Abstract
Chromyl chloride (CrO 2Cl 2) causes facile polymerization of iso-butyl vinyl ether (IBVE). In contradiction to the existing report, CrO 2Cl 2 alone or in combination with conventional modifiers fails to produce stereoregular poly(IBVE). Because of the fast polymerization at ambient temperature (30°), the kinetics of the polymerization of IBVE by CrO 2Cl 2 were studied at 0° and 15°. The polymerization is first order in CrO 2Cl 2 and second order in IBVE upto a threshold monomer concentration thereafter becoming independent of [IBVE]. The polymerization is inhibited by pyridine. Addition of HCl to CrO 2Cl 2 increases both rate of polymerization ( R P ) and [η]. Added water does not affect R P upto [H 2O]/[CrO 2Cl 2] ≈ 1.33 but thereafter enhances it sharply upto [H 2O]/[CrO 2Cl 2] ≈ 5.32. With increasing [H 2O], [η] falls to a limiting value. [η] is independent of [CrO 2Cl 2] but increases with [IBVE] upto 1.0mole/l. Both R P and [η] show a maximum at 47° in the Arrhenius plot over the range 10–72°. The features have been explained on the basis of a conventional cationic mechanism.
Published Version
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