Copolymerization of vinyl chloride and methyl acrylate catalyzed by ethylaluminium compounds

Abstract

The copolymerization of vinyl chloride (VC) and methyl acrylate (MA) in the presence of ethylaluminium compounds (C2H5AlCl2, (C2H5)2AlCl, and (C2H5)3Al) at low ethylaluminium compound (EAC)/MA mole ratios was investigated. An alternating copolymer was produced in this reaction when an excess of VC in the initial monomer feed was used. The addition of dibenzoyl peroxide (BPO) to the systems containing EAC resulted in an increase of the alternating copolymer yield. In polymerization systems containing EAC resulted in an increase of the alternating copolymer yield. In polymerization systems containing EAC combined with VOCl3 an enhancement of the alternating copolymer yield and formation of VC‐rich copolymers were observed. In the polymerization system with (C2H5)3AlVOCl3 a VC‐rich copolymer was the main product. It was concluded that VC‐rich copolymers are formed in the random radical copolymerization which occurs when most of EAC is complexed by the alternating copolymer chain. The structure of alternating and VC‐rich copolymers was studied in detail by means of 13C NMR spectroscopy.