Joanna Brzeska

Chemical and Enzymatic Hydrolysis of Polyurethane/Polylactide Blends

Polyether-esterurethanes containing synthetic poly[(R,S)-3-hydroxybutyrate] (R,S-PHB) and polyoxytetramethylenediol in soft segments and polyesterurethanes with poly(e-caprolactone) and poly[(R,S)-3-hydroxybutyrate] were blended with poly([D,L]-lactide) (PLA). The products were tested in terms of their oil and water absorption. Oil sorption tests of polyether-esterurethane revealed their higher response in comparison to polyesterurethanes. Blending of polyether-esterurethanes with PLA caused the increase of oil sorption. The highest water sorption was observed for blends of polyether-esterurethane, obtained with 10% of R,S-PHB in soft segments. The samples mass of polyurethanes and their blends were almost not changed after incubation in phosphate buffer and trypsin and lipase solutions. Nevertheless the molecular weight of polymers was significantly reduced after degradation. It was especially visible in case of incubation of samples in phosphate buffer what suggested the chemical hydrolysis of polymer chains. The changes of surface of polyurethanes and their blends, after incubation in both enzymatic solutions, indicated on enzymatic degradation, which had been started despite the lack of mass lost. Polyurethanes and their blends, contained more R,S-PHB in soft segments, were degraded faster.

Degradability of cross-linked polyurethanes based on synthetic polyhydroxybutyrate and modified with polylactide

AbstractIn many areas of application of conventional non-degradable cross-linked polyurethanes (PUR), there is a need for their degradation under the influence of specific environmental factors. It is practiced by incorporation of sensitive to degradation compounds (usually of natural origin) into the polyurethane structure, or by mixing them with polyurethanes. Cross-linked polyurethanes (with 10 and 30%wt amount of synthetic poly([R,S]-3-hydroxybutyrate) (R,S-PHB) in soft segments) and their physical blends with poly([d,l]-lactide) (PDLLA) were investigated and then degraded under hydrolytic (phosphate buffer solution) and oxidative (CoCl2/H2O2) conditions. The rate of degradation was monitored by changes of samples mass, morphology of surface and their thermal properties. Despite the small weight losses of samples, the changes of thermal properties of polymers and topography of their surface indicated that they were susceptible to gradual degradation under oxidative and hydrolytic conditions. Blends of PDLLA and polyurethane with 30 wt% of R,S-PHB in soft segments and PUR/PDLLA blends absorbed more water and degraded faster than polyurethane with low amount of R,S-PHB.

The influence of chemical structure on thermal properties and surface morphology of polyurethane materials

The surface morphology and thermal properties of polyurethanes can be correlated to their chemical composition. The hydrophilicity, surface morphology, and thermal properties of polyurethanes (differed in soft segments and in linear/cross-linked structure) were investigated. The influence of poly([R,S]-3-hydroxybutyrate) presence in soft segments and blending of polyurethane with polylactide on surface topography were also estimated. The linear polyurethanes (partially crystalline) had the granular surface, whereas the surface of cross-linked polyurethanes (almost amorphous) was smooth. Round aggregates of polylactide un-uniformly distributed in matrix of polyurethane were clearly visible. It was concluded that some modification of soft segment (by mixing of poly([R,S]-3-hydroxybutyrate) with different polydiols and polytriol) and blending of polyurethanes with small amount of polylactide influence on crystallinity and surface topography of obtained polyurethanes.

Branched Polyurethanes Based on Synthetic Polyhydroxybutyrate with Tunable Structure and Properties

Branched, aliphatic polyurethanes (PURs) were synthesized and compared to linear analogues. The influence of polycaprolactonetriol and synthetic poly([R,S]-3-hydroxybutyrate) (R,S-PHB) in soft segments on structure, thermal and sorptive properties of PURs was determined. Using FTIR and Raman spectroscopies it was found that increasing the R,S-PHB amount in the structure of branched PURs reduced a tendency of urethane groups to hydrogen bonding. Melting enthalpies (on DSC thermograms) of both soft and hard segments of linear PURs were higher than branched PURs, suggesting that linear PURs were more crystalline. Oil sorption by samples of linear and branched PURs, containing only polycaprolactone chains in soft segments, was higher than in the case of samples with R,S-PHB in their structure. Branched PUR without R,S-PHB absorbed the highest amount of oil. Introducing R,S-PHB into the PUR structure increased water sorption. Thus, by operating the number of branching and the amount of poly([R,S]-3-hydroxybutyrate) in soft segments thermal and sorptive properties of aliphatic PURs could be controlled.