含三氰乙烯基强吸电子基团的环氧树脂基非线性光学聚合物的合成

Synthesis of Epoxy-Based Nonlinear Optical Polymers Functionalized with Heteroaromatic Chromophore Bearing Tricyanovinyl Group

非线性光学聚合物材料及其在聚合物电光调制器中的应用是目前国内外研究的前沿。环氧树脂类聚合物具有很好的成膜性及可化学交联性能,是一类非常好的非线性光学聚合物的基体材料。本论文从分子设计的角度出发,将含三氰乙烯基强吸电子取代基及噻吩芳杂环共轭结构非线性光学生色团成功引入环氧树脂类聚合物,并在生色团侧基上引入甲基取代基。结果表明,苯胺残基中侧位甲基取代基对于先驱聚合物的亲电取代反应程度及最后聚合物的紫外-可见光最大吸收波长均有一定的影响,对于没有侧甲基的BP-TA-TC和一个侧甲基取代基的BP-3-TA-TC其官能化度均可以达到80%以上,而对于含两个甲基取代的BP-3,5-TA-TC先驱聚合物其官能化度则相对较低(低于10%)。随着甲基取代数目的增多,最后非线性光学聚合物的最大吸收波长也有不同程度的蓝移。

Nonlinear optical （NLO） polymers have attracted much attention in recent years. Epoxy based polymers with side hydroxyl groups have good film-forming properties and can be chemical cross- linked, which are good candidates for nonlinear optical polymers. In this paper, two kinds of iodinated aniline derivatives were synthesized by selective para-iodination between the reaction of 3-methyl aniline, 3, 5-dimethylaniline and iodine in a mixture of pyridine/dioxane under mild conditions. Three aniline derivatives with thiophene heterocycle substituent and different number of side methyl substituents were prepared by Suzuki coupling reaction between the iodinated aniline derivatives and 2- thiophenylboric acid. Three kinds of precursor epoxy based polymers were prepared by the polycondensation of diglycidyl ether of bisphenol-A and aniline derivatives prepared above. The precursor polymers were post-functionalized by tricyanovinylation reaction to prepare the final NLO polymers. The result polymers were characterized by 1H-NMR, UV-Vis, DSC, TGA and GPC methods. The methyl substitutes have much effect on the degree of electrophilic substitution reaction of the precursor polymers. For BP-TA-TC and BP-3-TA-TC, the degree of functionalization can be reached about 80%. Anyway, the degree of functionalization of BP-3, 5-TA-TC with two side methyl substitutes is less than 10%. With the increase of the number of methyl substitutes, the UV-visible maximum absorption of the final NLO polymers will decrease.