CN111154372A - 仿生超润滑自修复薄膜的制备方法 - Google Patents
仿生超润滑自修复薄膜的制备方法 Download PDFInfo
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Abstract
本发明公开了一种仿生超润滑自修复薄膜的制备方法,采用紫外光交联技术制备薄膜,首先将2‑甲基丙烯酰氧乙基磷酰胆碱(MPC)单体溶液与锚定剂单体混合均匀,超声后加入光引发剂2‑羟基‑4'‑(2‑羟乙氧基)‑2‑甲基苯丙酮(IRGACURE 2959)搅拌溶解完全,将溶液置于紫外光下交联后得到聚合物溶液,然后将其涂覆至氨基化的基底上,再用超纯水冲洗基底以去除未结合的聚合物,干燥后得到仿关节润滑素的超润滑薄膜,摩擦系数μ为0.01,本发明的制备方法操作简便,工艺简单,成本低且所需时间较短,可用于规模化生产。
Description
技术领域
本发明涉及一种仿生超润滑自修复薄膜的制备技术,属于生物材料制备的技术领域。
背景技术
摩擦现象存在于工业、医学及日常生活中,可导致机器磨损、维修或更换成本增大,医用植入材料的顺应性和患者适应性减弱,也可给生活带来不便,最近引起了广泛的关注。因为摩擦的减弱和磨损的下调,即赋予材料表面超润滑的性能,能够为很多领域带来福音,如降低维修及生产成本、加快推进组织和骨修复工程等。摩擦学研究和超润滑技术的快速发展离不开与生理微环境类似的精确设计的智能和智能生物材料的研发。因此,开发超润滑材料的表面研究及应用平台具有重要意义。特别是对于使用医用导管的医护工作者及患者受益良多,研究表明表面润滑性与表面粗糙度、摩擦系数、磨损率、刚度、表面润湿性以及材料组装方法有关,需要进一步的研究与开发。
发明内容
技术问题:本发明的目的是提供一种仿生超润滑自修复薄膜的制备方法,该方法简单易行,且所需时间较短,所需设备简单。选用的材料都是生物相容性较好的仿生材料,无体外细胞毒性。制备出的薄膜提供显著的超润滑及自修复特性。
技术方案:本发明中制备仿生超润滑薄膜重在从多角度研究润滑作用:薄膜中MPC形成的刷状聚合物,在摩擦过程中与水形成表面水化壳发挥超润滑作用,锚定剂起到将MPC聚合物固定到基底上防止磨损降低润滑性,并且氨基化基底表面利于锚定剂发挥固定作用,同时因为MPC使一种两性离子化合物,通过静电相互作用、氢键作用及离子-偶极相互作用赋予薄膜自修复性能。材料在遭受外界破坏时,可以通过其自修复功能恢复材料的完整性,延长使用寿命。
本发明的一种仿生超润滑自修复薄膜的制备方法为:首先将2-甲基丙烯酰氧乙基磷酰胆碱MPC单体溶液与锚定剂单体混合均匀,超声波处理后加入光引发剂2-羟基-4'-(2-羟乙氧基)-2-甲基苯丙酮IRGACURE 2959搅拌溶解完全,将溶液置于紫外光下交联后得到聚合物溶液,然后将聚合物溶液涂覆至氨基化的基底上,再用超纯水冲洗基底以去除未结合的聚合物,干燥后得到仿关节润滑素的超润滑自修复薄膜。
所述的MPC单体溶液浓度为0.05mol/L~0.5mol/L。
所述的光引发剂IRGACURE 2959用量为0.1wt%~5wt%。
所述的锚定剂单体为丙烯酸、N-丙烯酰氧基琥珀酰亚胺、3-甲基丙烯酰胺基多巴胺、季戊四醇四丙烯酸酯或甲基丙烯酸二甲氨基乙酯其中的一种或两者复合组成锚定剂,锚定剂单体的浓度为0.1mol/L~0.5mol/L。
所述的将聚合物溶液涂覆至氨基化的基底上,涂膜方式为旋涂1000rpm~3000rpm,时间为2min~10min,或者采用浸涂6h~24h,或者采用滴涂到氨基化的基底表面,多次重复上述过程从而得到多层薄膜。
所述的紫外光波长为365nm,光照强度为5mW/cm2~20mW/cm2,照射时间为15min~120min。
所述的基底为玻璃、聚乙烯、聚氨酯、聚氯乙烯、陶瓷、木板、环氧板、金属、硅片或细胞培养孔板。
所述的干燥温度为25℃~60℃,干燥时间为2h~24h。
有益效果:本发明利用紫外光交联MPC与锚定剂结合制备的超润滑自修复薄膜,具有以下优点:该方法简单易行,且所需时间较短,所需设备简单。选用的材料都是生物相容性较好的仿生材料,无体外细胞毒性。制备出的薄膜提供显著的超润滑及自修复特性。摩擦系数μ为0.01。
MPC单体的亲水端易于水化壳的形成赋予了薄膜超润滑性能,同时在紫外光下锚定剂的加入与MPC单体的碳碳双键交联在基底表面形成刷状聚合物,降低了摩擦磨损,并且氨基化后的基底使得刷状聚合物牢固的固定在基底上,增强了稳定性和耐受性;并且MPC为两性离子化合物,通过静电相互作用、氢键作用及离子-偶极相互作用赋予薄膜自修复性能。此外薄膜由关节润滑素仿生物质MPC组成,生物相容性优异,无体外细胞毒性,因此通过紫外光交联方法制备的薄膜可在多方面增强了薄膜的超润滑性。
附图说明
图1为聚氯乙烯、薄膜和泊洛沙姆的表面摩擦系数测定图。
具体实施方式
下面结合实施例和附图对本发明做更进一步地解释。下列实施例仅用于说明本发明,但并不用来限定本发明的实施范围。
本发明提供了一种仿生超润滑自修复薄膜的制备方法为:首先将2-甲基丙烯酰氧乙基磷酰胆碱(MPC)单体溶液与锚定剂单体混合均匀,超声后加入光引发剂2-羟基-4'-(2-羟乙氧基)-2-甲基苯丙酮(IRGACURE 2959)搅拌溶解完全,将溶液置于紫外光下交联后得到聚合物溶液,然后将其涂覆至氨基化的基底上,再用超纯水冲洗基底以去除未结合的聚合物,干燥后得到仿关节润滑素的超润滑自修复薄膜。
其中,
所述的MPC单体浓度为0.05mol/L~0.5mol/L,光引发剂IRGACURE 2959用量为0.1wt%~5wt%。
所述的锚定剂单体包括丙烯酸、N-丙烯酰氧基琥珀酰亚胺、3-甲基丙烯酰胺基多巴胺、季戊四醇四丙烯酸酯、甲基丙烯酸二甲氨基乙酯,其中的一种或两者复合组成锚定剂,锚定剂单体的浓度为0.1mol/L~0.5mol/L。
所述的涂膜方式为旋涂1000rpm~3000rpm,时间为2min~10min,或者采用浸涂6h~24h或者采用滴涂到氨基化的基底表面,可多次重复上述过程从而得到多层薄膜。
所述的紫外光照射波长为365nm,光照强度为5mW/cm2~20mW/cm2,照射时间为15min~120min。
所述的基底为玻璃、聚乙烯、聚氨酯、聚氯乙烯、陶瓷、木板、环氧板、金属、硅片或细胞培养孔板。
所述的干燥温度为25℃~60℃,干燥时间为2h~24h。
制备方法具体为:
利用MPC单体和锚定剂单体溶液通过紫外光交联法制备的自修复薄膜。
具体的,首先将MPC单体溶液与锚定剂单体混合均匀,超声后加入光引发剂IRGACURE2959搅拌溶解完全,将溶液置于365nm紫外光下交联后得到聚合物溶液,然后将其涂覆至氨基化的基底上,再用超纯水冲洗基底3次以去除未结合的聚合物,干燥后得到仿关节润滑素的超润滑自修复薄膜。
实施例1:
首先将0.05mol/L的MPC单体溶液与0.1mol/L锚定剂丙烯酸单体混合均匀,超声后加入光引发剂IRGACURE 2959(0.1wt%)搅拌溶解完全,将溶液置于365nm光照强度为5mW/cm2的紫外光下交联15min后得到聚合物溶液,然后将其1000rpm下旋涂2min至氨基化的聚氯乙烯基底上,再用超纯水冲洗基底3次以去除未结合的聚合物,25℃下干燥2h后得到15层超润滑自修复薄膜。
实施例2:
首先将0.5mol/L的MPC单体溶液与0.5mol/L锚定剂丙烯酸和3-甲基丙烯酰胺基多巴胺单体混合均匀,超声后加入光引发剂IRGACURE 2959(5wt%)搅拌溶解完全,将溶液置于365nm光照强度为20mW/cm2紫外光下交联120min后得到聚合物溶液,然后将其浸涂6h至氨基化的硅片基底上,再用超纯水冲洗基底3次以去除未结合的聚合物,60℃下干燥24h后得到10层超润滑自修复薄膜。
实施例3:
首先将0.15mol/L的MPC单体溶液与0.15mol/L锚定剂甲基丙烯酸二甲氨基乙酯单体混合均匀,超声后加入光引发剂IRGACURE 2959(2.5wt%)搅拌溶解完全,将溶液置于365nm光照强度为10mW/cm2紫外光下交联60min后得到聚合物溶液,然后将其滴涂至氨基化的聚乙烯基底上,再用超纯水冲洗基底3次以去除未结合的聚合物,40℃下干燥12h后得到5层超润滑自修复薄膜。
Claims (8)
1.一种仿生超润滑自修复薄膜的制备方法,其特征在于,该薄膜的制备方法为:首先将2-甲基丙烯酰氧乙基磷酰胆碱(MPC)单体溶液与锚定剂单体混合均匀,超声波处理后加入光引发剂2-羟基-4'-(2-羟乙氧基)-2-甲基苯丙酮IRGACURE 2959搅拌溶解完全,将溶液置于紫外光下交联后得到聚合物溶液,然后将聚合物溶液涂覆至氨基化的基底上,再用超纯水冲洗基底以去除未结合的聚合物,干燥后得到仿关节润滑素的超润滑自修复薄膜。
2.根据权利要求1所述的仿生超润滑自修复薄膜的制备方法,其特征在于,所述的MPC单体溶液浓度为0.05mol/L~0.5mol/L。
3.根据权利要求1所述的仿生超润滑自修复薄膜的制备方法,其特征在于,所述的光引发剂IRGACURE 2959用量为0.1wt%~5wt%。
4.根据权利要求1所述的仿生超润滑自修复薄膜的制备方法,其特征在于,所述的锚定剂单体为丙烯酸、N-丙烯酰氧基琥珀酰亚胺、3-甲基丙烯酰胺基多巴胺、季戊四醇四丙烯酸酯或甲基丙烯酸二甲氨基乙酯其中的一种或两者复合组成锚定剂,锚定剂单体的浓度为0.1mol/L~0.5mol/L。
5.根据权利要求1所述的仿生超润滑自修复薄膜的制备方法,其特征在于,所述的将聚合物溶液涂覆至氨基化的基底上,涂膜方式为旋涂1000rpm~3000rpm,时间为2min~10min,或者采用浸涂6h~24h,或者采用滴涂到氨基化的基底表面,多次重复上述过程从而得到多层薄膜。
6.根据权利要求1所述的仿生超润滑自修复薄膜的制备方法,其特征在于,所述的紫外光波长为365nm,光照强度为5mW/cm2~20mW/cm2,照射时间为15min~120min。
7.根据权利要求1所述的仿生超润滑自修复薄膜的制备方法,其特征在于,所述的基底为玻璃、聚乙烯、聚氨酯、聚氯乙烯、陶瓷、木板、环氧板、金属、硅片或细胞培养孔板。
8.根据权利要求1所述的仿生超润滑自修复薄膜的制备方法,其特征在于,所述的干燥温度为25℃~60℃,干燥时间为2h~24h。
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