第三章-自由基共聚合-李扬-高化楼311-Tel-87952444.pptVIP

* Q-e scheme To simplify the process of determine reactivity ratios, a semiempirical relationship has been developed that expresses the ratios in terms of constants that are characteristic of each monomer but independent of comonomer. P1 and Q2 are measures of the reactivity of radical and monomer related to resonance stabilization, e1 and e2 are measures of the polarity of the radical and monomer * Styrene was chosen as the standard and assigned value of Q=1.00 and e= - 0.80. Value of Q increase with increasing resonance stabilization, while e value become less negative as groups attached to the double bond become more electron attracting. The bigger the (e1-e2), the smaller the r1*r2. Assuming the e value of monomer and radical are same, * Application of Q-e equation Anticipate the reactivity ratio of monomer by Q-e equation. Compare the reactivity of monomer by Q value: High Q value --- high reactivity Compare the polarity of monomer by e: With electron-withdrawing group, +e; With electron-donating group, -e; Anticipate the copolymerization results by Q-e value Copolymerization is difficult for monomer pair with big ?Q Copolymerization is easy and becomes ideal when Q and e values of monomer are close alternative copolymerization occurs when monomer pair with big ?e * 7. Copolymerization rate * Chemically controlled termination Diffusion controlled termination * kp of copolymerization * * Summary Nomenclature of copolymer Reactivity ratio and copolymer composition equation Copolymer composition curve Copolymer composition with conversion Control of copolymer composition Copolymer composition distribution The reactivity of monomer and radical Q-e equation * * * * * Copolymer composition with conversion Polymerized monomer Monomer before polym. Monomer after polym. Since f varies with conversion, F1 also varies with conversion. Therefore, the average copolymer composition should be obtained by integration * Average copolymer composition M0=1 M St-MMA f10=