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Kinetic modelling in living polymerizations: The effect of modifiers on the degree of polymerization in batch and continuous stirred‐tank reactors

 

作者: Judit E. Puskas,  

 

期刊: Macromolecular Theory and Simulations  (WILEY Available online 1993)
卷期: Volume 2, issue 1  

页码: 141-149

 

ISSN:1022-1344

 

年代: 1993

 

DOI:10.1002/mats.1993.040020110

 

出版商: Hüthig&Wepf Verlag

 

数据来源: WILEY

 

摘要:

AbstractEquations for the calculation of the degree of polymerization in 'modified' living polymerizations (living polymerizations in the presence of deliberately added terminating and transfer agents) are developed from a mechanistic/kinetic model. It is shown that a modifier, acting by the mechanism discussed, would cause more chain transfer in a continuous stirred tank reactor (CSTR) than in a batch. This is found to be the case in the living polymerization of 1,3‐butadiene initiated by butyllithium in nonpolar solvents, such as cyclohexane, when 1,2‐butadiene was used as a modifier. Under similar conditions no chain transfer was detected in batch polymerizations, while ≈ 20% transfer was found in a CSTR. The equations developed can be used to calculate the ratio of the rates of propagation and termination,kp/kt. CSTR data yieldedkp/kt≈ 480 at 90°C; re‐evaluation of batch data published earlier by Adams et al. for the same system in hexane solvent yieldskp/kt≈ 1250 and 670 at 50° C and 70°C

 

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