Abstract

Cyclic PCL (c-PCL) has drawn great attention from academia and industry because of its unique, unusual structure and property characteristics due to the absence of end groups in addition to the biocompatibility and biodegradability of its linear analogue. As a result of much research effort, several synthetic methods have been developed to produce c-PCLs so far. Their chain, morphology and property characteristics were investigated even though carried out on a very limited basis. This feature article reviews the research progress made in the synthesis, morphology, and properties of c-PCL; all results and their pros and cons are discussed in terms of purity and molecular weight distribution in addition to the cyclic topology effect. In addition, we attempted to synthesize a series of c-PCL products of high purity by using intramolecular azido-alkynyl click cyclization chemistry and subsequent precise and controlled separation and purification; and their thermal degradation and phase transitions were investigated in terms of the cyclic topology effect.

Highlights

  • Linear poly(ε-caprolactone) (PCL) has attracted great attention from both academia and industry because of its wide application potential ranging from surgical sutures, stents, prosthetics, artificial implants, wound dressings, tissue engineering, drug delivery systems, to environmentally friendly material systems, based on its biocompatibility and biodegradability [1,2,3,4,5].The research interest has recently been extended to topological PCLs

  • We review the synthetic schemes, properties, and morphological structures of cyclic PCL (c-PCL) reported in the literature so far

  • Polymers 2018, 10, 577 was synthesized by using the intramolecular click chemistry of linear PCL precursors possessing an azido group on one chain end and an alkynyl group on the other chain end; their thermal properties were examined by using thermogravimetry (TGA) and differential scanning calorimetry (DSC)

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Summary

Introduction

Linear poly(ε-caprolactone) (PCL) has attracted great attention from both academia and industry because of its wide application potential ranging from surgical sutures, stents, prosthetics, artificial implants, wound dressings, tissue engineering, drug delivery systems, to environmentally friendly material systems, based on its biocompatibility and biodegradability [1,2,3,4,5]. The properties and structures of c-PCL products have been investigated on a very limited basis. In this feature article, we review the synthetic schemes, properties, and morphological structures of c-PCL reported in the literature so far. We discuss new results of the precise synthesis and thermal properties of c-PCL recently achieved in our laboratory. Polymers 2018, 10, 577 was synthesized by using the intramolecular click chemistry of linear PCL precursors possessing an azido group on one chain end and an alkynyl group on the other chain end; their thermal properties were examined by using thermogravimetry (TGA) and differential scanning calorimetry (DSC)

Synthesis
Ring-Expansion Polymerization
Intermolecular Cyclization
Intramolecular Cyclizations
Alkyne–Alkene Metathetic Cyclization
Chain Structure Characteristics
Hydrodynamic Volume
Solution Viscosity
Melt Viscosity and Chain Mobility
Properties
Acid–Catalytic Degradation
Thermal Degradation
Crystallization Characteristics
Morphological Characteristics
Findings
Summary and Perspectives

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