Solid-State Polymerization of Poly(trimethylene terephthalate): Reaction Kinetics and Prepolymer Molecular Weight Effects

2012 ◽  
Vol 51 (7) ◽  
pp. 2904-2912 ◽  
Author(s):  
Young Jun Kim ◽  
Jaehoon Kim ◽  
Seong-Geun Oh
Keyword(s):  
Molecular Weight ◽  
Solid State ◽  
Reaction Kinetics ◽  
Solid State Polymerization ◽  
Trimethylene Terephthalate

Preparation and characterization of high molecular weight poly(trimethylene terephthalate) by solid-state polymerization

e-Polymers ◽  
2011 ◽  
Vol 11 (1) ◽  
Author(s):  
Kim Seok Hoon ◽  
Kim Joon Ho
Keyword(s):  
Molecular Weight ◽  
Reaction Time ◽  
Solid State ◽  
High Molecular Weight ◽  
Melting Temperature ◽  
Average Molecular Weight ◽  
Pellet Size ◽  
Solid State Polymerization ◽  
Trimethylene Terephthalate ◽  
High Molecular Weight Poly

AbstractSolid-state polymerization has been widely used to prepare high molecular weight poly(ethylene terephthalate). Solid-state polymerization is generally carried out by heating solid, melt-phase-polymerized polymer below its melting temperature but above its glass transition temperature. Solid-state polymerization of poly(trimethylene terephthalate)(PTT) is not an independent process but rather an additional process with respect to melt polymerization that is used when PTT of a higher molecular weight is required. Two kinds of commercial PTT chips were polymerized in the solid state to prepare high molecular weight PTT, which were characterized by end group contents, molecular weight, thermal analysis and X-ray diffraction. In the solid-state polymerization of PTT, the overall reaction rate was governed by the reaction temperature, reaction time and pellet size. The content of carboxyl end groups was decreased during the solid-state polymerization with increasing reaction time and temperature. The melting temperature and crystallinity of solid-state-polymerized PTT were higher at longer times and higher temperatures of polymerization. The activation energy for the solid-state polymerization of PTT was in the range of 24~25 kcal/mol for each chip. Through the solid-state polymerization of commercial PTT chips, we could get high molecular weight polymers up to an intrinsic viscosity value of 1.63 dl/g, which is equivalent to about a 117,000 weight-average molecular weight.

Broadening of molecular-weight distribution in solid-state polymerization resulting from condensate diffusion

2000 ◽  
Vol 79 (5) ◽  
pp. 928-943 ◽  
Author(s):  
Michael D. Goodner ◽  
Stephen M. Gross ◽  
Joseph M. Desimone ◽  
George W. Roberts ◽  
Douglas J. Kiserow
Keyword(s):  
Molecular Weight ◽  
Solid State ◽  
Molecular Weight Distribution ◽  
Weight Distribution ◽  
Solid State Polymerization

scholarly journals Solid-State Polymerization of Poly(Ethylene Furanoate) Biobased Polyester, III: Extended Study on Effect of Catalyst Type on Molecular Weight Increase

Polymers ◽  
2019 ◽  
Vol 11 (3) ◽  
pp. 438 ◽  
Author(s):  
Yosra Chebbi ◽  
Nejib Kasmi ◽  
Mustapha Majdoub ◽  
George Papageorgiou ◽  
Dimitris Achilias ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Thermal Properties ◽  
Solid State ◽  
Intrinsic Viscosity ◽  
Weight Increase ◽  
Degree Of Crystallinity ◽  
Solid State Polymerization ◽  
End Groups ◽  
Poly Ethylene ◽  
Molecular Weight Increase

In this study, the synthesis of poly(ethylene furanoate) (PEF), catalyzed by five different catalysts—antimony acetate (III) (Sb Ac), zirconium (IV) isopropoxide isopropanal (Zr Is Ip), antimony (III) oxide (Sb Ox), zirconium (IV) 2,4-pentanedionate (Zr Pe) and germanium (IV) oxide (Ge Ox)—via an industrially common combination of melt polymerization and subsequent solid-state polymerization (SSP) is presented. In all reactions, proper amounts of 2,5-dimethylfuran-dicarboxylate (DMFD) and ethylene glycol (EG) in a molar ratio of DMFD/EG= 1/2 and 400 ppm of catalyst were used. Polyester samples were subjected to SSP procedure, under vacuum application, at different reaction times (1, 2, 3.5, and 5 h) and temperatures of 190, 200, and 205 °C. Carboxyl end-groups concentration (–COOH), intrinsic viscosity (IV), and thermal properties, via differential scanning calorimetry (DSC), were measured for all resultant polymers to study the effect of the used catalysts on the molecular weight increase of PEF during SSP process. As was expected, it was found that with increasing the SSP time and temperature, the intrinsic viscosity and the average molecular weight of PEF steadily increased. In contrast, the number of carboxyl end-groups content showed the opposite trend as intrinsic viscosity, that is, gradually decreasing during SSP time and temperature increase. It is worthy to note that thanks to the SSP process an obvious and continuous enhancement in the thermal properties of the prepared PEF samples was attained, in which their melting temperatures (Tm) and degree of crystallinity (Xc) increase progressively with increasing of reaction time and temperature. To predict the time evolution of polymers IV, as well as the hydroxyl and carboxyl content of PEF polyesters during the SSP, a simple kinetic model was developed. From both the theoretical simulation results and the experimental measurements, it was demonstrated that surely the Zr Is Ip catalyst shows the best catalytic characteristics compared to all other used catalysts herein, that is, leading in reducing—in a spectacular way—the activation energy of the involved both transesterification and esterification reactions during SSP.

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