Thermal degradation kinetics of the biodegradable aliphatic polyester, poly(propylene succinate)

Abstract The preparation of the biodegradable aliphatic polyester poly(propylene succinate) (PPSu) using 1,3-propanediol and succinic acid is presented. Its synthesis was performed by two-stage melt polycondensation in a glass batch reactor. The polyester was characterized by gel permeation chromatography, 1 H NMR spectroscopy and differential scanning calorimetry (DSC). It has a number average molecular weight 6880 g/mol, peak temperature of melting at 44 °C for heating rate 20 °C/min and glass transition temperature at −36 °C. After melt quenching it can be made completely amorphous due to its low crystallization rate. According to thermogravimetric measurements, PPSu shows a very high thermal stability as its major decomposition rate is at 404 °C (heating rate 10 °C/min). This is very high compared with aliphatic polyesters and can be compared to the decomposition temperature of aromatic polyesters. TG and Differential TG (DTG) thermograms revealed that PPSu degradation takes place in two stages, the first being at low temperatures that corresponds to a very small mass loss of about 7%, the second at elevated temperatures being the main degradation stage. Both stages are attributed to different decomposition mechanisms as is verified from activation energy determined with isoconversional methods of Ozawa, Flyn, Wall and Friedman. The first mechanism that takes place at low temperatures is auto-catalysis with activation energy E  = 157 kJ/mol while the second mechanism is a first-order reaction with E  = 221 kJ/mol, as calculated by the fitting of experimental measurements.

[1]  Joseph H. Flynn,et al.  A quick, direct method for the determination of activation energy from thermogravimetric data , 1966 .

[2]  S. Girois,et al.  Polym. Degrad. Stab. , 1996 .

[3]  W. Deckwer,et al.  Biodegradation behavior and material properties of aliphatic/aromatic polyesters of commercial importance , 1997 .

[4]  Sang Yup Lee,et al.  Batch and continuous fermentation of succinic acid from wood hydrolysate by Mannheimia succiniciproducens MBEL55E , 2004 .

[5]  Stephen Z. D. Cheng,et al.  Poly(trimethylene teraphthalate) crystal structure and morphology in different length scales , 2001 .

[6]  Y. Doi,et al.  Thermal degradation of poly((R)-3-hydroxybutyrate), poly(e-caprolactone), and poly((S)-lactide) , 2002 .

[7]  G. Madras,et al.  Kinetics of thermal degradation of poly(ε-caprolactone) , 2003 .

[8]  T. Ozawa.  A New Method of Analyzing Thermogravimetric Data , 1965 .

[9]  C. Ou.  Crystallization behavior and thermal stability of poly(trimethylene terephthalate)/clay nanocomposites , 2003 .

[10]  Y. Shirai,et al.  Pyrolysis kinetics of poly(l-lactide) with carboxyl and calcium salt end structures , 2003 .

[11]  J. Puiggalí,et al.  Poly(ester amide)s derived from 1,4-butanediol, adipic acid and 6-aminohexanoic acid. Part II: composition changes and fillers , 2003 .

[12]  D. Bikiaris,et al.  Synthesis, thermal characterization, and tensile properties of alipharomatic polyesters derived from 1,3‐propanediol and terephthalic, isophthalic, and 2,6‐naphthalenedicarboxylic acid , 2005 .

[13]  Mari Takahashi,et al.  Development of implant tablet for a week-long sustained release. , 2004, Journal of controlled release : official journal of the Controlled Release Society.

[14]  D. Bikiaris,et al.  Synthesis and characterisation of branched and partially crosslinked poly(ethylene terephthalate) , 2003 .

[15]  S. Vyazovkin.  Computational aspects of kinetic analysis. Part C. The ICTAC Kinetics Project — the light at the end of the tunnel? , 2000 .

[16]  Xiu-li Wang,et al.  Kinetics of thermal degradation of flame retardant copolyesters containing phosphorus linked pendent groups , 2003 .

[17]  D. Yan,et al.  Thermal decomposition kinetics of poly(trimethylene terephthalate) , 2000 .

[18]  R. Olayo,et al.  Synthesis and thermal degradation of poly(n-butylisocyanate) modified by 1,3-propanesultone , 2003 .

[19]  Zhilong Xiu,et al.  Optimization of dissimilation of glycerol to 1,3-propanediol by Klebsiella pneumoniae in one- and two-stage anaerobic cultures , 2004 .

[20]  C. Nakamura,et al.  Metabolic engineering for the microbial production of 1,3-propanediol. , 2003, Current opinion in biotechnology.

[21]  H. L. Friedman,et al.  Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic plastic , 2007 .

[22]  T. Ozawa,et al.  Kinetic analysis of derivative curves in thermal analysis , 1970 .

[23]  D. Achilias,et al.  Study of various catalysts in the synthesis of poly(propylene terephthalate) and mathematical modeling of the esterification reaction , 2003 .

[24]  H. E. Kissinger.  Reaction Kinetics in Differential Thermal Analysis , 1957 .

[25]  A. Zeng,et al.  Study of two-stage processes for the microbial production of 1,3-propanediol from glucose , 2002, Applied Microbiology and Biotechnology.

[26]  P. Xu,et al.  Microbial fed-batch production of 1,3-propanediol by Klebsiella pneumoniae under micro-aerobic conditions , 2003, Applied Microbiology and Biotechnology.

[27]  H. E. Kissinger.  Variation of Peak Temperature With Heating Rate in Differential Thermal Analysis , 1956 .

[28]  Alfonso Jiménez,et al.  Thermal degradation of mixtures of polycaprolactone with cellulose derivatives , 2003 .

[29]  P. Dubois,et al.  Mechanisms and Kinetics of Thermal Degradation of Poly(ε-caprolactone) , 2001 .

[30]  G. Madras,et al.  Thermal degradation of binary physical mixtures and copolymers of poly(ε-caprolactone), poly(D, L-lactide), poly(glycolide) , 2004 .

[31]  Dan Gilead,et al.  Degradable polymers : principles and applications , 1995 .

[32]  D. Yan,et al.  High-resolution thermogravimetric analysis of poly(trimethylene terephthalate) with different molecular weights , 2001 .

[33]  H. Chang,et al.  Succinic acid production with reduced by-product formation in the fermentation of Anaerobiospirillum succiniciproducens using glycerol as a carbon source. , 2001, Biotechnology and bioengineering.