Hemijska Industrija (Jan 2004)
Synthesis of thermoplastic poly(ester-olefin) elastomers
Abstract
A series of thermoplastic poly(ester-olefin) elastomers, based on poly(ethylene-stat-butylene), HO-PEB-OH, as the soft segment and poly (butylene terephthalate), PBT, as the hard segment, were synthesized by a catalyzed transesterification reaction in solution. The incorporation of soft hydrogenated poly(butadiene) segments into the copolyester backbone was accomplished by the polycondensation of α, ω-dihydroxyl telechelic HO-PEB-OH, (PEB Mn = 3092 g/mol) with 1,4-butanediol (BD) and dimethyl terephthalate (DMT) in the presence of a 50 wt-% high boiling solvent i.e., 1,2,4-trichlorobenzene. The molar ratio of the starting comonomers was selected to result in a constant hard to soft weight ratio of 60:40. The synthesis was optimized in terms of both the concentration of catalyst, tetra-n-butyl-titanate (Ti(OBu)4), and stabilizer, N,N'-diphenyl-p-phenylenediamine (DPPD), as well as the reaction time. It was found that the optimal catalyst concentration (Ti(OBu)4) for the synthesis of these thermoplastic elastomers was 1.0 mmol/mol ester and the optimal DPPD concentration was 1.0 wt-%. The extent of the reaction was followed by measuring the inherent viscosity of the reaction mixture. The effectiveness of the incorporation of the soft segments into the copolymer chains was proved by Soxhlet extraction with chloroform. The molecular structures, composition and the size of the synthesized poly(ester-butylene)s were verified by 1H NMR spectroscopy, viscometry of dilute solutions and the complex dynamic melt viscosity. The thermal properties of poly(ester-olefin)s were investigated by differential scanning calorimetry (DSC). The degree of crystallinity was also determined by DSC. The thermal and thermo-oxidative stability were investigated by thermogravimetric analysis (TGA). The rheological properties of poly(ester-olefin)s were investigated by dynamic mechanical spectroscopy in the melt and solid state.
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