Structure–rheology relationships of long-chain branched polypropylene: Comparative analysis of acrylic and allylic coagent chemistry

The relationship between product structure and melt-state rheological properties is established for series of branched PP derivatives prepared by the radical-mediated grafting of tri-functional coagents. Peroxide-initiated, solvent-free additions of linear PP to triallyl trimesate (TAM), trimethylolpropane triacrylate (TMPTA) and triallyl phosphate (TAP) at high temperature are shown to produce bimodal molecular weight and branching distributions. Low-frequency dynamic shear viscosities as well as extensional viscosities are shown to be highly responsive to a hyper-branched chain population, whose abundance and molecular weight correlate with the kinetic chain length of the grafting process, and the propensity of a coagent to oligomerize.