大连理工大学Wei-Min Ren团队近日研究了化学可回收聚四硫代原碳酸酯：结合高折射率和阿贝数。这一研究成果发表在2025年5月27日出版的《美国化学会杂志》上。

具有高折射率（n）和阿贝数（v_D）的聚合物具有用于先进光学器件的潜力。然而，由于光折射和色散之间的固有权衡，制造这种材料具有挑战性。研究组提出了一种有效的策略，通过以受控的方式交替共聚硫醚和环状三硫代碳酸酯，合成以四硫代原碳酸酯为官能团的富硫聚合物。值得注意的是，四硫代原碳酸酯具有高硫含量、环状结构和游离碳的特点C═S键具有优异的光学性能，在589.3nm下的n为1.706，v_D为40.9，光学透明度为90%。 

共聚过程的密度泛函理论计算表明，聚四硫代原碳酸酯（PTOC）的高选择性源于热力学上对三硫代碳酸酯阴离子的不利消除。特别是，PTOC可以通过简单的热解，经由螺环中间体回收为原始的硫醚和环状三硫代碳酸酯。

附：英文原文

Title: Chemically Recyclable Poly(tetrathioorthocarbonate)s: Combining High Refractive Index and Abbe Number

Author: Jin-Zhuo Zhao, Tian-Jun Yue, Bai-Hao Ren, Yi-Xuan Ma, Xiao-Bing Lu, Wei-Min Ren

Issue&Volume: May 27, 2025

Abstract: Polymers with high refractive index (n) and Abbe number (vD) have the potential to be used in advanced optical devices. However, fabricating such materials is challenging because of the inherent trade-off between light refraction and dispersion. Herein, we present an efficient strategy for synthesizing sulfur-rich polymers with tetrathioorthocarbonate as the functional group through the alternating copolymerization of thiiranes and cyclic trithiocarbonates in a controlled fashion. Notably, the tetrathioorthocarbonates with features of high sulfur content, cyclic structure, and free C═S bonds afforded excellent optical properties with an n under 589.3 nm of 1.706, vD of 40.9, and optical transparency of 90%. Density functional theory calculations of the copolymerization process suggest that the high selectivity of poly(tetrathioorthocarbonate)s (PTOCs) originates from the thermodynamically unfavorable elimination of trithiocarbonate anions. In particular, PTOCs can be recycled to the original thiiranes and cyclic trithiocarbonates via spiro intermediates by simple pyrolysis.

DOI: 10.1021/jacs.5c03424

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c03424