Kinetic study of the alternating copolymerization of butadiene and methyl methacrylate

Abstract

SynopsisA kinetic investigation of the alternating copolymerization of butadiene and methyl methacrylate with the use of a system of ethylaluminum dichloride and vanadyl chloride as a catalyst was undertaken. The relation between the polymer yield and the molar fraction of methyl methacrylate in the feed was examined by continuous variation of butadiene and methyl methacrylate, the concentrations of total monomer, ethylaluminum dichloride, and vanadyl chloride being kept constant. This continuous variation method revealed that the polymer yield attains its maximum value with a monomer feed containing less than the 0.5 molar fraction of methyl methacrylate. This value of the molar fraction of methyl methacrylate affording the maximum polymer yield decreased on increasing the total monomer concentration but was not changed on varying the concentration of ethylaluminum dichloride. The number of active species estimated from the relation between yield and molecular weight of the polymer was almost constant, regardless of the molar fraction of methyl methacrylate in the feed. Consequently, it can be said that the maximum polymer yield depends mainly on the propagation reaction, not on the initiation reaction or the termination reaction. Three types of the mechanism have been discussed for this alternating copolymerization: polymerization via alternating addition of butadiene and methyl methacrylate complexed with ethylaluminum dichloride by the Lewis-Mayo scheme; polymerization via the ternary intermediate of butadiene, methyl methacrylate, and ethylaluminum dichloride; polymerization via the complex formation of butadiene and methyl methacrylate complexed with ethylaluminum dichloride occurring only at the growing polymer radical. From the kinetic results obtained, it was shown that the first and third schemes are excluded, and polymerization by way of the ternary intermediate is compatible with the data.

Methylaluminoxane as a New Catalyst for Alternating Copolymerization between 1,3-Butadiene and Methyl Methacrylate

“…Typical results are shown in Table 1. The data obtained with EtAlCl 2 /VOCl 3 , 8 which was the most active catalyst system reported so far, are also included for reference. When MAO was added into the ampule, the polymerization solution gradually became viscous and was difficult to be stirred after 2 h. It is apparent from Table 1 that the polymer yields are strongly dependent upon the molar ratios of two monomers in the feed (f BD ), reaching a maximum at f BD ) 50 mol % (run 3).…”

“…d Mole fraction of BD in the copolymers. e Solvent, dichloromethane; [VOCl 3 ], 4 mmol/L; polymn temp, 0 °C; polymn time, 25 h (ref ).…”