CN111909392A - 一种超高固含水性聚氨酯树脂及其制备方法 - Google Patents

一种超高固含水性聚氨酯树脂及其制备方法 Download PDF

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CN111909392A
CN111909392A CN202010723586.XA CN202010723586A CN111909392A CN 111909392 A CN111909392 A CN 111909392A CN 202010723586 A CN202010723586 A CN 202010723586A CN 111909392 A CN111909392 A CN 111909392A
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aqueous polyurethane
polyurethane resin
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nonionic
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李维虎
郭文鹤
汪飞
赵曦
朱保凌
戴家兵
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Lanzhou Scisky Aqueous Polymer Material Co ltd
Hefei Scisky Technology Co ltd
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Abstract

本发明提供一种超高固含水性聚氨酯树脂的制备方法，所述制备方法包括：提供一水性聚氨酯预聚体；使用第一水性聚氨酯树脂乳化所述水性聚氨酯预聚体，所述第一水性聚氨酯树脂与所述水性聚氨酯预聚体不具有反应性，所述第一水性聚氨酯树脂的固含量为10％～40％，pH值为6～8；使用多元胺水溶液对乳化后的所述水性聚氨酯预聚体进行扩链，得到一反应乳液；对所述反应乳液进行后处理，制备得到超高固含的第二水性聚氨酯树脂，所述第二水性聚氨酯树脂的固含量为50％～65％，pH值为6～8。

Description

一种超高固含水性聚氨酯树脂及其制备方法
技术领域
本发明涉及水性聚氨酯合成领域，具体涉及一种超高固含水性聚氨酯树脂及其制备方法。
背景技术
水性聚氨酯作为一种绿色无污染高分子材料，由于其出色的物理机械性能和生物相容性，在皮革、胶黏剂、涂料、医疗器械等领域有着广泛的用途。目前市场使用的水性聚氨酯树脂的固含量偏低，通常为20％～40％，固含量偏低会增加产品的包装和运输费用，同时限制了在某些领域的应用，如粘合剂应用领域，通常需要含固量高于50％。因此生产超高固含量产品(50％以上)是水性聚氨酯发展的一个重要方向。
目前，例如可以通过将含有不同含量磺酸盐亲水基团的聚氨酯预聚体混合乳化，再经二次扩链，获得固含量50％以上的水性聚氨酯乳液，但是该方法获得的高固含水性聚氨酯乳液，不仅在实际生产过程中操作复杂，而且稳定性低。还可以使用含磺酸盐基团的多元醇制备高固含水性聚氨酯树脂，这也限制了使用领域。因此，如何制备高固含阴离子型、非离子型、阳离子型以及复合离子型水性聚氨酯树脂是市场亟待解决的问题。
发明内容
鉴于以上所述现有技术的缺点，本发明的目的之一在于提供一种超高固含水性聚氨酯树脂制备方法，利用本发明的制备的方法制备的超高固含水性聚氨酯树脂具有50％～65％的超高固含量，且制备方法简单。
本发明的另一个目的在于，提供一种经如上所述的制备方法制备的超高固含水性聚氨酯树脂。
为实现上述目的及其他相关目的，本发明提供了一种超高固含水性聚氨酯树脂的制备方法，所述制备方法包括：提供一水性聚氨酯预聚体；使用第一水性聚氨酯树脂乳化所述水性聚氨酯预聚体，所述第一水性聚氨酯树脂与所述水性聚氨酯预聚体不具有反应性，所述第一水性聚氨酯树脂的固含量为10％～40％，pH值为6～8；使用多元胺水溶液对乳化后的所述水性聚氨酯预聚体进行扩链，得到一反应乳液；对所述反应乳液进行后处理，制备得到超高固含的第二水性聚氨酯树脂，所述第二水性聚氨酯树脂的固含量为50％～65％，pH值为6～8。
在一些实施例中，所述水性聚氨酯预聚体选自阴离子型、非离子型、阳离子型、阴—非离子型、阳—非离子型水性聚氨酯预聚体中任意一种。
在一些实施例中，所述水性聚氨酯预聚体由多元醇化合物、多异氰酸酯化合物、第一扩链剂、第二扩链剂，以及根据需要的成盐剂反应而得到的。
在一些实施例中，所述多元醇化合物选自聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇中的任意一种或任意其组合，和/或所述多元醇化合物的数均分子量为500～5000g/mol。
在一些实施例中，第一扩链剂选自含羧基、磺酸盐、氮嗡离子、硫嗡离子、磷嗡离子、聚氧乙烯等亲水基团的双活性氢化合物中任意一种或上述任意其组合。
在一些实施例中，第一水性聚氨酯树脂选自阴离子、阳离子、非离子、阴—非离子、阳—非离子型水性聚氨酯树脂中的任意一种。
在一些实施例中，所述乳化的搅拌速率为200-500r/min，和/或搅拌时间为18-40min。
在一些实施例中，所述多元胺水溶液中多元胺的质量分数为10％～50％。
在一些实施例中，所述多元胺选自乙二胺、己二胺、异佛尔酮二胺、环己二甲胺、二乙烯三胺、三乙烯四胺、四乙烯五胺中任意一种或上述任意其组合。
本发明还提供了一种如上所述制备方法制备获得的超高固含水性聚氨酯树脂。
如上所述，根据本发明提供的超高固含水性聚氨酯树脂制备方法，利用多元醇和多异氰酸酯反应得到水性聚氨酯预聚体，并通过第一水性聚氨酯作为乳化剂乳化该水性聚氨酯预聚体，从而制备获得超高固含的第二水性聚氨酯树脂。进一步地，所述水性聚氨酯预聚体可以为阴离子型、非离子型、阳离子型、阴—非离子型、阳—非离子型，所述第一水性聚氨酯可以为阴离子型、非离子型、阳离子型、阴—非离子型、阳—非离子型，从而基于本发明的制备方法，可以将两种不同类型的水性聚氨酯树脂的特点结合，增加了所述第二水性聚氨酯树脂的性能可调控性。此外，根据本发明提供的超高固含水性聚氨酯树脂制备方法更加简单安全可靠、环境友好、步骤少、收率高，在超高固含水性聚氨酯树脂的产业化发展中具有很大的应用价值。
附图说明
图1示出了本发明提供的超高固含水性聚氨酯树脂制备方法的一具体实施方式的流程图。
具体实施方式
在下文的描述中，给出了大量具体的细节以便提供对本发明更为彻底的理解。然而，对于本领域技术人员而言显而易见的是，本发明可以无需一个或多个这些细节而得以实施。在其他的例子中，为了避免与本发明发生混淆，对于本领域公知的一些技术特征未进行描述。
应当理解的是，本发明能够以不同形式实施，而不应当解释为局限于这里提出的实施例。相反地，提供这些实施例将使公开彻底和完全，并且将本发明的范围完全地传递给本领域技术人员。如没有特别说明，以下实施例所示的“％”和“份”分别是指“质量％”和“质量份”。
本发明提供了一种超高固含水性聚氨酯树脂制备方法，所述制备方法包括但不限于以下步骤：
S1，提供一水性聚氨酯预聚体，
S2，使用第一水性聚氨酯树脂乳化所述水性聚氨酯预聚体，所述第一水性聚氨酯树脂与所述水性聚氨酯预聚体不具有反应性，所述第一水性聚氨酯树脂的固含量为10％～40％，pH值为6～8；
S3，使用多元胺水溶液对乳化后的所述水性聚氨酯预聚体进行扩链，得到一反应乳液；
S4，对所述反应乳液进行后处理，制备得到第二水性聚氨酯树脂，所述第二水性聚氨酯树脂的固含量为50％～65％，pH值为6～8。
根据本发明提供的超高固含水性聚氨酯树脂制备方法，利用多元醇和多异氰酸酯反应得到水性聚氨酯预聚体(例如标记A)，并通过第一水性聚氨酯(例如标记为B)作为乳化剂乳化该水性聚氨酯预聚体A，从而制备获得超高固含的第二水性聚氨酯树脂(例如标记A)。所述第二水性聚氨酯树脂C的固含量为50％～65％，例如55％、60％、65％，pH值为6～8，例如6、7、8。
如图1所示，在步骤S1中，所述水性聚氨酯预聚体A可以为阴离子型、非离子型、阳离子型、阴—非离子型、阳—非离子型的水性聚氨酯预聚体，从而所制备的第二水性聚氨酯C具有相应的离子特性。所述水性聚氨酯预聚体A由多元醇化合物、多异氰酸酯化合物、第一扩链剂、第二扩链剂，以及根据需要与异氰酸酯封端的水性聚氨酯预聚体中亲水基团进行反应的成盐剂反应而得到。
所述多元醇化合物为数均分子量为500～5000g/mol的多元醇化合物，例如500g/mol、1000g/mol、1200g/mol、3000g/mol、5000g/mol，所述多元醇化合物可以选自聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇中的任意一种或任意其组合，进一步地，可以仅由500～5000g/mol的聚碳酸酯多元醇构成，当分子量低于500g/mol时，制备的水性聚氨酯的成膜性不好，当分子量高于5000g/mol时，多元醇化合物活性低，难反应，反应后粘度大，不利于乳化，因此在上述范围内时，保证了第二水性聚氨酯C的均匀稳定性。
所述多异氰酸酯化合物为二异氰酸酯为脂肪族和/或芳香族二异氰酸酯，具体的例子可以列举选自1,3-亚苯基二异氰酸酯、1,4-亚苯基二异氰酸酯、2,4-甲苯二异氰酸酯(TDI)、2,6-甲苯二异氰酸酯、间苯二亚甲基二异氰酸酯(XDI)、4,4’-二苯基甲烷二异氰酸酯(MDI)、2,4-二苯基甲烷二异氰酸酯、间异氰酸苯基磺酰基异氰酸酯、对异氰酸苯基磺酰基异氰酸酯、异佛尔酮二异氰酸酯(IPDI)、4,4’-二环己基甲烷二异氰酸酯、环己烯二异氰酸酯、甲基环己烯二异氰酸酯、1,3-异氰酸甲基环己烷、双(2-异氰酸乙基)-4-环己烯-1,2-二羧酸酯、亚乙基二异氰酸酯、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯(HDI)、十二亚甲基二异氰酸酯、1,6,11-十一烷三异氰酸酯、2,2,4-三甲基六亚甲基二异氰酸酯、2,6-二异氰酸甲基己酸酯、2-异氰酸乙基-2,6-二异氰酸己酸酯，进一步地可以列举异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯。
所述第一扩链剂为含羧基、磺酸盐、氮嗡离子、硫嗡离子、磷嗡离子、聚氧乙烯等亲水基团的双活性氢化合物中任意一种或上述任意其组合，所述第一扩链剂起到自乳化的效果。
所述第二扩链剂为含2个或2个以上活泼氢的小分子多元醇中一种或多种。
所述成盐剂根据实际的需要进行添加，基于获得阳离子型水性聚氨酯预聚体的观点，所述成盐剂可以选择有机酸，例如乳酸。基于获得阴离子型水性聚氨酯预聚体的观点，所述成盐剂可以选自有机胺和/或无机胺盐，例如三乙胺。更进一步地，所述
进一步地，所述水性聚氨酯预聚体A的制备体系中，还进一步地包括催化剂，所述催化剂可以为有机金属催化剂，例如有机铋，从而保证了所述反应的快速形成。
所述水性聚氨酯预聚体可以在一反应介质中进行，例如丙酮，以保证所述反应体系中粘度可控，利于所述后续的乳化和扩链过程。
如图1所示，在步骤S2中，利用第一水性聚氨酯树脂B作为乳化水，对所述聚氨酯预聚体A进行乳化，该第一水性聚氨酯树脂B以水作为连续相，其中含有水性聚氨酯粒子为固体份，该第一水性聚氨酯树脂B的固含量为10％～40％，例如10％、30％、40％，从而在乳化水性聚氨酯预聚体A时，所得到的第二水性聚氨酯树脂C具有预期的固含量，进一步地，所述第一水性聚氨酯B的PH为6～8，例如6、7、8，所述第一水性聚氨酯B的粘度小于等于100mPa.S，例如45mPa.S、50mPa.S、60mPa.S、85mPa.S、90mPa.S，以保证乳化效果。具体而言，例如可以将步骤S1中的聚氨酯预聚体A转移至乳化设备中，并添加第一水性聚氨酯B在200-500r/min的条件下进行乳化分散18-40min，进一步地在18-26min，当所述乳化分散的速率低于200r/min时，搅拌速度过低，在乳化过程中，第一水性聚氨酯乳液和所述聚氨酯预聚体难以进行均匀的分散和混合，易导致乳化不完全。当所述速率高于500r/min，搅拌速度较高，对所述第一水性聚氨酯乳液和所述聚氨酯预聚体内部产生较大的剪切作用力，破坏乳液的稳定性，从而保证了所述第二水性聚氨酯乳液具体稳定的超高固含量。所述第一水性聚氨酯乳液中的固体份水性聚氨酯可以阴离子、阳离子、非离子、阴—非离子、阳—非离子型水性聚氨酯，并且与所述水性聚氨酯预聚体之间不具有反应性，从而利用本发明的乳化过程，可以将两种不同类型的水性聚氨酯树脂的特点结合，增加了第二水性聚氨酯树脂C的性能可调控性。
如图1所示，在步骤S3中，对乳化后的所述聚氨酯预聚体A进行进行多元胺水溶液扩链，以使得乳化后的水性聚氨酯预聚体A在进一步地分散的同时进行扩链，基于获得高固含和稳定性的观点，所述多元胺水溶液中多元胺质量分数为10％～50％，进一步地为18％～45％，例如20％、30％、45％，进一步地，所述多元胺可以选自乙二胺、己二胺、异佛尔酮二胺、环己二甲胺、二乙烯三胺、三乙烯四胺、四乙烯五胺中的任意一种，例如异佛尔酮二胺。
如图1所示，在步骤S4中，对扩链后形成的反应乳液进行后处理，例如反应乳液中的溶剂进行脱溶，具体而言，可以将扩链后的所述聚氨酯预聚体A转移至脱溶设备，从而脱去溶剂，从而获得高固含量第二水性聚氨酯树脂C。基于本发明的制备方法和制备过程，该第二水性聚氨酯树脂C具有50％～65％的超高固含量，性能稳定，安全环保，可以广泛粘合剂等领域。
下面结合实施例进一步阐述本发明。应理解，实施例仅用于说明本发明，而非限制本发明的范围。本专业领域的技术人员在本发明权利要求范围内做出的改进和调整也应属于本发明的权利和保护范围。
实施例1
一种超高固含水性聚氨酯树脂的制备方法，包含以下步骤：
1、制备水性聚氨酯预聚体A，所述水性聚氨酯预聚体制备方法如下：150g聚丙二醇2000、42g异佛尔酮二异氰酸酯、4g二羟甲基丙酸、2g的1,4-丁二醇、30g丙酮和1g有机铋在80℃反应6小时，然后加入70g丙酮和2.86g三乙胺，降温值20℃；
2、将上述过程1中水性聚氨酯预聚体转移至乳化设备中，使用475g阴离子聚酯型水性聚氨酯树脂B(固含量30％)作为乳化水乳化水性聚氨酯预聚体，乳化打开后加入10g的乙二胺5倍水溶液进行扩链；
3、将上述过程2中所获得的扩链后转移至脱溶设备，脱去溶剂，获得60％固含量水性聚氨酯树脂C；
实施例2
一种超高固含水性聚氨酯树脂的制备方法，包含以下步骤：
1、制备水性聚氨酯预聚体A，所述水性聚氨酯预聚体制备方法如下：150g的聚己二酸新戊二醇酯二醇2000、23.5g的甲苯二异氰酸酯、12g的异佛尔酮二异氰酸酯、2g的1,4-丁二醇、20g的丙酮和0.8g的有机铋催化剂在75℃反应7小时，然后加入100g丙酮，降温值50℃，加入6g的乙二氨基乙基磺酸钠反应30min；
2、将上述过程1中水性聚氨酯预聚体转移至乳化设备中，使用241g的阴离子聚醚型水性聚氨酯树脂B(固含量20％)作为乳化水，乳化水性聚氨酯预聚体，乳化打开后加入15g的乙二胺5倍水溶液进行扩链；
3、将上述过程2中所获得的水性聚氨酯乳液转移至脱溶设备，脱去溶剂，获得65％固含量水性聚氨酯树脂C；
实施例3
一种超高固含水性聚氨酯树脂的制备方法，包含以下步骤：
1、制备水性聚氨酯预聚体A，所述水性聚氨酯预聚体制备方法如下：150g的聚己二酸新戊二醇酯二醇3000、9.08g的六亚甲基二异氰酸酯和30g的异佛尔酮二异氰酸酯在90℃反应2小时，然后加入2g的1,4-丁二醇和20g丙酮在80℃反应1小时，然后降温值60℃，加入80g丙酮，60℃的情况下5分钟滴加6g的N-甲基二乙醇胺和30g丙酮的混合液、保持60℃反应1小时、然后降温至30℃加入6g的乳酸；
2、将上述过程1中水性聚氨酯预聚体转移至乳化设备中，使用580g的非离子聚醚型水性聚氨酯树脂B(固含量30％)作为乳化水，乳化水性聚氨酯预聚体，乳化打开后加入70g异佛尔酮二胺5倍水溶液进行扩链；
3、将上述过程2中所获得的水性聚氨酯乳液转移至脱溶设备，脱去溶剂，获得55％固含量水性聚氨酯树脂C；
实施例4
一种超高固含水性聚氨酯树脂的制备方法，包含以下步骤：
1、制备水性聚氨酯预聚体A，所述水性聚氨酯预聚体制备方法如下：150g的聚四氢呋喃醚二醇2000和42g的异佛尔酮二异氰酸酯在90℃反应2小时、然后加入4g的二羟甲基丙酸、2.3g的二甘醇、和20g的丙酮，80℃反应2小时，然后加入1g有机铋催化剂和20g丙酮，75℃反应3小时，加入100g丙酮，降温至20℃，加入2.9g三乙胺；
2、将上述过程1中水性聚氨酯预聚体转移至乳化设备中，使用600g非离子聚醚型水性聚氨酯树脂B(固含量35％)作为乳化水，乳化水性聚氨酯预聚体，乳化打开后加入10g乙二胺5倍水溶液进行扩链；
3、将上述过程2中所获得的水性聚氨酯乳液转移至脱溶设备，脱去溶剂，获得60％固含量水性聚氨酯树脂C；
性能检测：
上述上述实施例1-4所获得超高固含量水性聚氨酯树脂进行稳定性测试，按照50℃放置7天测试，测试结果见表1。
表1超高固含量水性聚氨酯树脂的稳定性
序号 实施例1 实施例2 实施例3 实施例4
实测固含量/％ 60.23 64.45 55.65 59.87
稳定性 无分层，沉淀 无分层，沉淀 无分层，沉淀 无分层，沉淀
外观 乳白带蓝光 乳白带蓝光 乳白带蓝光 乳白带蓝光
如表1所示，利用本发明的制备方法制备获得的水性聚氨酯树脂的固含量均在55.65以上，且在放置7天后外观和稳定性好，即所述水性聚氨酯树脂具有超高固含量，性能稳定，安全环保，可以广泛粘合剂等领域。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (10)

1.一种超高固含水性聚氨酯树脂的制备方法，其特征在于，所述制备方法包括：
提供一水性聚氨酯预聚体；
使用第一水性聚氨酯树脂乳化所述水性聚氨酯预聚体，所述第一水性聚氨酯树脂与所述水性聚氨酯预聚体不具有反应性，所述第一水性聚氨酯树脂的固含量为10％～40％，pH值为6～8；
使用多元胺水溶液对乳化后的所述水性聚氨酯预聚体进行扩链，得到一反应乳液；
对所述反应乳液进行后处理，制备得到超高固含的第二水性聚氨酯树脂，所述第二水性聚氨酯树脂的固含量为50％～65％，pH值为6～8。
2.根据权利要求1所述的超高固含水性聚氨酯树脂的制备方法，其特征在于，所述水性聚氨酯预聚体选自阴离子型、非离子型、阳离子型、阴—非离子型、阳—非离子型水性聚氨酯预聚体中任意一种。
3.根据权利要求1或2所述的超高固含水性聚氨酯树脂的制备方法，其特征在于，所述水性聚氨酯预聚体由多元醇化合物、多异氰酸酯化合物、第一扩链剂、第二扩链剂，以及根据需要的成盐剂反应而得到的。
4.根据权利要求3所述的超高固含水性聚氨酯树脂的制备方法，其特征在于，所述多元醇化合物选自聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇中的任意一种或任意其组合，和/或所述多元醇化合物的数均分子量为500～5000g/mol。
5.根据权利要求3所述的超高固含水性聚氨酯树脂的制备方法，其特征在于，第一扩链剂选自含羧基、磺酸盐、氮嗡离子、硫嗡离子、磷嗡离子、聚氧乙烯等亲水基团的双活性氢化合物中任意一种或上述任意其组合。
6.根据权利要求1或2所述的超高固含水性聚氨酯树脂的制备方法，其特征在于，所述第一水性聚氨酯树脂选自阴离子、阳离子、非离子、阴—非离子、阳—非离子型水性聚氨酯树脂中的任意一种。
7.根据权利要求1所述的超高固含水性聚氨酯树脂的制备方法，其特征在于，所述乳化的搅拌速率为200-500r/min，和/或搅拌时间为18-40min。
8.根据权利要求1所述的超高固含水性聚氨酯树脂的制备方法，其特征在于，所述多元胺水溶液中多元胺的质量分数为10％～50％。
9.根据权利要求1所述的超高固含水性聚氨酯树脂的制备方法，其特征在于，所述多元胺选自乙二胺、己二胺、异佛尔酮二胺、环己二甲胺、二乙烯三胺、三乙烯四胺、四乙烯五胺中任意一种或上述任意其组合。
10.一种由如权利要求1至9任一所述的超高固含水性聚氨酯树脂的制备方法制备获得的超高固含水性聚氨酯树脂。
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