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Synthesis and physical properties of linear and branch phenoxies

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Linear and branch phenoxies have been synthesized by reacting difunctional epoxy and diphenol or triphenol monomer, using phosphonium salt as the catalyst. The reaction kinetics is analyzed by the ASTM E 698 method, which is suitable for a first order reaction system. The bulky structure of the bisphenol Z moiety retards the reaction; therefore, the reaction temperature required is higher- at 200 degreesC, compared to 190 degreesC for the bisphenol A based system. The introduction of a branch structure increases both molecular weight and the polydispersity of the phenoxy. A slightly branched structure tends to increase the distance between the polymer chains and results in a lower shear viscosity for easier processing. A higher branch results in light crosslinking and decreases the mobility of the polymer. The branch structure has a negligible effect on its glass transition temperature because the average distance between branches is substantially longer than the critical mainchain length for T-1's Brownian motion. The 100/1 (bisphenol/ trisphenol) system has the lowest viscosity, but its mechanical properties and the gas permeation properties are poorer than those of the others. The bisphenol Z based phenoxy shows superior mechanical properties, higher T-g, lower coefficient of thermal expansion, and lower gas permeation properties than the corresponding bisphenol A based phenoxy because of the steric hindrance structure of the bisphenol Z moiety.

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