Kinetic and Mechanistic Studies of L-Lactide Polymerization in Supercritical Chlorodifluoromethane

Ji Won Pack, Soo Hyun Kim, Soo Young Park, Youn Woo Lee, Young Ha Kim

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

The ring-opening polymerization of L-lactide (L-LA) initiated by 1-dodecanol/tin(II) octoate was carried out in supercritical chlorodifluoromethane at 110 °C under a pressure of 200 bar. MALDI-TOF mass spectroscopy and 1H NMR studies suggested that polymerization proceeded via a traditional coordination-insertion mechanism involving a tin alkoxide bond and the cleavage of the acyl-oxygen bond of the monomer. The polymerization was controlled using the linear relation between ln([LA] 0/[LA]) on the polymerization time and the molecular weight on conversion. The relative polymerization rate constants increased with increasing tin(II) octoate and 1-dodecanol concentrations. Gel permeation chromatography analysis indicated that the molecular weight distribution was bimodal, at least for certain monomer conversion. The bimodal distribution may be a result of specific intermolecular interactions between chlorodifluoromethane and hydroxyl groups on 1-dodecanol or on dormant macromolecules. The mechanisms of the initiation and chain transfer steps of L-lactide polymerization in supercritical chlorodifluoromethane are proposed.

Original languageEnglish
Pages (from-to)8923-8930
Number of pages8
JournalMacromolecules
Volume36
Issue number24
DOIs
Publication statusPublished - 2003 Dec 2
Externally publishedYes

Fingerprint

Dodecanol
Tin
Polymerization
Kinetics
Monomers
Ring opening polymerization
Gel permeation chromatography
Molecular weight distribution
Macromolecules
Hydroxyl Radical
Rate constants
Molecular weight
Nuclear magnetic resonance
dilactide
fluorocarbon 22
Spectroscopy
Oxygen

ASJC Scopus subject areas

  • Materials Chemistry

Cite this

Kinetic and Mechanistic Studies of L-Lactide Polymerization in Supercritical Chlorodifluoromethane. / Pack, Ji Won; Kim, Soo Hyun; Park, Soo Young; Lee, Youn Woo; Kim, Young Ha.

In: Macromolecules, Vol. 36, No. 24, 02.12.2003, p. 8923-8930.

Research output: Contribution to journalArticle

Pack, Ji Won ; Kim, Soo Hyun ; Park, Soo Young ; Lee, Youn Woo ; Kim, Young Ha. / Kinetic and Mechanistic Studies of L-Lactide Polymerization in Supercritical Chlorodifluoromethane. In: Macromolecules. 2003 ; Vol. 36, No. 24. pp. 8923-8930.
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