2024-11-18 作者：wff 来源：文献：
基于悉尼酮—马来酰亚胺点击化学环状聚合物的制备及研究
文献链接：
https://kns.cnki.net/kcms2/article/abstract?v=nk1fxLknOKhHJ4wiVmRdR6hBxR3Qa4KOvY3hAbgq8sWuSU6RsGascuHOOYQO-cukH2dbzHA5CnHTw7AJqprTVvhW2zMZYMkAhon6C7WANpCIIX8E-P7XK4IygpKD5TsLfaD6FPoD3ZGwz0uGNJcMmCZeCFUlkZs2_CAKTzgXZaGI7og74o4_RARdO3xaphPriy97ge4NCVk=&uniplatform=NZKPT&language=CHS
作者：
刘玉萍
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原文摘要：
Cyclic polymers, due to the lack of end groups, reduce the entanglement between molecular chains and exhibit many specific properties compared to corresponding linear precursors, making them polymers with special structures. Due to the difficulties in synthesis and subsequent separation and purification, there are currently not many methods used for the preparation of cyclic polymers. The "Click" reaction between the two end groups of linear polymers, also known as the coupling reaction between the two end groups, is one of the ring closing methods of linear polymers. The coupling reactions currently used in cyclization reactions include the "1,3-dipolar cycloaddition" reaction between azide and alkyne, the "Diels Alder" (4+2) cycloaddition reaction, and the "Thiol ene" addition reaction. These intermolecular or intramolecular cyclization reactions used to prepare cyclic polymers typically require very dilute concentration conditions, and experiments often require the use of peristaltic pumps. Intermolecular cyclization reactions require strict control of the feed ratio of linear polymers and coupling agent small molecules, and the use of catalysts makes post-treatment more complicated and reduces the yield of cyclization products.
该文献利用悉尼酮(sydnone)与马来酰亚胺(maleimide)间特有的双环加成反应(SMDC)合成环状聚合物。通过分子设计制备了亲水性的单环聚环氧乙烷(c-PEO)和两亲性的蝌蚪形聚合物(l-PCL-c-PEO99-l-PCL)。将悉尼酮与马来酰亚胺间的SMDC反应引入到环状聚合物的合成中,会有以下优点:降低偶联剂小分子的官能团浓度,其浓度为常见分子间关环偶联剂小分子的一半,减少了分子间副反应的发生;对环状聚合物的制备无需采用蠕动泵的滴加方式可以一次投料且无需严格控制反应物投料比;反应不需催化剂,后处理的纯化过程简单。
图为：DBCO-MAL结构式
对聚环氧乙烷的两端的羟基进行改性修饰,使其两端均以马来酰亚胺基团封端,然后利用悉尼酮与马来酰亚胺间的1,3-偶极双环加成反应(SMDC),制备了两种不同分子量的亲水性单环聚合物,并系统探讨了反应时间、温度、浓度对单环聚合物制备的影响。聚合物样品的化学结构和分子量通过1HNMR、GPC、MALDT-TOF MS进行表征测试。
以羟基封端的聚环氧乙烷为原料,通过分子设计制备了以马来酰亚胺封端并含有两个活性羟基的聚环氧乙烷长链为线状前驱体,然后利用悉尼酮与马来酰亚胺基团间SMDC反应进行关环。随后分别通过线状前驱体与单环上的羟基与己内酯单体进行开环聚合反应(ROP)制备了带有不同链段长度的聚己内酯的两亲性蝌蚪形聚合物l-PCL-c-PE099-l-PCL(e1-4)和两亲性嵌段共聚物PCL-b-PEO99-b-PCL(f1-4),聚合物的化学结构和分子量通过1H NMR、GPC、MALDT-TOF MS进行表征。通过TEM对两亲性的蝌蚪形聚合物和嵌段共聚物的自组装行为进行了初步研究。此外还通过DSC对比研究了线状前驱体、单环及蝌蚪状共聚物和嵌段共聚物的热性能。
