CN106883375A - 一种超支化聚氨酯改性的水性聚氨酯、制备方法及应用 - Google Patents

一种超支化聚氨酯改性的水性聚氨酯、制备方法及应用 Download PDF

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CN106883375A
CN106883375A CN201710167849.1A CN201710167849A CN106883375A CN 106883375 A CN106883375 A CN 106883375A CN 201710167849 A CN201710167849 A CN 201710167849A CN 106883375 A CN106883375 A CN 106883375A
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柴春鹏
候婧辉
刘加
罗运军
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Beijing Institute of Technology BIT
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Abstract

本发明涉及一种超支化聚氨酯改性的水性聚氨酯及制备方法及应用，属于纺织化工技术领域。所述的水性聚氨酯以各组分质量总和为100％计，各组分及其质量百分比为：后扩链改性水性聚氨酯为88‑97％，超支化水性聚氨酯3‑12％。所述方法步骤如下：首先将聚醚二元醇、大分子交联剂、亲水型扩链剂、亲油型扩链剂与芳香族的异氰酸酯反应生成水性聚氨酯，再加入含磷二胺类扩链剂进行后扩链反应，然后与超支化水性聚氨酯共混，得到超支化聚氨酯改性的水性聚氨酯。有效提高了水性聚氨酯的拉伸强度和耐静水压。用做织物涂层时可以使织物功能化，使其具有防水、透湿等特殊功能。

Description

一种超支化聚氨酯改性的水性聚氨酯、制备方法及应用
技术领域
本发明涉及一种超支化聚氨酯改性的水性聚氨酯、制备方法及应用，属于纺织化工技术领域。
背景技术
水性聚氨酯是一种能够均匀涂布于织物表面的高分子类化合物，可通过粘合作用在织物表面形成一层或多层薄膜，它不仅能改善织物外观和风格，而且可以使织物功能化，使其具有防水、透湿、阻燃等特殊功能。水性聚氨酯以水为分散剂，具有环境友好、无毒、安全等优点。但是现阶段生产的水性聚氨酯的耐静水压并不理想，耐静水压普遍偏低，防水性不好，难以满足人们在耐静水压方面的要求。
超支化聚合物是一类具有高度支化结构的高分子，由于其含有大量的端基官能团和内部空腔结构，并且具有无缠绕、非结晶性等特点。超支化水性聚氨酯是由枝化基元组成的高度枝化但是结构不规整的水性聚氨酯。采用乙酸酐对超支化水性聚氨酯进行封端，就得到乙酸酐封端的超支化水性聚氨酯。
专利CN105316949A公布的硬段改性后扩链阻燃水性聚氨酯涂层剂及其制备方法，该专利中采用含磷二胺扩链剂合成了一系列后扩链阻燃水性聚氨酯，虽然也采用后扩链的方式对水性聚氨酯进行改性，得到了具有良好阻燃和力学性能的水性聚氨酯，其极限氧指数可达到31.1％，拉伸强度可达到29.5MPa。但是，其耐静水压能力并不能够满足市场使用要求。专利CN105133347A公布的耐静水压阻燃水性聚氨酯的制备方法，虽然制备的水性聚氨酯同时具备耐静水压和阻燃的性能，但是水性聚氨酯的耐静水压不高，仅为10-23kPa。唐本鑫等人发表的一篇文章中(唐本鑫，冯静静，葛震等.高耐静水压水性聚氨酯的制备与表征[J].涂料技术与文摘.2015，(10)：34-38)，虽然采用聚醚三元醇为交联剂，制得了具有耐静水压性能的水性聚氨酯织物涂层剂，但是制得水性聚氨酯的拉伸强度最高仅为19.13MPa，耐静水压仅为34.9kPa。目前，具有较高耐静水压和拉伸强度的水性聚氨酯还未见有人报道。
发明内容
有鉴于此，本发明的目的之一在于提供一种超支化聚氨酯改性的水性聚氨酯。目的之二在于提供一种超支化聚氨酯改性的水性聚氨酯的制备方法。目的之三在于提供一种超支化聚氨酯改性的水性聚氨酯的应用，该水性聚氨酯可以作为织物涂层使用。
本发明是这样实现的：
一种超支化聚氨酯改性的水性聚氨酯，所述的水性聚氨酯以各组分质量总和为100％计，各组分及其质量百分比为：后扩链改性水性聚氨酯为88-97％，超支化水性聚氨酯3-12％。
所述后扩链改性水性聚氨酯以配方中组分总质量为100％计，各组分质量百分比为聚醚二元醇32.04-40.34％，大分子交联剂6.91-7.15％，亲水性扩链剂7.84-7.92％，异氰酸酯19.62-20.90％，亲油性扩链剂1.70-1.73％，碱性成盐剂5.96-6.03％以及二胺扩链剂16.13-25.64％。
优选的，所述亲水性扩链剂为二羟甲基丙酸(DMPA)或二羟甲基丁酸。
优选的，所述异氰酸酯是芳香族二异氰酸酯化合物，更优选液化二苯基甲烷二异氰酸酯(液化MDI)、二苯基甲烷二异氰酸酯(MDI)或甲苯二异氰酸酯(TDI)。
优选的，所述聚醚二元醇为聚四氢呋喃二醇(PTMG)、聚丙二醇(PPG)或聚乙二醇。
优选的，所述大分子交联剂为三羟基聚醚(N330)。
优选的，所述亲油性扩链剂为1,4-丁二醇(BDO)、一缩二乙二醇、三羟甲基丙烷或季戊四醇。
所述碱性成盐剂为可以与羧酸反应的成盐剂，优选三乙胺、三正丁胺或氨水。
优选的，所述的二胺扩链剂为双氨基苯基氧化磷(BAPO)、双(氨基苯基)苯基氧化磷(BPPO)、双(3-氨基苯基)苯基氧化磷(BAPPO)或2,4,8,10-四氧杂-3,9-二磷杂螺环-3,9-二氧-3,9-二(3-氨基苯基)(BPPA)。
所述的超支化水性聚氨酯优选乙酸酐封端的超支化水性聚氨酯。
所述乙酸酐封端的超支化水性聚氨酯的制备方法如下：
将异佛尔酮二异氰酸酯(IPDI)与二羟甲基丙酸(DMPA)混合，在惰性气体氛围下，在60-80℃下反应4-6h，降温至-10℃～-5℃，得到反应中间体，缓慢加入二乙醇胺(DEOA)，反应2h后，升温至85℃，加入与二羟甲基丙酸等摩尔的三乙胺反应0.5h后，在70℃恒温旋蒸，去除溶剂，沉淀抽滤得到滤渣，将滤渣用无水乙醚冲洗3～5次后，在60℃下真空干燥24h后，得到未封端的超支化水性聚氨酯；在70～90℃下，取未封端的超支化水性聚氨酯和乙酸酐，溶于300mL吡啶中，以硫酸为催化剂，反应2～8h，得到液体，在60～80℃下恒温旋蒸，沉淀抽滤得到滤渣并用蒸馏水冲洗3～5次后，在80～120℃下真空干燥18～36h后，制得乙酸酐封端的超支化水性聚氨酯。
所述异佛尔酮二异氰酸酯与二羟甲基丙酸的摩尔比为2-8:1；
二乙醇胺与反应中间体的摩尔比为1-1.1:1；
未封端的超支化水性聚氨酯的质量：乙酸酐的体积＝1:1；
硫酸与乙酸酐的摩尔比≥0.2:1。
一种高耐静水压水性聚氨酯的制备方法，所述方法步骤如下：
在80℃下，将亲水性扩链剂和异氰酸酯加入干燥无水的聚醚二醇和大分子交联剂中，在80-85℃反应2-3h，加入有机溶剂1调节反应体系粘度至能够顺利搅拌，加入亲油性扩链剂反应3-5h，加入碱性成盐剂成盐后，加入去离子水和二胺扩链剂的有机溶液，分散均匀后得到后扩链改性水性聚氨酯的分散液，再取含有后扩链改性水性聚氨酯的分散液和含有超支化水性聚氨酯溶液混合后，搅拌分散均匀，去除有机溶剂1，得到一种超支化聚氨酯改性的水性聚氨酯；
所述去离子水与后扩链改性水性聚氨酯的反应原料总质量比为1.86-2.33:1。
所述有机溶剂1为丙酮、丁酮或四氢呋喃；二胺扩链剂的有机溶液中的有机溶剂为甲基吡咯烷酮。
所述超支化水性聚氨酯溶液是将超支化水性聚氨酯完全溶解在三乙胺质量分数为5％的水溶液中得到的。
所述制备的一种超支化聚氨酯改性的水性聚氨酯制成膜或织物涂层后各种性能不发生变化。
一种所述的超支化聚氨酯改性的水性聚氨酯的应用，其特征在于：所述超支化聚氨酯改性的水性聚氨酯用作织物涂层。
有益效果
本发明所述超支化聚氨酯改性的水性聚氨酯具有高的耐静水压和拉伸强度。本发明的制备方法工艺简单，是采用超支化水性聚氨酯对后扩链改性的水性聚氨酯进行改性，可以有效提高水性聚氨酯的拉伸强度和耐静水压。所述超支化聚氨酯改性的水性聚氨酯用做织物涂层时可以使织物功能化，使其具有防水、透湿等特殊功能。
具体实施方式
以下实施例中所用试剂以及仪器：
以下实施例中所用的乙酸酐封端的超支化水性聚氨酯通过以下方法制备：
(1)取17.7g的IPDI于四口烧瓶中，通入氮气，将体系温度升高为65℃，将5.364g的DMPA溶于25ml二甲基甲酰胺(DMF)中，在机械搅拌的条件下，缓慢滴入体系中，反应6h后，将反应体系温度降到-5℃，得到反应中间体。将4.23g的DEOA滴入体系中，反应2h后，升高体系温度至85℃，加入4.05g的三乙胺反应0.5h后，在70℃恒温旋蒸，去除溶剂，沉淀抽滤得到滤渣，将滤渣用无水乙醚冲洗多次后，在60℃下真空干燥24h后，制得未封端超支化水性聚氨酯白色粉末。
(2)在80℃下，将(1)制得的未封端超支化水性聚氨酯白色粉末取60g和60ml的乙酸酐，溶于300mL吡啶中，以硫酸为催化剂，加入7ml的硫酸，反应4h，得到红色透明液体，在60℃下恒温旋蒸，沉淀抽滤得到滤渣并用蒸馏水冲洗多次后，在90℃下真空干燥24h后，制得乙酸酐封端的超支化水性聚氨酯白色粉末。
使用前将1.5g、3g、6g的乙酸酐封端的超支化水性聚氨酯白色粉末分别完全溶于三乙胺质量分数为5％的50mL的水溶液中，得到含有超支化水性聚氨酯溶液。
以下实施例中所测胶膜的制备方法：
将实施例中制备的超支化聚氨酯改性的水性聚氨酯乳液倒入聚四氟模具中流延成膜，先自然干燥一周；再置于真空烘箱内70℃真空干燥至恒重，取出胶膜。
所测的织物涂层的制备方法：
取100g实施例中制备的超支化聚氨酯改性的水性聚氨酯，加入2-3滴消泡剂，搅拌均匀。再加入质量分数为2.5％的601H增稠剂，搅拌增稠至粘度在45kPa·s左右，搅拌均匀得到胶乳，然后将胶乳在平整的涤纶低弹丝布样上涂刮一次，然后置于定型烘干机中在160℃下烘50s，再重复上述涂刮、烘干步骤2次，得到织物涂层样品。
实施例1：
在250mL四口烧瓶中加入24.05g的分子量为2000的PTMG和4.16g的N330，真空110℃干燥2h后，降温至80℃，加入4.72g的DMPA与12.46g的TDI，升高温度至83℃反应2h，加入40g丙酮来降低反应体系的粘度至能顺利搅拌，再加1.03g的BDO反应3h，加3.59g三乙胺成盐，然后加入111g的去离子水和含9.62g BPPA的甲基吡咯烷酮溶液，分散均匀后得到后扩链改性水性聚氨酯分散液，将含有48.5g后扩链改性水性聚氨酯的后扩链改性水性聚氨酯分散液与含有1.5g乙酸酐封端的超支化水性聚氨酯的乙酸酐封端的超支化水性聚氨酯溶液混合后，搅拌分散均匀，旋转蒸发除去丙酮后，得到的乳液即一种超支化聚氨酯改性的水性聚氨酯。
将实施例1制备的一种超支化聚氨酯改性的水性聚氨酯乳液制成胶膜，用在AGS-J型拉力机对胶膜进行力学性能测试，测得的拉伸强度为23.5MPa。将一种超支化聚氨酯改性的水性聚氨酯乳液制成织物涂层样品，用数字式渗水性测定仪对织物涂层样品进行测试，测得的耐静水压为70kPa。
实施例2：
在250mL四口烧瓶中加入21g的分子量为2000的PTMG和4.05g的N330，真空110℃干燥2h后，降温至80℃，加入4.6g的DMPA与11.86g的TDI，升温至83℃反应2h，加入40g丁酮来降低反应体系的粘度至能顺利搅拌，加入1g的BDO反应3h，加3.5g的三乙胺成盐后加入117g去离子水和含12.6g BPPA的甲基吡咯烷酮溶液，分散均匀后得到后扩链改性水性聚氨酯分散液，将含有47g后扩链改性水性聚氨酯的后扩链改性水性聚氨酯分散液与含有3g乙酸酐封端的超支化水性聚氨酯的乙酸酐封端的超支化水性聚氨酯溶液混合后，搅拌分散均匀，旋转蒸发除去丁酮后，得到的乳液即一种超支化聚氨酯改性的水性聚氨酯。
将实施例2制备的一种超支化聚氨酯改性的水性聚氨酯乳液制成胶膜，用在AGS-J型拉力机对胶膜进行力学性能测试，测得的拉伸强度为25.5MPa。将一种超支化聚氨酯改性的水性聚氨酯乳液制成织物涂层样品，用数字式渗水性测定仪对织物涂层样品进行测试，测得的耐静水压为86kPa。
实施例3：
在250mL四口烧瓶中加入21.55g的分子量为2000的PTMG和4.81g的N330，真空110℃干燥2h后，降温至80℃，加入5.29g的DMPA与13.2g的MDI，升温至83℃反应2h，加入40g四氢呋喃来降低反应体系的粘度至能顺利搅拌，加入1.15g的BDO反应3h，加4.01g的三乙胺成盐后加入156g去离子水和含17.24g BPPO的甲基吡咯烷酮溶液，分散均匀后得到后扩链改性水性聚氨酯分散液，将含有44g后扩链改性水性聚氨酯的后扩链改性水性聚氨酯分散液与含有6g乙酸酐封端的超支化水性聚氨酯的乙酸酐封端的超支化水性聚氨酯溶液混合后，搅拌分散均匀，旋转蒸发除去四氢呋喃后，得到的乳液即一种超支化聚氨酯改性的水性聚氨酯。
将实施例3制备的一种超支化聚氨酯改性的水性聚氨酯乳液制成胶膜，用在AGS-J型拉力机对胶膜进行力学性能测试，测得的拉伸强度为18.3MPa。将一种超支化聚氨酯改性的水性聚氨酯乳液制成织物涂层样品，用数字式渗水性测定仪对织物涂层样品进行测试，测得的耐静水压为78kPa。

Claims (10)

1.一种超支化聚氨酯改性的水性聚氨酯，其特征在于：所述的水性聚氨酯以各组分质量总和为100％计，各组分及其质量百分比为：后扩链改性水性聚氨酯为88-97％，超支化水性聚氨酯3-12％；
所述后扩链改性水性聚氨酯以配方中组分总质量为100％计，各组分质量百分比为聚醚二元醇32.04-40.34％，大分子交联剂6.91-7.15％，亲水性扩链剂7.84-7.92％，异氰酸酯19.62-20.90％，亲油性扩链剂1.70-1.73％，碱性成盐剂5.96-6.03％以及二胺扩链剂16.13-25.64％。
2.如权利要求1所述的一种超支化聚氨酯改性的水性聚氨酯，其特征在于：所述聚醚二元醇为聚四氢呋喃二醇、聚丙二醇或聚乙二醇；所述大分子交联剂为三羟基聚醚；所述亲水性扩链剂为二羟甲基丙酸或二羟甲基丁酸；所述异氰酸酯为芳香族二异氰酸酯化合物；所述亲油性扩链剂为1,4-丁二醇、一缩二乙二醇、三羟甲基丙烷或季戊四醇；所述碱性成盐剂为三乙胺、三正丁胺或氨水。
3.如权利要求1所述的一种超支化聚氨酯改性的水性聚氨酯，其特征在于：所述异氰酸酯为液化二苯基甲烷二异氰酸酯、二苯基甲烷二异氰酸酯或甲苯二异氰酸酯。
4.如权利要求1所述的一种超支化聚氨酯改性的水性聚氨酯，其特征在于：所述的二胺扩链剂为双氨基苯基氧化磷、双(氨基苯基)苯基氧化磷、双(3-氨基苯基)苯基氧化磷或2,4,8,10-四氧杂-3,9-二磷杂螺环-3,9-二氧-3,9-二(3-氨基苯基)。
5.如权利要求1所述的一种超支化聚氨酯改性的水性聚氨酯，其特征在于：所述的超支化水性聚氨酯是乙酸酐封端的超支化水性聚氨酯。
6.如权利要求5所述的一种超支化聚氨酯改性的水性聚氨酯，其特征在于：所述乙酸酐封端的超支化水性聚氨酯的制备方法如下：
在惰性气体或氮气氛围，60-80℃下，搅拌条件下将异佛尔酮二异氰酸酯与二羟甲基丙酸混合均匀，维持原温度恒温反应4-6h，降温至-10℃～-5℃，得到反应中间体，滴入二乙醇胺，反应2h后，升温至85℃，加入与二羟甲基丙酸等摩尔的三乙胺反应0.5h后，在70℃恒温旋蒸，去除溶剂，沉淀抽滤得到滤渣，将滤渣用无水乙醚冲洗3～5次后，在60℃下真空干燥24h后，得到未封端的超支化水性聚氨酯；在70～90℃下，取未封端的超支化水性聚氨酯和乙酸酐，完全溶于吡啶中，以硫酸为催化剂，反应2～8h，得到液体，在60～80℃下恒温旋蒸，沉淀抽滤得到滤渣并用蒸馏水冲洗3～5次后，在80～120℃下真空干燥18～36h后，制得乙酸酐封端的超支化水性聚氨酯；
所述异佛尔酮二异氰酸酯与二羟甲基丙酸的摩尔比为2-8:1；
所述二乙醇胺与反应中间体的摩尔比为1-1.1:1；
未封端的超支化水性聚氨酯的质量：乙酸酐的体积＝1:1；
硫酸与乙酸酐的摩尔比≥0.2:1。
7.如权利要求6所述的一种超支化聚氨酯改性的水性聚氨酯，其特征在于：所述二羟甲基丙酸先完全溶解于二甲基甲酰胺中，再与异佛尔酮二异氰酸酯混合。
8.一种如权利要求1～7任意一项所述的超支化聚氨酯改性的水性聚氨酯的制备方法，其特征在于：所述方法步骤如下：
在80℃下，将亲水性扩链剂和异氰酸酯加入干燥无水的聚醚二醇和大分子交联剂中，在80～85℃反应2-3h，加入有机溶剂1调节反应体系粘度至能够顺利搅拌，加入亲油性扩链剂反应3-5h，加入碱性成盐剂成盐后，加入去离子水和二胺扩链剂的有机溶液，分散均匀后得到后扩链改性水性聚氨酯分散液，再取后扩链改性水性聚氨酯和超支化水性聚氨酯溶液混合后，搅拌分散均匀，去除有机溶剂1，得到一种超支化聚氨酯改性的水性聚氨酯；
所述去离子水与后扩链改性水性聚氨酯的反应原料总质量比为1.86-2.33:1；
所述超支化水性聚氨酯溶液是将超支化水性聚氨酯溶解在三乙胺质量分数为5％的水溶液中得到的。
9.如权利要求8所述的一种超支化聚氨酯改性的水性聚氨酯的制备方法，其特征在于：所述干燥无水的聚醚二醇和大分子交联剂是在110℃真空干燥2h得到的；所述有机溶剂1为丙酮、丁酮或四氢呋喃；二胺扩链剂的有机溶液中的有机溶剂为甲基吡咯烷酮。
10.一种如权利要求1～7任一项所述的超支化聚氨酯改性的水性聚氨酯的应用，其特征在于：所述超支化聚氨酯改性的水性聚氨酯用作织物涂层。
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CN112961301A (zh) * 2021-02-07 2021-06-15 武汉纺织大学 具有离子化线性主链的枝化聚氨酯增稠剂及其制备方法
CN113683748A (zh) * 2021-07-23 2021-11-23 江苏苏博特新材料股份有限公司 一种氟改性超支化水性聚氨酯树脂及使用其的水性纳米防腐自洁面漆
CN114752035A (zh) * 2022-05-30 2022-07-15 浙江大学衢州研究院 一种高固含量的水性聚氨酯分散体及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102851987A (zh) * 2012-10-11 2013-01-02 北京理工大学 一种超支化水性聚氨酯涂层剂
CN105484042A (zh) * 2016-01-11 2016-04-13 北京理工大学 一种后扩链阻燃高耐静水压水性聚氨酯织物涂层剂

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102851987A (zh) * 2012-10-11 2013-01-02 北京理工大学 一种超支化水性聚氨酯涂层剂
CN105484042A (zh) * 2016-01-11 2016-04-13 北京理工大学 一种后扩链阻燃高耐静水压水性聚氨酯织物涂层剂

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108948851A (zh) * 2018-03-06 2018-12-07 英德侗富贵科技材料有限公司 一种超支化分散剂及其制备方法
CN110527479A (zh) * 2019-08-19 2019-12-03 济南大学 一种超支化型热塑性聚氨酯胶黏剂及其在消防水带中的应用
CN110527479B (zh) * 2019-08-19 2021-05-18 济南大学 一种超支化型热塑性聚氨酯胶黏剂及其在消防水带中的应用
CN112359603A (zh) * 2020-12-04 2021-02-12 长春工业大学 一种具有抗紫外性能的水性超支化聚氨酯上浆剂及其制备方法
CN112961301A (zh) * 2021-02-07 2021-06-15 武汉纺织大学 具有离子化线性主链的枝化聚氨酯增稠剂及其制备方法
CN112961301B (zh) * 2021-02-07 2022-06-10 武汉纺织大学 具有离子化线性主链的枝化聚氨酯增稠剂及其制备方法
CN113683748A (zh) * 2021-07-23 2021-11-23 江苏苏博特新材料股份有限公司 一种氟改性超支化水性聚氨酯树脂及使用其的水性纳米防腐自洁面漆
CN114752035A (zh) * 2022-05-30 2022-07-15 浙江大学衢州研究院 一种高固含量的水性聚氨酯分散体及其制备方法和应用

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Application publication date: 20170623