Journal
MACROMOLECULES
Volume 48, Issue 4, Pages 950-958Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ma5022049
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Funding
- EPSRC through CASE DTA
- Infineum UK Ltd.
- Royal Society
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omega-Pentadecalactone (PDL) was copolymerized with lactones of varying sizes (6-, 7-, 9-, and 13-membered rings) in order to characterize the properties of PDL copolymers throughout the lactone range for copolymerizations catalyzed by magnesium 2,6-di-tert-butyl-4-methylphenoxide (Mg(BHT)(2)(THF)(2)). Kinetics of the copolymerization reactions were studied using quantitative C-13 NMR spectroscopy, which revealed that the polymerization of the smaller, strained lactone monomer occurred rapidly before the incorporation of PDL into the polymer. Furthermore, all polymers were randomly sequenced as a consequence of transesterification side reactions that occurred throughout polymerization. The copolymers were all shown to cocrystallize to produce polymers with melting and crystallization temperatures that displayed a linear relationship with respect to monomer ratio. Differences in degradation behavior of the smaller lactones enabled the synthesis of PDL copolymer materials that displayed independently controllable thermal and degradation properties.
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