The effect of chitosan form on the shape memory properties of polyurethane based composites
Introduction
Multifunctional biomaterials based on shape memory polymers (SMP) become promising class of materials for developing more advanced and user -friendly medical devices [1]. Shape-memory polymers (SMPs) are mechanically active or smart materials, which can be fabricated in a specific permanent shape, deformed and fixed in a second, temporary shape. The intrinsic mechanism for shape memory behavior in thermal responsive SMPs is the reversible freezing and activation of polymeric chain motion in the switching segments below and above the transition temperature (Ttrans), respectively. Polyurethane (PU) based on cross-linked poly(ε-caprolactone) (PCL) are one of the thermo-responsive SMP that exhibit reversible transition behavior associated with melting of PCL crystalline phase in a physiologically relevant range [2]. The previous study [3] revealed that chitosan incorporated into PU shape memory matrix may improve biocompatibility of the final material system due to its non-toxicity, antioxidant, antimicrobial, and antifungal bioactive properties. Despite the recent research on PU/chitosan composites [4], [5] the comprehensive data on structure - function correlation is required to design effective multifunctional material system. In this study the effect of the chitosan form i.e. microspheres or chitosan macromolecules on thermomechanical properties, microstructure and shape memory properties were evaluated.
Section snippets
Materials and methods
Two types of chitosan/polyurethane composites consisting of mixture of 3-branched and 2-branched PCL-based polyurethane matrix (PU-2/3 PCL) and chitosan microspheres (CH-Mic) or chitosan macromolecule units (CH-m) were developed. CH-Mic were prepared according to emulsification/chemical crosslinking method, using two types of crosslinkers – TPP solution 8% (v/v) and glutaraldehyde solution 35% (wt.%). Dimethyl sulfoxide - soluble chitosan was firstly prepared by the depolymerization of chitosan
Results and discussion
The functional properties i.e. shape memory capability, mechanical properties or transition temperature are strongly affected by chemical structure. The most significant features affecting shape memory and mechanical properties are hydrogen bonds. In case of PU macromolecules either intermolecular or intramolecular hydrogen bonds can be formed between urethane units. Moreover, chitosan active groups can also participate at hydrogen bond interaction. In order to analyze the chemical structure of
Conclusions
Development of multifunctional materials that exhibit independent material functions correlated with a particular component require in-depth structure/function analysis. In this study it was explored the crystallinity and shape memory properties of the composites consisting of PCL-based polyurethane matrix and chitosan incorporated in form of microspheres or macromolecule unit. Incorporation of chitosan in both forms led to small decrease shape recovery evaluated after first cycle.
CRediT authorship contribution statement
Monika Bil: Conceptualization, Investigation, Writing - original draft, Writing - review & editing, Project administration, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgment
This work was financed by National Science Centre Poland on the basis of a decision number DEC-2012/07/D/ST8/02588.
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