CN107011505A - 一种聚乳酸多孔微球的制备方法 - Google Patents

一种聚乳酸多孔微球的制备方法 Download PDF

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CN107011505A
CN107011505A CN201710125660.6A CN201710125660A CN107011505A CN 107011505 A CN107011505 A CN 107011505A CN 201710125660 A CN201710125660 A CN 201710125660A CN 107011505 A CN107011505 A CN 107011505A
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邓建平
杨博文
雍学勇
黄骅隽
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Beijing University of Chemical Technology
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Abstract

一种聚乳酸多孔微球的制备方法属于高分子材料领域，本发明提供一种基于沉淀聚合制备可控孔径聚乳酸微球材料的制备方法，以L‑丙交酯为原料，以1,8‑二氮杂二环十一碳‑7‑烯(DBU)作为催化剂，乙二醇作为引发剂，乙酸乙酯为溶剂通过沉淀聚合制备聚乳酸多孔微球，并通过加入D‑丙交酯来达到调控微球尺寸及孔隙的目的，本发明所得微球制备过程操作简便，后处理简单，微球粒径分布均匀，形貌多孔，比表面积大，微球尺寸及形貌可控，材料结晶度可调，是一种理想的多孔生物材料，可用于生物医药载体、组织工程材料等领域。

Description

一种聚乳酸多孔微球的制备方法
技术领域
本发明属于高分子材料领域，涉及一种新型聚乳酸多孔微球的制备方法。
背景技术
随着科学技术的发展，人们对于生物材料的需求日益增多。其中，聚乳酸已经成为最重要的合成高分子生物材料之一。由于其生物亲和性、生物可降解性、无毒性及优异的机械性能，聚乳酸材料被广泛应用于包装材料、药物载体以及组织工程材料。这些材料已经被批准用于人体当中，极大地促进了聚乳酸材料的发展。
对于现有的聚乳酸微球载药材料或是组织工程材料，制备方法大多是先通过丙交酯聚合成一定分子量的聚乳酸，再通过乳化、冻干、洗涤等步骤获得一定形貌的聚乳酸材料。这些聚乳酸材料存在制备工艺流程长、产品质量不均一、后处理复杂等缺点。对于组织工程材料，还有孔结构控制困难的问题。这些缺点严重制约了聚乳酸材料的发展及应用。
本发明基于以上背景及问题，利用丙交酯在1,8-二氮杂二环十一碳-7-烯(DBU)的催化下合成聚乳酸，并通过沉淀聚合的方式直接制备聚乳酸多孔材料，实现了从原料直接制备材料，简化了工艺流程。这种聚乳酸多孔微球的制备方法具有简便易行，后处理简单，所获微球的尺寸、表面多孔结构、材料结晶度可控等特点。其具有多孔结构，可广泛应用于生物医药材料领域。
发明内容
针对聚乳酸多孔材料的应用前景，本发明的目的是提供一种工艺流程简单、粒径及形貌可控的聚乳酸多孔微球的制备方法。
本发明的技术方案：通过沉淀聚合制备聚乳酸多孔微球，以DBU为催化剂，乙二醇为引发剂，丙交酯在乙酸乙酯为溶剂下发生聚合，同时利用聚乳酸在乙酸乙酯中的相分离过程，形成微米级微球并形成狭缝空隙，其中，通过调整L-丙交酯与D-丙交酯的比例，达到调整微球粒径及形貌的目的；
一种聚乳酸多孔微球的制备方法，其特征在于，包括如下步骤：
(1)将一定量的丙交酯单体加入到试管中，抽排试管中的空气并通入氮气，在氮气保护下加入乙酸乙酯作为溶剂，超声溶解丙交酯，待完全溶解后加入含引发剂及催化剂的乙酸乙酯溶液，丙交酯与引发剂与催化剂的摩尔比为70:1:1；丙交酯的质量分数为20％～30％；
(2)将上述含混合溶液的试管置于0～30度冰浴锅中，反应1～4小时后取出，所得产物经过过滤分离后用乙醇清洗，并于45度真空干燥箱中干燥至恒重，最终得到聚乳酸多孔微球。
进一步，所述的丙交酯是L-丙交酯、D-丙交酯或二者按一定比例组成的混合物，混合物中L-丙交酯或D-丙交酯质量分数不低于85％。
进一步，引发剂采用乙二醇、聚乙二醇，催化剂采用1,8-二氮杂双环十一碳-7-烯、N-甲基-1,5,7-三氮杂双环[4.4.0]癸-5-烯、4-N,N-二甲氨基吡啶。
所制备的聚乳酸多孔微球的粒径、表面多孔结构、表面积及材料结晶度是通过调节两种丙交酯质量比来控制；随着D-丙交酯含量的增加，材料结晶度随之减小，微球粒径逐渐减小，比表面积增大。
本发明的有益效果：
本发明所得微球制备过程操作简便，后处理简单，微球粒径分布均匀，形貌多孔，且粒径及形貌在一定范围内可控，是一种理想的聚乳酸多孔材料，可用于生物医药载体、组织工程材料等领域。
附图说明
图1：实例1中聚乳酸多孔微球的扫描电镜图像
图2：丙交酯比例对微球尺寸及表面空隙结构的影响。
图3：实施例1～6的差示扫描热分析曲线。
图4：实施例1～6的X射线衍射图像。
具体实施方式
图1为实例1中聚乳酸多孔微球的扫描电镜照片，如图所示，微球具有良好的球形，且粒径分布较为均一，表面富有狭缝状的孔隙结构。
图2为实例1、3、6中制备微球整体及表面放大的扫描电镜照片，如图所示，不同丙交酯比例的微球均具有规整的球形以及表面狭缝孔隙结构。并且通过调整丙交酯比例(L-丙交酯与D-丙交酯的质量比从40:0到35:5)，微球的粒径从115微米到20微米变化，微球表面的孔隙结构随着D-丙交酯含量的增加而逐渐减小。
图3为实例1～6中微球A的差示扫描热分析曲线，所得微球的结晶度在19％～55％之间，随着原料D-丙交酯含量的增加，由于破坏了聚左旋乳酸的结晶结构，微球的熔点及结晶度都随之减小。
图4为实例1～6中微球的X射线衍射图像，所得到聚乳酸多孔微球的结晶结构均为典型的α晶型，衍射角分别在12.3、14.9、16.8、19.1、22.3度，与之相对应的衍射晶面分别是(004)和(103)、(010)、(200)和(110)、(014)和(203),以及(015)。
下面给出本发明的具体实施例：
实例1：取0.4g L-丙交酯于试管中，反复抽排空气通入氮气三次，保证试管中为氮气气氛，加入0.6mL预先除水的乙酸乙酯溶剂，超声溶解，取0.0105g DBU催化剂及0.006g乙二醇溶解于0.4mL乙酸乙酯中，并在氮气保护下注入上述试管中，进一步超声至体系均一，将试管置于0度冰浴锅中反应2小时。所得产物经过滤分离后用乙醇清洗三次，并于℃45℃真空干燥箱中干燥至恒重，最终得到聚乳酸多孔微球；
所得微球其粒径在115微米，结晶度为54.4％，粒径均一，表面多孔，扫描电镜图像如图1所示。
实例2：取0.39g L-丙交酯和0.01g D-丙交酯于试管中，反复抽排空气通入氮气三次，保证试管中为氮气气氛，加入0.6mL预先除水的乙酸乙酯溶剂，超声溶解，取0.0105gDBU催化剂及0.006g乙二醇溶解于0.4mL乙酸乙酯中，并在氮气保护下注入上述试管中，进一步超声至体系均一，将试管置于0度冰浴锅中反应2小时。所得产物经过滤分离后用乙醇清洗三次，并于45℃真空干燥箱中干燥至恒重，最终得到聚乳酸多孔微球；
所得微球其粒径在89微米，结晶度为49.1％，粒径均一，表面多孔。
实例3：取0.38g L-丙交酯和0.02g D-丙交酯于试管中，反复抽排空气通入氮气三次，保证试管中为氮气气氛，加入0.6mL预先除水的乙酸乙酯溶剂，超声溶解，取0.0105gDBU催化剂及0.006g乙二醇溶解于0.4mL乙酸乙酯中，并在氮气保护下注入上述试管中，进一步超声至体系均一，将试管置于0度冰浴锅中反应2小时。所得产物经过滤分离后用乙醇清洗三次，并于45℃真空干燥箱中干燥至恒重，最终得到聚乳酸多孔微球；
所得微球其粒径在70微米，结晶度为40.4％，粒径均一，表面多孔，扫描电镜图像如图2-b所示。
实例4：取0.37g L-丙交酯和0.03g D-丙交酯于试管中，反复抽排空气通入氮气三次，保证试管中为氮气气氛，加入0.6mL预先除水的乙酸乙酯溶剂，超声溶解，取0.0105gDBU催化剂及0.006g乙二醇溶解于0.4mL乙酸乙酯中，并在氮气保护下注入上述试管中，进一步超声至体系均一，将试管置于0度冰浴锅中反应2小时。所得产物经过滤分离后用乙醇清洗三次，并于45℃真空干燥箱中干燥至恒重，最终得到聚乳酸多孔微球；
所得微球其粒径在43微米，结晶度为35.5％，粒径均一，表面多孔。
实例5：取0.36g L-丙交酯和0.04g D-丙交酯于试管中，反复抽排空气通入氮气三次，保证试管中为氮气气氛，加入0.6mL预先除水的乙酸乙酯溶剂，超声溶解，取0.0105gDBU催化剂及0.006g乙二醇溶解于0.4mL乙酸乙酯中，并在氮气保护下注入上述试管中，进一步超声至体系均一，将试管置于0度冰浴锅中反应2小时。所得产物经过滤分离后用乙醇清洗三次，并于45℃真空干燥箱中干燥至恒重，最终得到聚乳酸多孔微球；
所得微球其粒径在32微米，结晶度为23.4％，粒径均一，表面多孔。
实例6：取0.35g L-丙交酯和0.05g D-丙交酯于试管中，反复抽排空气通入氮气三次，保证试管中为氮气气氛，加入0.6mL预先除水的乙酸乙酯溶剂，超声溶解，取0.0105gDBU催化剂及0.006g乙二醇溶解于0.4mL乙酸乙酯中，并在氮气保护下注入上述试管中，进一步超声至体系均一，将试管置于0度冰浴锅中反应2小时。所得产物经过滤分离后用乙醇清洗三次，并于45℃真空干燥箱中干燥至恒重，最终得到聚乳酸多孔微球；
所得微球其粒径在20微米，结晶度为19.1％，粒径均一，表面多孔，扫描电镜图像如图2-c所示。

Claims (4)

1.一种聚乳酸多孔微球的制备方法，其特征在于，包括如下步骤：
(1)将一定量的丙交酯单体加入到试管中，抽排试管中的空气并通入氮气，在氮气保护下加入乙酸乙酯作为溶剂，超声溶解丙交酯，待完全溶解后加入含引发剂及催化剂的乙酸乙酯溶液，丙交酯与引发剂与催化剂的摩尔比为70:1:1；丙交酯的质量分数为20％～30％；
(2)将上述含混合溶液的试管置于0～30度冰浴锅中，反应1～4小时后取出，所得产物经过过滤分离后用乙醇清洗，并于45度真空干燥箱中干燥至恒重，最终得到聚乳酸多孔微球。
2.根据权利要求1所述制备方法，其特征是：所述的丙交酯是L-丙交酯、D-丙交酯或二者按一定比例组成的混合物，混合物中L-丙交酯或D-丙交酯质量分数不低于85％。
3.根据权利要求1所述制备方法，其特征是：引发剂采用乙二醇、聚乙二醇，催化剂采用1,8-二氮杂双环十一碳-7-烯、N-甲基-1,5,7-三氮杂双环[4.4.0]癸-5-烯、4-N,N-二甲氨基吡啶。
4.应用如权利要求1-3任意一项所述方法，其特征是：所制备的聚乳酸多孔微球的粒径、表面多孔结构、表面积及材料结晶度是通过调节两种丙交酯质量比来控制；随着D-丙交酯含量的增加，材料结晶度随之减小，微球粒径逐渐减小，比表面积增大。
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