Enzyme Initiated Radical Polymerizations.docVIP

Polymers 2012, 4, 759-793; doi:10.3390/polym4010759 OPEN ACCESS polymers ISSN 2073-4360 /journal/polymers Review Enzyme Initiated Radical Polymerizations Frank Hollmann * and Isabel W. C. E. Arends Department of Biotechnology, Delft University of Technology, Julianalaan 136, 2628BL Delft, The Netherlands; E-Mail: i.w.c.e.arends@tudelft.nl * Author to whom correspondence should be addressed; E-Mail: f.hollmann@tudelft.nl; Tel.: +31-15-27-81957; Fax: +31-15-27-81415. Received: 30 January 2012; in revised form: 27 February 2012 / Accepted: 28 February 2012 / Published: 6 March 2012 Abstract: Biocatalysis is propagating into practically every area of organic chemistry, amongst them radical polymerizations. A review of the recent developments of this dynamic and quickly evolving area of research is presented together with a critical evaluation of its potential to yield novel polymers and/or environmentally more benign synthetic procedures. Keywords: radical polymerization; laccase; peroxidase; biocatalysis 1. Introduction Great aspirations have been put on biocatalysts to make the chemical industry environmentally more benign and sustainable [1–3]. Indeed, more and more examples impressively demonstrate the potential of White Biotechnology to reduce resource consumption and waste generation [1,4–6]. However, most of the ?landmark‘ examples deal with the synthesis of small, chiral molecules useful for pharmaceuticals etc. Traditionally, the wastes generated in this industry are enormous, leaving room for significant improvements [7]. The global impact, however, is limited by the comparably low production volumes. In contrast, polymers are bulk products produced in huge annual quantities. Here, though the saving potential might be lower due to highly optimized ?traditional‘ production schemes, even comparably small improvements may have a dramatic global impact. Hence, it is