Synthesis, Properties, and Applications of Bio-Based Cyclic Aliphatic Polyesters

Abstract

Cyclic polymers have long been reported in the literature, but their development has often been stunted by synthetic difficulties such as the presence of linear contaminants. Research into the synthesis of these polymers has made great progress in the past decade, and this review covers the synthesis, properties, and applications of cyclic polymers, with an emphasis on bio-based aliphatic polyesters. Synthetic routes to cyclic polymers synthesized from bioderived monomers, alongside mechanistic descriptions for both ring closure and ring expansion polymerization approaches, are reviewed. The review also highlights some of the unique physical properties of cyclic polymers together with potential applications. The findings illustrate the substantial recent developments made in the syntheses of cyclic polymers, as well as the progress which can be made in the commercialization of bio-based polymers through the versatility this topology provides.

Facile synthesis of monocyclic, dumbbell-shaped and jellyfish-like copolymers using a telechelic multisite hexablock copolymer

“…With tremendous progress in current polymer science, some architectural polymers with linear, cyclic, star, graft, hyperbranched and more complex hybrid structures have been synthesized. Compared to their linear analogues, cyclic [1][2][3][4][5][6][7][8][9][10][11][12] and graft [13][14][15][16][17][18][19] polymers usually exhibit some differences in physicochemical properties and specific applications due to their more compact structures and variations of inter/ intramolecular interactions. As cyclic and comblike blocks are covalently bonded together, a diversity of cyclic-graft conjugates such as cyclic graft polymers [20][21][22][23][24][25][26][27][28][29][30] and jellyfish-like polymers (JFPs) [31][32][33] with tunable properties and multipurpose applications can be obtained.…”

Polycondensation in confined nanopores toward the selective formation of narrowly dispersed linear polyesters

“…10,11 While this observation led to the development of numerous methods to prepare macrocyclic polymers, 12,13 it also pointed out a strong limitation in the synthesis of linear polymers free from contamination by cyclic polymers by SGP. 14 Despite the fast advancement in the synthesis and applications of macrocyclic polymers in recent years, [15][16][17][18] some functional polymers require pure linear topologies. 14 In some bifunctional polycondensations conducted in bulk systems, linear chains are found as the major products.…”

A Comprehensive Investigation of the Structural, Thermal, and Biological Properties of Fully Randomized Biomedical Polyesters Synthesized with a Nontoxic Bismuth(III) Catalyst

“…Nevertheless, the resulted polymers may contain traces of metal pollutants, leading to their high toxicity, which is undesirable for biomedical application [ 3 ]. As a result, they have been studied extensively over the last few decades, and significant progress has been made in terms of their synthesis using well-defined metalloorganic catalysts [ 4 ]. Among these, the use of alternative green catalysts has received particular consideration.…”

“…Given the foregoing, in this work we will concentrate on bismuth(III) 2-ethylhexanoate (bismuth octoate, BiOct 3 ), a potential nontoxic organometallic catalyst. Bi(III) is one of the ultratrace elements and its salts have long been used in medicine as both externally and internally administered drugs [ 4 , 7 , 8 ]. For example, bismuth(III) subsalicylate (BiSS) is a commercial drug for travelers’ diarrhea, nonulcer dyspepsia, and gastrointestinal complaints [ 7 ].…”

“…These compounds are stable in storage and, most importantly, nontoxic in the quantities needed [ 8 ]. Comparing to other nontoxic metal catalysts, bismuth (III) compounds are, therefore, well suited to ROP of lactides [ 4 ] and may lead to unusual, random Cap and LL sequences in the polymeric chain [ 11 ].…”