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The kineics of polymerization of butadiene wiht n-buLi as initiator in cyclohexane was investigated under high vacuum with dilatometer and the microstuctures of polymer were determined by infrared spectroscopy.A relationship between the component rate of propagation of different structure units and concentration of initiator is obtained by comparing the data of kin- etics and microstructure.The following mechanism of propagation is propos- ed:The tetramer,dimer and monomer of active chain ends are in equilibrium (association dffect ),cis-1,4 units are propagated by monomeric species,trans- 1,4and vinyl units by dimeric species.Kinetic expression of propagation reaction at ℃ has obtained.The apparent rate constants of propagation of monomeric and dimeric species at 50℃are 0.057(11/4·mol11/4·min-1)and 0.43(11/2·mol 11/2·min-1)respectively.
The kineics of polymerization of butadiene wiht n-buLi as initiator in cyclohexane was investigated under high vacuum with dilatometer and the microstuctures of polymer were determined by infrared spectroscopy. A relationship between the component rate of propagation of different structure units and concentration of initiator is by comparing the data of kin- etics and microstructure.The following mechanism of propagation is propos- ed: The tetramer, dimer and monomer of active chain ends are in equilibrium (association dffect), cis-1, 4 units are propagated by monomeric species , trans- 1,4 and vinyl units by dimeric species. Kinetic expression of propagation reaction at ° C has been obtained. The apparent rate constants of propagation of monomeric and dimeric species at 50 ° C are 0.057 (11/4 · mol11 / 4 · min -1 ) and 0.43 (11/2 mol 11/2 min-1) respectively.