A DFT Study on Ring Opening Polymerization Driven by Ring Strain of Cyclic Ethers

Jun-hua LIU; Jun LING

doi:10.14028/j.cnki.1003-3726.2015.01.014

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A DFT Study on Ring Opening Polymerization Driven by Ring Strain of Cyclic Ethers

更新时间：2022-09-18

- A DFT Study on Ring Opening Polymerization Driven by Ring Strain of Cyclic Ethers
- Polymer Bulletin Vol. 28, Issue 1, Pages: 80-83(2015)
- 作者机构：
  
  教育部高分子合成与功能构造重点实验室　浙江大学高分子科学与工程学系，杭州　310027
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2015.01.014
  CLC：
- Published：2015-01，
  
  Received：19 December 2013，
  
  Revised：27 September 2014，
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Jun-hua LIU, Jun LING. A DFT Study on Ring Opening Polymerization Driven by Ring Strain of Cyclic Ethers. [J]. Polymer Bulletin 28(1):80-83(2015)
DOI：

Jun-hua LIU, Jun LING. A DFT Study on Ring Opening Polymerization Driven by Ring Strain of Cyclic Ethers. [J]. Polymer Bulletin 28(1):80-83(2015) DOI： 10.14028/j.cnki.1003-3726.2015.01.014.

摘要

高分子化学教学中

在向学生讲授环状单体开环聚合驱动力时

单体的环张力是决定其能否进行开环聚合的一个非常重要的热力学因素

但有时并非是根本因素。在部分教材上提及顺式-和反式-8-氧杂双环[4.3.0]壬烷(I)、顺式-和反式-7

9-二氧杂双环[4.3.0]壬烷(II)两对顺反异构体时

都认为它们是由于反式异构体环张力大而易于开环聚合。本文通过密度泛函理论(Density Functional Theory

DFT)方法分别计算了它们发生开环聚合的Gibbs自由能变化

发现前者I单体两个异构体能量非常接近

不存在环张力大小的区别

而反式异构体开环产物在能量上更加稳定

利于开环过程。后者II单体则确实是因为反式环状单体的环张力比顺式异构体高

从而有利于开环聚合。本文希望通过这两个实例的DFT计算

阐明这两种不同的机理

并且向学生们介绍量子化学计算方法。

Abstract

In the ring-opening polymerization chapter of the course Polymer Chemisty

students are told that ring strain is a driving force and an important thermodynamic parameter to determine whether a cyclic monomer can be polymerized or not. However

it is not always the truth. Some textbooks use two cis-and trans-isomers as examples

which are cis- and trans-8-oxabicyclo[4.3.0]-nonane (I) and cis- and trans-7

9-dioxabicyclo[4.3.0]-nonane (II)

and consider ring-strain as the only reason why trans-isomer is easier than the corresponding cis-one in both cases. In this work

we calculate the changes of Gibbs free energy of two ring-opening reactions with density functional theory (DFT). The Gibbs energies of cis-and trans-isomers I are very close to each other without difference in ring strain. Instead

the product of trans-isomer after ring opening reaction is more stable than that of cis-isomer by 1.81kcal/mol of ΔG. In contrary

the ring of trans-II is easier to be opened than that of cis-II because of higher ring strain by 3.00kcal/mol of ΔG. The above two different mechanisms are to be explained in class. DFT calculation are to be introduced as well.

关键词

开环聚合单体环张力热力学因素密度泛函理论

Keywords

Ring-opening polymerizationRing-strain of cyclic monomerThermodynamic parameterDensity functional theory

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