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Published on: February 27, 2017
Ring-opening polymerisation of beta-butyrolactone catalysed by distannoxane complexes: study of the mechanism
1Central Research Laboratory, Takasago International Corporation, Hiratsuka-City, Kanagawa, Japan.
Abstract:
The mechanism of the ring-opening polymerisation of beta-butyrolactones was studied. The ring-opening polymerisation of BL catatlysed by distannoxane complexes is of a living nature. The polymerisation of racemic BL gave a predominantly syndiotactic P(3HB). The temperature effect on syndiospecificity was used to determine the activation energy (deltaE = Esyndiotactic - Eisotactic) for syndiotactic versus isotactic diad placement. The deltaE value was obtained as -1.49 kcal/mol. The steric control leading to the observed syndiospecificity is due predominantly to diastereomeric interactions between the Sn-coordinated P(3HB) chain end. having a specific chain end stereochemistry, and the incoming BL enantiomeric monomers. The catalytic cycle derived from the mechanism of the polymerisation was proposed.
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