Synthesis of bio-based thermoplastic polyurethane elastomers containing isosorbide and polycarbonate diol and their biocompatible properties.

A new family of highly elastic polyurethanes (PUs) partially based on renewable isosorbide were prepared by reacting hexamethylene diisocyanate with a various ratios of isosorbide and polycarbonate diol 2000 (PCD) via a one-step bulk condensation polymerization without catalyst. The influence of the isorsorbide/PCD ratio on the properties of the PU was evaluated. The successful synthesis of the PUs was confirmed by Fourier transform-infrared spectroscopy and (1)H nuclear magnetic resonance. The resulting PUs showed high number-average molecular weights ranging from 56,320 to 126,000 g mol(-1) and tunable Tg values from -34 to -38℃. The thermal properties were determined by differential scanning calorimetry and thermogravimetric analysis. The PU films were flexible with breaking strains from 955% to 1795% at from 13.5 to 54.2 MPa tensile stress. All the PUs had 0.9-2.8% weight lost over 4 weeks and continual slow weight loss of 1.1-3.6% was observed within 8 weeks. Although the cells showed a slight lower rate of proliferation than that of the tissue culture polystyrene as a control, the PU films were considered to be cytocompatible and nontoxic. These thermoplastic PUs were soft, flexible and biocompatible polymers, which open up a range of opportunities for soft tissue augmentation and regeneration

Nanocomposites with shape memory behavior based on a segmented polyurethane and magnetic nanostructures

Shape-memory composites based on a commercial segmented polyurethane and magnetite (Fe⁠3O⁠4) nanoparticles(NPs) were prepared by a simple suspension casting method. The properties of the resulting nanocomposites,containing 1 to 10 nominal wt.% magnetic particles, were evaluated by thermogravimetric tests, contact anglemeasurements, differential scanning calorimetry, infrared and X-ray spectroscopy, static and thermal cyclic tensiletests, dynamic mechanical analysis and experiments of alternating-magnetic-field heating. It was found thatmost of the suspended NPs could be successfully incorporated into the polyurethane matrix, and thus compositesamples with up to 7 wt.% actual concentration were obtained. On the other hand, the incorporation of magnetitenanoparticles to the shape memory polyurethane did not significantly affect most of the matrix properties,including its shape memory behavior, while added magnetic response to the nanocomposites. Thus, nanocompositeswere able to increase their temperature when exposed to an alternating magnetic field, which allowedthem to recover their original shape quickly by an indirect triggering method.Fil: Soto, Guillermo Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Meiorin, Cintia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Actis, Daniel Guillermo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; ArgentinaFil: Mendoza Zélis, Pedro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; ArgentinaFil: Mosiewicki, Mirna Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Marcovich, Norma Esther. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentin

Application of high-strength biodegradable polyurethanes containing different ratios of biobased isomannide and poly (E-caprolactone) diol

Biodegradable–biocompatible polyurethanes were prepared with fixed hexamethylene diisocyanate and varying ratios of isomannide and poly(ϵ-caprolactone) diol using a simple one-step polymerization without a catalyst. The polyurethane structures were confirmed by 1H-nuclear magnetic resonance, Fourier transform infrared spectroscopy, and gel permeation chromatography. The glass transition temperatures were determined by thermal analysis to be between 25°C and 30°C. Degradation tests performed at 37°C in phosphate buffer produced mass losses of 5%–10% after 8 weeks. After 5 days of culture, using osteoblastic cells, the relative cell number on all the polyurethane films was only slightly lower than that of an optimized tissue culture plastic. These polymers offer significant promise with a simplistic synthesis and controlled degradation

Chemical recycling of poly(ethylene terephthalate). Application to the synthesis of multiblock copolyesters

The chemical recycling of the poly(ethylene terephthalate), (PET), has been successfully carried out by glycolysis in the presence of bis (2-hydroxyethyl) terephthalate (BHET) resulting in the formation of hydroxytelechelic oligomers. These oligomers were then treated with carboxytelechelic poly(ε-caprolactone) oligomers of Mn = 2300 and Mn = 730 g•mol–1 molecular weight, in the absence or presence of the titanium tetrabutyloxide (Ti(OBu)4) as a catalyst to get multiblock copolyesters. The chemical structure of the synthesized copolyesters was investigated by size exclusion chromatography (SEC) and proton Nuclear Magnetic Resonance (1H NMR) spectroscopy. Moreover the differential scanning calorimetry (DSC) was used to explore their thermal properties. The ester-ester interchange reaction was observed between the two oligopolyesters, was studied and discussed in detail

Reversible addition-fragmentation chain transfer copolymerization of styrene/divinylbenzene in aqueous suspension

The Reversible Addition-Fragmentation Chain Transfer (RAFT) copolymerization of styrene (S) and divinylbenzene (DVB) was performed at temperature range 110 to 150 °C in aqueous suspension, using AIBN as thermal initiator and 2-dodecylthiocarbonothioylthio-2-methylpropionic acid (DDMAT) as RAFT agent.inancial support by Fundação para a Ciência e a Tecnologia (FCT), Ministry of Science and Technology of Portugal (Program COMPETE - QCA III) and European Community through FEDER is gratefully acknowledged (project PTDC/EQU-EQU/098150/2008)

Tailoring the mechanical properties of the implantable polyurethanes by variation in the chain structures

Adapting characteristics of biomaterials specifically for in vitro and in vivo applications is becoming increasingly important in order to control interactions between material and biological systems. These complex interactions are influenced by surface properties like chemical composition, charge, mechanical and topographic attributes. In many cases it is not useful or even not possible to alter the base material but changing surface, to improve biocompatibility or to make surfaces bioactive, may be achieved by thin coatings. An already established method is the coating with polyelectrolyte multilayers (PEM). To adjust adhesion, proliferation and improve vitality of certain cell types, we modified the roughness of PEM coatings. We included different types nanoparticles (NP’s) in different concentrations into PEM coatings for controlling surface roughness. Surface properties were characterized and the reaction of 3 different cell types on these coatings was tested

Мультиблоксополимеры со смешанными гибкими и разнородными жесткими сегментами

Получены и исследованы политетраблокполимеры со смешанными полиэфирными гибкими сегментами и разнородными уретан-мочевинными жесткими блоками. Реокинетическими исследованиями реакционных смесей обоснована фрагментарная упорядоченность полимерных цепей нового типа полиуретанмочевин. Показано, что прочность этих материалов в 1.5 раза выше прочности полиуретанмочевин с индивидуальными гибкими сегментами. Продемонстрировано стабилизирующее влияние «рыхлой» структуры жесткой фазы на прочность эластомеров в широком интервале скоростей деформировани

Controllable degradation kinetics of POSS nanoparticle-integrated poly(ε-caprolactone urea)urethane elastomers for tissue engineering applications.

Biodegradable elastomers are a popular choice for tissue engineering scaffolds, particularly in mechanically challenging settings (e.g. the skin). As the optimal rate of scaffold degradation depends on the tissue type to be regenerated, next-generation scaffolds must demonstrate tuneable degradation patterns. Previous investigations mainly focussed on the integration of more or less hydrolysable components to modulate degradation rates. In this study, however, the objective was to develop and synthesize a family of novel biodegradable polyurethanes (PUs) based on a poly(ε-caprolactone urea)urethane backbone integrating polyhedral oligomeric silsesquioxane (POSS-PCLU) with varying amounts of hard segments (24%, 28% and 33% (w/v)) in order to investigate the influence of hard segment chemistry on the degradation rate and profile. PUs lacking POSS nanoparticles served to prove the important function of POSS in maintaining the mechanical structures of the PU scaffolds before, during and after degradation. Mechanical testing of degraded samples revealed hard segment-dependent modulation of the materials' viscoelastic properties, which was attributable to (i) degradation-induced changes in the PU crystallinity and (ii) either the presence or absence of POSS. In conclusion, this study presents a facile method of controlling degradation profiles of PU scaffolds used in tissue engineering applications