Selective graft modifications of polypropylene (PP) are demonstrated in which desirable functionality is introduced without the degradation that accompanies conventional radical-mediated processes. A range of modification strategies is presented, each exploiting triallyl trimellitate (TATM) or its derivatives to counteract the effects of macroradical fragmentation on the molecular weight. Model compound studies, as well as examinations of atactic PP reaction products, show that allylic ester activation occurs predominately by a radical-addition/hydrogen-transfer sequence, with a limited propensity for telomerization. The cografting of TATM and maleic anhydride leads to maleated PP of a high melt viscosity, whereas the apparent incompatibility of TATM with vinyltrimethoxysilane requires the use of TATM-assisted thiol-ene addition and/or diallyl silane grafting to produce moisture-curable PP derivatives. (c) 2005 Wiley Periodicals, Inc.