Block architecture influence on the structure and mechanical performance of drawn polyurethane elastomers

Fernández-d’Arlas, Borja; Corcuera, María Ángeles; Runt, James; Eceiza, Arantxa

doi:10.1002/pi.4669

Cited by 14 publications

(19 citation statements)

References 39 publications

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“…Crystalline HDI–BD blocks are more hydrophobic and strongly trend to interassociate through hydrogen bonding . The elastic modulus of the materials resulted highly dependent on copolymer composition, increasing almost linearly with the content of HDI–BD crystalline segments.…”

Section: Resultsmentioning

confidence: 89%

“…Other relevant physical properties are gathered in Table . It is observed that the molecular weights of the synthesized materials are typical of the two‐shoot synthesized segmented PU . The increase in stiffness of solid PU films increased notably with the increase of HDI–BD block content due to the increase in the hydrogen bonding between crystalline HDI–BD segments…”

Section: Resultsmentioning

confidence: 99%

“…Crystalline HDI-BD blocks are more hydrophobic and strongly trend to interassociate through hydrogen bonding. [ 32,40 ] The elastic modulus of the materials resulted highly dependent on copolymer composition, increasing almost linearly with the content of HDI-BD crystalline segments. These modulus values are higher to typical polyol-based PUs, [ 40 ] and this can be attributed to the high density of hydrogen bonding donors (NH) and acceptors (C = O) of these new type of PU copolymers.…”

Section: Dispersion Of Pus In Diluted Aqueous Hclmentioning

confidence: 99%

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Salting-Out Waterborne Catiomeric Polyurethanes for Drugs Encapsulation and Delivery

Fernández-d’Arlas

Eceiza

2015

Macromol. Chem. Phys.

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Novel polyurethane (PU) catiomers with high urethane density are explored as templates for self-assembling into drug-carrying nanomicelles via a salting-out method. The micelles sizes, the salting-out effi ciency, and drug encapsulation effi ciency have been analyzed by dynamic light scattering and UV-vis. The ratio catiomeric/hydrophobic in the PU blocks structure infl uences the micelle hydrodynamic diameters varying from ≈50 to 200 nm. The encapsulating effi ciencies of different model drugs (MDs) have been analyzed. The infl uence of MD nature and PU catiomeric/hydrophobic blocks ratio on MD release kinetics has been evaluated, showing how PU, MD nature, and the pH infl uence on the MD release patterns. These results pave the way to the design of tuned copolymers for controlled release kinetics of specifi c drugs. copolymers such as poly(lactic-co -glycolic acid) [23][24][25] or poly[(ethylene glycol)-co -( N -(2-hydroxypropyl)methacrylamide)] block copolymers, [ 26 ] are examples of macromolecular systems explored as carrying agents due to their biodegradability or interesting self-assembling mechanisms. Polyurethanes (PUs) appear as attractive and versatile materials for the development of drug carriers [ 27 ] due to the possibility of designing different block architectures with varied functionality, [ 28 ] and with biocompatible [ 29 ] and biodegradable [ 30,31 ] formulations and macromolecular structures that mimic protein structures, in terms of hydrogen bonding donors and acceptors density. [ 32 ] PUs are a class of copolymers that can be synthesized with very different block architectures and properties. [ 29,32 ] Aqueous soluble or waterborne PUs are attractive for developing solvent-free paints formulations, adhesives, [ 33 ] dopes for green fi ber processing, or drug carriers among other potential biological applications. [34][35][36] Recently, some investigations have claimed the ability of PU anionomers to self-assemble in aqueous media into vesicles and particles with diameters of about 250 nm, which were able to encapsulate a calcein dye. [ 37 ] Among the different polymeric nanoparticle formation techniques, salting-out with kosmotropic salts has been shown to be an effective and easy route to develop silk nanoparticles [ 20 ] with controlled size and also useful to

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Section: Resultsmentioning

confidence: 89%

Section: Resultsmentioning

confidence: 99%

Section: Dispersion Of Pus In Diluted Aqueous Hclmentioning

confidence: 99%

See 1 more Smart Citation

Salting-Out Waterborne Catiomeric Polyurethanes for Drugs Encapsulation and Delivery

Fernández-d’Arlas

Eceiza

2015

Macromol. Chem. Phys.

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“…5b) donde el PU glicol mantiene valores de tensión superior durante la relajación de muestras deformadas hasta 200%, durante un periodo de al menos diez minutos. Los perfiles de Tensión vs. t en los que la tensión se mantienen elevada durante un largo periodo de tiempo sugiere que, en comparación con otros materiales en los que no se mantiene, la estructura está más cohesionada, bien mediante fases cristalinas o fuertes enlaces intermoleculares tales como puentes de hidrógeno [12]. El perfil de relajación del PU glicol nos indica nuevamente su estructura altamente enlazada por puentes de hidrógeno, en comparación con el PU macrodiol .…”

Section: Propiedades Mecánicasunclassified

“…La comprensión de la influencia de la naturaleza y de la arquitectura de los segmentos en la morfología y propiedades de los especímenes orientados es importante para entender su papel en las propiedades mecánicas resultantes [7]. Así por ejemplo mientras los PU formados por diisocianatos voluminosos como el 4,4´-difenil metano diisocianato (MDI) o por el isoforon diisocianato (IPDI) proporcionan baja cristalinidad en las unidades asociables por puentes de hidrógeno, segmentos formados por 1,6-hexametilen diisocianato (HDI) forman políme-ros con unidades cristalinas altamente asociadas por puentes de hidrógeno, que evolucionan en materiales más rígidos y resistentes tras su orientación macromolecular [12]. Estos resultados ponen de manifiesto la importancia de los puentes de hidrógeno en las propiedades mecánicas finales por lo que en el objetivo de biomimetizar la tenacidad de la seda de araña (150-300 MJ•m -3 ) [13] se debería desarrollar materiales con una alta densidad de puentes de hidrógeno pero que a su vez posean cierta elasticidad que proporcione tenacidad al material final, en contraposición a materiales como el Kevlar (50 MJ•m -3 ) o el Nailon (80 MJ•m -3 ) [14].…”

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Diseño de nuevos poliuretanos inspiradospor la estructura macromolecularde la seda de araña

Bidegain

Mendiguren

2015

Matéria (Rio J.)

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RESUMENEn este trabajo se presentan los resultados de la síntesis en masa y caracterización de copolímeros de poliuretano (PU) formados a partir de 1,6-hexametilen diisocianato (HDI) y N-metil dietanolamina (MDEA) y 1,4-butanodiol (BD) como glicoles de las fases flexibles y rígidas, respectivamente. Se compara las propiedades mecánicas y morfológicas de este tipo de PU con las de un PU convencional formado con un policarbonato de peso molecular intermedio. Los materiales se han caracterizado mediante calorimetría diferencial de barrido, espectroscopia infrarroja de transformada de Fourier y mecánicamente mediante tracción uniaxial. Se ha observado que las unidades de MDEA que, pese a tener la capacidad de asociarse por puentes de hidrógeno, presentan características elástoméricas similares a las de glicoles de mayor peso molecular y separación entre unidades donoras-aceptoras de enlaces de hidrógeno. El comportamiento de esta nueva serie de PU con alta densidad de puentes de hidrógeno puede resultar interesante en el desarrollo de materiales resilientes y tenaces tales como las sedas.Palabras clave: Materiales super-tenaces, Mímesis de la seda, Poliuretanos elastoméricos, Arquitectura de bloques, Puentes de hidrógeno. ABSTRACTThis works presents results on the synthesis and characterization of a novel bio-inspired polyurethane (PU) elastomer with high density of hydrogen bonding. The PU were formed by the condensation of 1,6 hexamethylen-diisocyanate with N-methyl diethanolamine (MDEA) and 1,4-butanediol (BD) as components of the elastic and rigid phases, respectively. The mechanical performance and morphology of this PU are compared with those of a common PU elastomer formed with a medium molecular weight polycarbonate. The materials have been tested by means of Fourier-transformed infrared spectroscopy, differential calorimetry and by uniaxial tensile testing. It has been observed that units composed of MDEA segments present elastomeric behavior despite being highly hydrogen bonded with denser packaging between donor and acceptor of hydrogen bridges than in the case of an intermediate molecular weight polyol. The properties exhibited by these new type of PUs with high density of hydrogen bonding can be considered interesting for the development of resilient and tough materials such as silks.

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Polymeric Prosthetic Systems for Site‐Specific Drug Administration: Physical and Chemical Properties

Parisi

Manzano

Flor

et al. 2015

Handbook of Polymers for Pharmaceutical Technologies

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Block architecture influence on the structure and mechanical performance of drawn polyurethane elastomers

Cited by 14 publications

References 39 publications

Salting-Out Waterborne Catiomeric Polyurethanes for Drugs Encapsulation and Delivery

Salting-Out Waterborne Catiomeric Polyurethanes for Drugs Encapsulation and Delivery

Diseño de nuevos poliuretanos inspiradospor la estructura macromolecularde la seda de araña

Polymeric Prosthetic Systems for Site‐Specific Drug Administration: Physical and Chemical Properties

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