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Kinetics of copolycondensation of bis(4‐hydroxybutyl) terephthalate and bis(2‐hydroxyethyl) terephthalate by ester‐interchange reaction
Author(s) -
Lyoo Won Seok,
Kim Joon Ho,
Ha Wan Shik
Publication year - 1996
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/(sici)1097-4628(19961017)62:3<473::aid-app5>3.0.co;2-n
Subject(s) - condensation polymer , monomer , dimethyl terephthalate , polymer chemistry , catalysis , chemistry , kinetics , reaction rate constant , polymerization , polyethylene terephthalate , reactivity (psychology) , proton nmr , organic chemistry , materials science , polymer , medicine , physics , alternative medicine , composite material , quantum mechanics , pathology
The kinetics of polycondensation and copolycondensation reactions were investigated using bis(4‐hydroxybutyl) terephthalate (BHBT) and bis (2‐hydroxyethyl) terephthalate (BHET) as monomers. BHBT was prepared by ester interchange reaction of dimethyl terephthalate and 1,4‐butanediol. BHBT and BHET were polymerized at 270°C in the presence of titanium tetrabutoxide (TBT) as a catalyst. Applying second‐order kinetics for polycondensation, the rate constants of polycondensation of BHBT and BHET, k 11 and k 22 , were calculated as 3.872 min −1 and 2.238 min −1 , respectively. BHBT and BHET were also copolymerized at 270°C using TBT. The rate constants of crossreactions in the copolycondensation of BHBT and BHET, k 12 and k 21 , were obtained by using the results obtained from a proton nuclear magnetic resonance ( 1 H‐NMR) spectroscopy and a high‐performance liquid chromatography (HPLC). It was found that the rate constants during the copolycondensation of BHBT and BHET at 270°C decreased in the order k 21 > k 11 > k 22 > k 12 and the monomer reactivity ratio of BHBT was four or five times larger than that of BHET. In calculating the crossreactions, the method by the 1 H‐NMR spectroscopy gave more accurate results than that by the HPLC. © 1996 John Wiley & Sons, Inc.