CN113201164B - 一种医用高分子材料表面防污涂层的制备方法 - Google Patents

一种医用高分子材料表面防污涂层的制备方法 Download PDF

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CN113201164B
CN113201164B CN202011235487.3A CN202011235487A CN113201164B CN 113201164 B CN113201164 B CN 113201164B CN 202011235487 A CN202011235487 A CN 202011235487A CN 113201164 B CN113201164 B CN 113201164B
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孙秀花
吴予玮
高昌录
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Harbin Institute of Technology Weihai
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Abstract

本发明公开了一种医用高分子材料表面防污涂层的制备方法，主要包括：将高分子材料在含有偶氮二异丁腈或过氧化苯甲酰、乙烯基苄基氯的有机溶液中浸渍一定时间后取出，迅速在紫外光强值为0.5‑50 mW/cm2，辐照10~500秒引发自由基聚合，在高分子材料表面形成聚乙烯基苄基氯纳米层，然后以苄基氯为引发剂，在水相中通过ATRP接枝亲水防污组份，形成稳定的防污涂层，可以降低生物大分子及细菌吸附。该方法简单易行，适合于高分子类医疗器械表面的抗菌防污涂层的工业制备，应用前景十分广泛。

Description

一种医用高分子材料表面防污涂层的制备方法
技术领域
本发明属于高分子材料表面修饰的领域，具体涉医用高分子材料表面抗菌防污涂层的制备方法。
背景技术
生物医用高分子器械材料表面抗菌性能是衡量其医用安全的重要指标，据统计，在医疗手术中，30%的术后细菌感染都是源自手术过程中医疗器械表面缺乏抗菌性能引起的，因此通过表面修饰提高医用高分子材料防污性能是解决上述问题的重要手段。在水相中接枝防污材料于高分子材料表面是比较理想的工艺方式，可以避免有机溶剂对疏水医用高分子材料的影响。然而由于聚乙烯、聚氯乙烯等许多医用高分子材料自身的惰性的原因，难以在水相中通过化学反应进行表面接枝防污组份。因此需要对其表面进行功能化。
本发明公开了一种全新的医用高分子材料表面防污涂层的制备方法。通过紫外光引发乙烯基苄基氯在医用高分子材料如聚乙烯、聚氯乙烯等表面聚合，医用高分子材料可以和聚乙烯基苄基氯有效的融合，形成均相聚集结构的纳米涂层，从而实现在医用高分子表面引入苄基氯功能基团，解决了通用医用高分子材料表面惰性，不易功能化的难题，进而通过ATRP聚合的方法在水相中接枝防污涂层，实现医用高分子材料抗菌防污的目的，本发明操作简单，能够对大多数医用高分子材料，特别是高分子医疗器械表面抗菌防污修饰，具有普适性。
发明内容
本发明公开了一种医用高分子材料表面防污涂层的制备方法。利用自身带有功能基团的乙烯基苄基氯的特点，在紫外光作用下，实现其在医用高分子材料表面聚合，所形成的纳米涂层与医用高分子材料界面融合，形成稳定的功能纳米涂层，进而以该纳米涂层的苄基氯为ATRP聚合的引发剂，实现在水相中接枝防污聚合物涂层，实现对高分子材料表面的抗菌防污涂层的制备。本发明的优势在于所形成的聚乙烯基苄基氯涂层与医用高分子材料具有相似的极性，因此二者的界面可以高度融合，不分相，因此形成的聚乙烯基苄基氯涂层极其稳定，从而解决了聚烯烃类医用高分子材料表面不易功能化的难题。本发明的方法简单易行，适合于高分子类医疗器械表面的抗菌防污涂层的工业制备，应用前景十分广泛。
为了实现上述发明任务，本发明提供的技术方案如下：
一种医用高分子材料表面防污涂层的制备方法，包括将医用高分子材料浸渍在含有催化量的偶氮二异丁腈或过氧化苯甲酰、低浓度的乙烯基苄基氯的有机溶液，浸渍一定时间后取出，迅速在紫外辐照下，在医用高分子材料表面引发乙烯基苄基氯聚合形成纳米聚乙烯基苄基氯层；然后在氮气氛下，以氯化亚铜或溴化亚铜为催化剂，以BPY，或HMTETA为配体，以亲水防污单体的水溶液为ATRP反应体系，将医用高分子材料置于该体系中进行表面ATRP接枝反应，在25~90摄氏度下，振荡反应1~12小时，取出医用高分子材料，用去离子水洗涤除去铜离子，获得表面防污的医用高分子材料。
所述的医用高分子材料包括聚乙烯、聚苯乙烯、聚丙烯、聚氨酯，聚氯乙烯及其混合物。
所述的有机溶液包括氯仿、二氯甲烷、石油醚、乙酸乙酯溶液。
所述的亲水防污单体包括下式1~6所示的结构式：
Figure 818033DEST_PATH_IMAGE001
Figure 247877DEST_PATH_IMAGE002
1 2
Figure 692765DEST_PATH_IMAGE003
3 4
Figure 108834DEST_PATH_IMAGE004
5 6。
本发明的优点在于：1）采用光引发聚合乙烯基苄基氯单体，可以在疏水的医用高分子材料（特别是器械）表面形成连续相，因此形成功能纳米涂层十分稳定；2）同时与共混改性相比，不改变高分子材料（器械）的内部结构，因此不对其原有加工工艺及机械性能产生影响；3）采用水相聚合接枝亲水防污材料，反应效率高，对不溶于水的医用高分子材料（器械）的原有性能未造成损伤，易于工业化应用。
具体实施方式：
实施例1:
将2cmx2cm医用聚苯乙烯薄片浸渍在0.01%偶氮二异丁腈、1%乙烯基苄基氯的二氯甲烷溶液中， 5秒后取出，迅速在紫外光强值为50 mW/cm2辐照500秒，引发乙烯基苄基氯聚合，在聚苯乙烯表面形成纳米聚乙烯基苄基氯纳米层；然后在氮气氛下，以0.001M氯化亚铜催化剂，以0.002M的BPY为配体，3M的甲基丙烯酰乙基磺基甜菜碱水溶液为ATRP反应体系，将上述医用聚苯乙烯薄片置于该体系中进行表面ATRP接枝甜菜碱，在25摄氏度下，振荡反应时间12小时，取出聚苯乙烯薄片后用去离子水浸渍2小时，除去铜离子，测定水的接触角为30o（未修饰的聚苯乙烯的接触角为100o），从而获得表面防污的医用聚苯乙烯材料。
实施例2:
将2 cmx2 cm 医用聚丙烯薄片浸渍在0.04%过氧化苯甲酰、4%的乙烯基苄基氯的氯仿溶液中， 60秒后取出，迅速在紫外光强值为0.5 mW/cm2辐照10秒，引发乙烯基苄基氯聚合，在聚丙烯薄片表面形成纳米聚乙烯基苄基氯层；然后在氮气氛下，以0.01M溴化亚铜为催化剂，以0.02M的HMTETA为配体， 3M的2-甲基丙烯酰氧乙基磷酰胆碱水溶液为ATRP反应体系，将上述医用聚丙烯材料置于该体系中进行表面ATRP接枝反应，在90摄氏度下，振荡反应时间 8小时，取出医用聚丙烯薄片，用去离子水浸渍2小时除去铜离子，测定水的接触角为20o（注未修饰的聚苯乙烯的接触角为95o），获得表面防污的医用聚丙烯材料。
实施例3：
将2cmx2cm 医用聚氯乙烯薄片浸渍在0.02%过氧化苯甲酰、2%的乙烯基苄基氯的氯仿溶液中， 40秒后取出，迅速在紫外光强值为25mW/cm2辐照200秒，引发乙烯基苄基氯聚合，在聚氯乙烯薄片表面形成纳米聚乙烯基苄基氯层；然后在氮气氛下，以0.005M溴化亚铜为催化剂，以0.01M的HMTETA为配体， 1M的甲基丙烯酸羟乙酯水溶液为ATRP反应体系，将上述医用聚氯乙烯材料置于该体系中进行表面ATRP接枝反应，在70摄氏度下，振荡反应时间1小时，取出医用聚氯乙烯薄片，用去离子水浸渍2小时除去铜离子，测定水的接触角为35o（注未修饰的聚苯乙烯的接触角为85o），获得表面防污的医用聚氯乙烯材料。
实施例4：
将2cmx2cm医用聚氨酯材料浸渍在含有0.01%偶氮二异丁腈4%乙烯基苄基氯的石油醚溶液中， 5秒后取出，迅速在紫外光强值为10 mW/cm2辐照100秒，引发乙烯基苄基氯聚合形成纳米聚乙烯基苄基氯层；然后在氮气氛下，以0.01M氯化亚铜或为催化剂，以0.02M的BPY为配体，1M的甲基丙烯酸羧酸甜菜碱单体水溶液为ATRP反应体系， 将上述医用聚氨酯材料置于该体系中进行表面ATRP接枝羧基甜菜碱，在70摄氏度下，振荡反应时间5小时，取出医用聚氨酯材料，用去离子水浸渍2小时除去铜离子，测定水的接触角为30o（注未修饰的聚苯乙烯的接触角为80o）获得表面防污的医用聚氨酯材料。
实施例5：
将2cmx2cm医用聚苯乙烯薄片约50%的面积浸渍在0.01%偶氮二异丁腈、1%乙烯基苄基氯的二氯甲烷溶液中，其他条件按实施例1的操作方法，对上述聚苯乙烯薄片进行表面防污涂层制备。然后将经过上述处理的全部聚苯乙烯薄片浸渍在0.1mg/ML异硫氰酸荧光素标记的牛血清白蛋白中1小时后取出，用磷酸盐缓冲溶液冲洗三标。然后置于荧光显微镜下观察表面蛋白吸附情况。通过观察得知，未经聚聚合乙烯基苄基氯的表面粘附了大量的荧光标记的牛血清白蛋白，呈现明亮的绿色。而没有经过表面聚合防污涂层的聚苯乙烯没有明显的蛋白质吸附，未显示明显的绿色因此本发明公开的高分子材料表面制备涂层具有很好的防污效果。
以上对本发明提供的一种医用高分子材料表面防污涂层的制备方法进行了详细介绍，本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想，应指出的是，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也属于本发明权利保护的范围。

Claims (3)

1.一种医用高分子材料表面防污涂层的制备方法，包括将医用高分子材料浸渍在含有0.01~0.04%偶氮二异丁腈或过氧化苯甲酰、1~4%乙烯基苄基氯的有机溶液中， 5~60秒后取出，迅速在紫外光强值为0.5-50 mW/cm2辐照10~500秒，引发乙烯基苄基氯聚合形成纳米聚乙烯基苄基氯层；然后在氮气氛下，以0.001M~0.01M氯化亚铜或溴化亚铜为催化剂，以0.002~0.02M的联吡啶（BPY），或1,1,4,7,10,10-六甲基三亚乙基四胺（HMTETA）为配体，0.5~3M的亲水防污单体的水溶液为原子转移自由基聚合（ATRP）体系，亲水防污单体结构式如式1~6所示，
Figure 750363DEST_PATH_IMAGE001
Figure 667503DEST_PATH_IMAGE002
1 2
Figure 447240DEST_PATH_IMAGE003
3 4
Figure 780133DEST_PATH_IMAGE004
5 6,
将医用高分子材料置于该体系中进行表面ATRP接枝反应，在25~90摄氏度下，震动反应时间1~12小时，取出医用高分子材料，用去离子水浸渍2小时除去铜离子，获得表面防污的医用高分子材料。
2.根据权利要求1所述的一种医用高分子材料表面防污涂层的制备方法，其特征在于，所述的医用高分子材料包括聚乙烯、聚苯乙烯、聚丙烯、聚氨酯，聚氯乙烯及其混合物。
3.根据权利要求1所述的一种医用高分子材料表面防污涂层的制备方法，其特征在于，所述的有机溶液包括氯仿、二氯甲烷、石油醚、乙酸乙酯溶液。
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CN104710644A (zh) * 2015-03-04 2015-06-17 中国科学院长春应用化学研究所 一种在医用高分子材料表面上制备抗菌表面的方法
CN104857572A (zh) * 2014-12-05 2015-08-26 美昕医疗器械（上海）有限公司 在惰性高分子材料表面制备亲水润滑涂层的方法及其医疗器械
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