新型含砜基聚硅氧烷的设计合成及其性能研究

This project intends to design and synthesize sulfone modified organosilicon polymers with novel structures by thioether oxidation strategy, and explore their performance and application. First of all, a range of sulfone-containing silanes and siloxanes will be designed and synthesized by using thiol-ene "click" reactions and then thioether oxidation process. Next, oligomers of thioether-containing siloxanes are synthesized, the rearrangement of their Si-O-Si bonds will be deeply discussed during the process of thioether oxidation, and a series of sulfone-containing cyclosiloxanes will be got. By the studies of synthesizing sulfone-containing polysiloxanes via cyclic opening of the sulfone-containing cyclosiloxanes obtained, a new synthesis method of sulfone-containing polysiloxanes will be put forward，which may be widely used in the synthesis of various sulfone-containing linear siloxane polymers. The novel structures of organosilicon polymers obtained will show novel properties and therefrom broad applications. Furthermore, we will use sulfone-containing polysiloxanes in modification of polysulfone resins (PSF) as well as preparation of silicone rubber to get a variety of novel hybrid materials with good performance of both organosilicon polymers and polysulfones. This will provide a new way to explore functionalized organosilicon materials and broad the varieties as well as the application scope of organosilicon materials. The unique fluorescent properties of the silicon-sulfur coordinate bonds formed between silicon and sulfur atoms in the molecules will be also explored, which could provide a theoretical basis for the study of fluorescence of silicon-containing unconventional chromophore groups. In conclusion, this project would enrich and develop organosilicon chemistry as well as polymer chemistry for its novelty and significance, and promote the development of sulfone modified organosilicon polymers. At the same time, it has rich and systematic research contents, shows broad application prospect, innovative and unique characteristics, and has important scientific significance and practical values.

本项目拟采取硫醚氧化策略，设计合成新颖结构的砜基改性有机硅高分子,并探索其性能与应用。首先基于巯-烯点击反应和硫醚氧化反应，设计、优化合成含砜基硅烷、硅氧烷；在此基础上，研究含硫醚杂链低聚硅氧烷在硫醚氧化时伴随发生的Si-O-Si键重排反应, 制备含砜基杂硅氧烷环状单体，进而设计合成系列含砜基聚硅氧烷，为含砜基聚硅氧烷这一创新性领域提出合成新方法和新思路；合成的含砜基聚硅氧烷结构新颖，会有新性能、新用途；将含砜基聚硅氧烷用于聚砜树脂改性、硅橡胶制备等，获得有机硅与聚砜性能优势互补的特性材料，拓宽有机硅材料种类与应用范围。同时鉴于分子中的硅与硫原子能形成硅-硫配键，研究含砜基硅烷、（聚）硅氧烷的荧光性质，为含硅非传统生色团的荧光研究提供理论依据。本项目将促进含砜基有机硅高分子的发展，丰富有机硅化学、高分子化学等领域，立题新颖，研究内容系统丰富，创新性与特色突出，具有重要的科学意义与应用前景。

含砜基有机硅聚合物研究是有机硅化学中的一个创新性领域。本项目基于巯-烯点击反应、采取硫醚氧化策略，首次设计合成了含砜基杂硅氧烷大环单体（BSM）；通过探索BSM的开环聚合条件，成功设计制备了含砜基聚硅氧烷，提出了含砜基聚硅氧烷合成新方法和新思路。基于BSM开环均聚与共聚，合成了系列含砜基有机硅共聚物（PSRS），探究了BSM含量对其热性能、亲疏水性、荧光性能和力学性能的影响；研究了含砜基聚硅氧烷的降解重排反应与条件，发现在KHSO4存在下，含砜基聚硅氧烷可以高转化率降解，重新获得起始原料BSM，为含砜基聚硅氧烷的循环利用奠定了基础。基于设计合成的新型主链含芳砜基聚硅氧烷，通过电纺丝制备了纤维，首次获得含砜基聚硅氧烷基有机硅纤维发明专利。将无机卤化物钙钛矿纳米晶嵌入到含砜聚硅氧烷共聚物网络中，制备了系列力学性能较好、且显示强烈绿色荧光的钙钛矿-有机硅弹性体，并发现交联反应可在30 W家用LED灯照射下进行，制备条件温和、易行，展示出重要的应用前景。作为项目所涉及的巯-烯点击反应在有机硅领域的拓展应用，开展超分子硅橡胶的系统研究，一锅法合成了硼氮配键形成的可自愈合硅橡胶，制备了物理与化学交联高拉伸强度双网络硅弹性体，可用作智能和可持续的材料、生物成像中的细胞粘合剂等；基于含水杨醛亚胺结构的聚硅氧烷与锌离子配位，获得的自修复、可循环回收的光致发光超分子有机硅弹性体，拉伸强度高达10.0 MPa。同时基于巯-烯点击等反应，制备了超疏水的油水分离海绵材料，超亲油疏水、热绝缘和超高可压缩性大孔有机硅海绵材料，良好的压缩性能和低导热性的聚硅氧烷泡沫材料，阴离子型有机硅表面活性剂，POSS基功能材料等，并展示出在荧光传感器、油水分离材料、重金属选择吸附、染料废水处理等方面的良好应用前景。研究工作丰富和发展了有机硅化学等领域，具有重要的科学意义与实用价值。