The transesterification of three ethylene and alkyl acrylate random copolymers (alkyl=methyl, ethyl and n-butyl) with 3-phenyl 1-propanol (PPOH) was studied in 1,2,4-trichlorobenzene solution and in the melt. Various catalysts were used, with dibutyltin dilaurate (DBTDL) and dibutyltin oxide (DBTO) showing the highest activities. The reaction between the poly(ethylene-co-methyl acrylate) and PPOH in solution in a closed reactor confirmed that this reaction is reversible. When operated in the melt in a semi-open batch mixer at temperatures between 170 and 190°C the equilibrium was totally shifted to the product side due to effective removal of the lighter alcohols generated from the reaction. The mechanism and rate constants of reaction are identical, regardless of the reaction medium chosen. The reactivity of an alkyl acrylate group towards PPOH depends, to a large extent, on the chemical structure of the alkyl group, and it follows the order: methyl > ethyl > n-butyl. This is primarily attributed to the fact that the longer the alkyl group, the lower the electrophilicity of the carbonyl carbon of the acrylate, and the higher the steric hindrance, both being detrimental to the reactivity. The steric hindrance argument is supported by the activation energies observed in the presence of DBTO as the catalyst: 69.0, 81.6 and 96.6kJmot-1 for the methyl, ethyl and n-butyl, respectively. Mechanical mixing favoured the reaction rate.
Посилання на статтю:
Catalysis and reactivity of the transesterification of ethylene and alkyl acrylate copolymers in solution and in the melt / Guo-Hua Hu and Morand Lambla // Polymer. – 1994. – Vol 35. – P. 3082-3090.