CN110669242A - 具有抗蛋白粘附和抗菌功能的高分子材料的表面处理方法 - Google Patents
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Abstract
为了解决高分子材料表面吸附蛋白质或者细菌等其他杂质导致材料原功能丧失或者引起其他不良反应，本发明通过改性高分子材料表面化学结构，使其具有抗蛋白黏附和抗菌功能。该技术应用的产品是一切需要具备抗蛋白黏附和抗菌功能的高分子材料。具有抗蛋白粘附和抗菌功能的高分子材料的表面处理方法，包括：步骤一，以表面含有环氧乙烷基团的基底高分子材料作为载体，加入含巯基小分子进行反应，引入巯基；步骤二，将步骤一中的巯基与两性离子单体发生自由基聚合反应，从而两性离子单体接枝于基底高分子材料。
Description
技术领域
本发明涉及表面改性技术领域。更具体地说，涉及一种具有抗蛋白粘附和抗菌功能的高分子材料及表面处理方法。
背景技术
生物污染是非特异性的生物分子(蛋白质、细胞、细菌以及其他微生物)在材料表面或者界面上的黏附。而蛋白质在材料表面黏附引发的问题更为严重，因为其会引起细胞、细菌以及其他微生物的沉积，从而在材料表面上形成生物活化膜，诱发严重的生物污染。生物污染的存在会引起对生物医药、食品包装及储存、纺织品、污水净化处理以及海洋运输等基于表面功能的材料的寿命减少和效率下降等问题。
蛋白质广泛存在于生物体中，是构成生物体的主要物质，机体中每一个细胞和重要的组成部分都有蛋白质的参与。对于生物医药植入材料而言，降低植入材料表面对蛋白质吸附具有重要的意义。
一般来说，材料表面同蛋白质的相互作用主要是由于亲疏水性的差异造成的。蛋白质是亲水的，但其亲水性也只是介于水和材料表面之间，当向蛋白质水溶液加入植入材料时，水溶液中的蛋白质具有向材料表面亲和的趋势。此外，由于植入材料的疏水性质，表面的含水层与植入材料表面的作用很弱，当引入蛋白质时，相对亲水的蛋白质的存在便扰乱了植入材料表面水自身规则排列，造成了水分子排列趋于混乱，体系熵值增加。因此蛋白质在材料表面吸附便成为必然，并且植入材料表面的疏水性越高蛋白质吸附的趋势便越明显。聚合物表面与蛋白质的相互作用的第二个来源是基于电性作用，蛋白质多带负电，因此材料表面正电荷越强烈，蛋白质吸附越明显。
因此，减少材料表面对蛋白质等杂质的吸附，提高材料表面的亲水性是行之有效的方法。
目前，提高材料表面的亲水性，减少蛋白质吸附的策略有如下几种方法：
(1)在材料表面利用可反应官能团，接枝多糖类物质。由于多糖类化合物含有丰富羟基，因此可提高材料表面亲水性。但在材料表面接枝多糖类物质，需要有特定官能团(如氰基)的化合物作为材料基底组成物质，一般采用多异氰酸酯类物质，该物质具有一定毒性，用于生物材料容易引起毒性反应。
(2)在材料表面接枝聚乙二醇(PEG)亲水聚合物，由于聚乙二醇(PEG)聚合物含有丰富羟基，可提高材料表面亲水性。最广泛应用于表面改性的亲水物质聚乙二醇(PEG)，由于近年来研究发现，在氧气或其他氧化物的存在下，对聚乙二醇(PEG)具有氧化降解作用。此外，体内具有抗聚乙二醇抗体。这导致聚乙二醇在植入后，经链段降解而功能失效。
(3)利用超亲水两性离子聚合物在材料表面进行改性，由于两性离子聚合物与水溶液具有强静电作用和氢键作用，因此可提高材料表面亲水性。接枝两性离子的聚合物，接枝方法一般采用可逆加成-断裂链转移聚合法(RAFT)和原子转移自由基聚合(ATRP)。该方法需要严格无水无氧的环境中，且可逆加成-断裂链转移聚合法(RAFT)一般合成较低分子量聚合物，原子转移自由基聚合(ATRP)采用了金属离子和卤化物含有一定毒性，对于生物材料的使用具有一定限制。
(4)利用类肽聚合物在材料表面进行改性，提高材料表面亲水性。但类肽聚合物在体内容易被酶解。
发明内容
为了解决高分子材料表面吸附蛋白质或者细菌等其他杂质导致材料原功能丧失或者引起其他不良反应，本发明通过改性高分子材料表面化学结构，使其具有抗蛋白黏附和抗菌功能。
该技术应用的产品是一切需要具备抗蛋白黏附和抗菌功能的高分子材料。
具有抗蛋白粘附和抗菌功能的高分子材料的表面处理方法，包括：
步骤一，以表面含有环氧乙烷基团的基底高分子材料作为载体，加入含巯基小分子进行反应，引入巯基；
步骤二，将步骤一中的巯基与两性离子单体发生自由基聚合反应，从而两性离子单体接枝于基底高分子材料。
上述步骤一中，对基底高分子材料进行化学改性，以引入环氧乙烷基团，反应方程式为：
含巯基小分子可以为二硫苏糖醇，二硫苏糖醇与环氧乙烷基团反应，以引入巯基，反应方程式为：
上述步骤二中，巯基在中性条件下与两性离子单体发生自由基聚合反应，两性离子单体不局限于2-甲基丙烯酰氧乙基磷酸胆碱(MPC)、甲基丙稀酰乙基磺基甜菜碱(SBMA)、羧酸甜菜碱甲基丙烯酸甲酯(CBMA)，从而在基底高分子材料中引入两性离子基团，反应方程式为：
，其中R为两性离子单体，
为两性离子基团，不局限于PMPC、PSBMA、PCBMA。
若两性离子单体为2-甲基丙烯酰氧乙基磷酸胆碱，巯基在中性条件下与2-甲基丙烯酰氧乙基磷酸胆碱发生自由基聚合反应，从而在基底高分子材料中引入聚2-甲基丙烯酰氧乙基磷酸胆碱，反应方程式为：
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图；
图1为本发明制得的高分子材料与现有方法制备的高分子材料的亲水性对比图；
图2为本发明制得的高分子材料与现有方法制备的高分子材料的荧光蛋白吸附的对比图。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明通过基底高分子材料表面的环氧乙烷基团和含巯基小分子反应，引入巯基，含巯基小分子本身分子链段上含有多个羟基，亲水效果显著。然后巯基与两性离子单体发生自由基聚合反应，从而将两性离子单体共聚接枝于基底高分子材料中。
传统引入两性离子单体的方法，一般采用原子转移自由基聚合(ATRP)聚合方法。该方法使用卤化物作为引发剂，氯化亚铜与、2,2’-联二吡啶(催化剂活化剂)作为金属催化剂，通过氧化还原反应，在活性种和休眠种之间建立可逆动态平衡，维持自由基浓度较低水平，使自由基聚合反应有序可控进行。该方法需要在严格无水无氧环境下进行，且使用卤化物、氯化亚铜与2,2’-联二吡啶等毒性物质。这些物质一般在反应后很难从合成材料中除去，残留于材料本体中的有毒物质影响材料的使用范围，尤其对于生物材料。由于原子转移自由基聚合(ATRP)聚合方法合成过程复杂和严格，合成原料残留本体材料等原因，这种方法的实用性大大受限。
而本发明在高温下巯基与两性离子单体发生自由基聚合反应，无需加入产生自由基的引发剂，避免引入有毒卤化物作为引发剂。另外，由于巯基小分子反应活性更高，与两性离子单体发生自由基聚合反应不需要在无水无氧条件下进行，在一般的实验条件下即可高效发生自由基聚合反应，不需要特殊反应环境，反应条件温和。另外，不需要引入氯化亚铜作为金属催化剂，因此没有残留金属有害物的问题。
本发明中使用的含巯基小分子可以但不局限于是二硫苏糖醇(DTT)，也可以换成其他含巯基小分子。
两性离子单体可以但不局限于是2-甲基丙烯酰氧乙基磷酸胆碱(MPC)，可以换成其他两性离子单体。
具体的，首先对基底高分子材料进行化学改性，以引入环氧乙烷基团，反应方程式为：
TEMED可以催化APS产生自由基。
然后利用二硫苏糖醇(DTT)与环氧乙烷基团反应，反应结束后在基底高分子材料中引入巯基，反应方程式为：
然后，巯基在中性条件下与两性离子单体发生自由基聚合反应，从而在基底高分子材料中引入两性离子基团，反应方程式为：
两性离子单体不局限于2-甲基丙烯酰氧乙基磷酸胆碱(MPC)、甲基丙稀酰乙基磺基甜菜碱(SBMA)、羧酸甜菜碱甲基丙烯酸甲酯(CBMA)，
不局限于PMPC、PSBMA、PCBMA。
具体的，例如，巯基在中性条件下与两性离子单体2-甲基丙烯酰氧乙基磷酸胆碱(MPC)发生自由基聚合反应，从而在基底高分子材料中引入超亲水的聚2-甲基丙烯酰氧乙基磷酸胆碱(PMPC)。
反应方程式为：
综上，本发明利用二硫苏糖醇(DTT)与基底高分子材料中环氧乙烷基团发生反应，引入巯基，该巯基与2-甲基丙烯酰氧乙基磷酸胆碱(MPC)发生自由基反应，从而PMPC接枝于基底高分子材料。
以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (5)
1.具有抗蛋白粘附和抗菌功能的高分子材料的表面处理方法，其特征在于，包括：
步骤一，以表面含有环氧乙烷基团的基底高分子材料作为载体，加入含巯基小分子进行反应，引入巯基；
步骤二，将步骤一中的巯基与两性离子单体发生自由基聚合反应，从而两性离子单体接枝于基底高分子材料。
2.根据权利要求1所述的表面处理方法，其特征在于，步骤一中，所述含巯基小分子为二硫苏糖醇。
3.根据权利要求2所述的表面处理方法，其特征在于，步骤一中，对基底高分子材料进行化学改性，以引入环氧乙烷基团，反应方程式为：
4.根据权利要求3所述的表面处理方法，其特征在于，步骤一中，二硫苏糖醇与环氧乙烷基团反应，以引入巯基，反应方程式为：
5.根据权利要求4所述的表面处理方法，其特征在于，步骤二中，巯基在中性条件下与两性离子单体发生自由基聚合反应，从而在基底高分子材料中引入两性离子基团，反应方程式为：
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