In support of programs to identify polyhydroxyalkanoates with improved materials properties, we report on
our efforts to characterize the mechanical and thermal properties of copolyesters of 3-hydroxybutyrate (3HB)
and 3-hydroxyhexanoate (3HHx). The copolyesters, having molar fraction of 3HHx ranging from 2.5 to 35
mol % and average molecular weights ranging from 1.15 105 to 6.65 105, were produced by fermentation
using Aeromonas hydrophila and a recombinant strain of Pseudomonas putida GPp104. The polymers were
chloroform extracted and characterized by solution-state and solid-state nuclear magnetic resonance (NMR)
spectroscopy and a variety of mechanical and thermal tests. Solution-state 1H NMR data were used to
determine polymer composition-of-matter, while solution-state 13C NMR data provided polymer-sequence
information. Solvent fractionation and NMR spectroscopic characterization of these polymers showed that
polymers containing up to 9.5 mol % 3HHx had a Bernoullian compositional distribution. By contrast,
polymers containing more than 9.5 mol % 3HHx had a bimodal polymer composition. Solvent fractionation
of these 3HHx-rich polyesters produced two polymer fractions, each of which was again consistent with
Bernoullian polymerization statistics. Solid-state NMR relaxation experiments provided insight into aging
in poly(3HB-co-3HHx) copolymers, demonstrating increased polymer-chain motion with increasing 3HHx
content. The elongation-to-break ratio in the polyesters increased with increasing molar fraction of 3HHx
monomers. Aging properties of the poly(3HB-co-3HHx) copolymers were very similar to copolymers of
3HB and 3-hydroxyvalerate (3HV). However, poly(3HB-co-3HHx) exhibited increased activation energy
to thermal degradation with increasing 3HHx content.
In support of programs to identify polyhydroxyalkanoates with improved materials properties, we report onour efforts to characterize the mechanical and thermal properties of copolyesters of 3-hydroxybutyrate (3HB)and 3-hydroxyhexanoate (3HHx). The copolyesters, having molar fraction of 3HHx ranging from 2.5 to 35mol % and average molecular weights ranging from 1.15 105 to 6.65 105, were produced by fermentationusing Aeromonas hydrophila and a recombinant strain of Pseudomonas putida GPp104. The polymers werechloroform extracted and characterized by solution-state and solid-state nuclear magnetic resonance (NMR)spectroscopy and a variety of mechanical and thermal tests. Solution-state 1H NMR data were used todetermine polymer composition-of-matter, while solution-state 13C NMR data provided polymer-sequenceinformation. Solvent fractionation and NMR spectroscopic characterization of these polymers showed thatpolymers containing up to 9.5 mol % 3HHx had a Bernoullian compositional distribution. By contrast,polymers containing more than 9.5 mol % 3HHx had a bimodal polymer composition. Solvent fractionationof these 3HHx-rich polyesters produced two polymer fractions, each of which was again consistent withBernoullian polymerization statistics. Solid-state NMR relaxation experiments provided insight into agingin poly(3HB-co-3HHx) copolymers, demonstrating increased polymer-chain motion with increasing 3HHxcontent. The elongation-to-break ratio in the polyesters increased with increasing molar fraction of 3HHxmonomers. Aging properties of the poly(3HB-co-3HHx) copolymers were very similar to copolymers of3HB and 3-hydroxyvalerate (3HV). However, poly(3HB-co-3HHx) exhibited increased activation energyto thermal degradation with increasing 3HHx content.
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