第三章自由基共聚合.ppt

Chapter 3 Free Radical Copolymerization;1 Introduction;;Examples;1.2 Type of copolymer;poly(ethylene-co-propylene) 乙烯-丙烯共聚物 poly(ethylene-r-propylene) 乙烯-丙烯无规共聚物 poly(ethylene-b-propylene) 乙烯-丙烯嵌段共聚物 poly(ethylene-g-propylene) 乙烯-丙烯接枝共聚物 poly(ethylene-a-styrene) 乙烯-苯乙烯交替共聚物;Key topics in copolymerization;2. Copolymer composition;Essential Point;Possible propagation sequences in free-radical copolymerization;Assumptions in copolymerization;Reactions in copolymerization;The overall rates of consumption of monomers [M1],[M2] then follow these expressions:;;;Reactivity ratio （竞聚率）;Examples;Influnece of polymerization mechanism on r;;0;butadiene r1 = 1.39, styrene r2 = 0.78;A. r1=r2=1;Characteristics of ideal copolymerization;2. Alternative copolymerization (r1=r2=0);3. Others; r1 r2 = 1 random r1 = r2 = 0 alternative r1 1, r2 1 random r1 1, r2 1 block or mixture of homopolymer r1 1, r2 1 close to random;Azeotropic composition 恒比组成;Independent on feed ratio;2.3 Copolymer composition with conversion;r1 1，r2 1;Copolymer composition with conversion;Average copolymer composition;Controlling copolymer composition;Controlling copolymer composition;2.4 Copolymer microstructure and composition distribution;Monomer distribution and polymer propertiy;Chain-length distribution by Probability ;Number-fraction distribution;Number-average chain length;Special examples;Derivation of copolymer composition equation ;3. Multi-component copolymerization;Terpolymerization;4. Experimental evaluation of reactivity ratios;4.1 Method for measurement of reactivity ratio;Line cross;Fineman-Ross method;4.2 Variation of reactivity ratio;Effect of Pressure;5. Monomer structure and the copolymerization reactivity;5.1 Relative reactivity of monomer;So the 1/r1 can be applied to estimate the monomer reactivity. The larger the reciprocal of r1, the higher the reactivity of M1 compared to M2.;With respect