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The mechanism of the ring-opening polymerization of ε-caprolactone using tin(IV) carboxylates

The polymerization of epsilon-caprolactone using tin(IV) carboxylates has been investigated and related to literature research. Polymers with broad MWD were obtained in quantitative yield. At 100% conversion polymer molecular weights ranged from 50,000 to almost 60,000. After an initial induction period, the polymerization shows zero order kinetics with respect to monomer and near first order kinetics with respect to catalyst. The mechanism of the polymerization is coordination-type, and is dependent on the presence of water or an alcoholic initiator. Added water decreases polymer molecular weight to approx. 30,000 at 100% conversion. The polymer has a terminal hydroxyl group and a terminal carboxyl group. The hydroxyl end is the reactive end in propagation. The carboxyl end and free carboxylic acid produced by the hydrolysis of the catalyst are responsible for the induction period.

Identiferoai:union.ndltd.org:arizona.edu/oai:arizona.openrepository.com:10150/291748
Date January 1987
CreatorsBassi, Mitchell Brian, 1963-
ContributorsHall, Henry K., Jr.
PublisherThe University of Arizona.
Source SetsUniversity of Arizona
Languageen_US
Detected LanguageEnglish
Typetext, Thesis-Reproduction (electronic)
RightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.

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