Kinetic Features and Molecular-Weight Characteristics of Terpolymerization Products of the Systems Based on Vinyl Acetate and 2-tert-Butyl-peroxy-2-methyl-5-hexene-3-yne A. S. ZAICHENKO, S. A. VORONOV, O. M. SHEVCHUK, V. P. VASILYEV, A. I. KUZAYEV State University ‘‘Lvivska Politechnica,’’ S. Bandera 12, Lviv-13, 290646, Ukraine Received 7 November 1996; accepted 27 May 1997 ABSTRACT: Investigations of terpolymerization kinetics of the system on the basis of vinyl acetate (VA), peroxidic monomer (VEP) 2-tert-butyl-peroxy-2-methyl-5-hexene- 3-yne, and acrylic acid proved that it falls under the equation of faintly inhibited copolymerization in which VEP serves as a comonomer and a chain-transfer agent. The contribution of each stage to the summary process rate is defined by the monomer ratio and depends on their consumption rate. Combination of a low-active VA monomer and of a VEP faint inhibitor in the system allows the control of the Trommsdorf effect and molecular-weight characteristics of functional oligoperoxides by changing the compo- nent ratio. The new carbon chain oligomers containing ditertiary alkyl peroxide and polar functional groups have practical application as multicenter surface-active radical initiators of polymerization and structurization.  1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 1061 – 1066, 1998 Key words: peroxidic monomer ; terpolymerization; kinetics; molecular-weight char- acteristics INTRODUCTION and experimental analysis of the influence of un- saturated peroxide participating in all radical po- lymerization elementary stages on the kinetic fea- The promoting influence of maleic anhydride ( MA ) and acrylic acid (AAc) on the copolymerization of tures and on the molecular-weight characteristics of the terpolymerization products. the systems including low active monomers is well known. 1 The introduction of active comonomers (MA and AAc) into a vinyl acetate (VA) and 2- tert-butyl-peroxy-2-methyl-5-hexene-3-yne ( VEP ) EXPERIMENTAL binary system results in a copolymerization rate increase and in the anticipated peroxide-con- VEP (CH 2 |CH{CGC{C(CH 3 ) 2 {O : O{ taining copolymer yield. 2 C(CH 3 ) 3 ) had the following characteristics after At the same time, VEP participation in the re- vacuum distillation: d 20 4 Å 0.867 (refer. 0.867); action of chain propagation as well as in transfer n D 20 Å 1.4480 (refer. 1.4482); active oxygen con- and termination reactions by a radical-induced tent was 8.79% (Calcd. 8.75%). VA was purified decomposition mechanism 3 determines some spe- by double-column distillation at atmospheric cial features of such monomer system polymeriza- pressure; AAc was purified under vacuum. After tion kinetics. This work is devoted to a theoretical that, their constants conformed to reference data. 4 Benzoyl peroxide ( BP ) and dinitrile of azobisiso- Correspondence to: S. A. Voronov. butyric acid ( AIBN ) were purified by recrystalli- Journal of Applied Polymer Science, Vol. 67, 1061 – 1066 ( 1997 )  1998 John Wiley & Sons, Inc. CCC 0021-8995/98 / 061061-06 zation from ethanol. Dimethyl formamide ( DMF ) 1061 8EF6 4989 / 8EF6$$4989 12-02-97 12:27:32 polaa W: Poly Applied