Study of macroinitiator efficiency and microstructure–thermal properties in the atom transfer radical polymerization of methyl methacrylate

The atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) with poly vinylacetate macroinitiator (PVAc-CCl₃) and CuCl/PMDETA as catalyst was successfully carried out in bulk and solution. The apparent propagation rate constant (\(k_{\text{p}}^{{\text{app}}} \)) and concentration of active species ([P°]) were higher in the bulk. In solution they increased with polarity of solvent. Two different molecular weights of macroinitiators were used in ATRP of MMA. The linear relation of Ln[M]₀/[M] versus time was only confirmed for the low molecular weight macroinitiator. The ratio of \({{k_{\text{t}} } \mathord{\left/ {\vphantom {{k_{\text{t}} } {K_{{\text{eq}}} }}} \right. \kern-\nulldelimiterspace} {K_{{\text{eq}}} }} = 1.31 \times 10^{13} \;{\text{M}}^{ - 1} \,{\text{s}}^{ - 1} \) was calculated in the bulk reaction with the low molecular weight macroinitiator, this ratio was 1.77 × 10¹⁴ M⁻¹ s⁻¹ for larger macroinitiator in solution. The MWD of block copolymers were sharper with lower molecular weight macroinitiator in the solution, but it appeared broader in the bulk polymerization. Our results indicated that smaller molecular weight macroinitiator was more efficient and formed a block copolymer with lower PDI. Thermal analysis and microstructure of the block copolymers are investigated by ¹H NMR, FT-IR, TGA and DSC. The chain tacticity of the MMA units is found not to be sensitive to the kinetic of the reactions with two different molecular weights of macroinitiator. DSC measurement shows two different transitions at 39 and 108 °C assigned to PVAc and PMMA blocks. The TGA profile shows a three-step degradation. The initial small weight loss that occurs around 220 °C and two large weight loss around 238 and 310 °C are attributed to dechlorination step and decomposition of the PMMA and PVAc blocks.