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Synthesis of Poly (Styrene-Block-Vinyl Alcohol) by Successive Photo-Induced Charge Transfer Polymerization and Molecular Dynamics Simulation of Its Compatibility for the Blend System

In the present work, a rapid and novel route to prepare a diblock copolymer consisting of styrene and vinyl acetate (VAC) units was performed by successive photoinduced charge-transfer polymerization (CTP) under UV irradiation, and then a series of objective products PSm-b-PVAn bearing different ratios of PS and PVA was obtained by the hydrolysis of PSm-b-PVACn with sodium ethoxide as the catalyst. Additionally, the influences of the reaction time, concentration of monomer and photoinitiator and kinetics of copolymerization were investigated. Good linear relationships of ln([St] 0/[St]) and ln([VAc]0/[VAc]) with the polymerization time indicated a first-order control/‘living’ process. The copolymers were characterized in detail by means of Fourier transform infrared (IR) spectrometry, 1H NMR and gel permeation chromatography (GPC). Furthermore, the miscibility of the originally incompatible blend system was improved quite significantly, so a full atomistic molecular dynamics simulation was applied to discuss the binary and ternary systems through the Flory-Huggins parameters, enthalpy of mixing and Tg.