CN114231155A - 一种羟烷基水性有机硅改性聚氨酯水分散体组合物及其制备方法 - Google Patents
一种羟烷基水性有机硅改性聚氨酯水分散体组合物及其制备方法 Download PDFInfo
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- CN114231155A CN114231155A CN202111608895.3A CN202111608895A CN114231155A CN 114231155 A CN114231155 A CN 114231155A CN 202111608895 A CN202111608895 A CN 202111608895A CN 114231155 A CN114231155 A CN 114231155A
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
本发明公开了一种羟烷基水性有机硅改性聚氨酯水分散体及其制备方法，所述水分散体组分包括氨基硅烷1～10份、多元醇树脂20～50份、二羟基酸5～25份、多异氰酸酯10～50份、有机锡0.1～0.5份、防腐杀菌剂0.1～0.4份、3～15份三乙胺和去离子水150～338份。本发明的水分散组分可以用来制备油墨、纺织浆料及涂料，可以和水可分散的脂肪族多异氰酸酯配合固化，形成的涂层耐候性和力学性能兼优，本发明的水分散体组合物成膜后的强度可在较大范围内变化，同时满足成膜物质的相容性、机械性能和耐介质性能的要求。
Description
技术领域：
本发明涉及涂料制备领域，具体涉及一种羟烷基水性有机硅改性聚氨酯水分散体组合物及其制备方法。
背景技术：
WPU制备可根据目前较为常用的方法分为两种，分别为自乳化法和外乳化法。自乳化型的合成工艺又可被分为丙酮法、预聚体法、熔融分散法、酮亚胺-酮连氮法以及封端法等，而其中较常用的合成方法则是丙酮法和预聚体法。同时封端法目前也受到密切关注，因为封闭型异氰酸酯具有较好的稳定性，从而可以解决储存问题。此外，异氰酸酯单体活性比较高的缺点能够被较好地解决，可应用于WPU的制备。
WPU是作为树脂基料最为关键的底层基础物质，因此它自身的各种性能直接决定了胶粘剂的综合性能。因为WPU的成分中含有亲水基团，导致在应用中耐水性较差、干燥所需时间较久、初黏力较小和固化速度慢等缺陷。为了解决上述各种缺陷从而提高WPU的综合性能，实践中人们常常对其进行改性，例如用丙烯酸酯、环氧树脂、有机硅、有机氟、纳米材料、超支化预聚体和复合改性等方法。
有机硅的结构中由于存在无机结构的主链与有机结构的侧链，使得有机硅兼具有机物和无机物的双重特性。用此材料改性WPU，可以提高WPU固化膜的耐高低温性、耐水性、耐油污性、化学稳定性，并可使其拥有优良的粘接性能。因此，在提高WPU性能方面，研究有机硅材料对其进行改性非常具有价值。
周华利等以TDI、聚乙二醇制备出端-NCO基团的聚氨酯预聚体，再于有机硅反应，获得有机硅改性聚氨酯。实验研究了制备聚氨酯预聚体的最佳工艺条件，最佳反应温度为70℃，反应时间为70min，TDI和聚乙二醇配比为NCO：OH＝1.5：l。采用有机硅改性后，通过红外等测试证实改性材料的结构，热重分析说明有机硅的加入提高了改性材料的热稳定性，且改性材料仍具有良好的力学性能和耐化学稳定性，加入助剂可作为阻燃涂料。
田军等以端羟基聚二甲基硅氧烷与醇解蓖麻油改性的聚氨酯预聚体为原料合成了聚氨酯改性有机硅，发现共聚物的耐热性随着有机硅含量增加而提高。表面红外光谱显示，有机硅向表面迁移，使得共聚物的表面能减小。但是，这样得到的聚氨酯改性有机硅分子结构中含有Si-O-C键，不耐水，遇水易水解。
刘俊峰采用含羟基活性基团的有机硅与蓖麻油聚氨酯预聚物为原料，合成蓖麻油聚氨酯改性的有机硅树脂，实验数据表明，当聚氨酯含量为4％时，改性树脂的剪切强度为3.86MPa，冲击强度28.02MPa；当聚氨酯含量增加到20％时，剪切强度增加至9.26MPa，冲击强度却减小到16.11MPa，同时耐热性有所降低。TGA数据计算了改性树脂降解反应的级数及活化能、频率因子等参数。实验结果表明，改性树脂的热分解有两个过程，两个过程分别有不同的动力学参数，且改性树脂在这两个过程中的采用硅醇羟基封端的硅氧烷与异氰酸酯反应，可制备硅醇改性聚氨酯。这种改性在聚氨酯主链中生成的Si—O—C键易水解，改性聚氨酯乳液的稳定性能和耐水解性能较差，不适宜作为耐水材料。如杭州中一科技有限公司的方仕江等人发明了一种羟基硅油和偶联剂复合改姓的水性聚氨酯，所得产品成膜后均一光滑、耐水性好、表面疏水性高且力学性能优异等特点。张留成等用D4以膨润土为催化剂，醋酐为分子质量调节剂，合成相对分子质量为200～600的双三甲硅氧基丙基封端聚硅氧烷PDMS-OH，再与甲苯二异氰酸酯(TDI)及聚乙二醇(PEG)于丙酮中反应制得端异氰酸酯基的有机硅聚氨酯预聚体，再用3-(N-甲基二乙醇氯化铵)-1，2-环氧丙烷扩链，加水乳化制得阳离子型的有机硅聚氨酯嵌段共聚物水乳液。用作整理剂可改善织物的表面性能、吸湿性和抗静电性，同时可提高织物的力学性能和耐磨性能。
氨烷基有机硅是分子链中含有氨基的聚硅氧烷，又称氨基硅油(AEAPS)，通过氨基与异氰酸酯反应，将有机硅接入聚氨酯大分子链，得到有机硅改性WPU。因为氨基与异氰酸酯的反应性强，反应速度快、容易爆聚，所以要控制反应条件，如反应温度低于10℃、尽量稀释体系中异氰酸酯的浓度等。现阶段研究中，制备AEAPS改性WPU的主要方式是以AEAPS作为后扩链剂与聚氨酯预聚体反应，扩链改性后进行乳化，或在乳化中进行扩链改性。侯孟华等采用侧链氨基硅油(AEAPS)和直链氨基硅油(ATPS)，在无溶剂条件下制备了系列氨基硅油改性WPU。研究表明，AEAPS改性WPU涂膜的疏水性、耐水性均优于ATPS改性WPU，在AEAPS或ATPS上限质量分数不超过2.0％时，改性WPU的力学性能不受影响。CHEN等以TDI、PTMG与DMPA制备预聚体，在乳化过程中采用AEAPS扩链改性，得到稳定的改性WPU乳液，聚硅氧烷链段在WPU胶膜表面富集。改性后胶膜的水接触角由62.0°提高至78.0°，胶膜的吸水率由53.9％降低至15.0％，胶膜的耐水性得到明显改善；当AEAPS质量分数不超过6.0％时，改性WPU胶膜的断裂强度、断裂延伸度和未改性WPU相近。XU等采用聚碳酸亚丙酯多元醇(PPC)、DM-PA和IPDI合成WPU预聚体，通过AEAPS扩链接枝制备了改性WPU乳液和薄膜。结果表明，未改性WPU相对分子质量的分布范围较大，软硬段微相分离不明显，AEAPS改性提高了WPU的相对分子质量并使其分布范围变小，聚硅氧烷在胶膜表面有明显的富集，促进了WPU软、硬段微相分离的形成，显著提高了WPU薄膜的耐水、耐热性能。宋海香等采用AEAPS制备了有机硅改性WPU，当AEAPS为软段聚丙二醇质量的8.2％时，改性WPU的硬段Tg由62.7℃升高至68.1℃，胶膜邵氏硬度由65度下降至46度，改性WPU整理织物的手感柔软、滑爽。孟娜等采用PTMG为软段原料制备了AEAPS改性WPU，并应用于羊绒针织物的整理。AEAPS改性WPU胶膜的耐水性得到显著改善，整理织物的抗起毛起球性能提高了1～2级，AEAPS改性使WPU整理织物的手感得到较为明显的改善。
有机硅和聚氨酯各自具有独特的优异性能，有机硅对聚氨酯的改性是目前研究的热点之一，发展前景非常广阔。对环境保护日益重视的今天，以水性聚氨酯代替溶剂型聚氨酯是重要的发展方向。在聚氨酯分子主链中可采取不同手段引入具有特殊性能的改性材料，以提高水性聚氨酯的综合性能；利用聚氨酯分子的可设计性，探索新的合成工艺；根据不同产品规格要求，采用不同材料对聚氨酯进行复合改性，以大幅提升聚氨酯的综合性能，这是水性聚氨酯的研究和发展方向。
发明内容
针对目前的水性聚氨酯树脂涂料耐水解差，颜料相容性不好，交联密度低，干燥固化速度慢，耐磨耐候性差，初粘性差，耐海水性差，稳定性差及润湿性低的问题，本发明提供了一种羟烷基水性有机硅改性聚氨酯水分散体组合物的制备方法。
本发明提供的技术方案如下：
一种羟烷基水性有机硅改性聚氨酯水分散体组合物，包括以下重量份数的组分制成：氨基硅烷1～10份、多元醇树脂20～50份、二羟基酸5～25份、多异氰酸酯10～50份、有机锡0.1～0.5份、防腐杀菌剂0.1～0.4份、3～15份三乙胺和去离子水150～338份。
优选地，所述多元醇树脂为聚己内脂二元醇、聚四氢呋喃二元醇、聚丙二醇二元醇、聚丁二烯二元醇、聚醚二元醇及其类似结构多元醇中的一种或其中任意几种的混合物，分子量为200～3000。
优选地，所述多异氰酸酯为芳香族、脂肪族、脂环族二异氰酸酯、HDI三聚体、IPDI三聚体中的一种或几种。
优选地，所述氨基硅烷为γ-氨丙基三乙氧基硅烷、3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、N-(β-氨乙基-γ-氨丙基)三甲氧基硅烷中的一种或几种。
优选地，羟基丙烯酸酯为丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟乙酯、甲基丙烯酸羟乙酯的一种或几种。
优选地，二羟基酸为二羟基丙酸、二羟基丁酸的一种或几种。
优选地，所述催化剂为有机胺、有机锡或有机铋中的一种。
优选地，所述防腐剂为异噻唑啉酮类、苯并异噻唑啉酮类或呱三嗪类防腐剂。
优选地，氨基硅烷3～7份、多元醇树脂25～40份、二羟基酸10～20份、多异氰酸酯20～40份、有机锡0.2～0.4份、防腐杀菌剂0.2～0.35份、三乙胺5～12份和去离子水200～300份。
作为本发明的另一发明目的，本发明还提供了上述组合物的制备方法，包括以下步骤：
1)取聚酯多元醇、催化剂和多异氰酸酯，升温至70～80℃，反应2～4小时得到异氰酸酯预聚物；
2)降温至50～60℃，加入二羟基脂肪酸，升温至70～80℃，反应2～4小时得到扩链后的异氰酸酯预聚物；
3)投入氨基硅烷和羟基丙烯酸酯，升温至70～80℃，反应2～4小时得到氨基硅烷低聚物；
4)降温至50～60℃，按重量份数，加入三乙胺、氨基硅烷低聚物和异氰酸酯预聚物，升温到60～70℃，反应2～4小时得到羟烷基水性有机硅改性聚氨酯；
5)在50～60℃保温2小时后加入去离子水，搅拌乳化，然后加入防腐剂搅拌均匀，在80±2℃搅拌保温2小时制得。
作为本发明的另一发明目的，本发明还提供了上述组合物在制备高性能水性涂料中的应用，进而得到具有优异耐海水、耐候、耐磨、硬度、弹性等力学性能的涂料产品。
为避免由于氨基与异氰酸酯的反应性强、反应速度快、容易爆聚而导致的反应不可控的难题，本发明通过制备羟烷基仲氨基硅氧烷预聚物途径，再采用羟烷基仲氨基硅氧烷预聚物封端的方法制备的羟烷基有机硅改性水性聚氨酯组合物，反应过程平缓较为可控，反应形成的脲键的键能较高力学性能更为出色。
本发明运用离子亲水技术，成功避免了润湿性低、稳定性差及初粘性差的问题；设计了双固化体系从而大大提高了涂膜的耐磨耐候性差、耐海水性差和干燥固化速度慢的难题。再如本有机硅改性聚氨酯水分散体系的长期稳定性，颜料相容性，以及与阴离子丙烯酸乳液相容性和稳定性都比较优异，拓展了水性聚氨酯树脂的应用范围领域。
本发明组合物的水分散体系稳定性高，对底材及层间极佳的附着力，优异的耐候性、耐磨性、耐海水性、与颜料染料、阴离子丙烯酸乳液及强制乳化树脂乳液等良好的相容性和稳定性，优异的耐水性以及超低的VOC(挥发性有机物)和HAP(有害空气污染物)值，具有较低的粘度，为制备开发用于新型建筑型材如风电叶片涂层、新型高强度玻璃纤维复合材料涂层等高性能水性涂料、油墨、纺织浆料等有更佳水性树脂选择的应用前景。
本发明用水取代传统的溶剂作为载体，且按照使用领域可以采用相应的丙烯酸乳液、醇酸乳液、硅溶胶、无机高分子树脂、有机硅乳液或其他强制乳化的乳液来拼用，使涂料达到相应的耐候性、耐磨性、耐海水、丰满度外观、附着力及耐化学腐蚀的性能指标，使生产工艺成本大幅度降低，以40％的固含量来算，每吨可节约成本5000-15000元。如本发明选用HDI异氰酸酯制备羟烷基水性有机硅改性聚氨酯分散体树脂组合物与丙烯酸乳液拼用，然后使用水可分散多异氰酸酯固化，所得的漆膜耐沾污、耐水、抗划伤、耐磨、耐候、耐盐雾，性价比较高，使成品在木器、新型建筑复合材料、风电叶片、塑胶和陶瓷表面涂膜后，性能得到极大提升，使用范围更加广阔。
具体实施方式
下面对本发明的技术方案进行进一步说明。
实施例1
本实施例的制备方法如下：
1、取γ-氨丙基三乙氧基硅烷(KH550)22.1g和13.0g甲基丙烯酸羟乙酯，投入带有搅拌器、温度计和带冷却的反应器中，升温至50～70℃，反应1～2小时得到仲氨基改性硅预聚物35.1g；
2、取二羟基丁酸6.6g、14.9g四亚甲基二异氰酸酯(HDI)和1.2gHDI三聚体，投入带有搅拌器、温度计和带冷却的反应器中，升温至70～80℃，反应2～4小时得到异氰酸酯预聚物22.7g；
3、将1000分子量的聚己内酯二元醇树脂8.4g在100～120℃/-0.03～0.06MPa的条件下真空脱水2～3小时，然后降温至50～60℃，加入2步骤制备的异氰酸酯预聚物22.7g及0.1g二月桂酸二丁基锡，然后升温至70～80℃，反应1～2小时得到扩链后的异氰酸酯预聚物31.2g；
4)降温至50～60℃，按重量份数，加入4.4g三乙胺和1步骤仲氨基改性硅预聚物35.1g，升温到60～70℃，保温反应2～4小时；
5)匀速加入去离子水106.1g搅拌乳化，然后加入0.3g防腐剂，在80±2℃搅拌保温2小时制得目标发明组合物。
制得的成品为固含量40±2％(质量分数)一种羟烷基水性有机硅改性聚氨酯水分散体组合物，乳液为乳白至半透明状，贮存稳定性优异。
实施例2
本实施例的制备方法如下：
1、取γ-氨丙基三乙氧基硅烷(KH550)34.3g和20.3g甲基丙烯酸羟乙酯，投入带有搅拌器、温度计和带冷却的反应器中，升温至50～70℃，反应1～2小时得到仲氨基改性硅预聚物54.6g；
2、取二羟基丁酸8.0g和25.0四亚甲基二异氰酸酯(HDI)，投入带有搅拌器、温度计和带冷却的反应器中，升温至70～80℃，反应2～4小时得到异氰酸酯预聚物33.0g；
3、将1000分子量的聚己内酯二元醇树脂14.6g和1000分子量的聚己内酯三元醇2.2g在100～120℃/-0.03～0.06MPa的条件下真空脱水2～3小时，然后降温至50～60℃，加入2步骤制备的异氰酸酯预聚物33.0g及0.2g二月桂酸二丁基锡，然后升温至70～80℃，反应2～4小时得到扩链后的异氰酸酯预聚物50.0g；
4)降温至50～60℃，按重量份数，加入5.3g三乙胺和1步骤仲氨基改性硅预聚物54.6g，升温到60～70℃，保温反应2～4小时；
5)匀速加入去离子水164.6g搅拌乳化，然后加入0.3g防腐剂，在80±2℃搅拌保温2小时制得目标发明组合物。
制得的成品为固含量40±2％(质量分数)一种羟烷基水性有机硅改性聚氨酯水分散体组合物，乳液为乳白至半透明状，贮存稳定性优异。
实施例3
本实施例的制备方法如下：
1、取γ-氨丙基三乙氧基硅烷(KH550)28.1g和16.0g甲基丙烯酸羟乙酯，投入带有搅拌器、温度计和带冷却的反应器中，升温至50～70℃，反应1～2小时得到仲氨基改性硅预聚物44.1g；
2、取二羟基丁酸7.6g和18.1g四亚甲基二异氰酸酯(HDI)，投入带有搅拌器、温度计和带冷却的反应器中，升温至70～80℃，反应2～4小时得到异氰酸酯预聚物25.7g；
3、将1000分子量的聚四氢呋喃二元醇树脂8.4g在100～120℃/-0.03～0.06MPa的条件下真空脱水2～3小时，然后降温至50～60℃，加入2步骤制备的异氰酸酯预聚物25.7g及0.1g二月桂酸二丁基锡，然后升温至70～80℃，反应1～2小时得到扩链后的异氰酸酯预聚物34.2g；
4)降温至50～60℃，按重量份数，加入4.1g三乙胺和1步骤仲氨基改性硅预聚物44.1g，升温到60～70℃，保温反应2～4小时；
5)匀速加入去离子水123.6g搅拌乳化，然后加入0.3g防腐剂，在80±2℃搅拌保温2小时制得目标发明组合物。
制得的成品为固含量40±2％(质量分数)一种羟基水性有机硅改性聚氨酯水分散体组合物，乳液为乳白至半透明状，贮存稳定性优异。
实施例4
本实施例的制备方法如下：
1、取γ-氨丙基三乙氧基硅烷(KH550)20.1g和11.8g甲基丙烯酸羟乙酯，投入带有搅拌器、温度计和带冷却的反应器中，升温至50～70℃，反应1～2小时得到仲氨基改性硅预聚物31.9g；
2、取二羟基丁酸11.0g和30.0异氟尔酮二异氰酸酯(IPDI)，投入带有搅拌器、温度计和带冷却的反应器中，升温至70～80℃，反应2～4小时得到异氰酸酯预聚物43.0g；
3、将1000分子量的聚己内酯二元醇树脂5.6g和2000分子量的聚四氢呋喃二元醇树脂22.4g在100～120℃/-0.03～0.06MPa的条件下真空脱水2～3小时，然后降温至50～60℃，加入2步骤制备的异氰酸酯预聚物43.0g及0.2g二月桂酸二丁基锡，然后升温至70～80℃，反应2～4小时得到扩链后的异氰酸酯预聚物61.2g；
4)降温至50～60℃，按重量份数，加入5.7g三乙胺和1步骤仲氨基改性硅预聚物31.9g，升温到60～70℃，保温反应2～4小时；
5)匀速加入去离子水159.0g搅拌乳化，然后加入0.3g防腐剂，在80±2℃搅拌保温2小时制得目标发明组合物。
制得的成品为固含量40±2％(质量分数)一种羟基水性有机硅改性聚氨酯水分散体组合物，乳液为乳白至半透明状，贮存稳定性优异。
通过计算按比例将消泡剂Fs620、118润湿剂、流平剂SN4727、抗闪蚀剂SN-9779和增稠剂601加入到水性树脂中，搅拌均匀后与水性固化剂配制清漆，漆料配方见表1。将所得漆料与目前市面上销售的水性pu树脂在耐海水、耐磨及干燥速度上相差较明显，对比结果见表2。
表1漆料配方
表2检测结果
从上表看出实施例1到实施例4在耐海水、耐磨性及干燥速度上都比较优秀，实施例1的耐磨性最好，这是因为树脂结构中有三官能的异氰酸酯，增加了交联密度所致；实施例1到实施例4在干燥过程中，一方面有机硅烷氧基基团发生水解缩合反应，另一方面树脂的羟烷基与水分散的异氰酸酯固化剂进行反应；由于具有双固化的特点，干燥速度较快，交联密度增加，所以实施例形成涂层的干燥速度较快，耐海水性较优秀。
Claims (10)
1.一种羟烷基水性有机硅改性聚氨酯水分散体组合物，其特征在于，包括以下重量份数的组分制成：氨基硅烷1～10份、多元醇树脂20～50份、二羟基酸5～25份、多异氰酸酯10～50份、有机锡0.1～0.5份、防腐杀菌剂0.1～0.4份、三乙胺3～15份和去离子水150～338份。
2.根据权利要求1所述的一种羟烷基水性有机硅改性聚氨酯水分散体组合物，其特征在于，所述多元醇树脂为聚己内脂二元醇、聚四氢呋喃二元醇、聚丙二醇二元醇、聚丁二烯二元醇、聚醚二元醇及其类似结构多元醇中的一种或其中任意几种的混合物，分子量为200～3000。
3.根据权利要求1-2任一项所述的一种羟烷基水性有机硅改性聚氨酯水分散体组合物，其特征在于，所述多异氰酸酯为芳香族、脂肪族、脂环族二异氰酸酯、HDI三聚体、IPDI三聚体中的一种或几种。
4.根据权利要求1-3任一项所述的一种羟烷基水性有机硅改性聚氨酯水分散体组合物，其特征在于，所述氨基硅烷为γ-氨丙基三乙氧基硅烷、3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、N-(β-氨乙基-γ-氨丙基)三甲氧基硅烷中的一种或几种。
5.根据权利要求1-4任一项所述的一种羟烷基水性有机硅改性聚氨酯水分散体组合物，其特征在于，羟基丙烯酸酯为丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟乙酯、甲基丙烯酸羟乙酯的一种或几种。
6.根据权利要求1所述的一种羟烷基水性有机硅改性聚氨酯水分散体组合物，其特征在于，二羟基酸为二羟基丙酸、二羟基丁酸的一种或几种。
7.根据权利要求1所述的一种羟烷基水性有机硅改性聚氨酯水分散体组合物，其特征在于，所述催化剂为有机胺、有机锡或有机铋中的一种。
8.根据权利要求1所述的一种羟烷基水性有机硅改性聚氨酯水分散体组合物，其特征在于，所述防腐剂为异噻唑啉酮类、苯并异噻唑啉酮类或呱三嗪类防腐剂。
9.根据权利要求1所述的一种羟烷基水性有机硅改性聚氨酯水分散体组合物，其特征在于，包括以下重量份数的组分制成：氨基硅烷3～7份、多元醇树脂25～40份、二羟基酸10～20份、多异氰酸酯20～40份、有机锡0.2～0.4份、防腐杀菌剂0.2～0.35份、三乙胺5～12份和去离子水200～300份。
10.权利要求1-9任一项所述的一种羟烷基水性有机硅改性聚氨酯水分散体组合物的制备方法，其特征在于，包括以下步骤：
1)取聚酯多元醇、催化剂和多异氰酸酯，升温至70～80℃，反应2～4小时得到异氰酸酯预聚物；
2)降温至50～60℃，加入二羟基脂肪酸，升温至70～80℃，反应2～4小时得到扩链后的异氰酸酯预聚物；
3)投入氨基硅烷和羟基丙烯酸酯，升温至70～80℃，反应2～4小时得到氨基硅烷低聚物；
4)降温至50～60℃，按重量份数，加入三乙胺、氨基硅烷低聚物和异氰酸酯预聚物，升温到60～70℃，反应2～4小时得到羟烷基水性有机硅改性聚氨酯；
5)在50～60℃保温2小时后加入去离子水，搅拌乳化，然后加入防腐剂搅拌均匀，在80±2℃搅拌保温2小时制得。
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