CN111925509A - 一种聚己内酯的合成方法 - Google Patents

一种聚己内酯的合成方法 Download PDF

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CN111925509A
CN111925509A CN202010870843.2A CN202010870843A CN111925509A CN 111925509 A CN111925509 A CN 111925509A CN 202010870843 A CN202010870843 A CN 202010870843A CN 111925509 A CN111925509 A CN 111925509A
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谢传欣
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Qingdao University of Science and Technology
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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Abstract

本发明提供了一种聚己内酯的合成方法，将环己酮、酸、适量溶剂、催化剂加入到反应器中，在50℃‑100℃条件下慢慢滴加双氧水，反应3h‑24h结束后减压蒸馏除去多余的溶剂和水，得到聚己内酯。本发明的有益效果是：成本更低，产率更高，且溶剂和反应产物容易分离，提高了聚己内酯的纯度，整个反应是环境友好的，对环境影响小。

Description

一种聚己内酯的合成方法
技术领域
本发明属于化工行业，具体涉及一种聚己内酯的合成方法。
背景技术
聚己内酯(PCL)是一种聚合型聚酯，其外观为白色固体粉末，无毒，其作为一种新型材料，具有很多其他材料无法媲美的性能，比如PCL有很好的生物相容性和生物降解性，这使其在手术缝合线、心脏支架和药物载体等医用材料上有很大的应用空间，PCL还因其高结晶性和低熔点性在涂料、粘合剂、增塑剂等方面有很大的用途，所以PCL的合成成为目前的研究热点。
目前大多数文献和专利都是以ε-己内酯、引发剂和催化剂合成PCL，如CN108424512A、CN108912316A、CN109054001A等，ε-己内酯的催化体系可分为阴离子催化剂、阳离子催化剂、配位催化剂和酶催化剂这四类，但是这种方式最大的问题是ε-己内酯的来源和价格，国内ε-己内酯的产量较低，难以满足国内市场的需求，所谓大多依靠国外进口，这也使得ε-己内酯的价格高居不下；未解决这个问题，也有相关文献利用乙酸乙酯、环己酮、过氧化氢在脂肪酶的作用下合成聚己内酯，但是聚己内酯的收率仅有66.1％，虽然成本降低，但收益也有所下降，本课题组之前在专利CN109836561A中过氧化物与环己酮一起加入，有一定实验危险，本试验以滴加的形式将过氧化物加入到反应体系，大大降低了反应危险性，而且本技术方案在解决成本问题的同时，收率达90％以上，大大加提高了经济效益。
发明内容
为解决上述问题，本发明提供一项具体实验方案：将环己酮、酸、适量溶剂、催化剂加入到反应器中，在50℃-100℃条件下慢慢滴加双氧水，反应3h-24h结束后减压蒸馏除去多余的溶剂和水，得到聚己内酯。
优选的是，酸选自甲酸、苯甲酸、对甲苯磺酸、丁二酸、乙酸、柠檬酸、苹果酸、酒石酸、草酸、水杨酸、咖啡酸、奎宁酸、硫酸、盐酸、丙酸中的一种或几种。
优选的是，酸的加入量为环己酮的0-20％。
优选的是，溶剂选自苯甲腈、DMF、、DMSO、THF、乙二醇单苯醚、乙腈、NMP、甲醇、环己烷、甘油、丙酮、异丙醇、庚烷、水中的一种或几种，用量为环己酮质量的50％-300％。
优选的是，催化剂选自氧化镁、硼酸、钛硅分子筛、钨酸、磷钨酸、戊酸、阳离子酸性树脂中的一种或几种。
优选的是，催化剂用量为环己酮和酸质量的0.001％-5％。
优选的是，双氧水浓度为20％-70％。
优选的是，双氧水用量为环己酮质量的50％-200％。
本发明的有益效果是：
本技术以相较于市面大多数聚己内酯产品成本更低，相较于其他合成方式产率更高，且溶剂和反应产物容易分离，提高了聚己内酯的纯度，整个反应是环境友好的，对环境影响小。
具体实施方式
下面结合实例对本发明进一步描述。但本发明的保护范围不仅限于此。
实施例1
将环己酮70g、65％的硫酸8.5g、13g甲酸和30g甲醇混合加入到250ml的三口烧瓶中，在恒压滴液漏斗中加入30％的双氧水90g(装置加热后开始滴加)，在烧瓶上加上冷凝回流和温度计，组装好实验装置，在55℃条件下反应6h，通过在烧瓶中取样滴定过氧化物的含量反映其进度，待反应结束，减压蒸馏除去多余的溶剂和水，得到聚己内酯65.7g，聚己内酯产率93.9％。
实施例2-6
环己酮60g，其余参数见表1。
实施例7-11
环己酮70g，其余参数见表1。
实施例12-16
环己酮80g，其余参数见表1。
Figure BDA0002651024320000021
Figure BDA0002651024320000031
Figure BDA0002651024320000041
从表中可以看出，聚己内酯获得率大于90％。

Claims (8)

1.一种聚己内酯的合成方法，其特征在于，将环己酮、酸、适量溶剂、催化剂混合，在50℃-100℃条件下慢慢滴加双氧水，反应3h-24h结束后减压蒸馏除去多余的溶剂和水，得到聚己内酯。
2.如权利要求1所述一种聚己内酯的合成方法，其特征在于，酸选自甲酸、苯甲酸、对甲苯磺酸、丁二酸、乙酸、柠檬酸、苹果酸、酒石酸、草酸、水杨酸、咖啡酸、奎宁酸、硫酸、盐酸、丙酸中的一种或几种。
3.如权利要求1所述一种聚己内酯的合成方法，其特征在于，酸的加入量为环己酮的0-20％。
4.如权利要求1所述一种聚己内酯的合成方法，其特征在于，溶剂选自苯甲腈、DMF、、DMSO、THF、乙二醇单苯醚、乙腈、NMP、甲醇、环己烷、甘油、丙酮、异丙醇、庚烷、水中的一种或几种，用量为环己酮质量的50％-300％。
5.如权利要求1所述一种聚己内酯的合成方法，其特征在于，催化剂选自氧化镁、硼酸、钛硅分子筛、钨酸、磷钨酸、戊酸、阳离子酸性树脂中的一种或几种。
6.如权利要求1所述一种聚己内酯的合成方法，其特征在于，催化剂用量为环己酮和酸质量的0.001％-5％。
7.如权利要求1所述一种聚己内酯的合成方法，其特征在于，双氧水浓度为20％-70％。
8.如权利要求1所述一种聚己内酯的合成方法，其特征在于，双氧水用量为环己酮质量的50％-200％。
CN202010870843.2A 2020-08-26 2020-08-26 一种聚己内酯的合成方法 Pending CN111925509A (zh)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107266344A (zh) * 2017-07-17 2017-10-20 湘潭大学 一种过氧化环己酮的制备方法
CN109836561A (zh) * 2019-01-30 2019-06-04 青岛科技大学 一种6-羟基己酸低聚物的合成方法及其所得的低聚物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107266344A (zh) * 2017-07-17 2017-10-20 湘潭大学 一种过氧化环己酮的制备方法
CN109836561A (zh) * 2019-01-30 2019-06-04 青岛科技大学 一种6-羟基己酸低聚物的合成方法及其所得的低聚物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
况水根等: "液态过氧化环己酮的研制", 《热固性树脂》 *

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