CN114106361B - 加载两性离子聚合物涂层的聚丙烯材料及其制备方法 - Google Patents

加载两性离子聚合物涂层的聚丙烯材料及其制备方法 Download PDF

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CN114106361B
CN114106361B CN202010862405.1A CN202010862405A CN114106361B CN 114106361 B CN114106361 B CN 114106361B CN 202010862405 A CN202010862405 A CN 202010862405A CN 114106361 B CN114106361 B CN 114106361B
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zwitterionic polymer
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CN114106361A (zh
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张天柱
周乃珍
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Suzhou Zhishan New Material Technology Co ltd
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Abstract

本发明公开了一种加载两性离子聚合物涂层的聚丙烯材料及其制备方法，该材料是以两性离子聚合物单体、丙烯酸、多巴胺甲基丙烯酸酯为共聚单体，以去离子水或DMF为溶剂，在引发剂的作用下，20‑100℃反应8‑16小时，经自由基聚合原位接枝在基底聚丙烯表面得到两性离子聚合物涂层，涂层厚度在1~5μm之间可控，水接触角范围为10~30º之间，具有高度亲水性；两性离子聚合单体是甲基丙烯酸磺酸贝泰、甲基丙烯酸磷酸贝泰或甲基丙烯酸羧酸贝泰；所述的引发剂是偶氮二异丁腈或过硫酸铵。所得材料具有良好的抗污功能和亲水性的表面，且无毒无害，生物相容性好。

Description

加载两性离子聚合物涂层的聚丙烯材料及其制备方法
技术领域
本发明涉及聚丙烯材料表面亲水性和抗污性能设计制备领域，具体涉及一种基于聚（甲基丙烯酸磺酸贝泰）（PSBMA）涂层功能化聚丙烯材料及其制备方法。
背景技术
聚丙烯（PP）是一种热塑性树脂，是目前全球五大通用塑料之一，可分为等规聚丙烯（isotaetic polyprolene）、无规聚丙烯（atactic polypropylene）和间规聚丙烯（syndiotatic polypropylene）三种。 PP是一种半结晶性材料, 比聚乙烯（polyethylene,PE）有更大的硬度和更高的熔点。由于均聚型的聚丙烯具有一定的脆性，所以聚合时常常加入1～4%或更高含量的乙烯作为共聚单体从而获得聚丙烯聚乙烯的共聚物。均聚物型和共聚物型的PP材料都具有优良的抗吸湿性、抗酸碱腐蚀性和抗溶解性。医用聚丙烯已经作为医疗器械材料而广泛使用，如除了用作制造医用导管和血液净化滤膜等外，还在疝外科手术中广泛用作疝修补材料。然而在保持其本体力学性能不发生显著下降的前提下，如何提高这类材料的亲水性、抗粘接性和生物相容性等, 依然是技术难点和研究热点。
多巴胺作为一种广泛应用的嫁接涂层的介导分子，可以将不同的高分子通过化学键连接的方法嫁接在聚丙烯的表面。如专利号为CN201510335162.5的中国专利申请公开了一种基于震荡条件下多巴胺自聚合制备抗菌涂层的方法，是在弱碱性Tris缓冲溶液中，加入多巴胺固体，然后，将待修饰基底浸泡于该溶液中，从而在基底上制备成聚多巴胺涂层。对多种常见微生物都有很好地抑制作用。申请号为CN202010162811.7的中国专利申请公开了一基于多巴胺的锌表面载镓-氧化石墨烯复合涂层的制备方法，是将锌基片表面依次进行预处理后进行碱热处理后泡在浸硝酸镓溶液中获得以Zn/Ga标记的载镓涂层样本；将得到的载镓锌片在多巴胺溶液中浸泡得到以Zn/Ga/PDA标记的镓-多巴胺涂层，将所述镓-多巴胺涂层样本在氧化石墨烯溶液中，浸泡24小时获得镓-多巴胺-石墨烯的复合涂层。申请号为CN201710059415.X的中国专利申请公开了一种TiO2修饰多巴胺抗菌涂层的制备方法，是以固体材料为基底，在其表面进行多巴胺自聚，再用TiO2进行修饰，合成具有抗菌性能的涂层。中国专利（CN107312122）则公开了利用多巴胺甲基丙烯酰胺单体( DMA )和甲基丙烯酰乙基磺基甜菜碱单体( SB )无规共聚合成聚多巴胺甲基丙烯酰胺磺基甜菜碱( PDMASB)，利用多巴胺的邻二酚基的粘附性和磺基甜菜碱的亲水抗污性，通过聚合物水溶液浸涂的方式来实
现对不同基材的表面改性，可不同程度地提高材料的表面抗生物污染性能。
两性离子聚合物（zwitterionic polymers）的同一单体侧链上同时含有阴离子基团和阳离子基团，但是总体呈电中性，两性离子聚合物具有强亲水性和超低生粘污的特点。因此若能通过简单实用的方法将两性离子聚合物涂覆在聚丙烯材料的表面，则将可以极大提升聚丙烯材料的抗污性能和和作为生物医学材料的功能。
发明内容
为了克服现有技术的不足，本发明目的在于提供一种接枝两性离子聚合物涂层的聚丙烯材料及其制备方法，具体来说，是接枝了聚（甲基丙烯酸磺酸贝泰）（PSBMA）等涂层，该材料表面具有良好的抗污性能和亲水性。
为了实现上述发明目的，本发明技术方案如下：
加载两性离子聚合物涂层的聚丙烯材料，是以两性离子聚合物单体、羟基化的丙烯酸（O-PP）、多巴胺甲基丙烯酸酯（DMA）为共聚单体，以去离子水或DMF为溶剂，在引发剂的作用下，20-100℃反应8-16小时，经自由基聚合原位接枝在基底聚丙烯表面得到两性离子聚合物涂层。涂层厚度在1~5μm之间可控，并具有高度亲水性，水接触角范围为10~30º之间。和现有的技术相比（中国专利CN107312122A），本发明采用原位共聚接枝的方法，相对于先获得聚合物后浸涂的方法，最显著的优势在于步骤简单，嫁接效果更好。
由于多巴胺本身不能直接和两性离子单体共聚被负载在聚合物主链上，因此本发明采用其衍生物DMA，两性离子也一样必须使用其衍生物。
较佳地，进一步通过EDC/NHS的方法负载RGD, 增强生物相容性。
所述的引发剂是偶氮二异丁腈(AIBN)或过硫酸铵(APS)。
单体总的摩尔数和引发剂的摩尔数的比例在300:1~100:1，较佳地在300:1~200:1之间，因为在该范围内有利于控制聚合速率，获得更加理想的嫁接层。过快的聚合速率不利于嫁接层的形成，过慢的聚合速率又需要更多的时间。
所述的基底聚丙烯表面预先经过羟基化处理。
所述的两性离子聚合单体是甲基丙烯酸磺酸贝泰（sulfobetaine methacrylat，SBMA）、甲基丙烯酸磷酸贝泰或甲基丙烯酸羧酸贝泰。
上述加载两性离子聚合物涂层的聚丙烯材料的制备方法，具体包含以下步骤：
步骤一：将聚丙烯材料清洗、烘干，备用；
所述的聚丙烯材料形态是膜、网、丝、颗粒或者微球之任一种。材料的不同形态对于加载涂层材料没有显著影响。
步骤二：将上述聚丙烯（PP）材料通过氧等离子体处理得到表面羟基化的聚丙烯（O-PP），备用；
步骤三：取两性离子聚合物单体和多巴胺甲基丙烯酸酯加入去离子水或N,N-二甲基甲酰胺中，通入氮气搅拌；
步骤四：加入引发剂偶氮二异丁腈(AIBN)或过硫酸铵(APS)和步骤二中处理得到的表面羟基化的聚丙烯，65℃以上反应8-16小时；
步骤五：反应结束后，产物经清洗、干燥，既得加载两性离子聚合物涂层的聚丙烯材料，产物表面具有亲水性和抗污性。
步骤六：将步骤五反应获得的材料继续放在去离子水里，加入EDC/NHS，并加入RGD室温下反应6小时，取出并用去离子水清洗，就获得了表面嫁接有RGD的聚丙烯材料。修饰RGD有利于提高材料的生物相容性。
本发明与现有技术相比的优势：
（1）、既不同于预先获得聚（甲基丙烯酸磺酸贝泰）（PSBMA）再进行浸泡涂层，也不同于先用多巴胺进行表面涂覆再应用聚（甲基丙烯酸磺酸贝泰）进行沉积涂层(中国专利CN107312122)，本发明应用多巴胺甲基丙烯酸酯（DMA）为粘附介导分子，通过表面原位共聚的方法，在聚丙烯表面原位形成一层两性离子聚合物涂层。
（2）、通过引入共聚单体丙烯酸，可以在两性离子涂层中引入羧基官能团，从而可以进一步负载RGD，可以提高材料表面的生物相容性。
附图说明
图 1 步骤（2）应用氧等离子体对聚丙烯材料表面进行活化，在聚丙烯表面引入羟基，得到表面活化的聚丙烯。
图 2 以单体为SBMA为例，本发明在水溶液中两性离子单体原位共聚在聚丙烯表面上形成两性离子聚合物涂层的原理图。
具体实施方式
以下将结合具体实施例说明本发明的技术方案：
多巴胺盐酸盐购自国药集团，多巴胺甲基丙烯酸酯（DMA）根据已有文献合成（Nature, 2007, 448, 338-341）；
两性离子聚合单体是甲基丙烯酸磺酸贝泰（sulfobetaine methacrylat，SBMA）、甲基丙烯酸磷酸贝泰或甲基丙烯酸羧酸贝泰根据已有文献合成（J. Controlled Release2017, 261, 318−336）。
实施例1
本实施例的目的在于证明应用甲基丙烯酸磺酸贝泰单体和DMA单体进行原位共聚可以在聚丙烯表面形成聚甲基丙烯酸磺酸贝泰（PSBMA）涂层。
1.将 0.5 g 聚丙烯颗粒（或微球）, 用二氯甲烷清洗三次，每次 20 mL，清洗时间3 小时，并在 40℃ 条件下干燥 24 小时。
2.将上述聚丙烯材料通过氧等离子体处理 2 分钟。
3.取4.8 mmol甲基丙烯酸磺酸贝泰加入40 mL N,N-二甲基甲酰胺(DMF)中，通入氮气鼓泡并搅拌20分钟。
4.取1.2mmol的DMA溶于步骤3所述溶液中，并分别加入0.033g偶氮二异丁腈(AIBN)，步骤2中的聚丙烯材料，65℃环境中反应8小时。
5.取出步骤4中的聚丙烯材料，在蒸馏水中清洗10分钟，40℃鼓风干燥箱中干燥12小时。经上述程序处理后，就获得了表面具有亲水性和抗污性的聚丙烯颗粒。
实施例2
本实施例的目的在于证明应用另外一种两性离子单体甲基丙烯酸磷酸贝泰和DMA单体进行原位共聚可以在聚丙烯表面形成聚甲基丙烯酸磷酸贝泰涂层。
1.将 0.5 g 聚丙烯颗粒（或微球）, 用二氯甲烷清洗三次，每次 20 mL，清洗时间3 小时，并在 40℃ 条件下干燥 24 小时。
2.将上述聚丙烯材料通过氧等离子体处理 2 分钟。
3.取4.8 mmol甲基丙烯酸磷酸贝泰加入40 mL N,N-二甲基甲酰胺(DMF)中，通入氮气鼓泡并搅拌20分钟。
4.取1.2mmol的DMA溶于步骤3所述溶液中，并分别加入0.033g偶氮二异丁腈(AIBN)，步骤2中的聚丙烯材料，65℃环境中反应8小时。
5.取出步骤4中的聚丙烯材料，在蒸馏水中清洗10分钟，40℃鼓风干燥箱中干燥12小时。经上述程序处理后，就获得了表面具有亲水性和抗污性的聚丙烯颗粒。
实施例3
本实施例的目的在于证明应用另外一种两性离子单体甲基丙烯酸羧酸贝泰和DMA单体进行原位共聚可以在聚丙烯表面形成聚甲基丙烯酸羧酸贝泰涂层。
1.将 0.5 g 聚丙烯颗粒（或微球）, 用二氯甲烷清洗三次，每次 20 mL，清洗时间3 小时，并在 40℃ 条件下干燥 24 小时。
2.将上述聚丙烯材料通过氧等离子体处理 2 分钟。
3.取4.8 mmol甲基丙烯酸羧酸贝泰加入40 mL N,N-二甲基甲酰胺(DMF)中，通入氮气鼓泡并搅拌20分钟。
4.取1.2mmol的DMA溶于步骤3所述溶液中，并分别加入0.033g偶氮二异丁腈(AIBN)，步骤2中的聚丙烯材料，65℃环境中反应8小时。
5.取出步骤4中的聚丙烯材料，在蒸馏水中清洗10分钟，40℃鼓风干燥箱中干燥12小时。经上述程序处理后，就获得了表面具有亲水性和抗污性的聚丙烯颗粒。
实施例4
本实施例的目的在于证明应用两性离子单体甲基丙烯酸磺酸贝泰，丙烯酸和DMA单体进行原位共聚可以在聚丙烯表面形成聚甲基丙烯酸磺酸贝泰涂层，加入丙烯酸单体可进一步提高嫁接层的亲水性。和实施例1-3不同，所用溶剂为去离子水。
1.将 0.5 g 聚丙烯颗粒（或微球）, 用二氯甲烷清洗三次，每次 20 mL，清洗时间3 小时，并在 40℃ 条件下干燥 24 小时。
2.将上述聚丙烯材料通过氧等离子体处理 2 分钟。
3.称取4.8 mmol甲基丙烯酸磺酸贝泰和0.1 mmol丙烯酸加入40 mL 去离子水中，通入氮气鼓泡并搅拌20分钟。
4.取1.2mmol的DMA溶于步骤3所述溶液中，并分别加入0.033g过硫酸铵(APS)以及步骤2中的聚丙烯材料，65℃环境中反应8小时。
5.取出步骤4中的聚丙烯材料，在蒸馏水中清洗10分钟，40℃鼓风干燥箱中干燥12小时。经上述程序处理后，就获得了表面具有亲水性和抗污性的聚丙烯颗粒。
实施例5
本实施例的目的在于证明应用两种不同的两性离子单体甲基丙烯酸磺酸贝泰和甲基丙烯酸磷酸贝泰，丙烯酸和DMA单体进行原位共聚可以在聚丙烯表面形成甲基丙烯酸磺酸贝泰和甲基丙烯酸磷酸贝泰共聚物涂层。证明不同的两性离子单体的自由组合。
1.将 0.5 g 聚丙烯颗粒（或微球）, 用二氯甲烷清洗三次，每次 20 mL，清洗时间3 小时，并在 40℃ 条件下干燥 24 小时。
2.将上述聚丙烯材料通过氧等离子体处理 2 分钟。
3.称取2.4 mmol甲基丙烯酸磺酸贝泰、2.4 mmol甲基丙烯酸磷酸贝泰和0.1 mmol丙烯酸加入40 mL 去离子水中，通入氮气鼓泡并搅拌20分钟。
4.取1.2mmol的DMA溶于步骤3所述溶液中，并分别加入0.033g过硫酸铵(APS)以及步骤2中的聚丙烯材料，65℃环境中反应8小时。
5.取出步骤4中的聚丙烯材料，在蒸馏水中清洗10分钟，40℃鼓风干燥箱中干燥12小时。经上述程序处理后，就获得了表面具有亲水性和抗污性的聚丙烯颗粒。
实施例6
本实施例的目的在于证明应用两性离子单体甲基丙烯酸磺酸贝泰，丙烯酸和DMA单体进行原位共聚可以在聚丙烯表面形成聚甲基丙烯酸磺酸贝泰涂层，加入丙烯酸单体不仅可进一步提高嫁接层的亲水性，而且还可以引入活性基团羧基，进一步和RGD进行反应，从而在聚丙烯表面负载RGD，增加生物相容性。
1.将 0.5 g 聚丙烯网（或微球）, 用二氯甲烷清洗三次，每次 20 mL，清洗时间 3小时，并在 40℃ 条件下干燥 24 小时。
2.将上述聚丙烯材料通过氧等离子体处理 2 分钟。
3.称取4.8 mmol甲基丙烯酸羧酸贝泰和0.1 mmol丙烯酸加入40 mL 去离子水中，通入氮气鼓泡并搅拌20分钟。
4.取1.2 mmol的DMA溶于步骤3所述溶液中，并分别加入0.033g过硫酸铵(APS)，步骤2中的聚丙烯材料，65℃环境中反应8小时。
5.取出步骤4中的聚丙烯材料，在蒸馏水中清洗10分钟，然后放入100mL
的去离子水中，加入EDC/NHS(1:1)和 c(RGD)fk，室温下反应8小时。
6．将步骤5反应后的聚丙烯材料取出，并在蒸馏水中清洗10分钟，40℃环境中干燥12小时。经上述处理程序后，就获得了表面具有亲水性和抗污性的聚丙烯颗粒。
表1
样品 对照组（聚丙烯） 实施例1 实施例2 实施例3 实施例4 实施例5 实施例6
水接触角（º） 103 13 15 20 12 13 11
上述实施例表明，经过两性离子聚合接枝的聚丙烯表面的亲水性显著提高。水接触角见表1。

Claims (2)

1.加载两性离子聚合物涂层的聚丙烯材料，其特征在于，是以两性离子聚合物单体、丙烯酸、多巴胺甲基丙烯酸酯为共聚单体，以去离子水或DMF为溶剂，在引发剂的作用下，20-100℃反应8-16小时，经自由基聚合原位接枝在基底聚丙烯表面得到两性离子聚合物涂层；涂层厚度在1~5μm之间可控，并具有高度亲水性，水接触角范围为10~30º之间；
通过EDC/NHS的方法负载RGD；
所述的两性离子聚合单体是甲基丙烯酸磺酸贝泰、甲基丙烯酸磷酸贝泰或甲基丙烯酸羧酸贝泰；所述的引发剂是偶氮二异丁腈或过硫酸铵；
单体总的摩尔数和引发剂的摩尔数的比例在300:1~200:1之间;
所述的聚丙烯材料形态是膜、网、丝、颗粒或者微球之任一种，预先经过羟基化处理。
2.权利要求1所述的加载两性离子聚合物涂层的聚丙烯材料的制备方法，包含以下步骤：
步骤一：将聚丙烯材料清洗、烘干，备用；
步骤二：将上述聚丙烯材料通过氧等离子体处理得到表面羟基化的聚丙烯，备用；
步骤三：取两性离子聚合物单体和多巴胺甲基丙烯酸酯加入去离子水或N,N-二甲基甲酰胺中，通入氮气搅拌；
步骤四：加入引发剂偶氮二异丁腈或过硫酸铵和步骤二中处理得到的表面羟基化的聚丙烯，65℃以上反应8-16小时；
步骤五：反应结束后，产物经清洗、干燥，既得加载两性离子聚合物涂层的聚丙烯材料，产物表面具有亲水性和抗污性。
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