PENG Zhijian, SI Wenjie, FU Hejian, ZENG Hongmei, MIAO Hezhuo. SYNTHESIS AND CHARACTERIZATION OF BRANCHED COPOLYSILANES OF HIGH MOLECULAR WEIGHT. [J]. Acta Polymerica Sinica (3):301-308(2002)
DOI:
PENG Zhijian, SI Wenjie, FU Hejian, ZENG Hongmei, MIAO Hezhuo. SYNTHESIS AND CHARACTERIZATION OF BRANCHED COPOLYSILANES OF HIGH MOLECULAR WEIGHT. [J]. Acta Polymerica Sinica (3):301-308(2002)DOI:
SYNTHESIS AND CHARACTERIZATION OF BRANCHED COPOLYSILANES OF HIGH MOLECULAR WEIGHT
the process of“normal-sequence-dripping mode” was designed.And using such process
the monomers of dichloromethylphenethylsilane and dichloromethyl (n) hexylsilane were synthesized with high productivity(the maximal productivity of dichloromethylphenethylsilane
88%
and dichloromethyl-n-hexylsilane
96.2%) and low pollution (minute quantity of fumes in off-gas).By Wurtz reductive coupling reaction of dichlorosilane(dichloromethylphenethylsilane and dichloromethyl(n)hexylsilane)and trichlorosilane (trichloromethylsilane and trichlorophenylsilane)
four series of two-dimensionally branched copolysilanes were designed and synthesized using the two procedures of “pre-polymerization” and “mixed-polymerization” with or without diglyme. The polymers are polymethylphenethylsilene-co-methylsilynes
polymethyl-phenethylsilene-co-phenylsilynes
polymethyl-n-hexylsilene-co-methylsilynes
and polymethyl-n-hexylsilene-co-phenylsilynes.Through the characterization of GPC
UV
1H-NMR and 29Si-NMR
the properties of such copolysilanes were determined.The effects of such factors as monomer characteristics
solvent additive(diglyme)and reaction time on the polymer properties
such as productivity
molecular weight and UV absorption spectra
were studied and discussed.It was discovered that the branched copolysilanes of very high molecular weight with highly bulky substituents could be obtained with “pre-polymerization”.The maximum of the molecular weight of such branched copolysilanes could reach 2.8×105
which was at least ten times as those of the branched copolysilanes derived from the mixed-polymerization procedure.The mechanism of increasing the molecular weights of branched copolysilanes was proposed