Synthesis of colorless and high-refractive-index sulfoxide-containing polymers by the oxidation of poly(phenylene sulfide) derivatives
Synthesis of colorless and high-refractive-index sulfoxide-containing polymers by the oxidation of poly(phenylene sulfide) derivatives
复制标题
聚苯硫醚衍生物氧化合成无色高折射率含亚砜聚合物
DOI：
10.1039/d1py01654g
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发表时间：
2022-02-25
影响因子：
4.6
通讯作者：
Oyaizu, Kenichi
中科院分区：
文献类型：
--
作者：
Watanabe, Seigo;Takayama, Teru;Oyaizu, Kenichi
高折射率、热稳定性和透明的聚苯硫醚（PPS）衍生物部分包括S=O键。采用间氯过苯甲酸（mCPBA）对相应的PPS衍生物进行氧化，得到了具有高氧化选择性的亚砜或含砜聚合物。氧化后，聚合物的透明度和玻璃化转变温度（T-g）增强，同时保持其高折射率（n(D) = 1.66-1.71），这是由于引入了刚性亚砜/砜基团。这种体膜的漂白是由于硫原子上的孤对通过S=O键的形成而失去了硫键，这导致了更小的共轭长度和更弱的近紫外吸收。从摩尔折射率和分子体积的角度来看，加入亚砜部分是提高透明度和保持合适的高折射率T-g的最佳方法。
Highly refractive, thermostable, and transparent poly(phenylene sulfide) (PPS) derivatives partially including S=O bonds were reported. The polymers were prepared by m-chloroperbenzoic acid (mCPBA) oxidation of the corresponding PPS derivatives, affording sulfoxide or sulfone-containing polymers with high oxidation selectivity. After the oxidation, the transparency and glass-transition temperature (T-g) of the polymers enhanced while maintaining their high refractive indices (n(D) = 1.66-1.71), owing to the introduction of rigid sulfoxide/sulfone moieties. This bleaching of the bulk films was due to the loss of the lone pairs on the sulfur atom in the sulfide bonds through the formation of the S=O bonds, which led to a smaller conjugation length and weaker absorption in the near-UV region. From the viewpoint of both molar refraction and molecular volume, incorporating the sulfoxide moiety is the best way to enhance transparency and maintain a suitable T-g with a high refractive index.