱和该水溶液，用乙酸乙酯萃取产物。在真空中蒸发溶剂，将所得粘性材料溶解在乙醚中，通过1微米过滤器过滤。真空除去醚，产物无需另外纯化即可用于下一步骤。中间体1B-8B示于表1。
表1-氟烷基烷氧基化磷酸的特征
| 中间体 | 结构 |
| 1B | CF3(CF2)5(CH2CH2)-O-(CH2CH2O)2.6P(O)(OH)2 |
| 2B | CF3(CF2)5(CH2CH2)-O-(CH2CH(CH3)O)3.5P(O)(OH)2 |
| 3B | CF3(CF2)5(CH2CH2)-O-(CH2CH(CH3)O)4.4P(O)(OH)2 |
| 4B | CF3(CF2)5(CH2CH2)-O-(CH2CH(CH3)O)5.1P(O)(OH)2 |
| 5B | CF3(CF2)5(CH2CH2)-O-(CH2CH(CH2CH3)O)2.4P(O)(OH)2 |
| 6B | CF3(CF2)5(CH2CH2)-O-(CH2CH(CH2CH3)O)3.0P(O)(OH)2 |
| 7B | CF3(CF2)5(CH2CH2)-O-(CH2CH(CH2CH3)O)4.3P(O)(OH)2 |
| 8B | CF3(CF2)5(CH2CH2)-O-(CH2CH(CH2CH3)O)4.8P(O)(OH)2 |
磷酸盐的制备
中间体1C：磷酸盐的制备
将乙醇胺(1.2g)加入中间体1B(2.0g)中。然后加入去离子水(7.0克)，轻轻搅拌该混合物，得到澄清溶液。
中间体2C：磷酸盐的制备
将乙醇胺(0.2g)加入中间体2B(1.0g)中。然后加入去离子水(5.0克)，轻轻搅拌该混合物，得到澄清溶液。
中间体3C：磷酸盐的制备
将乙醇胺(1.0g)加入中间体3B(2.0g)中。然后加入去离子水(7.0克)，轻轻搅拌该混合物，得到澄清溶液。
中间体4C：磷酸盐的制备
将乙醇胺(0.8g)加入中间体4B(2.0g)中。然后加入去离子水(7.75克)，轻轻搅拌该混合物，得到澄清溶液。
中间体5C：磷酸盐的制备
将乙醇胺(1.1g)加入中间体5B(2.0g)中。然后加入去离子水(7.75克)，轻轻搅拌该混合物，得到澄清溶液。
中间体6C：磷酸盐的制备
将乙醇胺(1.1g)加入中间体6B(2.0g)中。然后加入去离子水(7.75克)，轻轻搅拌该混合物，得到澄清溶液。
中间体7C：磷酸盐的制备
将乙醇胺(0.2g)加入中间体7B(1.0g)中。然后加入去离子水(5.0克)，轻轻搅拌该混合物，得到澄清溶液。
中间体8C：磷酸盐的制备
将乙醇胺(0.8g)加入中间体8B(2.0g)中。然后加入去离子水(7.25克)，轻轻搅拌该混合物，得到澄清溶液。
缩写：
材料编号
缩写
Ti纯R-706金红石TiO2粉末 TiO2粉末
Foamstar A34消泡剂 消泡剂
TERGITOLTMTMN100X表面活性剂 表面活性剂
TAMOLTM1124分散剂 分散剂
AMPTM-95氨基醇 氨基醇
RHOPLEX AC-261LF丙烯酸类乳液聚合 丙烯酸类乳液聚合物
物
Optifilm增强剂400聚结剂 聚结剂
ACRYSOLTMRM-5000流变改性剂 增稠剂1
ACRYSOLTMRM-895流变改性剂 增稠剂2
TERGITOL、TAMOL、AMP、RHOPLEX和ACRYSOL均为陶氏化学公司(The Dow ChemicalCompany)或其附属公司的商标。
使用下表2中所述的材料制备漆制剂（缺少抗粘连添加剂），用量如下表2中所示。
表2-不含抗粘连添加剂的漆制剂
| 阶段 | 材料 | 重量(g) |
| 磨料 | ||
| TiO2 | 322.07 | |
| 水 | 110.00 | |
| 消泡剂 | 1.00 |
| 表面活性剂 | 2.23 | |
| 分散剂 | 6.08 | |
| 磨料小计 | 441.38 | |
| 稀释 | ||
| 丙烯酸类乳液聚合物 | 468.80 | |
| 消泡剂 | 2.01 | |
| 氨水(28%) | 0.30 | |
| 聚结剂 | 11.75 | |
| 增稠剂1 | 41.09 | |
| 增稠剂2 | 6.01 | |
| 水 | 137.06 | |
| 总计 | 1108.39 |
实施例1–制备含抗粘连添加剂的漆组合物
使用Miller GyroMixer将中间体1C(0.11g)与表2中所示的组合物(100g)在120毫升塑料容器中混合9分钟，以确保充分混合。
实施例2–制备含抗粘连添加剂的漆组合物
使用实施例1所述的步骤，不同之处在于，将中间体2C(0.13g)与表2中所示的组合物进行混合。
实施例3–制备漆组合物
使用实施例1所述的步骤，不同之处在于，将中间体3C(0.11g)与表2中所示的组合物进行混合。
实施例4–制备含抗粘连添加剂的漆组合物
使用实施例1所述的步骤，不同之处在于，将中间体4C(0.11g)与表2中所示的组合物进行混合。
实施例5–制备含抗粘连添加剂的漆组合物
使用实施例1所述的步骤，不同之处在于，将中间体5C(0.11g)与表2中所示的组合物进行混合。
实施例6–制备含抗粘连添加剂的漆组合物
使用实施例1所述的步骤，不同之处在于，将中间体6C(0.11g)与表2中所示的组合物进行混合。
实施例7–制备含抗粘连添加剂的漆组合物
使用实施例1所述的步骤，不同之处在于，将中间体7C(0.13g)与表2中所示的组合物进行混合。
实施例8–制备含抗粘连添加剂的漆组合物
使用实施例1所述的步骤，不同之处在于，将中间体8C(0.11g)与表2中所示的组合物进行混合。
实施例9–制备含抗粘连添加剂的漆组合物
使用实施例1所述的步骤，不同之处在于，将中间体2C(0.066g)与表2中所示的组合物进行混合。
实施例10–制备含抗粘连添加剂的漆组合物
使用实施例1所述的步骤，不同之处在于，将中间体4C(0.056g)与表2中所示的组合物进行混合。
实施例11–制备含抗粘连添加剂的漆组合物
使用实施例1所述的步骤，不同之处在于，将中间体5C(0.057g)与表2中所示的组合物进行混合。
实施例12–制备含抗粘连添加剂的漆组合物
使用实施例1所述的步骤，不同之处在于，将中间体8C(0.053g)与表2中所示的组合物进行混合。
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(birdapplicator)在白色Leneta卡片上制备涂料的刮涂膜。在进行光泽度和抗粘连性测试之前，在25℃和50％RH条件下将涂层干燥24小时。
测试方法：按照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方块，将橡皮塞(8号)放置在顶部，并使窄边与试样接触。将1000克砝码放置在各塞子顶部。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0至10的标尺表示室温抗粘连和热抗粘连结果。表3描述了报告抗剥落粘连性的评级体系。
表3-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4显示了由实施例1-8的制剂得到的涂料的抗粘连性质。以粘合剂固体的重量为基准计，所示抗粘连添加剂的浓度为0.1重量％。在25℃和50％相对湿度条件下干燥24小时后，测定抗粘连性。
表4：使用约0.1重量％添加剂的漆制剂的抗粘连性
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中间体1C-8C的制剂所制得的涂料在抗粘连性方面具有显著改善。在不含抗粘连添加剂的条件下，测得抗粘连性为1（室温条件）和0（热抗粘连条件）。
当抗粘连添加剂的浓度降低至0.05重量％时，仍观察到抗粘连性，但对于较长链长的烷氧基化基团的效率差异更明显，如表5所示。
表5：使用约0.05重量％添加剂2C、4C、5C、8C的漆制剂的抗粘连性
不受理论的限制，我们认为在漆干燥的过程中，较长的烷氧基化基团不利地增加了粘合剂相容性，这阻止了抗粘连添加剂起霜至涂层空气界面，使得效率降低。因此，短链烷氧基化基团显示出最佳的性能。
Claims (9)
1.一种组合物，该组合物包含粘合剂和以下化合物的磷酸盐的水性分散体：
其中，n是2-6；p是1、2或3；q是1-5；R1和R2中的一个是H、CH3或CH2CH3，并且R1和R2中的另一个是H；其中，以所述粘合剂的重量为基准计，所述磷酸盐的浓度为0.01-0.5重量％。
2.如权利要求1所述的组合物，其特征在于，所述磷酸盐是由以下结构表示的氟烷基磷酸盐的混合物：
其中，n是4-6；Y是OH或O-M+，其中M+是碱金属阳离子或铵阳离子。
3.如权利要求2所述的组合物，其特征在于，所述粘合剂选自下组：丙烯酸类和乙烯基酯-乙烯聚合物；以粘合剂固体的重量为基准计，氟烷基磷酸盐的浓度为0.02-0.2重量％。
4.如权利要求2所述的组合物，其特征在于，所述粘合剂选自下组：苯乙烯-丙烯酸类、乙烯基酯-丙烯酸类；以粘合剂固体的重量为基准计，氟烷基磷酸盐的浓度为0.02-0.2重量％。
5.如权利要求3或4所述的组合物，其特征在于，R2是H；n是4或6；q是2-4。
6.如权利要求3或4所述的组合物，其特征在于，R2是CH3；n是4或6；q是2-4。
7.如权利要求3或4所述的组合物，其特征在于，R2是CH2CH3；n是4或6；q是2-4。
8.如权利要求3或4所述的组合物，其特征在于，M+是N-(2-羟乙基)铵。
9.如权利要求1所述的组合物，其特征在于，所述组合物是一种漆制剂，其进一步包含TiO2和一种或多种选自下组的添加剂：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、流平剂以及中和剂。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1642939A2 (de) * | 2000-10-11 | 2006-04-05 | Chemetall GmbH | Verfahren zur Beschichtung von metallischen Oberflächen vor der Umformung mit einem lackähnlichen Ueberzug und Verwendung der derart beschichteten Substrate |
| CN1872924A (zh) * | 2005-03-14 | 2006-12-06 | Jds尤尼弗思公司 | 防潮防污涂层 |
| CN101535322A (zh) * | 2006-11-13 | 2009-09-16 | 纳幕尔杜邦公司 | 基于多氟醚的磷酸盐 |
| CN102186586A (zh) * | 2008-05-19 | 2011-09-14 | 纳幕尔杜邦公司 | 乙烯-四氟乙烯磷酸盐组合物 |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3083224A (en) | 1961-12-08 | 1963-03-26 | Du Pont | Polyfluoroalkyl phosphates |
| US3412181A (en) | 1965-04-09 | 1968-11-19 | Du Pont | Perfluoro phosphates |
| US3891591A (en) | 1973-08-13 | 1975-06-24 | Du Pont | Coating compositions |
| WO1998023553A1 (fr) | 1996-11-28 | 1998-06-04 | Asahi Glass Company Ltd. | Melange a ciment, beton, et procede de fabrication de composes de fluorooxyalylene |
| US6271289B1 (en) | 1999-11-16 | 2001-08-07 | E. I. Du Pont De Nemours And Company | Stain resistant compositions |
| IT1317861B1 (it) | 2000-02-29 | 2003-07-15 | Ausimont Spa | Uso di composti fluorurati per conferire proprieta' release. |
| ITMI20020056A1 (it) | 2002-01-15 | 2003-07-15 | Ausimont Spa | Composizioni acquose di fosfati di perfluoropolieteri e loro uso per conferire oleorepellenza alla carta |
| ITMI20020057A1 (it) | 2002-01-15 | 2003-07-15 | Ausimont Spa | Composizioni acquose di fosfati di perfluoropolieteri e loro uso per conferire oleorepellenza alla carta |
| US7196043B2 (en) * | 2002-10-23 | 2007-03-27 | S. C. Johnson & Son, Inc. | Process and composition for producing self-cleaning surfaces from aqueous systems |
| US20060229406A1 (en) | 2005-03-24 | 2006-10-12 | Silverman Lee A | Process for uniformly dispersing particles in a polymer |
| US20070212491A1 (en) * | 2006-03-08 | 2007-09-13 | Yen Jessica C | Fluorochemical and lecithin additive for coatings |
| US7470818B2 (en) | 2006-11-13 | 2008-12-30 | E.I. Du Pont De Nemours & Company | Fluoroalkyl phosphate compositions |
| US20080145552A1 (en) * | 2006-12-15 | 2008-06-19 | Mia Genevieve Berrettini | Fluorochemical and polyoxyalkylene siloxane additive for coatings |
| US7385077B1 (en) | 2007-03-27 | 2008-06-10 | E. I. Du Pont De Nemours And Company | Fluoroalkyl surfactants |
| US7399887B1 (en) | 2007-08-06 | 2008-07-15 | E. I. Du Pont De Nemours And Company | Fluorinated sulfonate surfactants |
| MX2010001500A (es) | 2007-08-28 | 2010-03-10 | Basf Se | Dioxido de titanio fotoactivo en materiales de revestimiento. |
| US8022238B2 (en) | 2009-03-20 | 2011-09-20 | E. I. Du Pont De Nemours And Company | Phosphate surfactants |
| WO2011034003A1 (ja) * | 2009-09-17 | 2011-03-24 | ユニマテック株式会社 | エマルジョンおよびそれを用いた離型剤 |
| US20110091408A1 (en) | 2009-10-20 | 2011-04-21 | E. I. Du Pont De Nemours And Company | Methods of using fluoroalkyl phosphate compositions |
| JP2011173959A (ja) * | 2010-02-23 | 2011-09-08 | Unimatec Co Ltd | 含フッ素ポリマーラテックスの製造法 |
| DE102012004138B3 (de) * | 2011-12-06 | 2012-09-27 | Ley & Co. Farbenwerke Wunsiedel KG | Verwendung einer zinkoxidhaltigen Fritte als UV-Schutzpigment |
-
2014
- 2014-01-22 CN CN201410029887.7A patent/CN103992680B/zh not_active Expired - Fee Related
- 2014-01-28 KR KR1020140010663A patent/KR20140103047A/ko not_active Application Discontinuation
- 2014-01-30 BR BR102014002398A patent/BR102014002398A2/pt not_active IP Right Cessation
- 2014-02-03 EP EP14153633.4A patent/EP2767565B1/en active Active
- 2014-02-04 AU AU2014200582A patent/AU2014200582B2/en not_active Ceased
- 2014-02-12 US US14/178,671 patent/US9006320B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1642939A2 (de) * | 2000-10-11 | 2006-04-05 | Chemetall GmbH | Verfahren zur Beschichtung von metallischen Oberflächen vor der Umformung mit einem lackähnlichen Ueberzug und Verwendung der derart beschichteten Substrate |
| CN1872924A (zh) * | 2005-03-14 | 2006-12-06 | Jds尤尼弗思公司 | 防潮防污涂层 |
| CN101535322A (zh) * | 2006-11-13 | 2009-09-16 | 纳幕尔杜邦公司 | 基于多氟醚的磷酸盐 |
| CN102186586A (zh) * | 2008-05-19 | 2011-09-14 | 纳幕尔杜邦公司 | 乙烯-四氟乙烯磷酸盐组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| BR102014002398A2 (pt) | 2020-01-28 |
| KR20140103047A (ko) | 2014-08-25 |
| CN103992680A (zh) | 2014-08-20 |
| US20140235772A1 (en) | 2014-08-21 |
| AU2014200582B2 (en) | 2017-06-01 |
| US9006320B2 (en) | 2015-04-14 |
| EP2767565B1 (en) | 2016-08-24 |
| EP2767565A1 (en) | 2014-08-20 |
| AU2014200582A1 (en) | 2014-09-04 |
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