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Abstract
Precise structure-property relation of a biodegradable polymer (e.g., aliphatic polyester) is anticipated only if monomer units and chiral centers are arranged in a defined primary sequence as a biomacromolecule. An emerging synthetic methodology, namely segmer assembly polymerization (SAP), is introduced in this paper to reveal the latest progress in polyester synthesis. Almost any periodic polyester envisioned can be synthesized via SAP using a programed linear or cyclic monomer. In this context, the macroscopic properties of a biodegradable polymer are fundamentally determined by microstructural information through a bottom-up approach. It can be highlighted that SAP ideally combines the precision of organic synthesis and the high efficiency of a polymerization reaction. Previously reported strategies including nucleophilic displacement, polyesterification, cross-metathesis polymerization (CMP), ring-opening polymerization (ROP), ring-opening metathesis polymerization (ROMP) and entropy-driven ring-opening metathesis polymerization (ED-ROMP) are critically reviewed in this paper to shed light on precision synthesis of aliphatic polyesters via SAP. Emerging yet challenging, SAP is a paradigm which reflects the convergence of organic and polymer chemistries and is also an efficient pathway to microstructural control. The current status, future challenges and promising trends in this realm are analyzed and discussed in this overview of the state-of-the-art.
Highlights
With the increasingly urgent demand for biocompatible and bioassimilable materials, synthetic biodegradable polymers elicit extensive attention from both academic and industrial communities [1].In particular, as typical healthcare materials, aliphatic polyesters are widely used in the biomedical field [2]
Most goes from homopolymers to of the precision aliphatic polyesters have already been reported in the literature, and the ones with even of the precision aliphatic polyesters have already been reported in literature, the literature, andones the ones with the precision aliphatic polyesters have already been reported in the and the with even more complex microstructures are anticipated to be obtainable in the near future
Selected examples of precision synthesis of aliphatic polyesters via segmer assembly polymerization (SAP) are listed below, which can be categorized as step-growth polymerization (nucleophilic displacement, polyesterification and Selected examples of precision synthesis of aliphatic polyesters via SAP are listed below, which can be categorized as step-growth polymerization (nucleophilic displacement, polyesterification and cross-metathesis polymerization (CMP)) together with chain-growth polymerization (ring-opening can be categorized as step-growth polymerization (nucleophilic displacement, polyesterification and cross-metathesis(ROP), polymerization (CMP))
Summary
With the increasingly urgent demand for biocompatible and bioassimilable materials, synthetic biodegradable polymers elicit extensive attention from both academic and industrial communities [1]. As typical healthcare materials, aliphatic polyesters are widely used in the biomedical field [2]. Aliphatic polyesters are among the most promising candidates for the replacement of petroleum-based polymers due to the wide availability of biorelevant monomers, ease of synthesis and biocompatibility of polymers and degradation products. Polycondensation and ring-opening polymerization (ROP) are the most widely used techniques for the synthesis of aliphatic polyesters (see Scheme 1). Application areas of aliphatic carboxyanhydrides [17]. Application areas of aliphatic polyesters range from clothing and packaging polyesters range from clothing and packaging agriculture and biomedicine [18,19,20,21,22,23,24,25,26,27,28].drug.
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