Catalysis in the synthesis of hyperbranched polyesters

Abstract

An AB2 monomer, dimethyl 5-(2-hydroxyethoxy)isophthalate was prepared on a scale of 3kg. It was successfully polymerised in the melt and the influence of reaction conditions and catalysts was studied. Structural and physical characterisation of these materials was performed using variety of analytical techniques, including SEC and MALDI-TOF MS. The polymerisations yielded high molecular weight materials with a broad polydispersity. All polymers were cyclised, the proportion of cyclised species increased with time, generally until complete cyclisation was achieved. The polymerisation process conditions were varied and a reaction protocol establishing a degree of reproducibility was achieved. Catalysts were found to promote polycondensation, cyclisation and transesterification reactions. The trends of increase in molecular weights were similar to those observed in uncatalysed reactions. Catalysts based on divalent metals showed a higher activity compared to those based on tri- and tetravalent metals. Qualitatively alcoholysis and cyclisation occurred at about the same rate whether catalysed or uncatalysed and ester-ester interchange was significantly slower under all circumstances. There were only relatively small differences between the effects of the catalysts investigated, apart from Vertec 400AC, which caused very fast reaction and yielded an insoluble product of unidentified structure. A new route to the synthesis of an A(_2)B monomer, methyl 3,5-bis(2-hydroxyethoxy)benzoate, was also reported. The monomer was synthesised on a 10g scale and successfully polymerised. The polymer samples were functionalised with acetoxy groups and characterised by SEC and MALDI-TOF MS. Evidences for the presence of polycondensation, cyclisation and ester-ester interchange reactions were observed. Growth in molecular weights and in cyclisation for poly(methyl 3,5-bis(2-hydroxyethoxy)benzoate)s was faster than that for poly(dimethyl 5-(2-hydroxyethoxy)isophthalate)s prepared under same conditions.