Synthesis of Oxetane-Functional Aliphatic Polyesters via Enzymatic Polycondensation

• Published in: Macromolecular chemistry and physics Vol. 213; no. 17; pp. 1783 - 1790
• Main Authors: Müller, Sophie S., Frey, Holger
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 14-09-2012; WILEY‐VCH Verlag; Wiley
• Subjects: 3,3‐bis(hydroxymethyl)oxetane; 3-bis(hydroxymethyl)oxetane; Applied sciences; enzyme CALB; Exact sciences and technology; Lipase B; Organic polymers; Physicochemistry of polymers; Polycondensation; polyesters; Preparation, kinetics, thermodynamics, mechanism and catalysts; Photochemical crosslinking; Sebacate copolymer; 3-bis(hydroxymethyl)oxetane; Triacylglycerol lipase; Enzymatic catalysis; Esterases; Condensation polymerization; Oxetane derivatives; Sebacate polymer; polycondensation; Cyclic ether copolymer; Aliphatic polymer; Catalytic reaction; enzyme CALB; Enzyme; Ester polymer; Experimental study; polyesters; Carboxylic ester hydrolases; Cardo polymer; Lipase B; Ester copolymer; Cyclic ether polymer; Light sensitive polymer; Preparation; Copolycondensation; Hydrolases; Light sensitive copolymer; Aliphatic copolymer
• ISSN: 1022-1352; 1521-3935
• DOI: 10.1002/macp.201200269

Synthesis, characterization, and thermal properties of a series of oxetane‐functional aliphatic polyesters are investigated. The incorporation of the acid‐sensitive 3,3‐bis(hydroxymethyl)oxetane (BHMO) into polymers is achieved by using the enzyme CALB (Candida antarctica Lipase B) as a catalyst. This mild synthetic strategy provides well‐defined, oxetane‐functional polyesters. The enzymatic polycondensation allows for the synthesis of a series of aliphatic polyesters containing various ratios of the difunctional monomers sebacic acid, 1,8‐octanediol, and BHMO with molecular weights between 5000–9800 g mol−1 and polydispersity indices (Mw/Mn) in the range of 1.25 and 1.92. Furthermore, crosslinking of BHMO and a polymer sample is carried out via opening of the pending oxetanes.
The incorporation of 3,3‐bis(hydroxymethyl)oxetane (BHMO) into aliphatic polyesters is described. The strategy introduces oxetane‐diols as a new type of reactive monomers for Lipase B (CALB) and demonstrates the possibilities of enzymatic polycondensation as an orthogonal strategy for acid‐labile diols. Additionally, the characterization, physical properties, and crosslinking are investigated.