3[1].4分子量和链转移.ppt

3.4 Molecular Weight and Chain  Transfer 3.4.1 Molecular weight without chain transfer 3.4.2 The effect of chain transfer on the degree of polymerization 3.4.3 Molecular weight distribution 3.4.1 Molecular Weight without  Chain Transfer Molecular weight is an important parameter to characterize polymers. Factors affect the rate of polymerization, such as the concentration of initiators, the concentration of monomers, the polymerization temperature, and so on, which also affect the molecular weight. Chain transfer reaction usually doesn’t affect the rate of the polymerization, however, affects the molecular weight very much. Molecular weight is also an important part in kinetics study. （1）Kinetic Chain Length and the Degree of Polymerization Kinetic chain length----is defined as the average number of monomer molecules consumed per each radical which initiates a polymer chain. Thus, it can be given by the ratio of the polymerization rate to the initiation rate. No Chain Transfer coupling termination， = 2 Disproportionation termination， ＝ The two modes coexist , 2 （2）Effect of Temperature on the Degree of Polymerization In initiator initiated system, DP usually decreases with the temperature rising. Photo Initiation and Radiation Initiation When initiated by photo or radiation, E′＝Ep－Et/2 ，is a very small positive value. This indicates that the effect of temperature on DP and polymerization is very little. 3.4.2 The Effect of Chain Transfer on DP General description The effect of chain transfer on DP To monomer To initiator To solvent or chain transfer agent （1）General Description Chain transfer reaction Effect of Chain Transfer on Polymerization Rate and DP If the activity of the new radical is comparable to that of the original one, there is no change in the reinitiation, propagation, and polymerization rate. If the activity of the new radical becomes weak, the