By B Monakov; Z M Sabirov; N N Sigaeva
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Additional resources for Active sites of polymerization: multiplicity: stereospecific and kinetic heterogeneity
Collect. Czech. Chern. , 1993, vol. 58(10), p. 2349. , Zh. Prikl. , 1986, vol. 59(1), p. 227. , Acta Polymerica, 1983, vol. 34(11/12), p. 667. Chapter 2. 1. HETEROGENEITY OF ACTIVE SITES IN HETEROGENEOUS POLYMERIZATION PROCESSES Similar to other chemical reactions, polymerization processes may be performed in both homogeneous and heterogeneous systems. There are different reasons for heterogeneity. For example, in the case of radical polymerization, a polymer or an initiator can be insoluble in the polymerization mixture or rather complex insoluble catalytic systems participate m ionic-coordinate polymerization processes.
It is common knowledge that microstructure of polydienes is highly sensitive to the origin of halogen in titanium, cobalt or nickel containing catalytic systems , whereas microstructure of polybutadiene is independent halogen origin in lanthanide catalytic system [48, 55, 56]. In polymerization of isoprene, at transition from chlorine- to bromine- and iodine-containing catalysts the content of 3,4-unit fraction slightly increased. As mentioned above, compared with chlorine- and bromine-containing analogues, catalytic systems derived from Lnh3TBP-OAC display reduced action stereospecificity in piperylene polymerization .
B. N. N. • Ji I . 9. Distribution by kinetic heterogeneity of NdBr3 3TBP-Al(i-C4H9)3 catalytic system at polymerization of piperylene. 0% (6) Contrary to NdCb·3TBP-AI(i-C4H9h system, for the bromine-containing catalytic system the first type of the active sites responsible for formation of the most lowmolecular fraction of polydiencs is absent. The third type of active sites preserves kinetic activity during polymerization for both catalytic systems. s in chlorine-containing system is also invariable during polymerization, whereas for NdBr 3 ·3TBP-Al(i-C 4H9)3 system it is significantly reduced.