CN108707219A - 一种具有形状记忆性质的聚氨酯弹性体的制备方法 - Google Patents
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Abstract
本发明提供了一种具有形状记忆性质的聚氨酯弹性体的制备方法。本发明采用80~100份的4‑甲基丁内酯二元醇为聚氨酯弹性体的合成基础,将1~5份的3‑苯基‑2‑丙烯酰胺结构进行侧链接枝到聚氨酯链段,成功制备了一种具有形状记忆性质的聚氨酯弹性体。本发明制备的聚氨酯弹性体具备同时对光照和温度这两种因素刺激响应的性能,扩大了智能聚合材料的应用范围。
Description
技术领域
本发明属于聚氨酯胶材料制备领域,具体关于一种具备同时对光照和温度这两种因素刺激响应的形状记忆聚氨酯弹性体的制备方法。
背景技术
形状记忆聚合物作为一类智能材料,在生物材料中占有重要的地位。在手术缝合线、支架、心脏瓣膜、组织工程、药物释放、矫形术及光学治疗等具有广泛的应用,生物相容性较好的聚氨酯材料智能材料在生物材料领域具有广泛的潜在应用价值。
CN103113551B公开了一种松香基形状记忆聚氨酯的制备方法,包括:将多元醇、二异氰酸酯、松香基扩链剂在催化剂作用下采用一步法或者两步法合成得到松香基形状记忆聚氨酯;松香扩链剂为式Ⅰ结构或式Ⅱ结构的化合物。本发明中,松香基形状记忆聚氨酯的制备方法,制备简单,易于实施,可操作性强,易于大规模工业化生产,同时,制备的松香基形状记忆聚氨酯具有优异的回复性,非常适合作为形状记忆材料,表现出优异的形状记忆的性能。
CN105524289B提供一种解决现有纸制品在使用过程中易产生褶皱磨损的问题的方法。覆膜溶液的制备:一、向脱水后的PCL加入干燥的DMF和MDI,在70~80℃下反应得到预聚物;二、预聚物中加入1,4—BDO和DMF,在70~80℃的温度下进行扩链反应,得到线形SMPU溶液;三、SMPU溶液涂敷在玻璃板上,进行干燥处理,得到形状记忆聚氨酯;四、加入DMF配制成溶液。应用过程是将纸制品浸入到形状记忆聚氨酯溶液中,干燥后完成覆膜。本发明当镀有薄膜的纸制品产生褶皱时,将其加热到聚合物的玻璃化转变温度以上时,纸制品能够恢复平整的状态。
CN103408713B公开一种超分子液晶形状记忆聚氨酯的制备方法,其包括如下步骤:将含吡啶基团的二元醇与二异氰酸酯在有机溶剂中70~90℃反应1~4h,然后加入短链二元醇进行扩链反应,得含吡啶的聚氨酯;将所述含吡啶的聚氨酯与烷氧基苯甲酸或烷氧基苯酚混合,得超分子液晶聚氨酯;将所述超分子液晶聚氨酯在140~180℃热处理5~30min,冷却至室温,获得所述超分子液晶形状记忆聚氨酯;其中,所述短链二元醇中碳原子的个数为2~6。以及提供该超分子液晶形状记忆聚氨酯的制备方法所制备的超分子液晶形状记忆聚氨酯在智能控制系统、光学器件、显示器材、电子器件、纺织、玩具和日常用品中的应用。
以上专利及公知技术生产的具有形状记忆聚氨酯胶产品,一般都是只有温度或其他单因素刺激响应的智能材料,一种材料不能同时对多种刺激进行响应。
发明内容
为了解决上述问题,本发明提供了一种具备同时对光照和温度这两种因素刺激响应的形状记忆聚氨酯弹性体的制备方法。
本发明的所述的一种具有形状记忆性质的聚氨酯弹性体的制备方法,按照质量份数,其技术方案如下:
在反应釜中加入80~100份的聚酯多元醇,加热到110~130℃,抽真空除水1~2.5h。除水完毕后通氮气破真空,降温到70~90℃,然后缓慢加入7~20份 4,4-二苯基甲烷二异氰酸酯,控温到60~80℃,搅拌下反应1~3h后,加入含1~5份的N,N-二羟丙基-3-苯基-2-丙烯酰胺的DMF溶液和0.4~1.5份的催化剂,0.2~2份的6-羧基荧光素琥珀酰亚胺醚,0.05~0.15份的单氯硼烷二甲基硫醚络合物,0.001~0.2份的异丙氧基钕,在70~90℃下反应5~10h后,得到黏稠状的液体。将该液体除气泡后倒入聚四氟乙烯模具中,在40~60℃的烘箱中干燥48~72h,即可得到一种具备同时对光照和温度这两种因素刺激响应的形状记忆聚氨酯弹性体。
所述的聚酯多元醇为聚4-甲基丁内酯二元醇;
所述的聚酯多元醇其平均分子量在1000~2500;
所述的聚酯多元醇羟值在45~85mgKOH/g;
所述的催化剂为草酸亚锡或硫酸亚锡或辛酸亚锡。
本发明的优点和创新点为:将3-苯基-2-丙烯酰胺结构进行侧链接枝到聚氨酯链段,成功制备了具备同时对光照和温度这两种因素刺激响应的形状记忆聚氨酯弹性体,扩大了智能聚合材料的应用范围。
具体实施方式
下面通过具体实施例对本发明作进一步说明:
实施例1
在反应釜中加入80g的聚4-甲基丁内酯二元醇(平均分子量在1140,羟值在84.36mgKOH/g),加热到110~105℃,抽真空除水2.5h。除水完毕后通氮气破真空,降温到70~75℃,然后缓慢加入7g 4,4-二苯基甲烷二异氰酸酯,控温到60~65℃,搅拌下反应1h后,加入含1.1g的N,N-二羟丙基-3-苯基-2-丙烯酰胺的DMF溶液和0.42g的催化剂辛酸亚锡,0.8g的6-羧基荧光素琥珀酰亚胺醚,0.1g的单氯硼烷二甲基硫醚络合物,0.008g的异丙氧基钕,在70~75℃下反应5h后,得到黏稠状的液体。将该液体除气泡后倒入聚四氟乙烯模具中,在40~45℃的烘箱中干燥48h,即可得到一种具备同时对光照和温度这两种因素刺激响应的形状记忆聚氨酯弹性体。样品编号为SD-1。
实施例2
在反应釜中加入90g的聚4-甲基丁内酯二元醇(平均分子量在1960,羟值在61.32mgKOH/g),加热到115~120℃,抽真空除水2h。除水完毕后通氮气破真空,降温到80~85℃,然后缓慢加入15g 4,4-二苯基甲烷二异氰酸酯,控温到70~75℃,搅拌下反应2h后,加入含3.2g的N,N-二羟丙基-3-苯基-2-丙烯酰胺的DMF溶液和0.82g的催化剂硫酸亚锡,0.2g的6-羧基荧光素琥珀酰亚胺醚,0.05g的单氯硼烷二甲基硫醚络合物,0.001g的异丙氧基钕,在80~85℃下反应8h后,得到黏稠状的液体。将该液体除气泡后倒入聚四氟乙烯模具中,在50~55℃的烘箱中干燥58h,即可得到一种具备同时对光照和温度这两种因素刺激响应的形状记忆聚氨酯弹性体。样品编号为SD-2。
实施例3
在反应釜中加入100g的聚4-甲基丁内酯二元醇(平均分子量在2460,羟值在41.32mgKOH/g),加热到125~130℃,抽真空除水1h。除水完毕后通氮气破真空,降温到85~90℃,然后缓慢加入20g 4,4-二苯基甲烷二异氰酸酯,控温到75~80℃,搅拌下反应3h后,加入含5g的N,N-二羟丙基-3-苯基-2-丙烯酰胺的DMF溶液和1.51gg的催化剂草酸亚锡,2g的6-羧基荧光素琥珀酰亚胺醚,0.15g的单氯硼烷二甲基硫醚络合物,0.2g的异丙氧基钕,在85~90℃下反应10h后,得到黏稠状的液体。将该液体除气泡后倒入聚四氟乙烯模具中,在55~60℃的烘箱中干燥72h,即可得到具备同时对光照和温度这两种因素刺激响应的形状记忆聚氨酯弹性体。样品编号为SD-3。
对比例1
不加N,N-二羟丙基-3-苯基-2-丙烯酰胺,使用乙二胺,其它同实施例1,样品编号为SD-4。
对比例2
不加N,N-二羟丙基-3-苯基-2-丙烯酰胺,使用1,4-丁二醇,其它同实施例1,样品编号为SD-5。
对比例3
不加催化剂,其它同实施例1,样品编号为SD-6。
对比例4
不加6-羧基荧光素琥珀酰亚胺醚,其它同实施例1,样品编号为SD-7。
对比例5
不加单氯硼烷二甲基硫醚络合物,其它同实施例1,样品编号为SD-8。
对比例6
不加异丙氧基钕,其它同实施例1,样品编号为SD-9。
表:不同工艺做出的试验样品的形状回复率比较。
Claims (7)
1.一种具有形状记忆性质的聚氨酯弹性体的制备方法,按照质量份数,其特征在于其技术方案如下:
在反应釜中加入80~100份的聚酯多元醇,加热到110~130℃,抽真空除水1~2.5h。
2.除水完毕后通氮气破真空,降温到70~90℃,然后缓慢加入7~20份 4,4-二苯基甲烷二异氰酸酯,控温到60~80℃,搅拌下反应1~3h后,加入含1~5份的N,N-二羟丙基-3-苯基-2-丙烯酰胺的DMF溶液和0.4~1.5份的催化剂,0.2~2份的6-羧基荧光素琥珀酰亚胺醚,0.05~0.15份的单氯硼烷二甲基硫醚络合物,0.001~0.2份的异丙氧基钕,在70~90℃下反应5~10h后,得到黏稠状的液体。
3.将该液体除气泡后倒入聚四氟乙烯模具中,在40~60℃的烘箱中干燥48~72h,即可得到一种具备同时对光照和温度这两种因素刺激响应的形状记忆聚氨酯弹性体。
4.根据权利要求1所述的一种具有形状记忆性质的聚氨酯弹性体的制备方法,其特征在于:所述的聚酯多元醇为聚4-甲基丁内酯二元醇。
5.根据权利要求1所述的一种具有形状记忆性质的聚氨酯弹性体的制备方法,其特征在于:所述的聚酯多元醇其平均分子量在1000~2500。
6.根据权利要求1所述的一种具有形状记忆性质的聚氨酯弹性体的制备方法,其特征在于:所述的聚酯多元醇羟值在45~85mgKOH/g。
7.根据权利要求1所述的一种具有形状记忆性质的聚氨酯弹性体的制备方法,其特征在于:所述的催化剂为草酸亚锡或硫酸亚锡或辛酸亚锡。
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Cited By (3)
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CN110527049A (zh) * | 2019-07-29 | 2019-12-03 | 青岛科技大学 | 一种可降解生物基聚酯型聚氨酯及其制备方法 |
CN110591036A (zh) * | 2019-08-15 | 2019-12-20 | 深圳大学 | 一种形状记忆聚合物及其制备方法和应用 |
CN113841944A (zh) * | 2021-09-10 | 2021-12-28 | 荣利服饰有限公司 | 一种设有形状记忆贴片塑形衣的制备方法 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110527049A (zh) * | 2019-07-29 | 2019-12-03 | 青岛科技大学 | 一种可降解生物基聚酯型聚氨酯及其制备方法 |
CN110591036A (zh) * | 2019-08-15 | 2019-12-20 | 深圳大学 | 一种形状记忆聚合物及其制备方法和应用 |
CN113841944A (zh) * | 2021-09-10 | 2021-12-28 | 荣利服饰有限公司 | 一种设有形状记忆贴片塑形衣的制备方法 |
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