Abstract
AbstractBulk, free‐radical polymerization of styrene was carried out in the presence of a new tetrafunctional initiator (JWEB50, ATOFINA Chemicals, Inc.). The objective was to investigate the effect of initiator functionality on the free radical polymerization process. Size exclusion chromatography (SEC) with an on‐line multi‐angle laser light scattering (MALLS) detector was used to measure molecular weight (MW), molecular weight distribution (MWD), and radius of gyration (Rg) of polystyrene. These results were compared to those with a monofunctional initiator, LupTBEC, also from ATOFINA. At equivalent molar concentrations, initiation with JWEB50 and LupTBEC produced polystyrene with similar MWs and MWDs. However, the rate of polymerization was faster with JWEB50. When LupTBEC was four times the molar concentration of JWEB50, equal rates of polymerization were achieved for both initiators. The MWDs were again similar, but the MWs were higher for the tetrafunctional initiation. Degree of branching and gelation were also investigated. A mixture of branched and linear polymer was produced by JWEB50, while no insoluble gel was formed. Decomposition of JWEB50, a tetrafunctional initiator.imageDecomposition of JWEB50, a tetrafunctional initiator.
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