Thermal degradation and mass-spectrometric fragmentation processes of polyesters studied by time/temperature-resolved pyrolysis-field ionization mass spectrometry

Plage, Bernd; Schulten, H.–R.

doi:10.1021/ma00212a008

Cited by 49 publications

(22 citation statements)

References 7 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In a study of degradation of aliphatic polyesters, the anomalous behavior of PPAd was explained through formation of specific degradation products. These are butyrodiketene, cyclopentanone, and a stable cyclic anhydride with seven‐membered ring 31. Thus, PPAd represents a unique case of aliphatic polyester, the degradation of which results in formation of favorable stable products.…”

Section: Resultsmentioning

confidence: 99%

Correlation between Chemical and Solid‐State Structures and Enzymatic Hydrolysis in Novel Biodegradable Polyesters. The Case of Poly(propylene alkanedicarboxylate)s

Bikiaris

Papageorgiou

Giliopoulos

et al. 2008

Macromolecular Bioscience

View full text Add to dashboard Cite

A series of seven fast-biodegrading aliphatic polyesters were prepared from 1,3-propanediol and aliphatic diacids with increasing number of methylene units (x). Melting points decreased from PPSu to PPAd and then increased again to PPAz and PPSeb. Crystallization rates and thermal stability increased steadily with increasing x. Glass transition temperatures decreased steadily to PPPim and subsequently increased. Enzymatic degradation of the polymers in the presence of a mixture of Rhizopus delemar and Pseudomonas cepacia lipases was much faster than that of poly(epsilon-caprolactone). All the polyester specimens were almost disintegrated within 36 h. PPSub exhibited the fastest enzymatic hydrolysis rates, PPAd and PPSuc the slowest.

show abstract

Section: Resultsmentioning

confidence: 99%

Correlation between Chemical and Solid‐State Structures and Enzymatic Hydrolysis in Novel Biodegradable Polyesters. The Case of Poly(propylene alkanedicarboxylate)s

Bikiaris

Papageorgiou

Giliopoulos

et al. 2008

Macromolecular Bioscience

View full text Add to dashboard Cite

show abstract

“…[14] Studies on the thermal stability of PLLA have been reported by several groups. [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] Based on the reported results, thermal degradation of PLLA is more complex than the simple reaction that gives lactide, and significant amounts of the other volatile decomposition products are also created during pyrolysis.…”

Section: Thermal Degradation Processes Of Poly(lactide)mentioning

confidence: 99%

Thermal Degradation of Environmentally Degradable Poly(hydroxyalkanoic acid)s

Abe

2006

Macromolecular Bioscience

104

View full text Add to dashboard Cite

Aliphatic polyesters have attracted industrial attention as environmentally degradable thermoplastics to be used for a wide range of applications. Besides intensive studies on the biodegradability of aliphatic polyesters, understanding of the thermal stability has importance for processing, application, and recycling. The details of thermal degradation processes of five types of aliphatic polyesters; namely, poly(L-lactide), poly(3-hydroxybutyric acid), poly(4-hydroxybutyric acid), poly(delta-valerolactone), and poly(epsilon-caprolactone), were investigated by means of several thermoanalytical techniques under both isothermal and non-isothermal conditions. In this feature article, the thermal degradation behaviors of aliphatic polyesters with different numbers of carbon atoms in the main chain of the monomeric unit are reviewed. In addition, the effects of chain-end structure and residual metal compounds on the thermal degradation processes of aliphatic polyesters consisting of hydroxyalkanoic acid monomeric units are presented. Schemes of thermal degradation reaction of poly(hydroxyalkanoic acid)s.

show abstract

“…[8][9][10][11][12][13][14][15] Iwabuchi et al 8 investigated the thermal degradation behavior under isothermal degradation condition at 220°C. By monitoring the time-dependent changes in sample weight and viscosity, they proposed a single step degradation mechanism, where the polymer degrades by specific removal of cyclic monomer from the end groups.…”

Section: Introductionmentioning

confidence: 99%

Effects of Residual Zinc Compounds and Chain-End Structure on Thermal Degradation of Poly(ε-caprolactone)

et al. 2004

View full text Add to dashboard Cite

Effects of chain-end structure and residual metal compounds on thermal degradation of poly(epsilon-caprolactone) (PCL) were investigated by means of thermogravimetric and pyrolysis-gas chromatograph mass spectrometric analyses. Four types of PCL samples with different chain-end structures (alpha-carboxylic acid-omega-hydroxyl-PCL, alpha-dodecyl ester-omega-hydroxyl-PCL, alpha-carboxylic acid-omega-acetyl-PCL, and alpha-dodecyl ester-omega-acetyl-PCL) were prepared by ring-opening polymerization of epsilon-caprolactone in the presence of zinc-based catalyst and by subsequent acetylation reaction of polymers with acetic anhydride. PCL samples with different zinc contents were obtained by washing with acetic acid in chloroform solution of polymer. Thermal degradation behaviors of these PCL samples with different chain-end structures were examined under both isothermal and nonisothermal conditions. From both the isothermal and nonisothermal experiments, the thermal degradation of PCL samples containing high amounts of residual zinc compounds from synthesis process revealed the selective unzipping depolymerization step below 300 degrees C producing epsilon-caprolactone exclusively. In contrast, zinc-free PCL samples were stable at temperatures below 300 degrees C, and the thermal degradation occurred only at temperatures above 300 degrees C regardless of the chain-end structure. From (1)H NMR analysis of the residual molecules after isothermal degradation of zinc-free PCL, it was confirmed that the omega-chain-end of residual molecules was 5-hexenoic acid unit. However, the cyclic monomer and oligomers were detected as the volatile products of zinc-free PCL samples. These results suggest that the dominant reaction of thermal degradation for PCL above 300 degrees C is a competition between the random chain scission via cis elimination reaction and the cyclic rupture via intramolecular transesterification of PCL molecules.

show abstract

Thermal degradation and mass-spectrometric fragmentation processes of polyesters studied by time/temperature-resolved pyrolysis-field ionization mass spectrometry

Cited by 49 publications

References 7 publications

Correlation between Chemical and Solid‐State Structures and Enzymatic Hydrolysis in Novel Biodegradable Polyesters. The Case of Poly(propylene alkanedicarboxylate)s

Correlation between Chemical and Solid‐State Structures and Enzymatic Hydrolysis in Novel Biodegradable Polyesters. The Case of Poly(propylene alkanedicarboxylate)s

Thermal Degradation of Environmentally Degradable Poly(hydroxyalkanoic acid)s

Effects of Residual Zinc Compounds and Chain-End Structure on Thermal Degradation of Poly(ε-caprolactone)

Contact Info

Product

Resources

About