CN110092879B - 一种具有亲/疏水链端的混合封端型水性聚氨酯的制备方法 - Google Patents

一种具有亲/疏水链端的混合封端型水性聚氨酯的制备方法 Download PDF

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CN110092879B
CN110092879B CN201910338263.6A CN201910338263A CN110092879B CN 110092879 B CN110092879 B CN 110092879B CN 201910338263 A CN201910338263 A CN 201910338263A CN 110092879 B CN110092879 B CN 110092879B
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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

本发明涉及一种具有亲/疏水链端的混合封端型水性聚氨酯的制备方法。本发明旨在解决水性聚氨酯耐水性能差以及高分子乳化困难的问题，为了达到目的，技术方案为：向聚氨酯预聚体中加入亲水封端剂和疏水封端剂，在70~80℃下反应1~3h，反应结束后，降温至30~40℃，用三乙胺中和20~40min后，降温至室温，最后在剧烈搅拌条件下缓慢加入蒸馏水，高速乳化30~40min，静置直到表层泡沫自动消除，即得到一种具有亲/疏水链端的混合封端型水性聚氨酯。本发明合成的水性聚氨酯，无毒，具有环境友好性，在乳液分散稳定性和疏水性方面有所提高，产品综合性能优良。

Description

一种具有亲/疏水链端的混合封端型水性聚氨酯的制备方法
技术领域
本发明属于有机聚合物技术领域，具体涉及一种具有亲/疏水链端的混合封端型水性聚氨酯的制备方法。
背景技术
近年来，随着社会生产的需求和人们环保意识的增强，高性能水性聚氨酯的发展是国内外一直关注的焦点。针对水性聚氨酯耐水性能差以及高分子乳化困难进行改性受到人们的广泛关注。常见的通过添加疏水物质提高水性聚氨酯的耐水性，虽然起到一定的效果，但因疏水物质普遍水溶性较差，使得产品乳化更加困难，这时需要更多的水乳化或添加亲水物质，与预期目标相矛盾，因此在提高耐水性的同时，消除或降低这些不利影响具有重要的实用价值。
发明内容
本发明的目的是要提供一种具有亲/疏水链端的混合封端型水性聚氨酯的制备方法，通过设计水性聚氨酯分子结构，使聚氨酯分子链端具有强的亲/疏水性，类似表面活性剂的结构赋予聚氨酯良好的乳化性能和成膜时的疏水性能，产品具有良好的储存稳定性和耐水性。
为了达到上述目的，本发明提供的一种具有亲/疏水链端的混合封端型水性聚氨酯的制备方法，包括以下步骤：
向聚氨酯预聚体PPU中加入亲水封端剂和疏水封端剂，亲水封端剂和疏水封端剂的质量比值为0.01~0.2，在70~80℃下反应1~3h，反应结束后，降温至30~40℃，用亲水扩链剂和亲水封端总物质的量的0.8~1.2倍的三乙胺中和20~40min后，降温至室温，最后在剧烈搅拌条件下缓慢加入以上所有反应物总质量的2~3倍的蒸馏水，高速乳化30~40min，静置直到表层泡沫自动消除，即得到一种具有亲/疏水链端的混合封端型水性聚氨酯MEPU。
上述步骤二中，亲水封端剂和疏水封端剂添加的物质的量的总量小于或等于PPU中-NCO的理论物质的量。
上述步骤二中，疏水封端剂为1-十六醇、1-十八醇、1-二十醇、1-二十二醇、1-十六胺、1-十八胺、1-二十胺、1-二十二胺、含氟一元醇、全氟一元醇、单端羟基硅油、单端氨基硅油中的一种。
上述步骤二中，亲水封端剂为氨基乙酸、3-氨基丙酸、γ-氨基丁酸、5-氨基戊酸、天门冬氨酸、乙醇酸、3-羟基丙酸、γ-羟基丁酸、3-氨基-1-丙磺酸、氨基甲磺酸、氨基乙磺酸、3-氨基-1-丙磺酸、4-羟基丁磺酸中的一种。
根据上述制备方法制得的一种具有亲/疏水链端的混合封端型水性聚氨酯
与现有技术相比，本发明的有益效果是：
本发明合成的改性水性聚氨酯，具有环境友好性，无毒。具有良好的应用前景。针对目前水性聚氨酯耐水性能的不足，在一定程度得到改善，产品综合性能优良。在结构上，亲/疏水末端可以充分发挥各自的作用，整体上减少了亲水扩链剂的使用提高了疏水效果，与一般的改性聚氨酯产品相比，所制得的聚氨酯在乳液分散稳定性和疏水性方面有所提高。
附图说明
图1为实施例1的混合封端型水性聚氨酯MEPU的合成路线。
图2为不同类型水性聚氨酯水接触角对比图。
具体实施方式
下面将结合具体实施例对本发明作进一步详细的描述，但本发明的实施方式包括但不限于以下实施例表示的范围。
本发明提供的一种具有亲/疏水链端的混合封端型水性聚氨酯的制备方法，依次包括以下步骤：
步骤一、聚氨酯预聚体PPU的制备；
步骤二、混合封端型水性聚氨酯MEPU的制备：
向步骤一制得的聚氨酯预聚体PPU中加入亲水封端剂和疏水封端剂，亲水封端剂和疏水封端剂的质量比值为0.01~0.2，在70~80℃下反应1~3h，反应结束后，降温至30~40℃，用亲水扩链剂和亲水封端总物质的量的0.8~1.2倍的三乙胺中和20~40min后，降温至室温，最后在剧烈搅拌条件下缓慢加入以上所有反应物总质量的2~3倍的蒸馏水，高速乳化30~40min，静置直到表层泡沫自动消除，即得到一种具有亲/疏水链端的混合封端型水性聚氨酯MEPU。
上述步骤二中，亲水封端剂和疏水封端剂添加的物质的量的总量小于或等于PPU中-NCO的理论物质的量。
上述步骤二中，疏水封端剂为1-十六醇、1-十八醇、1-二十醇、1-二十二醇、1-十六胺、1-十八胺、1-二十胺、1-二十二胺、含氟一元醇、全氟一元醇、单端羟基硅油、单端氨基硅油中的一种。
上述步骤二中，亲水封端剂为氨基乙酸、3-氨基丙酸、γ-氨基丁酸、5-氨基戊酸、天门冬氨酸、乙醇酸、3-羟基丙酸、γ-羟基丁酸、3-氨基-1-丙磺酸、氨基甲磺酸、氨基乙磺酸、3-氨基-1-丙磺酸、4-羟基丁磺酸中的一种。
实施例1
步骤一：聚氨酯预聚体PPU的制备
将真空脱水后的20g聚己二酸1，4-丁二醇酯（Mn=2000）和6.66g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2滴的催化剂二月桂酸二丁基锡，在70℃下反应1.5h；将温度调至80℃，加入1.33g二羟甲基丙酸，继续反应2.5h，得到水性聚氨酯预聚体PPU；
步骤二：混合封端型水性聚氨酯MEPU的制备
向步骤一制得的PPU中加入0.01g氨基乙酸和0.20g十八胺，在70℃下反应1h，降温至40℃后，加入1.01g三乙胺中和30min后，降温至室温，在剧烈搅拌条件下缓慢加入58mL蒸馏水，高速乳化30min，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聚氨酯MEPU。
实施例2
步骤一：聚氨酯预聚体PPU的制备
将真空脱水后的20g聚己二酸1，4-丁二醇酯（Mn=2000）和6.66g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2滴的催化剂二月桂酸二丁基锡，在70℃下反应1.5h；将温度调至80℃，加入1.33g二羟甲基丙酸，继续反应2.5h，得到水性聚氨酯预聚体PPU；
步骤二：混合封端型水性聚氨酯MEPU的制备
向步骤一制得的PPU中加入0.07g氨基乙酸和1.39g单端羟基硅油（Mn≈1500），在75℃下反应3h，降温至40℃加入1.09g三乙胺中和30min后，降温至室温，在剧烈搅拌条件下缓慢加入62mL的蒸馏水，高速乳化30min，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聚氨酯MEPU。
实施例3
步骤一：聚氨酯预聚体PPU的制备
将真空脱水后的20g聚四氢呋喃醚二醇（Mn=2000）和3.48g的甲苯二异氰酸酯加入干燥的三口烧瓶中，搅拌均匀，滴加2滴的催化剂二月桂酸二丁基锡，在70℃下反应1.5h；将温度调至80℃，加入二羟甲基丙酸（1.22g），继续反应2.5h，得到水性聚氨酯预聚体PPU；
步骤二：混合封端型水性聚氨酯MEPU的制备
向步骤一制得的PPU中加入0.03g的3-氨基丙酸和0.24g十八烷醇在70℃下反应3h，降温至45℃后，加入0.95g三乙胺中和25min后，降温至室温，在剧烈搅拌条件下缓慢加入50mL蒸馏水，高速乳化40min，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聚氨酯MEPU。
表1为不同类型的水性聚氨酯乳液性能和胶膜吸水率的结果，图2为不同类型水性聚氨酯水接触角对比图，其中PU为未改性的水性聚氨酯（先合成PPU，直接中和乳化得到PU），MEPU1为实施例1产品，MEPU2为实施例2产品。以上三者合成PPU的原料配比完全相同，并且中和度、乳化加水比例也相同。
表1：不同类型的水性聚氨酯乳液性能和胶膜吸水率对比表
类型 乳液外观 乳液稳定性 吸水率
PU 半透明 稳定 9.8%
MEPU1 透明 稳定 7.3%
MEPU2 透明 稳定 5.7%
由表1及图2可以看出，本发明制备得到的产品在乳液分散稳定性和疏水性方面相比于普通聚氨酯均有所提高，产品综合性能优良。
以上所述，仅为本发明的较佳实施例而已，并非用于限定本发明的保护范围。

Claims (3)

1.一种具有亲/疏水链端的混合封端型水性聚氨酯的制备方法，其特征在于，具体包括以下步骤：
步骤一：聚氨酯预聚体PPU的制备
将真空脱水后的Mn=2000的20g聚己二酸1，4-丁二醇酯和6.66g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2滴的催化剂二月桂酸二丁基锡，在70℃下反应1.5h；将温度调至80℃，加入1.33g二羟甲基丙酸，继续反应2.5h，得到水性聚氨酯预聚体PPU；
步骤二：混合封端型水性聚氨酯MEPU的制备
向步骤一制得的PPU中加入0.01g氨基乙酸和0.20g十八胺，在70℃下反应1h，降温至40℃后，加入1.01g三乙胺中和30min后，降温至室温，在剧烈搅拌条件下缓慢加入58mL蒸馏水，高速乳化30min，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聚氨酯MEPU。
2.一种具有亲/疏水链端的混合封端型水性聚氨酯的制备方法，其特征在于，具体包括以下步骤：
步骤一：聚氨酯预聚体PPU的制备
将真空脱水后的Mn=2000的20g聚己二酸1，4-丁二醇酯和6.66g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2滴的催化剂二月桂酸二丁基锡，在70℃下反应1.5h；将温度调至80℃，加入1.33g二羟甲基丙酸，继续反应2.5h，得到水性聚氨酯预聚体PPU；
步骤二：混合封端型水性聚氨酯MEPU的制备
向步骤一制得的PPU中加入0.07g氨基乙酸和Mn≈1500的1.39g单端羟基硅油，在75℃下反应3h，降温至40℃加入1.09g三乙胺中和30min后，降温至室温，在剧烈搅拌条件下缓慢加入62mL的蒸馏水，高速乳化30min，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聚氨酯MEPU。
3.一种具有亲/疏水链端的混合封端型水性聚氨酯的制备方法，其特征在于，具体包括以下步骤：
步骤一：聚氨酯预聚体PPU的制备
将真空脱水后的Mn=2000的20g聚四氢呋喃醚二醇和3.48g的甲苯二异氰酸酯加入干燥的三口烧瓶中，搅拌均匀，滴加2滴的催化剂二月桂酸二丁基锡，在70℃下反应1.5h；将温度调至80℃，加入二羟甲基丙酸1.22g，继续反应2.5h，得到水性聚氨酯预聚体PPU；
步骤二：混合封端型水性聚氨酯MEPU的制备
向步骤一制得的PPU中加入0.03g的3-氨基丙酸和0.24g十八烷醇在70℃下反应3h，降温至45℃后，加入0.95g三乙胺中和25min后，降温至室温，在剧烈搅拌条件下缓慢加入50mL蒸馏水，高速乳化40min，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聚氨酯MEPU。
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