Copolymerization of Benzoylphenyl Methacrylate with Methyl Methacrylate: Synthesis, Characterization and Determination of Monomer Reactivity Ratios

Abstract

4‐Benzoylphenyl methacrylate (BPM) was prepared by reacting 4‐hydroxy benzophenone dissolved in methyl ethyl ketone (MEK) with methacryloyl chloride in the presence of triethylamine. The copolymers of BPM with methyl methacrylate (MMA) having different copolymer composition were synthesized in a MEK solution using benzoyl peroxide (BPO) as a free radical initiator at 70±1°C. The copolymers were characterized by FT‐IR, 1H‐NMR and 13C‐NMR spectroscopic techniques. The molecular weights (M¯w and M¯n) and polydispersity indices (M¯w/M¯n) of the polymers were determined using gel permeation chromatograph. The glass transition temperatures (Tg) of the copolymers determined by differential scanning calorimeter reveals that Tg increases with increase in BPM content in the copolymer. Thermogravimetric analysis of the polymers performed in air shows that the stability of the copolymer increases with an increase in BPM content. The solubility of the polymers was tested in various polar and non‐polar solvents. Copolymer compositions were determined by the 1H‐NMR spectroscopy by comparing the integral peak areas of well separated aromatic and aliphatic proton peaks. The monomer reactivity ratios were determined by the application of conventional linearization methods such as Fineman‐Ross (r1=2.201: r2=0.814), Kelen Tüdös (r1=2.121: r2=0.634), extended Kelen Tüdös (r1=2.153: r2=0.698), as well as by a non‐linear error‐in‐variable model method (EVM) using a computer program RREVM (r1=1.638: r2=0.543).