CN110156948A - 一种端氨基超支化聚硅氧烷改性水性聚氨酯的制备方法 - Google Patents

一种端氨基超支化聚硅氧烷改性水性聚氨酯的制备方法 Download PDF

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CN110156948A
CN110156948A CN201910338290.3A CN201910338290A CN110156948A CN 110156948 A CN110156948 A CN 110156948A CN 201910338290 A CN201910338290 A CN 201910338290A CN 110156948 A CN110156948 A CN 110156948A
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任龙芳
牛巧宣
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Shaanxi University of Science and Technology
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Abstract

本发明涉及一种端氨基超支化聚硅氧烷改性水性聚氨酯的制备方法，首先以3‑氨基丙基三乙氧基硅烷（kh550）和三甲基氯硅烷（TMCS）为原料，通过水解缩合制备端氨基超支化聚硅氧烷（HPSi‑NH2）。以HPSi‑NH2为交联剂，与聚氨酯预聚体（PPU）反应，支化扩链制得端氨基超支化聚硅氧烷改性水性聚氨酯（HSiPU），同时在合成过程中通过添加封端剂控制反应程度，改性后的水性聚氨酯具有传统有机硅水性聚氨酯的性能优势，同时减少了有机硅改性水性聚氨酯的相分离，增加了产品的力学性能和粘结性能，所得乳液综合性能优异，可用作皮革胶黏剂或耐水涂层。

Description

一种端氨基超支化聚硅氧烷改性水性聚氨酯的制备方法
技术领域
本发明涉及有机硅聚合物技术领域，具体涉及一种端氨基超支化聚硅氧烷改性水性聚氨酯的制备方法。
背景技术
随着环境保护的提倡，水性聚氨酯代替溶剂型聚氨酯已成为趋势。针对水性聚氨酯在耐水性、耐热性等方面的不足进行改性受到人们的广泛关注。有机硅具有疏水、耐热、化学性质稳定等特性，传统有机硅改性水性聚氨酯的制备方法简述如下：将直链有机硅作为混合软段形成有机硅嵌段改性水性聚氨酯；或将有机硅接枝形成有机硅侧链水性聚氨酯；也有人通过后扩链的方式用小分子kh550改性水性聚氨酯。但现有技术存在如下的问题：1、由于有机硅和聚氨酯两者溶度参数相差较大，当有机硅添加量超过一定限度时，两者相分离严重。2、有机硅的强疏水性导致改性产品乳化困难，乳液稳定性降低。3、有机硅力学性能较差，且化学性质稳定，对基材的作用力小，导致改性产品在力学性能和粘结性方面有所不足。
发明内容
本发明提供了端氨基超支化聚硅氧烷改性水性聚氨酯的制备方法，以克服现有技术存在的相分离严重、乳液稳定性低和在力学性能和粘结性方面有所不足的问题。
为了实现上述目的，本发明采用的技术方案为：一种端氨基超支化聚硅氧烷改性水性聚氨酯的制备方法，其特征在于：包括以下步骤：
步骤一：将kh550、水、乙醇加入到三口烧瓶中，kh550与水与乙醇的物质的量之比为1：1～2：5～15，向体系缓慢滴加三甲基氯硅烷(TMCS)，kh550与TMCS的物质的量之比为1：1～1.5在40～55℃下反应5～6h得到无色透明液体，用乙醇钠调节pH至中性，离心除去生成的盐，减压蒸馏，得到端氨基超支化聚硅氧烷(HPSi-NH2)；
步骤二：PPU在室温下乳化，乳化同时加入PPU总质量0.5～5％的 HPSi-NH2，封端剂的添加量小于PPU中-NCO的理论物质的量，乳化后静置消泡，最后减压蒸馏去除有机溶剂后得到改性水性聚氨酯HSiPU。
所述步骤中，PPU在室温下乳化前，先向PPU中加入封端剂，封端剂含氨基时，直接进行后续降温中和，过程中保持搅拌状态，然后再在室温下乳化。
步骤二中封端剂是乙胺、正丙胺、正丁胺、正戊胺中的一种。
步骤二：PPU在室温下乳化前，先向PPU中加入封端剂，封端剂含羟基时，在75～85℃反应2～3h后，进行后续降温中和，然后再在室温下乳化。
步骤二中封端剂是乙醇、正丙醇、正丁醇、季戊四醇三丙烯酸酯、丙烯酸羟乙酯中的一种。
与现有技术相比，本发明的优点是：
本发明合成的改性水性聚氨酯具有一般有机硅改性聚氨酯的性能优势外，同时超支化有机硅作为交联剂，使得分子链互相缠绕，增加了聚氨酯与有机硅两相相容性，超支化有机硅位于分子内部减少了对乳液稳定性的影响，乳化的同时支化扩链可以改善大分子直接乳化带来的困难，在一定程度上改善了有机硅改性聚氨酯带来的负面影响，同时通过添加封端剂控制反应程度，分子中含有部分未反应的活性硅羟基，在应用时增加了与基材的相互作用，产品具有良好的耐水耐热稳定性，并且粘结性和力学性能优异，可用做皮革胶黏剂和耐水涂层。
本发明合成了端氨基超支化聚硅氧烷改性的水性聚氨酯，降低了传统有机硅改性水性聚氨酯带来的相分离、乳化困难的问题，同时具有良好的力学性能和粘结性能，具有环境友好性，具有良好的应用前景。
附图说明
图1为实施例1的的合成路线图。
具体实施方式
下面结合具体实施例对本发明做进一步详细说明。其中实施例1所得产品效果最好。
实施例1
步骤一：HPSi-NH2的制备
将3.6g水加入22.14g的kh550中，并向体系加入20mL的乙醇，在搅拌条件下，缓慢滴加10.8g的TMCS，在50℃下不断回流搅拌反应5h，反应结束后，用乙醇钠调节体系的pH至中性，再用离心机高速离心除去生成的固体盐，最后用旋转蒸发仪除去小分子乙醇，得到端氨基超支化聚硅氧烷 HPSi-NH2；
步骤二：HSiPU的制备
首先将真空脱水后的20g聚己二酸1.4-丁二醇酯(Mn＝2000)和8.89g 异佛尔酮二异氰酸酯加入干燥的三口烧瓶中，搅拌均匀，滴加3滴的催化剂二月桂酸二丁基锡，在75℃下反应1.5h；加入1.45g二羟甲基丙酸，继续反应2.5h，至预聚体中-NCO含量固定不变，得到聚氨酯预聚体(PPU)；
然后将得到的PPU降温至40℃，加入三乙胺中和30min后，继续降温至室温，在剧烈搅拌下缓慢加入蒸馏水高速乳化40min，乳化的同时加入 0.58g的HPSi-NH2，乳化结束后，静置直到表层泡沫自动消除，最后减压蒸馏去除丙酮后即得到改性水性聚氨酯乳液。
实施例1的合成路线图如图1所示
实施例2
步骤一：HPSi-NH2的制备
将1.8g水加入22.14g的kh550中，并加入20mL的乙醇，在搅拌条件下缓慢加入10.8g的TMCS，在50℃下不断回流搅拌反应6h，用乙醇钠调节溶液pH至中性，用离心机除去反应生成的盐，利用旋转蒸发仪除去小分子乙醇，得到端氨基超支化聚硅氧烷HPSi-NH2；
步骤二：HSiPU的制备
首先将真空脱水后的10g聚四氢呋喃醚二醇(Mn＝1000)和5.22g甲苯二异氰酸酯加入干燥的三口烧瓶中，搅拌均匀，滴加3滴的催化剂二月桂酸二丁基锡，在75℃下反应1.5h；加入1.33g二羟甲基丙酸，继续反应2.5h，至预聚体中-NCO含量固定不变，得到聚氨酯预聚体PPU；
然后向得到的PPU中加入0.73g丁胺并降温，降温至40℃加入三乙胺中和30min后，继续降温至室温，在剧烈搅拌下缓慢加入蒸馏水和1.12g的 HPSi-NH2，高速乳化40min后，静置直到表层泡沫自动消除，最后减压蒸馏去除丙酮后即得到改性水性聚氨酯乳液。
实施例3
步骤一：HPSi-NH2的制备
将3.6g水加入22.14g的kh550中，并加入30mL的乙醇，在搅拌条件下缓慢加入15.0g的TMCS，在55℃下不断搅拌回流反应5h，用乙醇钠调节体系pH至中性，用离心机除去生成的固体盐，利用旋转蒸发仪除去小分子乙醇，得到端氨基超支化聚硅氧烷HPSi-NH2；
步骤二：HSiPU的制备
将真空脱水后的20g聚乙二醇(Mn＝2000)和5.04g六亚甲基二异氰酸酯加入干燥的三口烧瓶中，搅拌均匀，滴加3滴的催化剂二月桂酸二丁基锡，在75℃下反应1h；加入1.60g二羟甲基丙酸，继续反应2h，至预聚体中-NCO 含量固定不变，得到PPU；
然后向得到的PPU中加入2.40g季戊四醇三丙烯酸酯，在80℃下反应 2h，降温至30℃，加入三乙胺中和25min后，在剧烈搅拌下缓慢加入蒸馏水和0.17g的HPSi-NH2，高速乳化1h，静置直到表层泡沫自动消除，最后减压蒸馏去除丙酮后即得到改性水性聚氨酯乳液。

Claims (5)

1.一种端氨基超支化聚硅氧烷改性水性聚氨酯的制备方法，其特征在于：包括以下步骤：
步骤一：将kh550、水、乙醇加入到三口烧瓶中，kh550与水与乙醇的物质的量之比为1：1~2：5~15，向体系缓慢滴加三甲基氯硅烷（TMCS），kh550与TMCS的物质的量之比为1：1~1.5在40~55℃下反应5~6h得到无色透明液体，用乙醇钠调节pH至中性，离心除去生成的盐，减压蒸馏，得到端氨基超支化聚硅氧烷（HPSi-NH2）；
步骤二：PPU在室温下乳化，乳化同时加入PPU总质量0.5~5%的HPSi-NH2，封端剂的添加量小于PPU中-NCO的理论物质的量，乳化后静置消泡，最后减压蒸馏去除有机溶剂后得到改性水性聚氨酯HSiPU。
2.根据权利要求1所述的端氨基超支化聚硅氧烷改性水性聚氨酯的制备，其特征在于：所述步骤中，PPU在室温下乳化前，先向PPU中加入封端剂，封端剂含氨基时，直接进行后续降温中和，过程中保持搅拌状态，然后再在室温下乳化。
3.根据权利要求2所述的端氨基超支化聚硅氧烷改性水性聚氨酯的制备，其特征在于：步骤二中封端剂是乙胺、正丙胺、正丁胺、正戊胺中的一种。
4.根据权利要求1所述的端氨基超支化聚硅氧烷改性水性聚氨酯的制备，其特征在于：步骤二：PPU在室温下乳化前，先向PPU中加入封端剂，封端剂含羟基时，在75~85℃反应2~3h后，进行后续降温中和，然后再在室温下乳化。
5.根据权利要求4所述的端氨基超支化聚硅氧烷改性水性聚氨酯的制备，其特征在于：步骤二中封端剂是乙醇、正丙醇、正丁醇、季戊四醇三丙烯酸酯、丙烯酸羟乙酯中的一种。
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