Page 64 - 《精细化工》2023年第11期

第 40 卷第 11 期 精 细 化 工 Vol.40, No.11
2 023 年 11 月 FINE CHEMICALS Nov. 2023

功能材料
环氧烷烃与硫代内酯交替共聚制备

聚酯硫醚及其性能

*
杨寒寒，李宜宁，吕小兵
（大连理工大学 精细化工国家重点实验室，辽宁 大连 116024）

t
摘要：以金属铬配合物〔SalphCr(Ⅲ)Cl〕/双-(三苯基正膦基)氯化铵（PPNCl）/叔丁醇锂（ BuOLi）组成三组分
1
13
催化体系，实现了多种环氧烷烃与 γ-硫代丁内酯（TBL）高活性开环共聚。采用 HNMR、 CNMR、ESI-MS 及
FTIR 对聚合物结构进行了表征，考察了不同结构聚酯硫醚的热性能以及光学性能。结果表明，聚合过程中叔丁
醇锂可有效稳定链末端硫负离子，抑制其回咬，保证了反应活性以及聚合物相对分子质量。聚酯硫醚均具有完
全交替结构且呈现无定形形态，玻璃化转变温度（T g ）处于−53~−18 ℃之间，热失重 5%温度在 258300 ℃之
间。将叔丁基缩水甘油醚与 TBL 共聚物中的硫醚结构氧化为亚砜和砜时，其聚合物 T g 分别提高了 49 和 60 ℃。
顺式 2,3-环氧丁烷与 TBL 的共聚物折射率可达 1.59，表明主链中的硫原子赋予聚酯硫醚良好的光学性能。
关键词：环氧烷烃；γ-硫代丁内酯；金属铬(Ⅲ)配合物；聚酯硫醚；光学材料；功能材料
中图分类号：O633.3；TQ317 文献标识码：A 文章编号：1003-5214 (2023) 11-2376-10

Preparation and properties of poly(ester-thioether)s from alternating
copolymerization of epoxides and γ-thiobutyrolactone

*
YANG Hanhan, LI Yining, LYU Xiaobing
（State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, Liaoning, China）

Abstract: Highly active ring-opening copolymerization of different epoxides with γ-thiobutyrolactone
(TBL) was achieved by using a three-component catalytic system consisting of chromium complex
t
[SalphCr(Ⅲ)Cl], bis(triphenylphosphine)iminium chloride (PPNCl) and lithium tert-butoxie ( BuOLi). The
13
1
structure of copolymer obtained was characterized by HNMR, CNMR, ESI-MS and FTIR. And the
thermal and optical properties of the resulting poly(ester-thioether)s were further analyzed. The results
t
showed that in the polymerization process, BuOLi could effectively stabilize the negative sulfur anions at
the chain ends and suppress backbiting reaction to ensure the reaction activity and molecular weight of the
polymer. The resultant copolymers displayed perfect alternating structures and amorphous forms, with glass
transition temperatures (T g) ranging from –53 ℃ to –18 ℃ and the decomposition temperatures at 5%
mass loss between 258 and 300 ℃, showing good thermal stability. Taking the copolymer of tert-butyl
glycidyl ether and TBL as an example, the thioether was oxidized to sulfoxide and sulfone structure, and the
T g was increased by 49 and 60 ℃, respectively. The refractive index of cis-2,3-epoxybutane copolymer
with TBL can reach 1.59, indicating that the sulfur atoms in the main chain give the poly(ester-thioether)s
good optical properties.
Key words: epoxides; γ-thiobutyrolactone; chromium(Ⅲ) complex; poly(ester-thioether)s; optical materials;
functional materials

收稿日期：2023-02-15; 定用日期：2023-05-09; DOI: 10.13550/j.jxhg.20230102
基金项目：国家自然科学基金项目（21920102006）
作者简介：杨寒寒（1997—），女，硕士生，E-mail：yanghanxc@163.com。联系人：吕小兵（1970—），男，教授，E-mail：xblu@dlut.
edu.cn。