Polythioethers with Controlled alpha,omega-End Groups Prepared by Visible Light Induced Thiol-Ene Click Polymerization of Dithiol and Divinyl Ether with 4-(N,N-diphenylamino)benzaldehyde as Organocatalyst
Polythioethers with Controlled alpha,omega-End Groups Prepared by Visible Light Induced Thiol-Ene Click Polymerization of Dithiol and Divinyl Ether with 4-(N,N-diphenylamino)benzaldehyde as Organocatalyst
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4-(N,N-二苯氨基)苯甲醛为可见光诱导硫醇-烯点击聚合制备α,omega端基受控聚硫醚
DOI：
10.1002/macp.201900557
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发表时间：
2020
影响因子：
2.5
通讯作者：
Yang Wantai
中科院分区：
文献类型：
--
作者：
Wang Yiran;Zhang Xianhong;Ma Yuhong;Chen Dong;Zhao Changwen;Yang Wantai
本文报道了在可见光照射下，4-（N，N-二苯氨基）苯甲醛（DPAB）催化1，4-苯二甲烷（BDMT）和二甘醇二乙烯基醚（DEGVE）的逐步生长点击聚合反应。DPAB在苯甲醚中在350 nm处有很强的紫外-可见吸收，在480 nm处有很强的荧光发射。BDMT与DPAB之间存在较强的荧光猝灭作用。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，通过简单改变BDMT与DEGVE的摩尔比，成功合成了α，ω-二硫醇和α，ω-二乙烯基遥爪聚硫醚低聚物。1H NMR和MALDI-TOF MS谱图表明，该低聚物具有高的末端基团保真度。此外，当α，ω-二硫醇封端的聚硫醚与N-（1-芘基）马来酰亚胺加成时，观察到强荧光，表明所制备的聚硫醚带有反应性硫醇端基。此外，高分子量聚硫醚通过用反应性聚硫醚低聚物作为大分子单体进行扩链来制备。例如，α，ω-二乙烯基低聚物（Mn= 2000 g mol-1）可以进一步与α，ω-二硫醇低聚物（Mn= 2400 g mol-1）反应以形成高分子量聚硫醚（Mn= 6000 g mol-1）。
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 withN‐(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 (Mn= 2000 g mol−1) could further react with α,ω‐dithiol oligomer (Mn= 2400 g mol−1) to form high molecular weight polythiolether (Mn= 6000 g mol−1).