Effect of Metal Alkoxide Complexes on Condensation Reactions of Hydrolyzed Phenyltriethoxysilane

Metal alkoxide complexes, in which alkoxy groups were substituted with ethyl acetoacetate (EAcAc), were found to accelerate condensation reactions of hydrolyzed phenyltriethoxysilane (PTES) and affect the structure of phenylsiloxane networks. The ²⁹Si NMR study revealed that the acceleration effect increased in the order Al(O-sec-C₄H₉)_3–x (EAcAc) _x < Ta(OC₂H₅)_5–x (EAcAc)_x < Ti(OC₂H₅)_4–x (EAcAc) _x . However, the GPC study revealed that the solution contained the high molecular weight species in the order Al(O-sec-C₄H₉)_3–x (EAcAc) _x < Ti(OC₂H₅)_4–x (EAcAc) _x < Ta(OC₂H₅)_5–x (EAcAc) _x . In the case of Ti(OC₂H₅)_4–x (EAcAc) _x , the smaller size of phenylsiloxane networks with a low content of silanol groups was formed in the solution. In the case of Ta(OC₂H₅)_5–x (EAcAc) _x , the larger size of phenylsiloxane networks with a high content of silanol groups was formed in the solution. In the case of Al(O-sec-C₄H₉)_3–x (EAcAc) _x , the small size of phenylsiloxane networks with a high content of silanol groups was formed in the solution. During gelation, the catalytic effect of the metal alkoxide complexes on the development of phenylsiloxane networks was also found. However, the average molecular weight of the gels increased in the order Ta(OC₂H₅)_5–x (EAcAc) _x < Ti(OC₂H₅)_4–x (EAcAc) _x Al(O-sec-C₄H₉)_3–x (EAcAc) _x . The metal alkoxide complexes were hydrolyzed and finally incorporated into the phenylsiloxane networks of gels to form M—O—Si bonds, which were indicated by the results of FT-IR analysis.     

Synthesis and Properties of Polyphenylsilsesquioxane Modified Phenolic Resin by in-situ Polymerization from Phenyltriethoxysilane Precursor

A series of phenolic resin-polyphenylsilsesquioxane (PR-PPSQ) composites were prepared by in situ formation from phenyltriethoxysilane (PTES) precursor during polymerization of the PR. The precursor was firstly hydrolyzed in a solution, and then the sol was added to the PR polymerization system. The structures of the composites were investigated by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and solid-state ²⁹Si nuclear magnetic resonance (Si-NMR). The PPSQs were spherical particles with a diameter of about 3 µm and nearly uniformly dispersed in the matrix, as revealed by scanning electron microscopy (SEM). The influence of PTES content on the thermal behavior of the PR was characterized by thermogravimetric analysis (TGA) in nitrogen and air atmospheres. The results showed that the onset temperature and residual weight of the composite containing 20 wt% PTES content were improved by 47°C and 8.4%, respectively, compared to the pure PR. The thermal oxidative stability was also greatly increased; the 50 wt% weight loss temperature rose from 567°C for PR to 601°C. The flexural strength of the composites was improved; in particular, the value of the composite containing 15 wt% PTES content was elevated by 32% (from 41.66 to 55.33 MPa).