Mechanisms and Kinetics of Thermal Degradation of Poly(ε-caprolactone)

Abstract

Thermogravimetric analysis (TGA) simultaneously coupled with mass spectrometry (MS) and Fourier transform infrared spectrometry (FTIR) was developed as an original technique to study the thermal modification/degradation of poly(epsilon-caprolactone) (PCL) through in depth analysis of the evolved gas. Perfectly well-defined PCL samples with controlled end groups, predictable molecular weight, and narrow molecular weight distribution were synthesized by living "coordination-insertion" ring-opening polymerization of epsilon-caprolactone initiated by aluminum triisopropoxide. TGA analyses carried out on purified PCL samples, deprived from any residual catalyst or monomer, highlighted a two-step thermal degradation. Evolved gas analysis by both MS and FTIR showed that the first process implies a statistical rupture of the polyester chains via ester pyrolysis reaction. The produced gases were identified as H(2)O, CO(2), and 5-hexenoic acid. The second step leads to the formation of epsilon-caprolactone (cyclic monomer) as result of an unzipping depolymerization process. The influence of parameters such as polyester molecular weight, nature of the PCL end groups, and presence of catalytic residues as well as the type of purge gas were investigated. The activation energy of the thermal degradation was also studied.

Fire and Gas Barrier Properties of Poly(styrene-co-acrylonitrile) Nanocomposites Using Polycaprolactone/Clay Nanohybrid Based-Masterbatch

“…Previous studies have shown [28,29] the possible degradation of PCL in the presence of catalytic residues. In order to avoid any undesirable parallel effect, Irganox MD1024 (0.05 wt%), a metal deactivator, was blended with SAN using a Brabender internal mixer operating at 220…”

Preparation and Characterizations of Poly(ethylene glycol)-Poly(ε-caprolactone) Block Copolymer Nanoparticles

“…Furthermore, it is recently reported that the PEG-PCL block copolymer showed an excellent potential for internalization into cellular cytoplasm by endocytosis. [20][21][22] Although a number of studies of PCL based amphiphilic block copolymers have well documented for the synthesis and characterization, [23][24][25][26][27][28] biodegradation, [29][30][31] and application for drug delivery systems, 32-34 the microscopic physicochemical properties of the diblock copolymers with different hydrophilic/hydrophobic balances still remain unclear. In this paper, we synthesized PEG-PCL diblock copolymers that have different PCL lengths with the fixed PEG chain length (MW 2000 Da), investigating their nanoparticle formations and physicochemical properties of the formed nanoparticles.…”

Effect of nanofiber content on bone regeneration of silk fibroin/poly(ε-caprolactone) nano/microfibrous composite scaffolds

“…19 Furthermore, its low melting temperature makes it suitable for melt electrospinning. 20 In this study, PCL was used as the main component in the microfibers. SF, a natural fibrous protein, gives high mechanical strength, elasticity, and softness.…”