Oxygen permeation of blends of copolymers of siloxanes and poly(methylmethacrylate)

Abstract
A series of low molecular weight (≈40000) copolymers of methylmethacrylate (MMA) and 4‐(methacryloyloxy)butylpentamethyldisiloxane (MBPD) have been synthesized by free radical polymerization in dimethylformamide solution. The microstructure, as derived from 13C NMR spectra, indicates that the copolymers are about 80% syndiotactic with an overall random distribution of mers. At room temperature, copolymers rich in MMA are clear, rigid glasses but become liquid at high MBPD content. Blends of these copolymers with PMMA are all heterogeneous with visible phase separation over most of the composition range. Differential scanning calorimetry studies show the presence of two Tg's when the relative concentration of PMMA to copolymer is high. Blends of two co‐polymers of similar siloxane content produce clear films with no indication of phase separation. The permeability to oxygen at 25°C increases from 0.20 for pure PMMA to 3.0 (fmol/m·s·Pa.) for a copolymer of MMA/MBPD of the mole ratio of 3:1. Evaluation of the permeation behaviors of the blends suggests that blends rich in siloxane exist as a layered structure with the PMMA rich component dominating the observed permeability.

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