Polythioethers with Controlled α,ω‐End Groups Prepared by Visible Light Induced Thiol–Ene Click Polymerization of Dithiol and Divinyl Ether with 4‐(N,N‐diphenylamino)benzaldehyde as Organocatalyst,Macromolecular Chemistry and Physics

当前位置： X-MOL 学术 › Macromol. Chem. Phys. › 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.)

Polythioethers with Controlled α,ω‐End Groups Prepared by Visible Light Induced Thiol–Ene Click Polymerization of Dithiol and Divinyl Ether with 4‐(N,N‐diphenylamino)benzaldehyde as Organocatalyst
Macromolecular Chemistry and Physics ( IF 2.5 ) Pub Date : 2020-02-24 , DOI: 10.1002/macp.201900557
Yiran Wang ₁ , Xianhong Zhang ₁ , Yuhong Ma ₁ , Dong Chen ₁ , Changwen Zhao ₁ , Wantai Yang _{1,

2}

Affiliation

This study reports a step‐growth click‐polymerization of 1,4‐benzenedimethane (BDMT) and diethylene glycol divinyl ether (DEGVE) with 4‐(N,N‐diphenylamino)‐benzaldehyde (DPAB) as a photoredox catalyst under irradiation of visible light. DPAB exhibits a strong UV–vis absorption at 350 nm and a strong fluorescence emission at 480 nm in anisole. There is a strong fluorescence quenching between BDMT and DPAB. The molecular weight of the polythiolether can be controlled by reaction time and monomer feed ratios. More importantly, α,ω‐dithiol and α,ω‐divinyl telechelic polythiolether oligomers are successfully synthesized by simply changing the molar ratios of BDMT to DEGVE. ¹H NMR and MALDI‐TOF MS spectra demonstrate that the oligomers have high end group fidelity. In addition, strong fluorescence is observed when the α,ω‐dithiol terminated polythiolether adds with N‐(1‐pyrenyl) maleimide, indicating that the as‐prepared polythiolether bears reactive thiol end groups. Furthermore, high molecular weight polythiolether are prepared by chain extension with reactive polythiolether oligomers as macro‐monomers. For example, α,ω‐divinyl oligomer (M_n = 2000 g mol⁻¹) could further react with α,ω‐dithiol oligomer (M_n = 2400 g mol⁻¹) to form high molecular weight polythiolether (M_n = 6000 g mol⁻¹).

中文翻译：

可见光诱导的Thiol–Ene制备的具有受控α，ω-端基的聚硫醚，以4-（N，N-二苯氨基）苯甲醛为有机催化剂，对二硫醇和二乙烯基醚进行点击聚合

这项研究报告了在可见光照射下1,4-苯二甲烷（BDMT）和二甘醇二乙烯基醚（DEGVE）与4-（N，N-二苯氨基）-苯甲醛（DPAB）作为光氧化还原催化剂的逐步增长点击聚合光。DPAB在苯甲醚中在350 nm处具有很强的UV-vis吸收能力，在480 nm处具有很强的荧光发射能力。BDMT和DPAB之间存在强烈的荧光猝灭。聚硫醚的分子量可以通过反应时间和单体进料比来控制。更重要的是，只需改变BDMT与DEGVE的摩尔比，即可成功合成α，ω-二硫醇和α，ω-二乙烯基远螯多硫醚低聚物。^1个1 H NMR和MALDI-TOF MS光谱表明，低聚物具有较高的端基保真度。此外，当α，ω-二硫醇封端的聚硫醚与N-（1-吡啶基）马来酰亚胺加成时，观察到强烈的荧光，表明所制备的聚硫醚具有反应性硫醇端基。此外，高分子量聚硫醚通过与活性聚硫醚低聚物作为大分子单体的扩链来制备。例如，α，ω-二乙烯基低聚物（M _n = 2000 g mol ^-1）可以进一步与α，ω-二硫醇低聚物（M _n = 2400 g mol ^-1）反应形成高分子量聚硫醚（M _n = 6000 g mol ^-1）。

更新日期：2020-02-24

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