CN104610533B - 基于聚乳酸的可降解聚酯及其制备方法 - Google Patents
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Abstract
基于聚乳酸的新型可降解聚酯及其制备方法，属于可降解功能材料领域。本发明选择对环境无负荷的可再生资源——10‑羟基癸酸(10‑HDA)、乳酸二聚体丙交酯为主要单体，先将10‑羟基癸酸与1，4‑丁二醇缩合聚合制成大分子单体，再用大分子单体和丙交酯开环聚合制备出一种新型可降解的嵌段共聚物。通过改变原料配比、投料方式、催化剂种类与用量、以及聚合反应时间与反应温度等条件，调控聚合物的链结构与组成，得到不同相对分子量及性能的可降解聚酯。本发明制得的可降解聚酯具有优良的热性能、柔韧性和生物相容性，可控的降解周期。这种新型的可降解聚酯材料将广泛应用在包装、农业、医药等领域。
Description
技术领域
基于聚乳酸的新型可降解聚酯及其制备方法，属于可降解功能材料领域。
背景技术
近年来，随着材料科学和生物医学的不断发展以及对环境重视程度的不断增加，可降解材料广泛应用于食品包装领域和生物医学领域。可降解高分子材料废弃后，在土壤或水中，数个月内会自动在微生物、酸和碱的作用下彻底地分解成为二氧化碳和水，最后在植物的光合作用下，又会成为淀粉的起始原料，不仅不会对环境造成污染，而且还是一种完全自然循环型的可生物降解材料。
生物降解高分子材料具有无毒、可生物降解及良好的生物相容性等优点，所以其应用极为广泛，市场潜力非常大，包括医用、农业、工业包装、家庭娱乐等领域。在人工合成的可降解高分子中，聚乳酸(PLA)和聚3-羟基丁酸酯(PHB)是最具代表性的聚合物，具有生物降解性能的材料，已广泛应用在我们的日常生活中，但它们存在着性脆和热性能低的缺点；本发明利用开环聚合的方法在聚乳酸中引入长链的链段单元-10-羟基癸酸(HAD)与1，4-丁二醇的熔融缩聚产物PHDA-OH，以提高其柔韧性能和热性能，所得到的可降解聚酯具有很好的降解性能、热性能、柔韧性以及疏水性能，通过调节第一单体的配比可以实现聚合物的相对分子量、降解速度与力学性能的控制。本发明所得的可降解聚酯材料将广泛应用在包装、农业、生物医药等领域。
发明内容
本发明的目的是提供基于聚乳酸的新型可降解聚酯及其制备方法，使其具有良好的降解性、热性能和柔韧性，以具有更广泛的应用前景。
本发明的技术方案：基于聚乳酸的新型可降解聚酯的制备方法，其特征在于以10-羟基癸酸(10-HDA)和1，4-丁二醇(BDO)熔融缩合聚合合成大分子单体PHDA-OH，以乳酸二聚体丙交酯为第二单体，采用开环聚合的方法得到新型的可降解聚酯；
配比为：合成大分子单体，10-羟基癸酸：1，4-丁二醇(摩尔比)为50～150∶1；合成可降解嵌段共聚物，大分子单体：丙交酯(摩尔比)为1∶100。
所得共聚物的结构为：
表示成PLA-b-PHD-b-PLA。
通过红外光谱仪、核磁共振仪、差示扫描量热仪、凝胶渗透色谱仪、热重分析仪等表征方法对所得聚酯的结构和性能进行表征，结果表明聚合物结构明确，具有较好的生物降解性能、热性能与力学性能。
本发明的有益效果：根据本发明制备的可降解聚酯具有优异的热稳定性、可降解性能和力学性能等；可以通过调节第一单体的配比和反应参数，控制热分解温度在240℃以上，在pH 7.4的磷酸盐缓冲溶液中75天后质量减少了25％，拉伸强度在40Mpa以上，模量大于1750Mpa，断裂伸长率～600％。本发明制得的聚合物具有很好的可降解性以及力学性能，可作为智能可降解材料广泛应用在包装、环保和组织工程等领域。
附图说明
图1大分子单体PHDA-OH(a)及共聚物PLA-b-PHD-b-PLA(b)的核磁谱图。
具体实施方式
实施例1：合成大分子单体PHDA-OH
HDA与BDO投料比为125∶1时，具体实验步骤如下。准确称量HDA固体5.6478g(30mmol)于双口烧瓶中，将双口烧瓶置于油浴锅中，搭建减压蒸馏装置，设置温度控制仪的温度在80℃使油浴锅保持恒温，而后在氮气的保护下使其熔化成液体，反应大概进行1个小时。再称取固体BDO 0.0216g(0.24mmol)、催化剂p-TSA和SnCl2·2H2O分别为0.0283g和0.0371g加入其中，升温至110℃，使反应进行2个小时。之后再将温度升高至150℃，继续反应3个小时。之后，将通氮气的装置撤离，在整个装置的尾端换接上高压泵，使整个装置处于真空的状态中，此时压强约为200～500Pa。将温度升高至180℃，进行减压蒸馏以得到中间产物PHDA-OH，此蒸馏过程约2个小时。接下来是将蒸馏得到的液体进行提纯，先将得到的液体降温至50℃以下，再加入氯仿CHCl3溶解，再用冰甲醇CH3OH使其中的PHDA-OH沉淀。将得到的沉淀用甲醇溶液洗涤三次，再将其放入40℃的烘箱中烘干24个小时。即得到纯净的第一单体PHDA-OH。
实施例2、合成嵌段共聚物PLA-b-PHD-b-PLA
称取丙交酯2.1620g置于两口烧瓶中，调节油浴锅的温度至100℃，使烧瓶中的丙交酯充分熔融。待其熔融后，向烧瓶中加入0.8052g的低聚物，搭建冷凝回流装置，再向其中加入15ml的二甲苯做溶剂，用1滴辛酸亚锡做催化剂，通氮气，使整个反应装置处于100摄氏度的温度下反应1h，1h之后调节温度至150℃反应24小时。反应结束后，升温至180℃，在真空中减压蒸馏4小时，除 掉二甲苯溶剂，即可得到最终产物三嵌段共聚酯。再对得到的产物进行提纯，先将得到的液体降温至50℃以下，再加入氯仿CHCl3溶解，再用冰甲醇CH3OH使其中的共聚物沉淀。将得到的沉淀用甲醇溶液洗涤三次，再将其放入40℃的烘箱中烘干24个小时。即可得到纯净的共聚酯PLA-b-PHD-b-PLA。
Claims (3)
1.基于聚乳酸的可降解聚酯，其特征在于以10-羟基癸酸和1，4-丁二醇熔融缩合聚合制备得到大分子单体，以乳酸二聚体——丙交酯为第二单体，采用开环聚合的方法得到的可降解聚酯；
合成大分子单体的摩尔配比为，10-羟基癸酸：1，4-丁二醇为50～150∶1；合成可降解嵌段共聚物的摩尔配比为，大分子单体：丙交酯为1∶100。
2.根据权利要求1所述的可降解聚酯，其特征是以10-羟基癸酸和1，4-丁二醇合成大分子单体，以丙交酯为第二单体时，所得共聚物的结构为：
表示成PLA-b-PHD-b-PLA。
3.根据权利要求2所述的可降解聚酯，其特征在于该聚酯具有很好的可降解性、热性能以及疏水性能，通过调节合成第一单体的配比和聚合反应参数可以实现聚合物的相对分子量、降解速度、热性能与力学性能的控制；制得的可降解聚酯可作为食品包装材料、农用地膜、手术缝合线和药物缓释载体而广泛应用于相关领域。
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| CN101787115A (zh) * | 2009-12-28 | 2010-07-28 | 江南大学 | 一种具有光活性的三元双亲性聚酯的制备方法 |
| CN104140522A (zh) * | 2014-06-27 | 2014-11-12 | 江南大学 | 一种可降解的聚羟基脂肪酸酯 |
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| CN101787115A (zh) * | 2009-12-28 | 2010-07-28 | 江南大学 | 一种具有光活性的三元双亲性聚酯的制备方法 |
| CN104140522A (zh) * | 2014-06-27 | 2014-11-12 | 江南大学 | 一种可降解的聚羟基脂肪酸酯 |
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| Amphiphilic multi-arm block copolymer based on hyperbranched polyester, poly (L-lactide) and poly (ethylene glyol) as a drug delivery carrier;Mani Prabaharan et al.;《Macromolecular bioscience》;20081216;第9卷(第5期);第515-524页 * |
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