Computational examination of the electrophilic reaction on oxidative polymerization of phenyltrimethylsilane with sulfur chloride

Abstract

Phenyltrimethylsilane possesses a higher HOMO energy (–9.34 eV) than nonsubstituted benzene (>0.41 eV). The π electron of the phenyltrimethylsilane localizes on the benzene ring at the ipso position rather than at the para position. Two center energies calculated by the MNDO‐PM3 method indicate that the CSi bond is facilitated to cleave in comparison with the CH (para position) one of the benzene ring. Phenyltrimethylsilane and phenyl bis(trimethylsilane) were polymerized with sulfur chloride through the cationic oxidative polymerization. The product is isolated as oligo(p‐phenylene sulfide), with a melting point of 150–190°C. An electrophile attacks the carbon atom linked to the Si atom in phenyltrimethylsilane. The new synthetic route of PPS can be established on the basis of the computational calculation.

Synthesis of high-molecular-weight poly(phenylene sulfide) by oxidative polymerization via poly(sulfonium cation) from methyl phenyl sulfoxide

“…an electrophilic reaction and oxidative polymerization. [16][17][18][19][20][21] The polymerization proceeds at room temperature and provides pure PPS, but it results in a low molecular weight due to its poor solubility.…”