Thermolyzable polymer networks and star polymers containing a novel, compact, degradable acylal‐based dimethacrylate cross‐linker: Synthesis, characterization, and thermolysis

A compact, cleavable acylal dimethacrylate cross‐linker, 1,1‐ethylenediol dimethacrylate (EDDMA), was synthesized from the anhydrous iron(III) chloride‐catalyzed reaction between methacrylic anhydride and acetaldehyde. The ability of EDDMA to act as cross‐linker was demonstrated by using it for the preparation of one neat cross‐linker network, four star polymers of methyl methacrylate (MMA), and four randomly cross‐linked MMA polymer networks using group transfer polymerization (GTP). For comparison, the corresponding polymer structures based on the commercially available ethylene glycol dimethacrylate (EGDMA) cross‐linker (isomer of EDDMA) were also prepared via GTP. The number of arms of the EDDMA‐based star polymers was lower than that of the corresponding EGDMA polymers, whereas the degrees of swelling in tetrahydrofuran of the EDDMA‐based MMA networks were higher than those of their EGDMA‐based counterparts. Although none of the EDDMA‐containing polymers could be cleanly hydrolyzed under basic or acidic conditions, they could be thermolyzed at 200 °C within 1 day giving lower molecular weight products.