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Effect of sulfur compounds on the polymerization of vinyl monomers. I. Influence of tetramethylthiuram disulfide on the polymerization of styrene

E. Štaudner, J. Beniska, and G. Znamenáková

Department of Organic Technology, Slovak Technical University, Bratislava


Abstract: The polymerization kinetics of styrene in the presence of tetramethylthiuram disulfide (I) as the initiator at 2.11 × 10-4 to 0.167 mole/l, and at 80, 95, 115, and 130° were studied. A deviation from the linear dependence of the function Rp, = f ([I]0.1) was detd. Based on the reaction scheme which was derived from the termination of the polymeric radicals, from the termination of the reaction of the macroradical with the radical of the initiator and the 2 primary radicals, the equation for the total rate of the polymerization was detd.: Rp = (Rpio2 + R2pto)0.5 × (1 + B [I])-0.5, where Rpio is the rate at a single concn. of I and Rpto is the rate in the absence of initiator. The participation of the primary radicals (RS•), which were formed by the decompn. of I to the termination and transition was expressed by the complex const. B, which was calcd. for the given temps. from the exptl. data. The theoretical rates of polymerization (Rp) calcd. from B values are in good agreement with the exptl. data, which also confirms the reaction scheme. The participation of the various types of the termination (φ1 and φ2), calcd. from the known B values show that the termination by the reaction P • + RS • is considerable even at low concns. of I and increases with the concn. and temp., which can be explained by the relative stability of the RS• radicals.

Full paper in Portable Document Format: 201a18.pdf (in Slovak)


Chemical Papers 20 (1) 18–27 (1966)

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