Oxidative Copolymerisation of para-Functionalized Phenols Catalyzed by Horseradish peroxidase and Thermocrosslinking via Diels-Alder and (1+3) Cycloaddition

• Published in: Macromolecular bioscience Vol. 1; no. 3; pp. 85 - 90
• Main Authors: Reihmann, Matthias H., Ritter, Helmut
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag GmbH 01.03.2001; WILEY‐VCH Verlag GmbH; Wiley-VCH
• Subjects: Applied sciences; Copolymerization; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Preparation, kinetics, thermodynamics, mechanism and catalysts; Phenylene derivative copolymer; Enzyme; Nitrone; Furan derivatives; Diels Alder addition; Enzymatic catalysis; Experimental study; Functional polymer; Thermosetting resin; Peroxidases; Curing(plastics); Preparation; Phenols; Peroxidase; Oxidoreductases; Oxidative polymerization; Chemical reactivity
• ISSN: 1616-5187; 1616-5195
• DOI: 10.1002/1616-5195(20010301)1:3<85::AID-MABI85>3.0.CO;2-N

The horseradish peroxidase‐ (HRP‐) catalyzed polyrecombination of N‐(4‐hydroxyphenyl)‐2‐furamide (2) and 4‐hydroxyphenylmaleimide (1) is described. The resulting copolymer was used to build crosslinked materials via Diels‐Alder and cycloaddition reactions. We followed the enzymatic copolymerization process of an equimolar mixture of 1 and 2 using high pressure liquid chromatography (HPLC), size‐exclusion chromatography (SEC) and by matrix assisted laser desorption/ionization‐time of flight mass spectroscopy (MALDI‐TOF MS) analysis and found that the polymerization of 2, which has a significant higher highest occupied molecular orbital (HOMO) energy, proceeds much faster. The HOMO energies of 1 and 2 were calculated using a differential Fourier transform (DFT) method. Furthermore, we tested copolymers consisting of the monomer units 4‐hydoxybenzaldehyde‐methylnitrone (3) and N‐methacryloyl‐11‐aminoundecanoyl‐4‐hydroxyanilide (4) on their ability to form networks via 1,3‐dipolaric cycloaddition reactions upon heating. The crosslinking of all copolymers was proven by Fourier transform infrared (FT‐IR) spectroscopy.