新型乙炔基封端硅氮烷的合成及表征

Synthesis & Characterization of New Acetylene-terminated Silazanes

以四氢呋喃为溶剂、三乙胺作HCl吸收剂,将4-乙炔基苯胺分别与二甲基二氯硅烷、二苯基二氯硅烷、甲基二氯硅烷进行胺解反应,合成了3种乙炔基封端的硅氮烷N,N'-双(4-乙炔基苯基)-1,1-二甲基硅烷二胺、N,N'-双(4-乙炔基苯基)-1,1-二苯基硅烷二胺、N,N'-双(4-乙炔基苯基)-1-甲基硅烷二胺。红外光谱及核磁共振谱(1H NMR、13C NMR、29Si NMR)证实,得到了目标产物;差示扫描量热及热失重分析表明,硅原子上取代基明显影响硅氮烷的熔点和聚合反应的放热量,而对热聚合反应温度基本没有影响。

Three acetylene-terminated silazane monomers,namely,N,N’-bis（ 4-ethynylphenyl）-1,1-dimethylsilanediamine,N,N’-bis（ 4-ethynylphenyl）-1,1-diphenylsilanediamine and N,N’-bis（ 4-ethynylphenyl）-1-methylsilanediamine,were synthesized by aminolysis between 4-ethynylaniline and dimethyldichlorosilane,diphenyldichlorosilane,or methyldichlorosilane,respectively,in tetrahydrofuran with triethylamine as the acid scavenger. Their structures were characterized by Fourier transfer infrared spectra and Nuclear Magnetic Resonance spectra（1H NMR,13 C NMR and29 Si NMR）. Results of thermogravimetric analyses（ TGA）and differential scanning calorimetry（ DSC） indicated that the melting point and thermal polymerization enthalpy of the compounds were obviously affected by the substituent attached on silicon atom,whereas the peak temperature of the thermal polymerization was substituent independence.