Cellulose is one of the most abundant biopolymers on earth and is the cornerstone of products such as paper, cardboard and clothing. However, due to the excellent material properties of cellulose, such as high strength and low weight, it is foreseen that with proper modification, cellulose could be employed in various other applications.1,2 An interesting approach to cellulose modification is through long chain grafting, a topic that has been extensively studied since the 50’s.3 One particularly interesting polymerization method for this purpose is ring opening polymerization (ROP), as it can be initiated from the hydroxyl groups on the cellulose backbone and hence no modification of the cellulose is necessary in order to form grafts.4 There exist several reports in the literature on the grafting of both PCL and PLA utilizing ROP from cellulose surfaces. Herein, the surface-initiated ROP of trimethylene carbonate (TCM) and hexamethylcyclotrisiloxane (HMCS) employing organocatalytic systems, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), has been investigated. The ability to control the grafting length of the polymer from the surface was demonstrated by either altering the time of the polymerisation or the ratio of free initiator to monomer. TBD was a highly efficient catalyst, both for TCM and HMCS, resulting in hydrophobic paper in as little as one minute. However; when DBU was employed for the ROP of HMCS, no polymer was formed. This polymerisation route provides milder conditions than conventional metal-catalysed ROP, greatly reducing reaction times and thus is an attractive method for modification of natural biopolymers compared to previously described methods. 1 G. Siqueira, J. Bras, A. Dufresne, Polymers, 2010, 2, 728–765 2A. Carlmark, Macromol. Chem. Phys., 2013, 214(14), 1539-1544 3D. Roy, M. Semsarilar, J. T. Guthrie, S. Perrier, Chem. Soc. Rev., 2009, 38(7), 2046–2064 4A. Carlmark Larsson, E. Malmström, Europ. Polym. J., 2012, 48(10), 1646-1659

Surface-initiated ring opening polymerization of carbonates and siloxanes from cellulose surfaces

249th National Meeting (2015)

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