Reactivity ratios for new copolymerizations relevant to thermosetting resins

Free radical copolymerizations of four new systems, namely (1) methyl methacrylate (MMA) with β‐acryloxypropionic acid (AOPA); (2) MMA with p‐styrene sulphonyl chloride (SSC); (3) 2‐[(phenylamino) carbonyl] oxyethyl methacrylate (PCOMA) with 2‐phenoxyethyl methacrylate (PEMA); and (4) PCOMA with 1‐methyl‐2‐phenoxyethyl methacrylate (MPEMA), have been carried out at 60°C for systems 1 and 2 and at 70°C for systems 3 and 4. The copolymer compositions were analysed by acid‐base titration for system 1 and by FTIR for systems 2–4. The monomer reactivity ratios as well as the 95% individual confidence intervals and 95% joint confidence intervals were calculated from the Kelen‐Tüdős method, the Extended Kelen‐Tüdőos method, and from a new iterative linear method by Mao and Huglin. The results show that all these copolymerizations are strictly linear systems describable by the Mayo‐Lewis equation based on the terminal model and that accurate reactivity ratio data can be obtained. The Q‐e values of the monomers AOPA and SSC have been estimated. Some physical properties of AOPA, PEMA and MPEMA are also presented for the first time.