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Abstract
The modification of poly(ε-caprolactone) (PCL) was successfully conducted during reactive processing in the presence of dicumyl peroxide (DCP) or di-(2-tert-butyl-peroxyisopropyl)-benzene (BIB). The peroxide initiators were applied in the various amounts of 0.5 or 1.0 pbw (part by weight) into the PCL matrix. The effects of the initiator type and its concentration on the structure and mechanical and thermal properties of PCL were investigated. To achieve a detailed and proper explication of this phenomenon, the decomposition and melting temperatures of DCP and BIB initiators were measured by differential scanning calorimetry. The conjecture of the branching or cross-linking of PCL structure via used peroxides was studied by gel fraction content measurement. Modification in the presence of BIB in PCL was found to effectively increase gel fraction. The result showed that the cross-linking of PCL started at a low content of BIB, while PCL modified by high DCP content was only partially cross-linked or branched. PCL branching and cross-linking were found to have a significant impact on the mechanical properties of PCL. However, the effect of used initiators on poly(ε-caprolactone) properties strongly depended on their structure and content. The obtained results indicated that, for the modification towards cross-linking/branching of PCL structure by using organic peroxides, the best mechanical properties were achieved for PCL modified by 0.5 pbw BIB or 1.0 pbw DCP, while the PCL modified by 1.0 pbw BIB possessed poor mechanical properties, as it was related to over cross-linking.
Highlights
The growing consciousness of the importance of environmental protection, as well as the impact of manufacturing and application of polymers on the state of the environment, have resulted in increased interest in the development of eco-friendly materials [1,2,3,4]
The decomposition of the organic peroxides gives primary radicals that can be a source for secondary alkyl or aryl, which are formed by β-scission of primary radicals
Results of differential scanning calorimetry (DSC) analysis allowed to define the temperature of reactive processing for the reactive modification of PCL via free radical reaction initiated by organic peroxide
Summary
The growing consciousness of the importance of environmental protection, as well as the impact of manufacturing and application of polymers on the state of the environment, have resulted in increased interest in the development of eco-friendly materials [1,2,3,4]. Attention-grabbing aliphatic polyesters, especially poly(lactic acid) (PLA), polyhydroxyalkanoates including poly(3-hydroxybutyrate) (PHB), or poly(ε-caprolactone) (PCL) are biodegradable linear polymers, obtained from both renewable and petroleum sources [5,6,7]. Their industrial implementation is still limited due to their considerable drawbacks (e.g., low thermal stability, insufficient mechanical properties, high cost), which have led to the necessity of their further modification and reinforcing [8,9,10]. The cross-linking of biodegradable polyesters can be performed by reactive processing [15,16,17,18,19] or by irradiation such as β or γ [20,21,22]
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