环氧烷烃与硫代内酯交替共聚制备聚酯硫醚及其性能  

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

作　　者：杨寒寒 李宜宁 吕小兵[1] YANG Hanhan;LI Yining;LYU Xiaobing(State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian 116024,Liaoning,China)

机构地区：[1]大连理工大学精细化工国家重点实验室,辽宁大连116024

出　　处：《精细化工》2023年第11期2376-2385,共10页Fine Chemicals

基　　金：国家自然科学基金项目(21920102006)。

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(tBuOLi)组成三组分催化体系,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^(1)HNMR、^(13)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。Highly active ring-opening copolymerization of different epoxides withγ-thiobutyrolactone(TBL)was achieved by using a three-component catalytic system consisting of chromium complex[SalphCr(Ⅲ)Cl],bis(triphenylphosphine)iminium chloride(PPNCl)and lithium tert-butoxie(tBuOLi).The structure of copolymer obtained was characterized by ^(1)HNMR,^(13)CNMR,ESI-MS and FTIR.And the thermal and optical properties of the resulting poly(ester-thioether)s were further analyzed.The results showed that in the polymerization process,tBuOLi 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.

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 

分 类 号：O633.3[理学—高分子化学] TQ317[理学—化学]