CN110105733B - 一种聚乳酸/聚乳酸接枝聚多巴胺复合材料的制备方法 - Google Patents
一种聚乳酸/聚乳酸接枝聚多巴胺复合材料的制备方法 Download PDFInfo
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Abstract
本发明提供一种聚乳酸/聚乳酸接枝聚多巴胺复合材料的制备方法，所述方法利用多巴胺氧化自聚而得的聚多巴胺纳米粒子为引发剂，对丙交酯进行开环聚合，在PDA NPs的表面接枝PLA链，制备了聚乳酸接枝聚多巴胺复合纳米粒子，以提高纳米粒子在聚乳酸(PLA)基质中的分散性和相容性；进而将PDA NPs‑PLA作为纳米填料与PLA复合成型，制备得到聚乳酸/聚乳酸接枝聚多巴胺复合材料。本发明制备所得的复合材料具有较低的冷结晶温度、较高的紫外屏蔽性能及良好的力学性能与生物可降解性，可作为包装材料、农用膜材料、工程塑料、生物医用材料等应用于多个领域。
Description
技术领域
本发明涉及一种聚乳酸/聚乳酸接枝聚多巴胺复合材料的制备方法，属于高分子材料和生物可降解材料技术领域。
背景技术
近年来，生物可降解高分子材料因其生物来源广、环境友好等诸多优势而引起了广泛的关注。聚乳酸(PLA)具有无毒、无刺激、生物可降解、生物相容性好等优异性能，因而成为一种最有发展潜力的生物可降解高分子材料。尽管PLA具有较好的力学性能，但其韧性较差，在某些领域难以满足使用要求。同时，PLA材料缺乏一定的功能性，特别是在包装材料、工程塑料等领域中使用时，缺乏紫外屏蔽性能，因而限制了其使用领域。将生物可降解聚合物材料与纳米填料混合不仅可以改善其机械和热性能，而且还能够赋予材料额外的功能，如导电性、紫外屏蔽性、气体阻隔性和抗菌性等。而前期的研究报道称，碳纳米材料或金属纳米粒子等纳米填料可以极大地改善PLA的热学、电学和光学性质，但这些无机纳米填料与PLA间的相容性较差，且其存在一定的生物不相容性与生理毒性，极大地限制了其在生物可降解基复合材料中的应用。因而，选用具有生物可降解性的有机纳米粒子为填料，有望解决上述问题。
2007年，美国西北大学Messersmith教授团队发现L-3,4-二羟苯丙氨酸(DOPA)可在弱碱性溶液及氧气中发生氧化自聚，且其表现出令人惊叹的黏附性，即几乎可在所有材料表面形成聚多巴(PDOPA)涂层，这一发现拉开了研究多巴及其衍生物的序幕。多巴胺(DA)是一种多巴的常见衍生物，其具有与多巴相类似的性质：可氧化自聚成聚多巴胺纳米粒子(PDA NPs)、优异的黏附性能、生物相容性、光热转化性、紫外屏蔽性等，而且PDA NPs中富含儿茶酚基、氨基、亚氨基等功能性基团，可与多种化合物和聚合物有较强的相互作用也可发生二次反应。因此，PDA NPs作为纳米填料具有很大的研究和应用价值。
然而，直接将PDA NPs与PLA复合，存在两者不相容而使PDA NPs聚集，从而PDA NPs不能很好的分散于PLA基材中而未能实现提高PLA性能的目的。
发明内容
本发明目的是提供一种聚乳酸/聚乳酸接枝聚多巴胺复合材料的制备方法，制备得到的复合材料具有良好的热学性能与紫外屏蔽性。
本发明的设计思路是：首先利用多巴胺在弱碱性环境下的氧化自聚自组装制备不同粒径(100～550nm)的聚多巴胺纳米粒子(PDA NPs)；再将其作为引发剂，利用丙交酯的开环聚合将聚乳酸链段接枝至PDA NPs的表面，以提高纳米粒子在PLA基质中的分散性和相容性，进而提高纳米粒子与PLA基材的相互作用；最后将两者复合制备PLA/PDA NPs-PLA复合材料。
本发明的技术方案如下：
利用多巴胺在弱碱性条件下的氧化自聚自组装，并利用氨水调节反应体系的pH，制备了不同粒径的PDA NPs；再以辛酸亚锡为催化剂、无水甲苯为溶剂，进行丙交酯的开环聚合，将PLA链段接枝至PDA NPs的表面，制备得到PDA NPs-PLA复合纳米粒子；最后通过溶液浇铸复合成型，待溶剂挥发后，真空干燥24h至恒重，制备得到PLA/PDA NPs-PLA复合材料。
其中，通过控制氨水的添加量为0.5～3.5 L，所制备得到的PDA NPs的粒径可以控制在550～100nm；PDA NPs与LA的投料质量比为1:20～1:100，催化剂辛酸亚锡的用量为单体(LA)的1wt％，反应温度为130℃，得到PDA NPs-PLA复合纳米粒子；将其均匀分散在PLA基质中，并使聚乳酸/聚乳酸接枝聚多巴胺复合材料中PDA NPs-PLA的含量为0.5～3wt％。
本发明的有益效果：
本发明为更好地改善PDA NPs与PLA基材间的相容性，设计发明了一种聚乳酸/聚乳酸接枝聚多巴胺复合材料的制备方法，利用多氧化自聚得到的聚多巴纳米粒子(PDANPs)为引发剂，开环丙交酯(LA)聚合，得到聚乳酸接枝聚多巴胺复合纳米粒子(PDA NPs-PLA)，再将其与PLA基材复合成型，制备得到了聚乳酸/聚乳酸接枝聚多巴胺(PLA/PDA NPs-PLA)复合材料。
本发明以多巴胺为原料，自聚后的PDA NPs中含有羟基可开环丙交酯得到表面接枝聚乳酸链段的PDA纳米粒子，再将其与聚乳酸复合得到纳米粒子分散良好的复合材料。所得复合材料的冷结晶温度可降低至110℃以下，对UVA和UVB的紫外屏蔽率可达到92％以上，最高可达99％，在包装材料、农用材料、工程塑料、生物医用材料等领域有潜在的应用。
附图说明
图1为本发明PDA NPs-0.5(a)，PDA NPs-1.0(b)，PDA NPs-1.5(c)，PDA NPs-3.5(d)，PDA NPs-0.5-PLA-100(e)，PDA NPs-1.0-PLA-100(f)，PDA NPs-1.5-PLA-100(g)和PDANPs-3.5-PLA-100(h)的扫描电镜照片示意图；
图2 LA/PDA NPs-PLA复合材料的制备示意图；
图3 PLA和PLA/PDA NPs-PLA-100复合材料的紫外屏蔽性。
具体实施方式
下面结合附图和实施例，对本发明进行具体描述。
实施例1、聚多巴胺纳米粒子(PDA NPs)的制备
准确量取4 L无水乙醇与9 L的去离子水并将其混合，再移取0.5 L的氨水加入到混合溶液中，并将混合溶液置于30℃的水浴锅中加热搅拌。称取50g盐酸多巴胺(DA)并用1mL去离子水溶解后加入到上述混合溶液中，反应24h。将反应后的混合液用去离子水洗涤三次、离心并冷冻干燥待用，所制备的聚多巴胺纳米粒子记作PDA NPs-0.5，粒径为550nm，其扫描电镜图见图1中(a)，其表面光滑。
需要说明的是，当氨水的用量为1 L、1.5 L和3.5 L，所制备的聚多巴胺纳米粒子分别记作PDA NPs-1.0、PDA NPs-1.5和PDA NPs-3.5，粒径分别为370nm、270nm、150nm，扫描电镜图分别见图1中(b)、(c)、(d)，其特征如图1中(a)基本一致。
实施例2、PDA NPs-PLA复合纳米粒子的制备
称取1g先前合成的PDA NPs-0.5并将其分散在40mL无水甲苯中，将分散液移入100mL三口烧瓶中并加热至50℃，再加入100g的丙交酯(LA)，持续搅拌待丙交酯完全溶解后，通入N2排出空气，再加入1wt％异辛酸亚锡(Sn(Oct)2)并升温至130℃冷凝回流反应24h；反应结束后用氯仿离心洗涤三次以除去未反应的单体和副产物；将所得的产物在60℃下真空干燥24h待用，所制备的纳米粒子为聚乳酸接枝聚多巴胺纳米粒子，记作PDA NPs-0.5-PLA-100，扫描电镜图如图1中(e)所示，其粒径略有增加，约为600nm，但其表面稍变粗糙，表明PLA接枝至PDA NPs表面。
需要说明的是，PDA NPs可以是PDA NPs-0.5、PDA NPs-1.0、PDA NPs-1.5和PDANPs-3.5；当丙交酯的用量为20g、50g、80g、100g时，所得的纳米粒子分别记作PDA NPs-n-PLA-20、PDA NPs-n-PLA-50、PDA NPs-n-PLA-80、PDA NPs-n-PLA-100，其中n为0.5，1.0，1.5或3.5。
实施例3、聚乳酸/聚乳酸接枝聚多巴胺(PLA/PDA NPs-PLA)复合材料的制备称取250mg PDA NPs-PLA并将其分散在0.7 L CHCl3中，充分分散后，向其中加入50g PLA，静置待PLA充分溶解后，再轻微搅拌使各组分充分分散，最后将混合液浇铸成型；将培养皿静置待溶剂挥发后，放入60℃真空干燥至恒重，得到PDA NPs-PLA 质量分数为0.5％的PLA/PDANPs-PLA复合材料，记作PLA/PDA NPs-PLA-0.5％。
需要说明的是，当PDA NPs-PLA的质量为500mg、1g和1.5g时，纳米粒子的质量分数分别为1％、2％和3％，并分别记作PLA/PDA NPs-PLA-1％、PLA/PDA NPs-PLA-2％和PLA/PDANPs-PLA-3％。
当在PLA中加入PDA NPs-PLA，其所得聚乳酸/聚乳酸接枝聚多巴胺纳米复合材料具有优异的紫外屏蔽性能，对UVA和UVB的紫外屏蔽率可达到92％以上。当加入PDA NPs-0.5-PLA-100为1％时，对UVA和UVB的紫外屏蔽率达到最佳，为99％。
Claims (6)
1.一种聚乳酸/聚乳酸接枝聚多巴胺复合材料的制备方法，其特征在于，所述制备方法包括如下步骤：
(1)以多巴胺氧化自聚制备得到的聚多巴胺纳米粒子为引发剂，丙交酯开环聚合得到聚乳酸接枝的聚多巴胺纳米粒子，称为聚乳酸接枝聚多巴胺复合纳米粒子；
(2)以聚乳酸为连续相，聚乳酸接枝聚多巴胺复合纳米粒子为纳米填料，两者复合制备得到聚乳酸/聚乳酸接枝聚多巴胺复合材料。
2.根据权利要求1所述的制备方法，其特征在于，所述聚多巴胺纳米粒子的粒径为100～550nm。
3.根据权利要求1所述的制备方法，其特征在于，所述开环聚合反应的过程中所述聚多巴胺纳米粒子与丙交酯的质量比为1:20～1:100，聚乳酸接枝聚多巴胺复合纳米粒子表示为PDA NPs-PLA。
4.根据权利要求1所述的制备方法，其特征在于，所述聚乳酸/聚乳酸接枝聚多巴胺复合材料中PDA NPs-PLA的含量为0.5～3wt％。
5.根据权利要求1所述的制备方法，其特征在于聚乳酸/聚乳酸接枝聚多巴胺纳米复合材料冷结晶温度可降低至110℃以下；且具有紫外屏蔽性能，对UVA和UVB的紫外屏蔽率可达到92％以上。
6.根据权利要求5所述的制备方法，其特征在于所述聚乳酸/聚乳酸接枝聚多巴胺纳米复合材料对UVA和UVB的紫外屏蔽率最高可达99％。
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