Amorphous Unsaturated Aliphatic Polyesters Derived from Dicarboxylic Monomers Synthesized by Diels−Alder Chemistry

Abstract

A versatile method for synthesizing functionalized amorphous degradable polyesters via step growth polycondensation was investigated. A series of dicarboxylic acids and anhydrides were synthesized by Diels−Alder reactions of fumaric acid and maleic anhydride, respectively, with various dienes. The resulting difunctional monomers were reacted with 1,8-octanediol in the presence of tin octanoate catalyst at 160 °C and 30 mmHg for 24 h to form new unsaturated aliphatic polyesters. Each polyester had molecular weight 〈M n〉 between 1.0 × 104 and 2.0 × 104 g mol-1 and a polydispersity index near 2.0. All of the materials were amorphous and had glass transition temperatures between −30 and −15 °C. Each polymer repeat unit necessarily featured a double bond, which was exploited to cross-link the materials yielding degradable elastomers. Amine- and ether-containing polyesters were synthesized by using monomers formed from the corresponding polar functionalized dienes. Using this broad cycloaddition scheme, a variety of amorphous, functionalized polyesters were successfully synthesized.

Aqueous Micellar Systems Formed by Surfactant Ionic Liquids. Application in Diels-Alder Reactions

“…The micellar system selected as a reaction medium for the development of the cycloaddition between the mentioned diene and dienophile was found to be effective for the generation of cycloalkenes that present industrial interest. This statement is evidenced by the acceptable yield of the obtained cycloadducts: 24 h, 60%; 48 h, 70% using more benign conditions than those reported [5,6]. The use of adequate reaction media in these "economic in atoms" processes provides an approach aimed at improving both the chemical and environmental efficiency of these cycloaddition reactions.…”

Synthetic biodegradable elastomers for drug delivery and tissue engineering

“…For example, elastomers may be composed of polyols condensed with diacids [19], polyacids condensed with diols [21] (Fig. 2), and various other combinations including anhydrides, amines, ethers, and vinyl-containing components [20,22]. The preparation of biodegradable elastomers using step-wise addition polycondensation exhibits numerous disadvantages, however.…”

Synthesis and properties of polycarbonate copolymers of trimethylene carbonate and 2‐phenyl‐5,5‐bis(hydroxymethyl) trimethylene carbonate

“…In recent years, biodegradable aliphatic polycarbonates, such as poly(trimethylene carbonate) (PTMC) and poly(5,5‐dimethyl trimethylene carbonate) (PDTC), have attracted great interest for their use as biodegradable materials in drug delivery and tissue engineering because of their good medicine permeability, low immunogeneity, low toxicity, good elasticity, good biocompatibility, and degradability of surface erosion 1–7. Several aliphatic polycarbonates and their copolymers, such as PTMC, PDTC, and poly( L ‐lactic acid‐ co ‐trimethylene carbonate), have been investigated extensively for use in drug delivery, soft tissue implants, and tissue regeneration 8–22…”