Polycaprolactone-based Polyurethane Research Articles

High-performance TEMPO-oxidized cellulose nanofibril/quantum dot nanocomposites

Two different sizes of polydopamine-coated layered double hydroxides (D-LDHs) are incorporated into polycaprolactone-based polyurethane (PU) to enhance the mechanical and shape memory properties of the PU. The results show that D-LDH interacts strongly with hard segments and hence enhancing phase separation between hard and soft segments. It is found that the tensile moduli of the PU/D-LDH nanocomposites are much higher than that of neat PU at 60 °C. In comparison with neat PU, the nanocomposite with 2 wt% of small D-LDH exhibits a 60% increase in recovery stress while shape fixity and strain recovery ratio are also improved simultaneously. This is because at low filler loading, most small D-LDH nanosheets interact with hard domains and they are not large enough to connect neighbor hard domains. They can hence reinforce the hard domains without sacrificing the elasticity of the system. Two-dimensional X-ray diffraction studies indicate that most small D-LDH nanosheets are able to rotate back from aligned state to original random state in shape recovery process, justifying the improved strain recovery ratio.

A Facile Approach Toward Scalable Fabrication of Reversible Shape-Memory Polymers with Bonded Elastomer Microphases as Internal Stress Provider.

The present communication reports a novel strategy to fabricate reversible shape-memory polymer that operates without the aid of external force on the basis of a two-phase structure design. The proof-of-concept material, crosslinked styrene-butadiene-styrene block copolymer (SBS, dispersed phase)/polycaprolactone-based polyurethane (PU, continuous phase) blend, possesses a closely connected microphase separation structure. That is, SBS phases are chemically bonded to crosslinked PU by means of a single crosslinking agent and two-step crosslinking process for increasing integrity of the system. Miscibility between components in the blend is no longer critical by taking advantage of the reactive blending technique. It is found that a suitable programming leads to compressed SBS, which serves as internal expansion stress provider as a result. The desired two-way shape-memory effect is realized by the joint action of the temperature-induced reversible opposite directional deformabilities of the crystalline phase of PU and compressed SBS, accompanying melting and orientated recrystallization of the former. Owing to the broadness of material selection and manufacturing convenience, the proposed approach opens an avenue toward mass production and application of the smart polymer.

Effect of hard segment architecture on shape memory properties of polycaprolactone-based polyurethane containing azobenzene

In this work, we synthesized two kinds of polyurethanes with azobenzene as hard segments in the side chains and in the main chains. Their thermal stabilities were high enough for their shape memory application. For polyurethane with azobenzene in the side chain (PU), the azobenzene has more distinctly effect on inhibiting crystallization of polycaprolactone (PCL) because of irregular orientation of azobenzene. For polyurethane with azobenzene in the main chain (PUR), the crystallinity of PCL is mainly affected by its molecular weight. PU-3500 and PUR-3500 exhibit perfect shape fixing ability of 99 % with recovery ratio of 98 % at 50 % strain. The recovery ratio is decreased for PU-3500 and increased for PUR-3500 as the applied strain increased. The mechanism of the hard segment structures effect on the shape memory behavior is briefly discussed. Importantly, the two molecules behave trans–cis isomerization under UV irradiation. This work is crucially important for the structural design of shape memory polyurethane and applications in the smart devices.

Effect of block ratio and strain amplitude on thermal, structural, and shape memory properties of segmented polycaprolactone-based polyurethanes

In this work, the effects of changing molecular weight of polyol (2000, 3000, and 4000) and block ratio as well as deformation amplitude on thermal, structural, and shape memory properties of polyester urethanes based on diphenylmethane diisocyanate, polycaprolactone diol, and 1,4-butanediol were investigated. Fourier transform infrared spectroscopy was used to check the accomplishment of the polyurethanes synthesis. Thermal, structural, and shape memory properties of synthesized SMPUs were measured using differential scanning calorimetry, wide angle X-ray diffraction, and tensile cyclic tests, respectively. It was found that as the crystallinity of soft segments increased, the ability of the samples in fixation of temporary shape was higher. On the other hand, the shape recovery was dominated by the hard segment content and there was a minimum critical HSC for the samples to show appropriate shape memory effects.

Shape memory polyurethane with polydopamine-coated nanosheets: Simultaneous enhancement of recovery stress and strain recovery ratio and the underlying mechanisms

Two different sizes of polydopamine-coated layered double hydroxides (D-LDHs) are incorporated into polycaprolactone-based polyurethane (PU) to enhance the mechanical and shape memory properties of the PU. The results show that D-LDH interacts strongly with hard segments and hence enhancing phase separation between hard and soft segments. It is found that the tensile moduli of the PU/D-LDH nanocomposites are much higher than that of neat PU at 60°C. In comparison with neat PU, the nanocomposite with 2wt% of small D-LDH exhibits a 60% increase in recovery stress while shape fixity and strain recovery ratio are also improved simultaneously. This is because at low filler loading, most small D-LDH nanosheets interact with hard domains and they are not large enough to connect neighbor hard domains. They can hence reinforce the hard domains without sacrificing the elasticity of the system. Two-dimensional X-ray diffraction studies indicate that most small D-LDH nanosheets are able to rotate back from aligned state to original random state in shape recovery process, justifying the improved strain recovery ratio.

Development of volume-stable adipose tissue constructs using polycaprolactone-based polyurethane scaffolds and fibrin hydrogels

Adipose tissue engineering aims at the restoration of soft tissue defects and the correction of contour deformities. It is therefore crucial to provide functional adipose tissue implants with appropriate volume stability. Here, we investigate two different fibrin formulations, alone or in combination with biodegradable polyurethane (PU) scaffolds as additional support structures, with regard to their suitability to generate volume-stable adipose tissue constructs. Human adipose-derived stem cells (ASCs) were incorporated in a commercially available fibrin sealant as well as a stable fibrin hydrogel previously developed by our group. The composite constructs made from the commercially available fibrin and porous poly(ε-caprolactone)-based polyurethane scaffolds exhibited increased volume stability as compared to fibrin gels alone; however, only constructs using the stable fibrin gels completely maintained their size and weight for 21 days. Adipogenesis of ASCs was not impaired by the additional PU scaffold. After induction with a common hormonal cocktail, for constructs with either fibrin formulation, strong adipogenic differentiation of ASCs was observed after 21 days in vitro. Furthermore, upregulation of adipogenic marker genes was demonstrated at mRNA (PPARγ, C/EBPα, GLUT4 and aP2; qRT-PCR) and protein (leptin; ELISA) levels. Stable fibrin/PU constructs were further evaluated in a pilot in vivo study, resulting in areas of well-vascularized adipose tissue within the implants after only 5 weeks. Copyright © 2013 John Wiley & Sons, Ltd.

Prefabrication of 3D Cartilage Contructs: Towards a Tissue Engineered Auricle – A Model Tested in Rabbits

The reconstruction of an auricle for congenital deformity or following trauma remains one of the greatest challenges in reconstructive surgery. Tissue-engineered (TE) three-dimensional (3D) cartilage constructs have proven to be a promising option, but problems remain with regard to cell vitality in large cell constructs. The supply of nutrients and oxygen is limited because cultured cartilage is not vascular integrated due to missing perichondrium. The consequence is necrosis and thus a loss of form stability. The micro-surgical implantation of an arteriovenous loop represents a reliable technology for neovascularization, and thus vascular integration, of three-dimensional (3D) cultivated cell constructs. Auricular cartilage biopsies were obtained from 15 rabbits and seeded in 3D scaffolds made from polycaprolactone-based polyurethane in the shape and size of a human auricle. These cartilage cell constructs were implanted subcutaneously into a skin flap (15×8 cm) and neovascularized by means of vascular loops implanted micro-surgically. They were then totally enhanced as 3D tissue and freely re-implanted in-situ through microsurgery. Neovascularization in the prefabricated flap and cultured cartilage construct was analyzed by microangiography. After explantation, the specimens were examined by histological and immunohistochemical methods. Cultivated 3D cartilage cell constructs with implanted vascular pedicle promoted the formation of engineered cartilaginous tissue within the scaffold in vivo. The auricles contained cartilage-specific extracellular matrix (ECM) components, such as GAGs and collagen even in the center oft the constructs. In contrast, in cultivated 3D cartilage cell constructs without vascular pedicle, ECM distribution was only detectable on the surface compared to constructs with vascular pedicle. We demonstrated, that the 3D flaps could be freely transplanted. On a microangiographic level it was evident that all the skin flaps and the implanted cultivated constructs were well neovascularized. The presented method is suggested as a promising alternative towards clinical application of engineered cartilaginous tissue for plastic and reconstructive surgery.

Adhesion and collagen production of human tenocytes seeded on degradable poly(urethane urea)

The aim of this study was to investigate whether human tenocytes taken from ruptured quadriceps tendon could be seeded on a biodegradable polycaprolactone-based polyurethanes (PU) urea scaffold. Scaffold colonization and collagen production after different culture periods were analyzed to understand whether tenocytes from ruptured tendons are able to colonize these biodegradable scaffolds. Human primary tenocyte cultures of ruptured quadriceps tendons were seeded on PU scaffolds. After 3, 10 and 15days of incubation, the samples were stained with haematoxylin and eosin and were examined under white light microscopy. After 15 and 30days of incubation, samples were examined under transmission electron microscope. Total collagen accumulation was also evaluated after 15, 30 and 45days of culture. After 15 and 30days of culture, tenocyte-seeded scaffolds showed cell colonization and cell accumulation around interconnecting micropores. Tenocyte phenotype was variable. Collagen accumulation in seeded scaffolds demonstrated a progressive increase after 15, 30 and 45days of culture, while control non-seeded scaffolds show no collagen accumulation. These results showed that human tenocytes from ruptured quadriceps tendon can be seeded on polycaprolactone-based PU urea scaffolds and cultured for a long time period (45days). This study also showed that human tenocytes from ruptured tendons seeded on PU scaffolds are able to penetrate the scaffold showing a progressively higher collagen accumulation after 15, 30 and 45days of incubation. This study provides the basis to use this PU biodegradable scaffold in vivo as an augmentation for chronic tendon ruptures and in vitro as a scaffold for tissue engineering construct.

Preparation, characterization and gas permeation properties of a polycaprolactone based polyurethane-silica nanocomposite membrane

The effect of silica nanoparticles on the gas permeation properties of polycaprolactone-based polyurethane membranes was investigated. Polyurethane and polyurethane-silica nanocomposite membranes were prepared by solution blending and casting-evaporation methods. Silica nanoparticles were prepared by sol–gel method using hydrolysis of tetraethoxysilane (TEOS). Polyurethane was synthesized by bulk two-step polymerization, including polycaprolactone 2000(PCL)/hexamethylene diisocyanate (HMDI)/1,4-butanediol (BDO). The homogeneity and nano scale distribution of the prepared polyurethane-silica membranes were characterized using Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and thermal gravimetric analysis (TGA). Gas permeation properties of these membranes with different silica contents, was studied for pure CO2, CH4, N2 and O2 gases. The results showed reduction in gas permeability, but enhancement in CO2/N2, CO2/CH4 and O2/N2 ideal selectivity. Also the effect of temperature and pressure on permeation properties of these membranes was investigated. The modified Higuchi model was applied to predict the permeability of polyurethane-silica nanocomposite membranes. Good agreement between the experimental data and the predicted gas permeability was obtained.

Shape memory properties of polycaprolactone‐based polyurethanes prepared by reactive extrusion

AbstractThe shape memory properties of polycaprolactone‐based polyurethanes (PCLUs) synthesized via a novel route of reactive extrusion were investigated in terms of the deformation amplitude, temperature, and rate by differential scanning calorimetry (DSC), dynamic mechanical analyzer, and polarized optical microscopy (POM). DSC analysis shows that the crystalline melting temperature and crystallinity of PCLU increased monotonically with increasing the average polymerization degree $ ( \overline {DPn}) $ of poly(ε‐caprolactone) (PCL) block. The retract force increased with increasing the temperature and reached the maximum (6–7 MPa) within 45–55°C. Furthermore, a modified model with two recovery stages was postulated to elucidate the shape memory process, which is visually presented by POM analysis. The two stages of tensile and compressive recovery are distinguished by the inflexion temperature, within 43–48°C and 64–66°C, respectively. The shape fixity is about 60–70% and can be improved to 100% by choosing proper deformation temperature. The tensile deformation recovery ratio was 80–98% due to the water absorption, whereas the compressive deformation recovery ratio was almost 100%. Besides, recovery tests show that the lowest recovery temperature ranged from 24 to 47°C was influenced by the deformation temperature, rate and the PCL block $ ( \overline {DPn}) $. Thus, the shape memory properties can be adjusted according to different purposes. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

In Situ synthesis of multiblock copolymers of poly(ϵ‐caprolactone) with different poly(ether diols) based polyurethane by reactive extrusion

AbstractPolyurethanes with multiblock copolymers of poly(ϵ‐caprolactone) (PCL) and poly(tetramethylene oxide) glycol (PTMG) or poly(ethylene glycol) (PEG) as a soft segment were synthesized in situ via reactive extrusion from ϵ‐caprolactone (CL) and 4,4′‐diphenylmethane diisocyanate (MDI). The titanium alkoxide mixture generated from an ester‐exchange reaction between titanium propoxide [Ti(OPr)4], and excessive PTMG or PEG was used as an initiator and catalyst. Compared to the reported fabrication of polycaprolactone‐based polyurethane (PCLU), the in situ reactive extrusion preparation not only explored a new rapid route for the fabrication of PCLU but also offered a simplified, controllable approach for the production of PCLU in a successive mass scale. A series of PTMG–PCLUs and PEG–PCLUs with different PCL block‐average degrees of polymerization (DPn's) were prepared by only an adjustment of the relative concentration of CL in the reaction system, with a certain constant molar ratio of MDI to titanium alkoxide. 1H‐NMR, gel permeation chromatography, and differential scanning calorimetry results indicate that all of the CL monomers were converted in the polymerization, and the molecular weight of the copolymers was about 8 × 104 g/mol with a polydispersity index of approximate 2.4. With an increase in the PCL block‐average DPn in PTMG–PCLU from 25 to 40, the tensile strength increased from 16.5 to 22.7 MPa, and the melting point increased from 46.1 to 49.5°C. It was also verified by PEG–PCLU prepared with organic Ti of lowered content in the initiator mixture that the mechanical properties could be greatly affected and dropped with decreasing content of organic Ti in the initiator mixture. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

A comparison of the effects of fibre alignment of smooth and textured fibres in electrospun membranes on fibroblast cell adhesion

A polyester polycaprolactone-based polyurethane elastomer (PU) and poly-(l-lactide) (PLLA), two common biomaterials, were electrospun to produce membranes with fibres either randomly orientated or aligned. PU was used to produce membranes consisting of smooth fibres. PLLA was used to prepare fibres with a textured surface. Contact angle measurements of the PU and PLLA cast films reveal that they were both below 90° and fully wetted in less than 60 s. These membranes were investigated for the effect of fibre topography and fibre alignment on cell adhesion, using mouse L929 fibroblasts. It was found that the alignment of electrospun fibres controls the directional spreading of fibroblast independent of fibre being smooth or textured.

Foreign-Body Reaction to the Artelon CMC Joint Spacer: Case Report

The Artelon CMC spacer (Small Bone Innovations, Inc., Morrisville, PA) is a relatively new device that was developed for the treatment of basal joint arthritis. It is composed of a biodegradable polycaprolactone-based polyurethane urea that acts to resurface the distal part of the trapezium and stabilize the trapeziometacarpal joint by augmenting the joint capsule. This is a case report of a foreign-body tissue reaction to the Artelon CMC spacer.

In VitroandIn VivoCartilage Engineering Using a Combination of Chondrocyte-Seeded Long-Term Stable Fibrin Gels and Polycaprolactone-Based Polyurethane Scaffolds

The use of either a hydrogel or a solid polymeric scaffold alone is often associated with distinct drawbacks in many tissue engineering applications. Therefore, in this study, we investigated the potential of a combination of long-term stable fibrin gels and polyurethane scaffolds for cartilage engineering. Primary bovine chondrocytes were suspended in fibrin gel and subsequently injected into a polycaprolactone-based polyurethane scaffold. Cells were homogeneously distributed within this composite system and produced high amounts of cartilage-specific extracellular matrix (ECM) components, namely glycosaminoglycans (GAGs) and collagen type II, within 4 weeks of in vitro culture. In contrast, cells seeded directly onto the scaffold without fibrin resulted in a lower seeding efficiency and distinctly less homogeneous matrix distribution. Cell-fibrin-scaffold constructs implanted into the back of nude mice promoted the formation of adequate engineered cartilaginous tissue within the scaffold after 1, 3, and 6 months in vivo, containing evenly distributed ECM components, such as GAGs and collagen. Again, in constructs seeded without fibrin, histology showed an inhomogeneous and, thus, not adequate ECM distribution compared to seeding with fibrin, even after 6 months in vivo. Strikingly, a precultivation for 1 week in vitro elicited similar results in vivo compared to precultivation for 4 weeks; that is, a precultivation for longer than 1 week did not enhance tissue development. The presented composite system is suggested as a promising alternative toward clinical application of engineered cartilaginous tissue for plastic and reconstructive surgery.

The effect of gamma radiation on molecular stability and mechanical properties of biodegradable polyurethanes for medical applications

Experimental biodegradable medical polyurethanes with varying hydrophilic-to-hydrophobic segment ratios based on hydrophilic poly(ethylene oxide) MW=600 (PEO) and hydrophobic poly(ε-caprolactone) diol MW=530 and 2000 (PCL), were exposed to gamma radiation at the standard dose of 25 kGy used for sterilization. Irradiated polymers degraded to a various extent, this being associated with a reduction of mechanical properties. For the more hydrophobic polyurethanes based exclusively on polycaprolactone diol the decrease of molecular weight was in the range of 12–30% and the decrease of tensile strength was 12%. For the more hydrophilic polyurethanes based on mixtures of polycaprolactone diol and polyethylene oxide the decrease of molecular weight was in the range of 30–50% and the decrease of tensile strength was 50%. Gamma radiation insignificantly affected surface roughness of hydrophobic polycaprolactone-based polyurethanes and caused a slight increase of contact angle. For the hydrophilic polymers based on polycaprolactone diol and polyethylene oxide, gamma radiation increased by 36–76% surface roughness and decreased by 20–45% contact angle. There was also an evident change in thermal properties of the irradiated materials.