Chemical modification of polypropylene by nitroxide-mediated radical graft polymerization of styrene

Nitroxide-mediated free radical polymerization (LREP) was employed for the first time to prepare graft copolymer by having arylated polypropylene (Cl-PP) as a backbone and polystyrene (PS) as branches. The graft copolymerization of styrene was initiated by arylated PP carrying 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) groups as a macroinitiator. Thus, maleic anhydride was grafted onto polypropylene by peroxide-catalyzed swell grafting method (PP-MAH). Next, PP-MAH reacted with ethanolamine to produce a hydroxyl group containing polypropylene (PP-OH) and the obtained PP-OH was treated with a-phenyl chloroacetyl chloride and converted to a chloroacetyl group containing polypropylene (PP-Cl). Finally, 1-hydroxyl-2,2,6,6-tetramethylpiperidine (TEMPO-OH) was synthesized by reducing TEMPO with sodium ascorbate and this functional nitroxyl compound was coupled with a-phenyl chloroacetylated polypropylene. The resulting macroinitiator (PP-TEMPO) for free radical polymerization was then heated in the presence of styrene for the formation of the graft copolymer. The prepared graft copolymer was characterized by Fourier transform infrared spectroscopy and H-1 NMR techniques. Glass transition temperature of grafted copolymer was investigated using thermogravimetric analysis and differential scanning calorimetric techniques. This approach using nitroxide-mediated macroinitiators is an effective method for the preparation of new materials.