Selective synthesis of cyclic-polymer-free poly(ether sulfone)s with OH ends or F ends by non-stoichiometric, reversible polycondensation,Polymer Chemistry

当前位置： X-MOL 学术 › Polym. Chem. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Selective synthesis of cyclic-polymer-free poly(ether sulfone)s with OH ends or F ends by non-stoichiometric, reversible polycondensation
Polymer Chemistry ( IF 4.1 ) Pub Date : 2024-06-14 , DOI: 10.1039/d4py00348a
Takayoshi Katoh ₁ , Reo Yamato ₁ , Yoshihiro Ohta ₁ , Tsutomu Yokozawa ₁

Affiliation

Reversible polycondensation of bis(phenol) silyl ether 1 and bis(4-fluorophenyl) sulfone 2 with an excess of one monomer in the presence of base was investigated for the synthesis of telechelic poly(ether sulfone) (PES) end-capped with the excess monomer, without the formation of cyclic polymer. In the polycondensation of an excess of bisphenol A bis(trimethylsilyl ether) (1a) and 2 in the presence of K₂CO₃ in N-methyl-2-pyrrolidone (NMP) ([2]₀ = 1.0 M) at 145 °C, PES having a phenol moiety derived from 1a at both ends (designated as HO/OH) was obtained. The molecular weight increased up to M_n = 8380 as the excess ratio of 1a was decreased, but the product was contaminated with cyclic polymer; this issue was overcome by increasing the monomer concentration ([2]₀ = 4.0 M). On the other hand, in the polycondensation using an excess of 2, CsF was an effective base to obtain PES with a fluorophenyl sulfone moiety at both ends (designated as F/F). The polycondensation using 1.05 equivalents of 2 in N,N-dimethylacetamide (DMAc) ([1a]₀ = 4.0 M) at 165 °C afforded high-molecular-weight PES with F/F ends (M_n = 11 200), free from cyclic polymer. Furthermore, other compounds 1 were polymerized with 2 under the optimized conditions established for the polycondensation of 1a with 2. The polycondensation of 1.1 equivalents of 1c, having a bis(trifluoromethyl) group, with 1.0 equivalent of 2 afforded PES with HO/OH ends, whereas the polycondensation of 1.0 equivalent of 1b, bearing a cyclohexylidene group, with 1.1 equivalents of 2 afforded PES with F/F ends. In the polycondensation of unsubstituted bisphenol silyl ether 1d with 2, gelation occurred when an excess of either 1d or 2 was used.

中文翻译：

通过非化学计量可逆缩聚选择性合成具有 OH 端或 F 端的无环聚合物聚醚砜

研究了双（苯酚）甲硅烷基醚 1 和双（4-氟苯基）砜 2 与过量的一种单体在碱存在下的可逆缩聚反应，以合成封端的遥爪聚醚砜（PES）。过量单体，不形成环状聚合物。过量双酚A双(三甲基硅醚)(1a)与2在K ₂ CO ₃ 存在下在N-甲基-2-吡咯烷酮(NMP)中缩聚([2] ₀ = 1.0 M)在145℃下，得到两端具有源自1a的酚部分(指定为HO/OH)的PES。随着1a过量率的降低，分子量增加至M _n = 8380，但产物受到环状聚合物的污染；通过增加单体浓度（[2] ₀ = 4.0 M）解决了这个问题。另一方面，在使用过量2的缩聚反应中，CsF是获得两端具有氟苯砜部分（称为F/F）的PES的有效碱。使用 1.05 当量的 2 在 N,N-二甲基乙酰胺 (DMAc) ([1a] ₀ = 4.0 M) 中于 165 °C 进行缩聚，得到具有 F/F 末端的高分子量 PES (M < b6> = 11 200)，不含环状聚合物。此外，在为1a与2缩聚建立的优化条件下，其他化合物1与2聚合。1.1当量的具有双(三氟甲基)基团的1c与1.0当量的2的缩聚提供具有HO/OH末端的PES ，而1.0当量的带有亚环己基的1b与1.1当量的2的缩聚提供了具有F/F末端的PES。在未取代的双酚甲硅烷基醚1d与2的缩聚中，当使用过量的1d或2时发生凝胶化。

更新日期：2024-06-18

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南