CN109312172A - 在水相中稳定化的基料 - Google Patents

在水相中稳定化的基料 Download PDF

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CN109312172A
CN109312172A CN201780035088.2A CN201780035088A CN109312172A CN 109312172 A CN109312172 A CN 109312172A CN 201780035088 A CN201780035088 A CN 201780035088A CN 109312172 A CN109312172 A CN 109312172A
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base material
carrier base
group
functional molecules
resistance
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W·布雷姆泽
M·德罗尔
O·泽瓦尔德
E·尼森-瓦肯廷
L·沙赫特西克
M·特劳特
M·施万布
D·瓦泽法伦
V·佐特克
A·弗伦克尔
R·艾林霍夫
S·格罗尔德
N·S·克尔法拉
F·克列门哈根
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Chemetall GmbH
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Abstract

本发明涉及在水相中稳定化并且能够与离子源凝胶形成剂共沉淀的基料，所述基料借助基料上的反应性基团用亲水性官能分子改性。

Description

在水相中稳定化的基料
本发明涉及在水相中稳定化的基料和颗粒，其能够与离子源凝胶形成剂共沉积并且所述基料选自聚丙烯酸酯、聚氨酯、聚环氧化物、氨基甲酸酯丙烯酸酯、芳族和(环)脂族环氧丙烯酸酯、聚酯及其混合物。就此而言，颗粒应理解为有机和无机颜料、功能性填料及其混合物。
文献WO 2012034976A1、WO 2013117611A1和WO 2015004256A1公开了无电涂覆金属基材表面的方法，其使用阴离子、两性离子、位阻、阳离子和/或非离子稳定化的基料并通过在添加聚电解质下形成离子源凝胶而使其耐漂洗地沉积，并且还通过干燥以及烘烤使它们固化。
鉴于通过形成离子源凝胶而无电涂覆各种基材表面的方法(尤其是各种金属的那些)的工业应用，以及在耐腐蚀性和抗划伤性方面对涂层的要求越来越高，有意提供用于形成稳定的含水分散体的广谱基料。获得的分散体旨在于添加聚电解质下形成离子源凝胶来沉积。此时，沉积凝胶的耐漂洗性是一个重要的标准，并且在漂洗方法的情况下，要求承受至少0.2巴的典型工业喷雾压力；或者要求承受浸没式漂洗方法，此时这意味着沉积的膜不发生剥离。在金属表面上形成均匀的不透性涂层。
本发明所要解决的问题是描述在水相中稳定化的基料，以及制备该分散体的方法。由此稳定化的基料(在下文中称为载体基料)形成稳定的含水分散体，其在添加聚电解质下在金属阳离子的诱导下，在各种基材表面上形成离子源凝胶。这些膜的显著之处在于非常好的耐漂洗性，承受至少0.2巴的喷雾压力或承受浸没式漂洗方法，从而在漂洗后留下均匀的不透性膜。根据本发明，稳定的含水分散体为胶体水溶液，其中颗粒通过排斥力彼此分开。
此外，就本发明而言，聚电解质为用于离子源沉积并且已在WO 2012034976A1、WO2013117611A1和WO 2015004256A1的说明书中详细描述的多糖。
所设想的基材表面如下：金属基材，例如钢、镀锌钢、铝及其合金，和金属掺杂的材料。
根据本发明，所述问题通过载体基料解决，所述载体基料在水相中稳定化并且能够与离子源凝胶形成剂共沉积，其中借助基料上的反应性基团使用亲水性官能分子对基料进行改性。载体基料可为树脂或聚合物。其优选选自聚丙烯酸酯、聚氨酯、聚环氧化物、氨基甲酸酯丙烯酸酯、芳族和(环)脂族环氧丙烯酸酯、聚酯及其混合物，它们借助基料上的反应性基团由亲水性官能分子改性，并且在水相中稳定化。在本发明的意义上，基料上的反应性基团为：异氰酸酯基、羟基、羧基、环氧乙烷基、乙烯基和胺基。
亲水性官能分子有利地为提供有疏水性端基并且由乙二醇单元组成的调聚物，其中调聚物中的乙二醇单元数量为1-20。5-10的乙二醇单元数量是有利的，因为在这种情况下，亲水-疏水部分之间存在良好的平衡。
特别优选地，亲水性官能分子具有300-1000g/mol的分子量Mn。
非常特别优选地，亲水性官能分子具有C1-C4烷基或C6-C12芳基端基。
为了制备载体基料，使亲水性官能分子与基料共价连接。由此制得的载体基料在水相中形成至少在6个月，优选高达12个月或更长的时间内稳定的分散体。
在一个特别有利的变型中，未与初始基料连接的亲水性官能分子的疏水性端基是反应性的。就本发明而言，这是指能够进行进一步热反应的乙烯基或羟基。所述基团可在烘烤操作期间通过自由基反应或者通过加成反应或缩合反应来促进交联。因此，可制得交联的不透性涂层，所述涂层耐水、耐化学品且耐腐蚀，并且显示出提高的抗划伤性、铅笔硬度、高柔韧性，可拉伸性、低温成形性和高粘合性。
上述颗粒有利地用硅烷、氨基硅烷、含磷基团的有机分子和/或含胺的有机分子、磷酸盐或者用导电或非导电有机涂层进行表面改性，其中涂层包含用于与载体基料共价或相互作用地连接的反应性基团，所述基团具有用于与待处理基材表面连接的官能团。通过在其表面上吸附亲水性官能分子，可获得不具有反应性基团或不适于连接至其表面上的反应性基团的颗粒。
本发明的制备载体基料的方法包括通过基料的反应性基团反应形成亲水性官能分子的1-9个链单元来改性初始基料。
制得的载体基料具有额外的乳化性质，因此能够允许其他基料和颗粒的离子源沉积。
制备所述载体基料的一种非排他可能性是亲水性官能分子的氨基甲酸酯形成反应的反应。取决于粘度，所述反应优选在有机溶剂存在下进行，随后将其移除。
使用异氰酸酯官能化的聚乙二醇分子作为亲水性组分，并且使用分子量Mn为1000-3000g/mol的聚酯多元醇。存在于初始基料上的反应性基团为羟基，其能够形成氨基甲酸酯键。
所用的聚酯多元醇有利地包含100-5000g/eq的反应性基团。
进一步优选的载体基料的制备以下述方式进行：
使多环异氰酸酯(例如VL)官能化的聚乙二醇分子(优选聚乙二醇甲醚)与二异丙胺(DIPA)或与DIPA和/或优选丁酮肟(或其他酮肟)或带有官能团的其他异氰酸酯反应并共价键合。
存在的反应性基团为羟基，或者优选为分子上的仲胺，其能够形成例如氨基甲酸酯键或脲衍生物。
下文合成方法中描述了一种特别优选的基于具有丙烯酸酯封端的聚合物链的聚氨酯(PU)分散体的载体分散体的变型。该PU分散体基载体分散体在上述乳化性载体基料的存在下导致具有高防腐蚀性的特别耐漂洗的涂层。优选通过在第一步骤中首先引入具有异氰酸酯封端形式的基料，并在第二步骤中通过形成氨基甲酸酯使其与亲水性官能分子反应来改性初始PU基料。
具有丙烯酸酯封端的聚合物链的PU分散体基载体分散体的亲水性可通过添加基于叔胺的乳化剂(例如具有末端亲水性叔胺化合物的脂肪酸改性的乳化剂，例如可商购获得的EFKA6225)来提高，从而允许在至多pH 3的pH范围内产生足够的稳定化。
下文使用4个实施例更详细地阐述本发明。
实施例1：制备聚氨酯丙烯酸酯分散体—甲基丙烯酸羟乙酯封端的(PUD-HEMA)分散体I
实验装置由500mL玻璃反应器构成，其具有回流冷凝器、含气体入口的搅拌导向器、RPG搅拌马达和紧间隙桨式搅拌器。使用具有加热功能的磁力搅拌器和温度传感器以及硅油浴进行加热。操作在没有水并且在整个反应期间连续流过氮气的情况下进行。首先，将获自Croda的聚酯多元醇3192或XL 101引入丁-2-酮中，将该初始装料在65℃下以120rpm的搅拌速率均化10分钟(min)。随后加入二醇—新戊二醇(NPG)和含羧基的二醇—2,2-双羟甲基丙酸(DMPA)作为扩链剂，再均化15min。随后加入二异氰酸酯—4,4-二苯基甲烷二异氰酸酯。将溶液温度保持在82℃下，这对应于94℃的外夹套温度，持续6小时。在6小时后，以甲基丙烯酸2-羟乙酯(HEMA)的形式加入端基的部分亲水性结构单元。在约80min后，加入二甲基乙醇胺以中和羧基官能团。当这发生时，将乙二醇单丁醚加入到反应中。最后，加入DI水，在连续搅拌下冷却，并在旋转蒸发器上移除溶剂。固体级分的测定给出了22.71重量％的值。使用Nano Zetasizer测得的聚合物粒度为约73nm。
实施例2：制备聚氨酯丙烯酸酯分散体—聚乙二醇甲基丙烯酸酯封端的(PUD-PEGMA500)分散体II
在具有回流冷凝器、含气体入口的搅拌导向器、RPG搅拌马达和紧间隙桨式搅拌器的500mL玻璃反应器中，将获自Croda的聚酯多元醇3192引入丁-2-酮中，并将该初始装料在65℃下以120rpm的搅拌速率均化10min。随后加入二醇—新戊二醇(NPG)和含羧基的二醇—2,2-双羟甲基丙酸(DMPA)作为扩链剂，再均化15min。随后加入二异氰酸酯—4,4-二苯基甲烷二异氰酸酯。将溶液温度保持在82℃下，这对应于94℃的外夹套温度，持续6小时。在6小时后，以数均分子量Mn＝500g/mol聚乙二醇甲基丙烯酸酯(PEGMA-500)的形式加入端基的部分亲水性结构单元。在约80min后，加入二甲基乙醇胺以中和羧基官能团。当这发生时，将乙二醇单丁醚加入到反应中。最后，加入DI水，随后在连续搅拌下将反应冷却30min，并在旋转蒸发器上移除溶剂。PUD-PEGMA500的固体级分为25重量％。使用NanoZetasizer测得的聚合物粒度为约73nm，固含量(SC)为24.80重量％。
配制剂-3192-PUD-PEGMA-500如下所示：
由以下混合物获得可承受0.5巴的喷雾压力的涂料配制剂：
配制剂由作为载体分散体的2.5g分散体I、2.5g分散体II和5g用聚乙二醇单元封闭的异氰酸酯交联剂组成，并借助Ultraturrax(具有S 10 N-10 G分散工具的IKA T 10Basic ULTRA--IKA)以4级混合10min。引入利用剪切力进行以例如形成均匀的胶束，从而使得整个混合物在pH降低时足够稳定。
或者，在较大量的混合物(1kg)的情况下，也可例如使用具有低粘度叶片的实验室分散器，其以2000rpm运行约30min以产生相应的各成分的均匀分配。
通过加入约1-2g双酚A二缩水甘油醚(BADGE)或双酚F二缩水甘油醚，额外产生特别高的腐蚀防护。
随后，加入12g 1重量％浓度的凝胶形成剂溶液，并通过搅拌过夜引入。对于该应用，将分散体I和II的固含量调节至20-25重量％。
实施例3：载体分散体的合成方法
具有高耐漂洗性和高腐蚀防护的另一优选的混合变型是两种载体分散体的混合物，其由聚丙烯酸酯-DPE载体分散体和另一载体分散体组成，其具有聚乙二醇甲醚(例如获自Covestro的产品BL 5335+BADGE)作为亲水性异氰酸酯交联剂，这形成了耐漂洗涂层。
两步合成在具有紧间隙的双桨式搅拌器的5L玻璃反应器中进行。还安装有回流冷凝器、氮气入口和出口、气泡计数器、具有恒温器的加热夹套和Gravidos进料器。在第一步骤中，向反应器中装入1300g水，并在120rps搅拌速率和完整氮气流下加热至40℃。当达到40℃时，将氮气流减少至1个气泡/秒。随后加入25g苯乙烯、21.8g聚乙二醇甲醚甲基丙烯酸酯Mn500g/mol和2.055g 1,1-二苯基乙烯。加入100g水以用于随后的漂洗。将溶液搅拌约5min，然后将4.056g过二硫酸铵溶于100g水中并加入。然后将溶液在约45min的温度-时间坡度内加热至90℃。
在第二步骤中，借助Gravidos系统经4小时的时间以约2.188g/min的计量速率由Gravidos容器滴加500g甲基丙烯酸丁酯和25g甲基丙烯酸羟乙酯的混合物。由第二Gravidos容器以4小时0.416g的计量速率计量加入50g环氧丙烯酸于50g丁酮中的溶液。环氧丙烯酸如下所述制备。借助氮气流再次从反应器中部分移除丁酮。或者，其可随后在旋转蒸发器上几乎完全移除。在单体添加结束后，在90℃下继续搅拌2小时。将分散体冷却，进行过滤，然后测定固体的粒度、pH以及固含量(SC)。
然后，可向该分散体中加入10-50重量％的BL 5335，因此其具有约40重量％的SC。在这种情况下，必须制备约1-1.2倍量的SC为1重量％的多糖溶液，并将其与分散体混合约24小时。
实施例4：合成方法，具有乳化剂性质的载体基料
实验装置由500mL的玻璃反应器组成，其具有回流冷凝器、含气体入口的搅拌导向器、RPG搅拌马达和紧间隙桨式搅拌器。使用具有加热功能磁力搅拌器和温度传感器以及硅油浴进行加热。操作在没有水并且在整个反应期间连续流过氮气的情况下进行。首先，引入聚乙二醇甲醚Mn750g/mol和79.8g多环甲基二苯基异氰酸酯(MDI)，例如获自Covestro或Bayer的VL，并将该初始装料在70℃下在使用桨式搅拌器以120rpm连续搅拌下加热2小时。然后，在搅拌下加入17.4g丁酮肟，并且使组分在70℃的反应器内部温度下反应2小时。随后加入20.21g二异丙胺，并在70℃下搅拌40min。反应的完全转化可借助红外光谱(IR光谱)由2200-2400cm-1波数下的异氰酸酯带的降低来监测。随后使用双蒸水将基料调节至35-40重量％的固体级分，并且在连续搅拌和引入剪切力的情况下，制备对各种类型的树脂如双酚A二缩水甘油醚或PUD树脂具有乳化作用的分散体。

Claims (12)

1.一种载体基料，其在水相中稳定化并且能够与离子源凝胶形成剂共沉积，其中基料借助基料上的反应性基团用亲水性官能分子改性。
2.根据权利要求1的载体基料，其中基料与离子源凝胶形成耐漂洗涂层，所述耐漂洗涂层具有耐至少0.2巴喷雾压力的耐漂洗性或浸没式漂洗方法后的耐漂洗性，其中基料构成了载体基料胶束的核，其借助具有乙二醇单元的聚氨酯形成胶束，所述乙二醇单元具有疏水性端基。
3.根据权利要求2的载体基料，其中基料为树脂或聚合物。
4.根据权利要求1或2的载体基料，其中亲水性官能分子为提供有疏水性端基并且由乙二醇单元组成的调聚物，其中调聚物中的乙二醇单元数量为1-20。
5.根据权利要求1-4中任一项的载体基料，其中亲水性官能分子具有300-1000g/mol的分子量。
6.根据权利要求1-5中任一项的载体基料，其中亲水性官能分子具有C1-C4烷基或C6-C12芳基端基。
7.根据权利要求1至6中任一项的载体基料，其中亲水性官能分子的疏水性端基是反应性的。
8.根据权利要求1-7中任一项的载体基料，其以0.01-50重量％的量包含粒度为5-800nm的无机颗粒。
9.根据权利要求8的载体基料，其中无机颗粒选自颜色效应和光泽效应颜料、抗腐蚀颜料、UV保护颜料或具有其他功能性质的颗粒，其不会导致分散体通过形成多价阳离子而过早凝胶化。
10.根据权利要求9的载体基料，其中无机颗粒用硅烷、氨基硅烷、含磷基团的有机分子和/或含胺的有机分子、磷酸盐或者用导电或非导电有机涂层进行表面改性，其中涂层可包含用于与载体基料共价或相互作用地连接的反应性基团。
11.根据权利要求10的载体基料，其中无机颗粒的反应性基团为伯、仲、叔胺基，环氧基，异氰酸酯基或羟基。
12.一种制备根据权利要求1-10中任一项的在水相中稳定化的载体基料的方法，其中通过基料的反应性基团反应形成亲水性官能分子的1-9个链单元来改性基料。
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