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•Fully biobased poly(butylene 2,5-furanoate/diglycolate) copolymers are synthesized.•Ether-linkages introduction results in an increase of the film hydrophilicity.•Copolymers can be ...ranged from rigid plastics to elastomers by changing BDG content.•Copolymerization does not cause a worsening of the very good PBF barrier properties.•Copolymerization improves the biodegradation rate in compost.
Novel fully biobased aliphatic-aromatic poly(butylene 2,5-furanoate/diglycolate) random copolyesters were successfully synthesized from 2,5-furandicarboxylic acid, diglycolic acid and 1,4-butanediol through two-stage melt polycondensation using titanium tetrabutoxide and titanium tetraisopropoxide as catalysts. The synthesized polymers were characterized in terms of molecular and solid-state properties, among these, barrier properties to different gases. In addition, biodegradability studies in compost have been conducted.
All the polymers showed a good thermal stability, even higher than that of the thermally stable homopolymer poly(butylene furanoate), and at room temperature appeared as semicrystalline materials. The main effect of copolymerization was a lowering, up to 60°C, in Tm respect to the homopolymer. The dependence of Tm on composition for copolymers was well described by Baur’s equation. Diffractometric measurements indicated that only the poly(butylene furanoate) crystalline phase is present in the copolymers under investigation. Amorphous samples showed a monotonic decrement of Tg, up to 30°C, as the content of butylene diglycolate units is increased and this can be explained on the basis of the higher flexibility induced in the polymer chain by the ether-oxygen atoms. A Wood-type equation was found to fit the Tg data of completely amorphous samples.
Final properties and biodegradation rate of the materials under study were strictly dependent on the copolymer composition and the crystallinity degree. As a matter of fact, hydrophilicity regularly increased with the increasing of butylene diglycolate mol%, due to the highly electronegative ether-oxygen atoms present in the co-units (water contact angle decreased of almost 15°). The elastic modulus decreased till one order of magnitude and the elongation to break increased, up to 400%, as co-unit content was increased.
Regarding the gas barrier properties, copolymerization did not imply a worsening with respect to the homopolymer. A slight increment of the gas transmission rate was recorded just for the copolymer containing the highest amount of butylene diglycolate units, as a consequence of the increasing flexibility of the macromolecular chain due to the ether-oxygen atoms. This behavior was more evident with CO2 gas test than with O2, N2 and C2H4 ones.
A new high molecular weight aliphatic copolyester of PLLA characterized by a ABA triblock architecture was successfully synthesized by ring opening polymerization, using as initiator a low molecular ...weight hydroxyl terminated random copolymer of PBS, poly(butylene/triethylene succinate). To increase the final polymer molecular weight, thus ensuring both good processability and mechanical properties, chain extension reaction has been performed with hexamethylene diisocyanate (HDI) as chain extender. All the synthetic steps have been carried out in solvent-free conditions. Specifically, the A block consists of LLA sequences, whereas the B one is an aliphatic biodegradable and biocompatible random copolyester of poly(butylene succinate) containing “PEG-like” moiety. The so-obtained material was first characterized by the molecular point of view and then, prior to further characterization, subjected to two different annealing treatments. Annealing revealed to be an efficient tool to control the kind and amount of crystalline phase developed by the material, as confirmed by WAXS structural analysis, and to tailor the mechanical properties, typical of thermoplastic elastomers. Thermal treatment was found to affect also the mechanism of polymer degradation under physiological conditions. Last, but not least, in order to explore the possible use of such new PLLA-based copolymer in vascular tissue engineering, preliminary biocompatibility tests, using endothelial cells, were carried out.
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•PLLA-based block copolymer was obtained by polycondensation, ROP and chain extension.•Flexibility, amount and kind of crystalline phase depend on thermal annealing.•Thermoplastic elastomer's behaviour was reached through thermal treatment.•Copolymerization and annealing did not alter PLLA biocompatibility.
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•New PLLA-based copolymers with ABA architecture have been successfully synthesizied.•Copolymerization of PLLA leads to better mechanical and barrier properties.•The B aliphatic ...central block facilittes compostability process.
Novel poly(lactic acid)-based chain extended triblock copolymers have been successfully synthesized in melt. The new polymers are characterized by a triblock ABA architecture, where A, is poly(lactic acid) and B is an ad hoc synthesized random biobased aliphatic copolyester poly(propylene/neopentyl glycol succinate). PLLA homopolymer has been also prepared for the sake of comparison. The samples under study were deeply characterized from the molecular, thermal and structural point of view. Mechanical and barrier properties and compostability were also investigated, in order to assess the potentiality of these materials in food packaging applications. The results obtained show that copolymerization leads to better mechanical response and barrier properties with respect to poly(lactic) acid homopolymer. Moreover, the presence of the central B block in the main polymer chain facilitates the process of compostability.
Keratin (Ker) protein regenerated from readily available and low-cost wastes (e.g. raw wool, feathers and textile by-products) is a promising natural polymer for tissue engineering and drug delivery.
...Nevertheless, while showing good bioactivity and great drug carrier properties, keratin lacks of suitable mechanical characteristics. To overcome this drawback, keratin was blended with poly(butylene succinate) (PBS), a biodegradable and biocompatible polyester able to confer mechanical integrity to the keratin based materials.
Despite the poor compatibility at the molecular level between keratin and PBS, their 50-50 blends were successfully electrospun into manageable mats, made of randomly oriented nanofibers with mean diameter of 290 nm. Along with mechanical properties, PBS improves also the thermal stability of the keratin based nanofibrous mats. On the other hand, compared to PBS-only electrospun mats, the presence of keratin improves both swelling ability and biodegradability and amplifies the capacity of drug release as well as fibroblast proliferation of the blend mat.
•Immiscible Keratin-polybutylene succinate (PBS) solution has been successfully electrospun.•Homogeneous nanofibers of about 290 nm were obtained.•PBS confers mechanical properties and thermal stability to the keratin-based nanofibrous mat.•Keratin confer higher swelling and biodegradability to the keratin-based nanofibrous mat.•Keratin stimulates the fibroblast adhesion and growth.
Within the context of new bioplastic materials, poly(butylene succinate) (PBS) and four novel poly(butylene/thiodiethylene succinate) random copolymers (PBS-PTDGS), in sheets as well as in films, ...were exposed to gamma radiation, in air and in water, and their behavior along with the effect on their biodegradability was investigated. The molecular weight data obtained from gel permeation chromatography indicate that the sensibility to radiation increases with the amount of sulfur-containing co-unit (TDGS). At 200 kGy the average molecular weight of PBS film halves, while for P(BS60TDGS40) the residual molecular weight is about 20%. The calculated intermolecular crosslink Gx and scissioning Gs yields confirmed that degradation is predominant over crosslink for all the aliphatic systems. As shown by thermal analyses, gamma radiation affects the thermal properties, leading to an increased crystallinity of the systems, remarkable for PBS, and lower decomposition temperatures. Variations of crystallinity with the increasing absorbed dose were confirmed also by PALS analyses. Water contact angle measurements revealed post-irradiation wettability alterations that could positively affect polymer biodegradability. In particular, when irradiated in water at 100 kGy PBS film exhibits a water contact angle decrease of about 17%, indicating an enhanced wettability. After degradation in compost, changes in the surface morphology were observed by means of SEM and sample weight losses were determined, at different extent, according to the irradiation environment. Interestingly, after 52 days in compost PBS films, both pristine and irradiated in air at 25 kGy, showed a residual weight of about 60%, while the ones irradiated in water at 25 kGy of about 44%. Experimental data confirmed that gamma irradiation could represent a viable treatment to enhance biodegradation in compost of PBS and PBS-based copolymers.
•Gamma irradiation of PBS-based random copolymers was investigated.•A radiation treatment to enhance degradation in compost was considered.•Gamma irradiation increases the wettability of PBS-based random copolymers.•Degradability in compost of irradiated PBS-based copolymers is enhanced.•Degradation of irradiated PBS is favored when treated in water with respect to air.
Quantitative mapping of the mechanical properties of a series of polylactic acid/natural rubber/organoclay bionanocomposites has been accomplished by using nanoindentation with atomic force ...microscopy. Topography, elastic modulus and adhesion maps were obtained simultaneously revealing nanoscopic mechanical features in the samples associated to the different phases. For polylactic acid and polylactic acid/natural rubber a single distribution of Young’s moduli was obtained whose maximum correlates well with the macroscopic measurements. Bionanocomposites with high organoclay loads exhibit a bimodal distribution of elastic moduli whose maxima can be associated to the polylactic acid matrix and to the reinforcing levels provided by the organoclay component. Adhesion maps allow one to obtain mechanical contrast between polylactic acid and organoclay, at high loadings, revealing the good compatibility of the organoclay with the polymer.
Dielectric spectra of the polyester poly(propylene succinate) were measured upon crystallization. For this model aliphatic polyester the alpha and beta relaxations appear simultaneously and are well ...resolved in the experimental frequency window. During isothermal crystallization, this fact allows one to use the beta relaxation to characterize the crystalline structural development while the alpha relaxation provides information about the evolution of the amorphous phase dynamics. In this way structure development and dynamics evolution can be characterized by a single experiment during the crystallization process. The unambiguous analysis of the dielectric loss clearly supports the existence of precursors of crystallization in the induction period.
Polyesters based on 1,3-propanediol glycol and aliphatic dicarboxylic acids with different chain length were synthesized by melt polycondensation, obtaining samples characterized by high and ...comparable
M
n. The polymers were subjected to molecular and thermal characterization. All polymers showed a good thermal stability, even though depending on the chain length. At room temperature all the polymers appeared as semicrystalline materials; the effect of the chain length was a lowering in the
T
g value, an odd–even fluctuation for
T
m and an increase of the crystallization rate. A comparison of the X-ray data revealed that the polymers with odd carbon number per repeat unit, show similar patterns, different from those of samples with even carbon atoms number. Multiple endotherms were evidenced in melt isothermally crystallized samples, due to melting and recrystallization processes. By applying the Hoffman–Weeks' method, the
T
m
0
of the samples was derived. Lastly, the presence of an interphase was not evidenced.
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