Zhang Huayu, Xue Lei, Li Jianquan, Ma Qingyu
Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, China.
School of Materials Science and Engineering, University of Jinan, Jinan 250022, China.
Polymers (Basel). 2020 Mar 17;12(3):672. doi: 10.3390/polym12030672.
Silicon-containing hyperbranched polymers (Si-HBPs) have drawn much attention due to their promising applications. However, the construction of Si-HBPs, especially those containing functional aromatic units in the branched backbones by the simple and efficient Piers-Rubinsztajn (P-R) reaction, has been rarely developed. Herein, a series of novel hyperbranched polycarbosiloxanes were prepared by the P-R reactions of methyl-, or phenyl-triethoxylsilane and three Si-H containing aromatic monomers, including 1,4-bis(dimethylsilyl)benzene, 4,4'-bis(dimethylsilyl)-1,1'-biphenyl and 1,1'-bis(dimethylsilyl)ferrocene, using B(CF) as the catalyst for 0.5 h at room temperature. Their structures were fully characterized by Fourier transform infrared spectroscopy, H NMR, C NMR, and Si NMR. The molecular weights were determined by gel permeation chromatography. The degrees of branching of these polymers were 0.69-0.89, which were calculated based on the quantitative Si NMR spectroscopy. For applications, the ferrocene-linked Si-HBP can be used as precursors to produce functional ceramics with good magnetizability after pyrolysis at elevated temperature.
含硅超支化聚合物（Si-HBPs）因其广阔的应用前景而备受关注。然而，通过简单高效的皮尔斯-鲁宾斯泰因（P-R）反应构建Si-HBPs，尤其是那些在支链主链中含有功能性芳香单元的Si-HBPs，却鲜有报道。在此，通过甲基或苯基三乙氧基硅烷与三种含硅氢的芳香单体（包括1,4-双（二甲基硅基）苯、4,4'-双（二甲基硅基）-1,1'-联苯和1,1'-双（二甲基硅基）二茂铁）的P-R反应，以B(CF)为催化剂，在室温下反应0.5小时，制备了一系列新型超支化聚碳硅氧烷。通过傅里叶变换红外光谱、氢核磁共振、碳核磁共振和硅核磁共振对其结构进行了全面表征。通过凝胶渗透色谱法测定了分子量。这些聚合物的支化度为0.69-0.89，是基于定量硅核磁共振光谱计算得出的。在应用方面，二茂铁连接的Si-HBP可作为前驱体，在高温热解后制备具有良好磁性的功能陶瓷。
