CN104558504B - 一种聚乳酸‑聚乙二醇共聚物的制备方法 - Google Patents

一种聚乳酸‑聚乙二醇共聚物的制备方法 Download PDF

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CN104558504B
CN104558504B CN201510011315.0A CN201510011315A CN104558504B CN 104558504 B CN104558504 B CN 104558504B CN 201510011315 A CN201510011315 A CN 201510011315A CN 104558504 B CN104558504 B CN 104558504B
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王治
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YANGLING RUIFENG ENVIRONMENTAL PROTECTION TECHNOLOGY Co Ltd
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Abstract

本发明公开了一种聚乳酸‑聚乙二醇共聚物的制备方法，其在氮气气氛下，将乳酸在80～100℃加热，减压脱水得到聚乳酸；在聚乳酸中加入聚乙二醇和催化剂，经反应得到端羟基改性聚乳酸；在端羟基改性聚乳酸中再加入聚乙二醇、扩链剂，经反应得到聚乳酸‑聚乙二醇共聚物。本发明乳酸经聚合后参与共聚反应，不易发生蒸发而损耗，获得的共聚物分子链中，因同时含有亲脂性的乳酸硬段和亲水性的聚乙二醇软段，具有一定的柔韧性和良好的亲水性。

Description

一种聚乳酸-聚乙二醇共聚物的制备方法
技术领域
本发明涉及一种聚乳酸-聚乙二醇共聚物的制备方法，属于高分子合成技术领域。
背景技术
聚乳酸（PLA）是一种可生物降解的热塑性聚合物，在外科手术修复、药物运输***、组织工程等领域具有广阔的应用前景。但因其结晶度较高、质硬而韧性差，因分子中含有大量疏水性的酯键，降低了它的生物相容性，限制了应用领域和效果。因此，采用增塑、共聚、共混、分子修饰、复合等对聚乳酸进行改性成为目前研究的热点。
聚乙二醇（PEG）具有较好的两亲性、生物相容性和端基反应性，分子量范围广、选择余地大，并被美国批准可用于人体， 故作为最常用的聚乳酸改性手段之一， 聚乙二醇改性聚乳酸日益受到重视。聚乙二醇改性聚乳酸可有效提高其亲水性能，从而有效提高材料的生物相容性。聚乙二醇改性聚乳酸的方法主要分为共混改性和共聚改性两种。上海交通大学，武汉理工大学，浙江工业大学等对聚乙二醇共混改性聚乳酸就行了研究，结果表明，聚乙二醇的加入明显提高了聚乳酸的结晶速度，可有效提高聚乳酸改性材料的断裂伸长率，玻璃化温度降低，聚乳酸分子链间作用力减弱，常温塑性增强，并提高聚乳酸在土壤中的水解速率，从而加快其降解速率。
发明内容
本发明的目的在于提供一种易于生物降解和较好加工性能的聚乳酸-聚乙二醇共聚物的制备方法。
本发明的实现过程如下：
一种聚乳酸-聚乙二醇共聚物的制备方法，包括以下步骤：
（1）在氮气气氛下，将乳酸在80～100℃加热，减压脱水得到聚乳酸；
（2）在聚乳酸中加入聚乙二醇和催化剂，经反应得到端羟基改性聚乳酸；
（3）在端羟基改性聚乳酸中再加入聚乙二醇、扩链剂，经反应得到聚乳酸-聚乙二醇共聚物。
上述步骤（2）所述的催化剂选自辛酸亚锡或氯化亚锡，聚乙二醇分子量为200～1000（如PEG-200、PEG-400、PEG-600、PEG-800、PEG-1000），聚乳酸与聚乙二醇的质量比为6:1～10:1，反应温度为140～170℃；
步骤（3）所述的扩链剂选自1，6-六亚甲基二异氰酸酯、2，4-甲苯二异氰酸酯，端羟基改性聚乳酸、聚乙二醇及扩链剂的质量比为10～20:10～20:1～2，聚乙二醇分子量为2000～20000（如PEG-2000、PEG-4000、PEG-6000、PEG-8000、PEG-10000、PEG-20000），反应温度为160～180℃。
本发明的优点和积极效果：（1）乳酸作为原料，价廉且来源广泛；（2）在制备端羟基改性聚乳酸和聚乳酸-聚乙二醇共聚物两个不同反应阶段使用分子量不同的聚乙二醇反应，得到的产物更易于降解；（3）乳酸经聚合后参与共聚反应，不易发生蒸发而损耗；（4）获得的共聚物分子链中，因同时含有亲脂性的乳酸硬段和亲水性的聚乙二醇软段，具有一定的柔韧性和良好的亲水性。
具体实施方式
通过以下实施例对本发明作进一步说明。
实施例1
将10g乳酸在90℃反应4小时得到聚乳酸，然后加入1.5g聚乙二醇（PEG-400）和0.1g辛酸亚锡催化剂，在150℃反应10小时，得到端羟基改性聚乳酸；再加入10g聚乙二醇（PEG-12000）、1，6-六亚甲基二异氰酸酯扩链剂1g，经180℃反应5小时，得到聚乳酸-聚乙二醇共聚物。
实施例2
将10g乳酸在100℃反应4小时得到聚乳酸，然后加入1.0g聚乙二醇（PEG-800）和0.1g辛酸亚锡催化剂，在150℃反应10小时，得到端羟基改性聚乳酸；再加入8g聚乙二醇（PEG-4000）、1，6-六亚甲基二异氰酸酯扩链剂1g，经180℃反应5小时，得到聚乳酸-聚乙二醇共聚物。
实施例3
将10g乳酸在90℃反应4小时得到聚乳酸，然后加入1.5g聚乙二醇（PEG-600）和0.1g辛酸亚锡催化剂，在160℃反应10小时，得到端羟基改性聚乳酸；再加入10g聚乙二醇（PEG-20000）、1，6-六亚甲基二异氰酸酯扩链剂1g，经175℃反应5小时，得到聚乳酸-聚乙二醇共聚物。
对比实例1
将10g乳酸在90℃反应4小时得到聚乳酸，然后加入1.5g聚乙二醇（PEG-12000）和0.1g辛酸亚锡催化剂，在150℃反应10小时，得到端羟基改性聚乳酸；再加入10g聚乙二醇（PEG-12000）、1，6-六亚甲基二异氰酸酯扩链剂1g，经180℃反应5小时，得到聚乳酸-聚乙二醇共聚物。
对比实施例2
将10g乳酸在90℃反应4小时得到聚乳酸，然后加入1.5g聚乙二醇（PEG-200）和0.1g辛酸亚锡催化剂，在150℃反应10小时，得到端羟基改性聚乳酸；再加入10g聚乙二醇（PEG-200）、1，6-六亚甲基二异氰酸酯扩链剂1g，经180℃反应5小时，得到聚乳酸-聚乙二醇共聚物。
实施例4
测试不同反应条件合成得到的产品的降解性，将不同的高分子制成膜片，浸入37℃的pH=7.3的磷酸盐缓冲溶液中结果，观察膜片降解情况，如表1所示。

Claims (1)

1.一种聚乳酸-聚乙二醇共聚物的制备方法，包括以下步骤：
（1）在氮气气氛下，将乳酸在80～100℃加热，减压脱水得到聚乳酸；
（2）在聚乳酸中加入聚乙二醇和催化剂，经反应得到端羟基改性聚乳酸，所述的催化剂选自辛酸亚锡或氯化亚锡，反应温度为140～170℃；聚乙二醇分子量为200～1000，聚乳酸与聚乙二醇的质量比为6:1～10:1；
（3）在端羟基改性聚乳酸中再加入聚乙二醇、扩链剂，经反应得到聚乳酸-聚乙二醇共聚物，所述的扩链剂选自1，6-六亚甲基二异氰酸酯、2，4-甲苯二异氰酸酯；端羟基改性聚乳酸、聚乙二醇及扩链剂的质量比为10～20:10～20:1～2；聚乙二醇分子量为2000～20000，反应温度为160～180℃。
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CN105348501A (zh) * 2015-08-17 2016-02-24 宁波天益医疗器械有限公司 一种低酸值双恶唑啉扩链聚乳酸多元醇及其制备方法
CN105294970A (zh) * 2015-11-24 2016-02-03 深圳光华伟业股份有限公司 一种生物基热塑性聚氨酯弹性体材料及其的制备方法
CN105924635B (zh) * 2016-07-13 2017-12-29 蚌埠学院 锡类催化剂催化合成聚乳酸共聚改性产物的方法
CN108003321A (zh) * 2017-12-21 2018-05-08 中国科学院长春应用化学研究所 一种高分子量聚乳酸多嵌段共聚物的制备方法
CN110054875B (zh) * 2018-01-18 2021-10-29 深圳市七号科技有限公司 一种用于3d打印的聚乳酸组合物及其制备方法
CN114479139B (zh) * 2022-01-14 2023-08-25 江西冠德新材科技股份有限公司 一种纤维基降解薄膜及其制备方法

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