CN106750144A - 一种新型线性温敏型聚氨酯及其制备方法 - Google Patents
一种新型线性温敏型聚氨酯及其制备方法 Download PDFInfo
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Abstract
本发明涉及高分子功能材料领域,具体涉及一种新型线性温敏型聚氨酯及其制备方法。其制备方法为:将聚碳酸酯二醇和二羟甲基丙酸加入有机溶剂中,75‑85℃及氮气保护下搅拌均匀,然后加入六亚甲基二异氰酸酯和催化剂,在75‑85℃下搅拌反应3h以上生成异氰酸根为端基的线性聚氨酯,然后加入乙二胺和三乙胺,继续搅拌反应2h以上,得氨基为端基的线性聚氨酯,再加入N‑异丙基丙烯酰胺,继续搅拌反应应12h以上,然后加入去离子水,真空旋蒸去除有机溶剂,即得。本发明提供的新型线性温敏型聚氨酯的聚氨酯链段两端直接由N‑异丙基丙烯酰胺封端,不含有其他链段,合成方法简单,省略了聚N‑异丙基丙烯酰胺的合成和化学接枝步骤,同时也节省了合成原料,降低了成本。
Description
技术领域
本发明涉及高分子功能材料领域,具体涉及一种新型线性温敏型聚氨酯及其制备方法。
背景技术
温敏型聚氨酯将聚氨酯(PU)优异的机械性能和温敏物质的温度敏感性结合在一起,具有良好的水溶性、环境污染小、粘黏性好、较高的强度和耐磨性等优点,除此之外还具有智能的温度刺激响应性、形状记忆效应等特点,近年来在涂料、生物材料等方面得到广泛应用。
现阶段,无论是和物理共混法,还是化学接枝法,合成的温敏聚氨酯的分子,从结构上分为两个部分,一部分是聚氨酯链段,一部分是具有温度敏感特性的聚合物链段。N-异丙基丙烯酰胺的聚合物是具有低临界溶解温度(LCST)的温敏材料,近年来有关其的报道与日俱增,它在药物控制释放、细胞培养、温敏开关膜等方面的潜在应用价值引起各国学者浓厚的兴趣。以N-异丙基丙烯酰胺的聚合物为温敏链段的温敏型聚氨酯具有较好的温敏特性,应用前景广阔,但其合成方法主要为化学接枝法,即要分别合成聚氨酯链段和聚N-异丙基丙烯酰胺链锻,然后用后者对前者化学接枝,合成方法较为复杂,生产成本高。
发明内容
本发明所要解决的技术问题是提供一种新型线性温敏型聚氨酯及其制备方法,制得的新型线性温敏型聚氨酯具有温敏特性,制备方法简单。
本发明解决上述技术问题的技术方案如下:一种新型线性温敏型聚氨酯的制备方法,其包括如下步骤:将摩尔比为2.1-2.5:1的聚碳酸酯二醇和二羟甲基丙酸加入有机溶剂中,75-85℃及氮气保护下搅拌均匀,然后加入六亚甲基二异氰酸酯和催化剂,其中六亚甲基二异氰酸酯与二羟甲基丙酸的摩尔比为4-5:1,在75-85℃下搅拌反应3h以上生成异氰酸根为端基的线性聚氨酯,然后加入乙二胺和三乙胺,其中乙二胺与二羟甲基丙酸的摩尔比为1.3-1.4:1,三乙胺与二羟甲基丙酸的摩尔比为1.5-1.7:1,继续搅拌反应2h以上,得氨基为端基的线性聚氨酯,加入与乙二胺等摩尔量的N-异丙基丙烯酰胺,继续搅拌反应应12h以上,然后加入去离子水,真空旋蒸去除有机溶剂,即得所述的新型线性温敏型聚氨酯,反应方程式如下:
具体的,S2中的催化剂为二月桂酸二丁基锡,二羟甲基丙酸与催化剂的摩尔比为3-6:1。
具体的,S2中的有机溶剂为N-甲基吡咯烷酮和丙酮任意比例的混合。
具体的,二羟甲基丙酸与有机溶剂的用量比为0.004mol:40-60mL。
具体的,S2中三乙胺与去离子水的用量比例为0.004mol:150-200mL。
优选的,S2中聚碳酸酯二醇和二羟甲基丙酸的摩尔比为2.3:1,S2中六亚甲基二异氰酸酯与二羟甲基丙酸的摩尔比为4:1。
具体的,S2中的聚碳酸酯二醇在加入有机溶剂之前经过真空除水处理,真空度为-0.095MPa,除水温度为130℃。
具体的,S2中聚碳酸酯二醇的分子量为500、1000或2000。
具体的,S2中真空旋蒸的真空度为-0.095MPa、旋蒸温度为20-25℃。
本发明还提供一种新型线性温敏型聚氨酯,其通过上述的方法制备得到。
与现有技术相比,本发明的有益效果是:
本发明提供的新型线性温敏型聚氨酯起温敏作用的为N-异丙基丙烯酰胺,聚氨酯链段的两端直接由N-异丙基丙烯酰胺封端,不含有其他链段,合成方法较为简单,省略了聚N-异丙基丙烯酰胺链锻的合成和化学接枝步骤,同时也节省了合成原料,节约了成本;本发明提供的新型线性温敏型聚氨酯经测试具有较好的温敏效果,具有在生物胶囊、药物载体、药物缓释等生物材料方面的潜在应用。
附图说明
图1为本发明实施例1制备出的新型线性温敏型聚氨酯(TSPU)的红外光谱图;
图2为本发明实施例1制备出的新型线性温敏型聚氨酯(TSPU)在水中的胶粒粒径随温度的变化曲线。
具体实施方式
以下结合附图及具体实施例对本发明作进一步的详细描述,所举实例只用于解释本发明,并非用于限定本发明的范围。
实施例1
一种新型线性温敏型聚氨酯,其制备方法如下:
在250mL四口瓶中,加入0.007mol(7g)的聚碳酸酯二醇(PCDL-1000,表示分子量为1000),在130℃,真空度为-0.095MPa下真空除水2h,加入0.003mol(0.4024g)二羟甲基丙酸(DMPA)、10mL N-甲基吡咯烷酮(NMP)和50mL丙酮。然后升高温度至80℃且在氮气保护下,加入0.012mol(2.0183g)六亚甲基二异氰酸酯(HDI),并加入0.0008mol(0.5g)的催化剂二月桂酸二丁基锡(DBTDL),此条件下反应3h,然后再依次加入0.004mol(0.2405g)的乙二胺单体、0.0049mol(0.50g)三乙胺,反应条件不变得情况下,反应2h,得氨基为端基的线型聚氨酯,随后加入0.004mol(0.4526g)N-异丙基丙烯酰胺,在反应条件不变的情况下,反应12h,最后加入200mL去离子水,在常温且真空度为-0.095MPa下,旋蒸除去丙酮,得水溶性的线性温敏型聚氨酯乳液,也即所述的新型线性温敏型聚氨酯。
实施例2
一种新型线性温敏型聚氨酯,其制备方法如下:
在250mL四口瓶中,加入0.0063mol(12.6g)的聚碳酸酯二醇(PCDL-2000),在130℃,真空度为-0.095MPa下真空除水2h,加入0.003mol(0.4024g)二羟甲基丙酸(DMPA)、10mLN-甲基吡咯烷酮(NMP)和40mL丙酮。然后升高温度至85℃且在氮气保护下,加入0.015mol(2.5229g)六亚甲基二异氰酸酯(HDI),并加入0.0005mol(0.3g)的催化剂二月桂酸二丁基锡(DBTDL),此条件下反应3h,然后再依次加入0.0042mol(0.2525g)的乙二胺单体、0.0045mol(0.46g)三乙胺,反应条件不变得情况下,反应2h,得氨基为端基的线型聚氨酯,随后加入0.0042mol(0.4752g)N-异丙基丙烯酰胺,在反应条件不变的情况下,反应12h,最后加入180mL去离子水,在常温且真空度为-0.095MPa下,旋蒸除去丙酮,得水溶性的线性温敏型聚氨酯乳液,也即所述的新型线性温敏型聚氨酯。
实施例3
一种新型线性温敏型聚氨酯,其制备方法如下:
在250mL四口瓶中,加入0.0075mol(3.75g)的聚碳酸酯二醇(PCDL-500),在130℃,真空度为-0.095MPa下真空除水2h,加入0.003mol(0.4024g)二羟甲基丙酸(DMPA)、10mL N-甲基吡咯烷酮(NMP)和30mL丙酮。然后升高温度至75℃且在氮气保护下,加入0.012mol(2.0183g)六亚甲基二异氰酸酯(HDI),并加入0.0005mol(0.3g)的催化剂二月桂酸二丁基锡(DBTDL),此条件下反应3h,然后再依次加入0.0039mol(0.2345g)的乙二胺单体、0.0051mol(0.52g)三乙胺,反应条件不变得情况下,反应2h,得氨基为端基的线型聚氨酯,随后加入0.0039mol(0.4413g)N-异丙基丙烯酰胺,在反应条件不变的情况下,反应12h,最后加入150mL去离子水,在常温且真空度为-0.095MPa下,旋蒸除去丙酮,得水溶性的线性温敏型聚氨酯乳液,也即所述的新型线性温敏型聚氨酯。
图1为实施例1合成的线性温敏型聚氨酯的红外光谱,从图中可见3459cm-1为羧基中-OH的伸缩振动峰,2941cm-1与2855cm-1附近为甲基亚甲基伸缩振动峰,1632cm-1为酰胺基中羰基的伸缩振动峰,1553cm-1为酰胺键中C-N的伸缩振动峰,1240cm-1为聚碳酸酯中C-O伸缩振动峰,1050cm-1为C-O伸缩振动峰,724cm-1附近为多个亚甲基峰,表明已经成功合成目标产物。图2为实施例1合成的新型线性温敏型聚氨酯在水中的胶粒粒径随温度变化的情况(将反应制得的水性线性温敏聚氨酯乳液在5000r/min的条件下离心5min,将上清液在截留分子量14000的透析袋中透析7天,每6-8h换水一次,然后将经过离心透析处理过的乳液在马尔文粒径分析仪上测试不同温度下的粒径变化),从图2中可见随着温度升高,胶粒的粒径逐渐减小,其中温度升高,粒径减小的变化率如下表所示:
从上表可见,温度由25℃升至37℃时,胶粒粒径减小4.9%,即实施例1合成的聚氨酯具有较明显的温敏效果,具有在生物胶囊、药物载体、药物缓释等生物材料方面的潜在应用。N-异丙基丙烯酰胺由亲水的酰胺基团与疏水的异丙基构成,是一种两亲性分子。N-异丙基丙烯酰胺的聚合物在水溶液中32℃左右存在一个低临界溶解温度(LCST)。N-异丙基丙烯酰胺与乙醇胺反应生成温敏单体分子M,并由该温敏单体分子M对聚氨酯链段的两端封端,此时得到的聚合物在端部类似于N-异丙基丙烯酰胺的聚合物,使得被单体分子M封端的聚合物也具有一个低临界溶解温度(LCST),则即当温度低于LCST时,本发明提供的温敏型聚氨酯呈现亲水状态,吸水溶胀,胶束粒径变大;当温度高于LCST,N-异丙基丙烯酰胺呈现憎水状态,聚合物收缩与水分离,胶束粒径变小。这与氢键的存在与破坏有关,当温度低于LCST,聚合物端部的N-异丙基丙烯酰胺残基与水分子间能形成大量稳定的氢键,故聚合物呈现亲水状态,而当温度高于LCST时,大量氢键遭到破坏,异丙基的疏水作用占主导地位,聚合物就呈现憎水状态。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种新型线性温敏型聚氨酯的制备方法,其特征在于,包括如下步骤:将摩尔比为2.1-2.5:1的聚碳酸酯二醇和二羟甲基丙酸加入有机溶剂中,75-85℃及氮气保护下搅拌均匀,然后加入六亚甲基二异氰酸酯和催化剂,其中六亚甲基二异氰酸酯与二羟甲基丙酸的摩尔比为4-5:1,在75-85℃下搅拌反应3h以上生成异氰酸根为端基的线性聚氨酯,然后加入乙二胺和三乙胺,其中乙二胺与二羟甲基丙酸的摩尔比为1.3-1.4:1,三乙胺与二羟甲基丙酸的摩尔比为1.5-1.7:1,继续搅拌反应2h以上,得氨基为端基的线性聚氨酯,加入与乙二胺等摩尔量的N-异丙基丙烯酰胺,继续搅拌反应应12h以上,然后加入去离子水,真空旋蒸去除有机溶剂,即得所述的新型线性温敏型聚氨酯,反应方程式如下:
2.根据权利要求1所述一种新型线性温敏型聚氨酯的制备方法,其特征在于,催化剂为二月桂酸二丁基锡,二羟甲基丙酸与催化剂的摩尔比为3-6:1。
3.根据权利要求1所述一种新型线性温敏型聚氨酯的制备方法,其特征在于,有机溶剂为N-甲基吡咯烷酮和丙酮任意比例的混合。
4.根据权利要求1所述一种新型线性温敏型聚氨酯的制备方法,其特征在于,二羟甲基丙酸与有机溶剂的用量比为0.004mo l:40-60mL。
5.根据权利要求1所述一种新型线性温敏型聚氨酯的制备方法,其特征在于,三乙胺与去离子水的用量比例为0.004mol:150-200mL。
6.根据权利要求1所述一种新型线性温敏型聚氨酯的制备方法,其特征在于,聚碳酸酯二醇和二羟甲基丙酸的摩尔比为2.3:1,S2中六亚甲基二异氰酸酯与二羟甲基丙酸的摩尔比为4:1。
7.根据权利要求1所述一种新型线性温敏型聚氨酯的制备方法,其特征在于,聚碳酸酯二醇在加入有机溶剂之前经过真空除水处理,真空度为-0.095MPa,除水温度为130℃。
8.根据权利要求1所述的一种新型线性温敏型聚氨酯的制备方法,其特征在于,聚碳酸酯二醇的分子量为500、1000或2000。
9.根据权利要求1至8任一项所述的一种新型线性温敏型聚氨酯的制备方法,其特征在于,真空旋蒸的真空度为-0.095MPa、旋蒸温度为20-25℃。
10.一种新型线性温敏型聚氨酯,其特征在于,通过如权利要求1至9任一项所述的方法制备得到。
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