Polydimethylsiloxane-(PDMS-) grafted fluorocopolymers by a "grafting through" strategy based on atom transfer radical (Co)polymerization
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Three types of PDMS-grafted fluorocopolymers with various branching features were synthesized based on atom transfer radical polymerization (ATRP) techniques via a "grafting through" approach using methacryloxypropyl-terminated PDMS (PDMSMA) as macromonomer. Copolymers 1, with a linear fluorinated backbone and linear PDMS grafts, were prepared by copolymerizations of 2,3,4,5,6-pentafluorostyrene (PFS) with PDMSMA. Copolymers 2, with a hyperbranched fluorinated backbone and linear PDMS-based grafts, were prepared by self-condensing vinyl copolymerization (SCVCP) of an inimer, p-chloromethylstyrene (CMS), with PFS and PDMSMA. Copolymers 3, with a hyperbranched fluorinated core and linear PDMS grafts, were prepared by ATRP of PDMSMA, initiated by benzylic chloride-functionalized hyperbranched fluorocopolymer (obtained by SCVCP of PFS and CMS). A series of characterization methods, including 1H, 13C, and 19F NMR spectroscopies, gel permeation chromatography, elemental analysis, thermogravimetric analysis, and solubility tests, were used to investigate the reaction kinetics, and the compositions, molecular weights, and properties of these copolymers. 2007 American Chemical Society.