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Citation: SHIEH HONG-CHUAN, SHEN SHIN-CHUNG. KINETIC STUDIES OF CIS-1,4-POLYMERIZATION OF BUTADIENE WITH HOMOGENEOUS CATALYST COMPOSED OF COBALT CHLORIDE PYRIDENE COMPLEX AND DIETHYL ALUMINIUM CHLORIDE[J]. Acta Polymerica Sinica, ;1965, 7(1): 18-25. shu

KINETIC STUDIES OF CIS-1,4-POLYMERIZATION OF BUTADIENE WITH HOMOGENEOUS CATALYST COMPOSED OF COBALT CHLORIDE PYRIDENE COMPLEX AND DIETHYL ALUMINIUM CHLORIDE

Received Date: 15 May 1964

Kinetics of polymerization of butadiene with soluble Ziegler-type catalyst CoCl2·4C5H5N一(C2H5)2AlCl have been studied by means of dilatometer．The results indicate that the polymerization rate in benzene is first order with respect tO both mono-met and cobalt chloride concentration．and is one-half order witll respect to diethyl alu-minium chloride concentration．The activation energy of polymerization has been deter-mined to be 8.7±0.5 kcal／mole．When the solvent benzene is partly substituted by heptane，the polymerization rate is decreased and can be represented as：-dm-dt={β[Co][Al]1／2—δV}[M] where V represents the volume percentage of heptane in solvent，β and δ are constants．If small amount of certain electron donors is added to the polymerization system，the rate equation may be represented as： -dm-dt={β[Co][Al]1／2—a[D]}[M] where [D] is the concentration of electron donor and a represents the characteristic cons-tant of the electron donor．The value of a for different electron donors decreases in the following order：triethylamine>tetrahydrofuran>ethyl ether>anisole．
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