含硅芳基炔丙基醚树脂及其复合材料的制备与性能

Preparation and Properties of Silicon-Containing Arylpropargyl Ether Resins and Their Composites

将双酚二炔丙醚和氯硅烷缩聚合成了两种含硅芳基炔丙基醚(PSPE)树脂:含硅双酚A二炔丙醚(PSPE-A)树脂和含硅二苯醚二炔丙醚(PSPE-O)树脂,并用乙炔基苯基封端PSPE制备了端乙炔基苯基PSPE(DPSPE)。合成的PSPE树脂固化温度高,用乙炔基苯基封端后可明显降低PSPE树脂的固化温度和固化反应表观活化能,并可使其在氮气中5%热失重温度(T)和800℃残留率(Y)分别提升至486.3℃和75.1%,玻璃化转变温度(T)高于400℃。石英纤维布(QF)/PSPE-A的弯曲强度和层间剪切强度分别为461.3 MPa和35.6 MPa,T300碳纤维布(T300CF)/PSPE-A的弯曲强度和层间剪切强度分别为655.2 MPa和39.3 MPa。

Dipropargyl ether of bisphenols and dichlorosilane were polymerized by the Grignard process to obtain silicon-containing propargyl ether of bisphenol A resin(PSPE-A) and silicon-containing propargyl ether of diphenyl ether resin(PSPE-O), respectively. The silicon-containing propargyl ether of bisphenol resins(PSPE) were further endcapped with diethynyl benzene to obtain the ethynylphenyl-terminated PSPE-A resin(DPSPE-A) and PSPE-O resin(DPSPE-O). The four resins obtained were characterized by proton nuclear magnetic resonance and size exclusion chromatograph. The cure reactions, thermal stability and mechanical properties of the resins were studied. The mechanical properties of the quartz fiber cloth(QF) and carbon fiber cloth(T300CF) reinforced resin composites were also examined. The results show that the synthesized PSPE resins has a high curing temperature. The curing temperature and apparent activation energy of the PSPE resins can be significantly reduced by using diethynyl benzene as the end-capping agent. The viscosity at 110 ℃ of PSPE-A and PSPE-O is below 300 mPa·s, which the latter is much lower than the former. The temperature of 5% weight loss(T) and residual yield at 800 ℃(Y) in Nof the cured ethynylphenyl-terminated PSPE resin are found to be 486.3 ℃ and 75.1%, respectively. The glass transition temperature(T) of the cured DPSPE is higher than 400 ℃. However, the flexural strength and impact strength of the cured PSPE resin decrease to 27.8 MPa and 3.27 kJ/m^(2) after end-capping with ethynylphenyl groups, respectively. The flexural strength and interlaminar shear strength(ILSS) of the QF/PSPE-A and T300CF/PSPE-A composites are 461.3 MPa and 35.6 MPa, 655.2 MPa and 39.3 MPa, respectively.