Atom transfer radical polymerization of dimethyl(methacryloyloxymethyl) phosphonate

• ATRP of dimethyl(methacryloyloxymethyl) phosphonate was studied.
• ATRP resulted in a well-defined homopolymer.
• Also, a block copolymer with polystyrene was prepared.

Atom transfer radical polymerization (ATRP) of dimethyl(methacryloyloxymethyl) phosphonate (DMMAMP, also referred to as MAPC1) with a copper/2,2′-bipyridine based catalytic system in DMSO resulted in a homopolymer with narrow molecular weight distribution. Initiators for continuous activator regeneration (ICAR) ATRP of this monomer was also successful when using tris[(2-pyridyl)methyl]amine as ligand and azobisisobutyronitrile as supplementary initiator for the regeneration of the CuI activator. Normal ATRP provided better control compared to ICAR ATRP. Differential scanning calorimetry measurements of the resulting poly(DMMAMP) revealed a glass transition temperature (Tg = 63 °C), lower than that of poly(methyl methacrylate). Chain extension of the poly(dimethyl(methacryloyloxymethyl) phosphonate) macroinitiator with styrene was successfully achieved with a high fraction of block copolymer.

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