超支化含硅芳炔聚合物的合成、结构与性能研究

项目名称： 超支化含硅芳炔聚合物的合成、结构与性能研究

项目编号： No.20874028

项目类型： 面上项目

立项/批准年度： 2009

项目学科： 金属学与金属工艺

项目作者： 齐会民

作者单位： 华东理工大学

项目金额： 35万元

中文摘要： 超支化聚合物具有类似球形结构及大量末端官能团，可改善溶解性及工艺性能，本项目展开了超支化含硅芳炔聚合物（hb-PSAs）和超支化含硅芳炔芳醚聚合物（hb-PSAEs）的合成和结构表征及耐热和光电性能的研究。首先，用苯乙炔格氏试剂与三氯硅烷反应合成了三苯乙炔基硅烷（TPSs），用红外光谱和核磁共振谱表征了其结构，并对其结构进行了模拟。其次，用二乙炔基苯格氏试剂(A2)与三氯硅烷(B3)的缩聚反应，合成了hb-PSAs，研究了合成条件对反应的影响，包括反应物浓度、投料方式、物料配比等。研究了hb-PSAs支化度的表征方法，用1H-NMR、13C-NMR、29Si-NMR估算其支化度介于0.67-0.98。用示差扫描量热法分析了hb-PSAs的固化特性，用TGA研究了其耐热性能，氮气下Td5为592℃#65292;800℃#26102;的热解残留率高达91.2%；用UV及荧光色谱分析了其光电性能。最后，探索了用二乙炔基苯格氏试剂、双酚A或二羟基二苯醚格氏试剂(A2)与三氯硅烷(B3)的缩聚反应合成了hb-PSAEs，研究了反应条件对结构的影响，并用29Si-NMR图谱估算其支化度为0.60-0.80。

中文关键词： 超支化聚合物；含硅聚合物；热稳定性；光电性能；支化度

英文摘要： Silicon-containing arylacetylene resin offers excellent high temperature resistant and optical properties, which has great potential applications in aerospace and electronic information field as heat-resistant and functional material. However, silicon-containing arylacetylene resin is likely to crystallize at room temperature and the cured resin is highly cross-linked and exhibits brittleness. Moreover, hyperbranched polymers have many characteristics, such as enhanced solubility and processability, due to their globular structure and a great amount of terminal groups. This work focused on synthesis, characterization, thermal and optical properties of hyperbranched silicon-containing arylacetylene polymers (hb-PSAs) and hyperbranched silicon-containing aryl-acetylene-aryl-ether polymers (hb-PSAEs), in order to understand the relationship between structure and properties. Firstly, tri(phenylethynyl)silanes (TPSs) with different substitutes (Vinyl-, Methyl-, Hydro- and Phenyl-) attached to silicon atom were synthesized through condensation reaction between phenylethynyl Grignard reagent and trichlorosilanes, and their structure were characterized by using Infrared Spectroscopy (FTIR) and Nuclear Magnetic Resonarce (1H NMR) spectroscopy. The molecular structure of tri(phenylacetylene)silanes were made by using the optimized geometry of the MM2 calculation, triphenylethynylsilanes molecule possesses a center silicon atom, and three phenylethynyl group attached on it rotated as propeller. Secondly, hb-PSAs, such as hyperbranched poly(diethynylbenzene-methylsilane) (hb-PSAM), hyperbranched poly(diethynylbenzene-vinylsilane) (hb-PSAV), hyperbranched poly(diethynylbenzene-silane) (hb-PSAH), hyperbranched poly(diethynylbenzene-phenyl- silane) (hb-PSAP), were synthesized through polycondensation reaction between diethynylbenzene Grignard reagent (A2) and trichlorosilanes (B3), and their structure were characterized by FT-IR, 1H-NMR, 13C-NMR, Gel Permeation Chromatography (GPC) and Element Analysis (EL). The effects of synthesis conditions on the structures of hb-PSAs, including monomers concentration, feeding method and material ratio were examined. The molecular weight and its PDI of hb-PSAs could be controlled by addition of terminals, and terminals was added in the former process easy to generate small-molecule products, then this phenomenon can be avoided by added in the last process. The degrees of branch (DB) of hb-PSAs were calculated according to 1H-NMR, 13C-NMR and 29Si-NMR spectroscopy, and values of 0.67-0.98 were given. The curing behavior of hb-PSAs was investigated by DSC and thermal stabilities of cured hb-PSAs were examined by TGA. The result showed that hb-PSAs had excellent high temperature resistant properties, the decomposition temperature (temperature at 5% weight loss, Td5) of hb-PSAP was 592℃and residual at 800℃was 91.2% under nitrogen. The optical properties of hb-PSAs were studied by UV-Vis spectrometer and fluorescence spectra, and the results showed that hb-PSAs displayed a strong absorption due to π#960;* transition and exhibited the most intensity structured emission with a maximum around 500 nm. Thirdly, hb-PSAEs were synthesized through polycondensation reaction among diethynylbenzene Grignard reagent, bisphenol A Grignard reagent or 4,4'-dihydroxy ether Grignard reagent (A2) and methyltrichlorosilane (B3), and their structures were characterized by FT-IR, 1H-NMR and 29Si-NMR. The effects of process conditions on the structures of hb-PSAEs, including monomers concentration, feeding methods, reaction time, reactants ratios, were examined. The degree of branching (DB) of hb-PSAEs estimated by using 29Si-NMR were ranging from 0.60～0.80.

英文关键词： hyperbranched; silicon-containing polymers; thermal stabilities; optical properties; degree of branching (DB)