Single-component poly(ε-caprolactone) composites

Non-covalently bonded crystalline inclusion compounds (ICs) have been formed by threading host cyclic starches, α-cyclodextrins (α-CDs), onto guest poly(ε-caprolactone) (PCL) chains and by co-crystallization of guest PCL and host urea (U). PCLs were coalesced from both ICs by appropriate removal of the α-CD and U hosts. When added at low concentrations, PCL coalesced from its α-CD–IC served as an effective self-nucleating agent for the bulk crystallization of as-received PCL from the melt. Film sandwiches consisting of two layers of as-received (asr) (control), and one layer each of asr and self-nucleated (nuc) (composite) PCLs were produced by melt pressing. A composite sandwich consisting of a film of neat PCL coalesced from its U–IC (c-PCL) and a film of asr-PCL was also melt pressed. DSC showed that both composite films maintain their characteristic structures and properties even after melt-pressing them together. Both single component film sandwiches exhibited strong interfaces and better mechanical properties than the asr-PCL/asr-PCL control composite sandwiches. These results are similar to those previously obtained on similarly prepared nylon-6 (N-6) sandwich composites made with asr- and nuc-N-6 films with the same levels of crystallinity. However, while the elongation at break was greatly reduced in the asr-N-6/nuc-N-6 composite, asr-/asr-, asr-/c-, and asr-/nuc-, PCL/PCL-composites all showed similarly large elongations at break. The above room temperature and well below room temperature glass-transition temperatures of N-6 and PCL are likely the cause of their widely different elongations at break.     

Multilayer biopolymer/poly(ε-caprolactone)/polycation nanoparticles

Combining two or more materials for carrier construction is one of the topical approaches to avoid/diminish deficiencies and to increase functionality in delivery systems for bioactive compounds. In this context, here, multilayered nanoparticles comprising both natural (atelocollagen—AteCol; hyaluronic acid derivative—HA) and synthetic [poly(ε-caprolactone)—PCL; polyethylenimine—PEI; poly(l-lysine)—PLL] polymers were prepared and characterized. The combination of a modified double-emulsion method with polymer modification reactions allowed improvement of the polymer particle’s functionality. Fourier transform infrared spectroscopy (FTIR), UV–Vis spectroscopy, fluorescence spectroscopy, dynamic light scattering, transmission/scanning electron microscopy and fluorescence microscopy investigations confirmed the obtention of the envisaged nanomaterials with the expected composition and structure. The double-layered biopolymer/PCL-based nanoparticles formed in a first synthesis step could be successfully coated with PEI and PLL. The gel electrophoresis assay attested the DNA packing ability of the formed nano-vehicles involving surface grafting of the former biopolymer/PCL-based nanoparticles in the case of both cationic polymers, for N/P ratios of 10 (PEI coating) and 3.5 (PLL coating), respectively. According to the FTIR registration, the protein’s native form was preserved. Considering the advantage of biocompatibility and high versatility (controlled size, tuned chemistry and biodegradation rate) some of the resulted nanomaterials may appear as potential candidates for biomedical uses (i.e., drug/gene delivery and tissue engineering).     

In vitro degradation of poly(l-lactide)/poly(ε-caprolactone) blend reinforced with MWCNTs

The physical and mechanical properties of poly(l-lactide)/poly(??-caprolactone) (PLLA/PCL) blends reinforced with multiwalled carbon nanotubes (MWCNTs) before and after in vitro degradation were investigated. Because of brittleness, PLLA needs to be plasticized by PCL as a soft polymer. The MWCNTs are used to balance the stiffness and the flexibility of PLLA/PCL blends. The results showed that with incremental increase in concentration of MWCNTs in composites, the agglomerate points of MWCNTs were increased. The physical and mechanical properties of prepared PLLA/PCL blends and MWCNT/PLLA/PCL nanocomposites were characterized. The X-ray diffraction analysis of the prepared blends and composites showed that MWCNTs, as heterogeneous nucleation points, increased the lamella size and therefore the crystallinity of PLLA/PCL. The mechanical strength of blends was decreased with incremental increase in PCL weight ratio. The mechanical behavior of composites showed large strain after yielding and high elastic strain characteristics. The tensile tests results showed that the tensile modulus and tensile strength are significantly increased with increasing the concentration of MWCNTs in composites, while, the elongation-at-break was decreased. The in vitro degradation rate of polymer blends in phosphate buffer solution (PBS) increased with higher weight ratio of PCL in the blend. The in vitro degradation rate of nanocomposites in PBS increased about 65% when the concentration of MWCNTs increased up to 3% (by weight). The results showed that the degradation kinetics of nanocomposites for scaffolds can be engineered by varying the contents of MWCNTs.     

Effect of poly(ε-caprolactone) and titanium (IV) dioxide content on the UV and hydrolytic degradation of poly(lactic acid)/poly(ε-caprolactone) blends

The effect of accelerated weathering degradation on the properties of poly(lactic acid) (PLA)/poly(ε-caprolactone) (PCL) blends and PLA/PCL/titanium (IV) dioxide (TiO₂) nanocomposites are presented in this paper. The results show that both polymers are susceptible to weathering degradation, but their degradation rates are different and are also influenced by the presence of TiO₂ in the samples. Visual, microscopic and atomic force microsocpy observations of the surface after accelerated weathering tests confirmed that degradation occurred faster in the PLA/PCL blends than in the PLA/PCL/TiO₂ nanocomposites. The X-ray diffraction results showed the degradation of PCL in the disappearance of its characteristic peaks over weathering time, and also confirmed that PLA lost its amorphous character and developed crystals from the shorter chains formed as a result of degradative chain scission. It was further observed that the presence of TiO₂ retarded the degradation of both PLA and PCL. These results were supported by the differential scanning calorimetry results. The thermogravimetric analysis results confirmed that that PLA and PCL respectively influenced each other's thermal degradation, and that TiO₂ played a role in the thermal degradation of both PLA and PCL. The tensile properties of both PLA/PCL and PLA/PCL/TiO₂ were significantly reduced through weathering exposure and the incorporation of TiO₂.     

Synthesis and self-assembly of a new amphiphilic thermosensitive poly(N-vinylcaprolactam)/poly(ε-caprolactone) block copolymer

New amphiphilic thermosensitive poly(N-vinylcaprolactam)/poly(ε-caprolactone) (PNVCL-b-PCL) block copolymers were synthesized by ring-opening polymerization of ε-caprolactone with hydroxy-terminated poly(N-vinylcaprolactam) (PNVCL-OH) as a macroinitiator. The structures of the polymers were confirmed by IR, ¹H NMR and GPC. The critical micelle concentrations of copolymer in aqueous solution measured by the fluorescence probe technique reduced with the increasing of the proportion of hydrophobic parts, so did the diameter and distribution of the micelles determined by dynamic light scattering. The shape observed by transmission electron microscopy (TEM) demonstrated that the micelles are spherical. On the other hand, the UV–vis measurement showed that polymers exhibit a reproducible temperature-responsive behavior with a lower critical solution temperature (LCST). The LCST of PNVCL-OH can be adjusted by controlling the molecular weights, and that of copolymers can be adjusted by controlling the compositions and the concentration. Variable temperature TEM measurements demonstrated that LCST transition was the result of transition of individual micelles to larger aggregates.     

Rheological properties of poly(ε-caprolactone) and poly(styrene-co-acrylonitrile) blends

Summary Rheological properties of poly(-caprolactone) (PCL) and Poly (styrene-co-acrylonitrile) (SAN) blends were examined as a function of the acrylonitrile (AN) content in SAN, to systematically understand the correlation between the interaction parameter and the theological properties of miscible polymer blends. When the plateau modulus (G _N ⁰) and zero shear viscosity ( ₀) of the PCL/SAN blends are plotted against the AN content in SAN, a minimum is observed. Qualitatively, the results obtained parallel the variation of the interchain interaction with the AN content. The negative deviation ofG _N ⁰ and ₀ from linearity seems to be attributed to the increase in the entanglement molecular weight between dissimilar chains which results from the chain extension caused by interchain interaction.     

Reversibility of thermodynamic lower critical solution temperature phenomenon in miscible poly(ε-caprolactone)/poly(benzyl methacrylate)

Differential scanning calorimetry and optical microscopy were performed to examine the reversibility of phase separation at above the lower critical solution temperatures in a miscible poly(ε-caprolactone) (PCL)/poly(benzyl methacrylate) (PBzMA) blend system. Upon heating, phase separation occurred via a binodal nucleation and growth (NG) mechanism at above 240 °C, which is a lower critical solution temperature (LCST). The pattern of phase domains suggests that the phase separation was meta-stable. Interestingly, the LCST phase separation was found to be readily reversible to original homogeneity upon cooling at regularly accessible rates. A major factor may be that the temperature window between the LCST curve and blend T_g curve is wide, resulting in a convenient temperature range for the polymer chains to kinetically reorganize to a state favored by the thermodynamic conditions.     

Controlled release of doxycycline within core/shell poly(ε-caprolactone)/poly(ethylene oxide) fibers via coaxial electrospinning

The development of fibers with desired drug release properties has gained a high research interest for water-soluble drugs with controlled drug delivery systems obtained by coaxial electrospinning technique. The objective of this study is to achieve the controlled-release of doxycycline hyclate (DOXH) from the fabricated electrospun fibers. In this case, three different electrospun core/shell fibers have been successfully fabricated using this technique and the model drug, DOXH, has been entrapped in the core layers. The results of the structural properties and in vitro release studies have been compared with electrospun monostructural fibers fabricated by conventional electrospinning technique. Scanning electron microscopy and transmission electron microscopy images have proved that the fabricated electrospun fibers have core/shell structures. Fourier transform infrared spectroscopy has shown convenient interaction and compatibility between polymers and the model drug. X-ray diffraction analysis has revealed that all the encapsulated DOXH are transferred into amorphous physical state and lost its crystalline state in the fibers. Moreover, drug release studies have demonstrated that the electrospun core/shell fibers show a better-controlled release than the monostructural fibers. It can be concluded that the fibers obtained by blending hydrophilic and hydrophobic polymers such as poly(ε-caprolactone) and poly(ethylene oxide) in both shell and core sides are promising candidate for controlled drug release.     

Fabrication of highly porous poly (ε-caprolactone) microfibers via electrospinning

Highly porous Poly (ε-caprolactone; PCL) microfibers were successfully fabricated by collecting the fibers into a water bath during electrospinning. The morphology of the fibers collected with and without the water bath was investigated. We observed that altering the pH of the water bath affected both the fiber diameter and the size of pores on the fibers. Acidic or basic condition was found to be more favorable than neutral conditions for the formation of well-porous fibers. The morphology and pore size of the microfibers were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The average diameter of the fibers and the pore size on the surface of the microfibers were found to be 12–14.5 and 0.3–0.7 μm, respectively. The crystallinity and thermal properties of the PCL mats were investigated by DSC. This highly porous nature of the microfibers makes PCL less crystalline and increases the surface to volume ratio of the mat. Therefore, the PCL mat obtained by water bath electrospinning may be more effective for tissue scaffolds and drug delivery than the mat obtained without water bath.     

Rheologically determined phase diagram of poly(ε-caprolactone)/poly(styrene-co-acrylonitrile) blends: Role of ramp rate in dynamic measurements

The phase behavior of poly(ε-caprolactone) (PCL)/poly(styrene-co-acrylonitrile) (SAN) blends, with a lower critical solution temperature (LCST)-type phase diagram over a virtual upper critical solution temperature (UCST) one, was investigated through thermal analysis and dynamic rheological measurements as a function of ramp rate. The LCST phase diagram was detected rheologically from the observed slope changes in the dynamic temperature ramps of storage modulus (G′). The determined phase transition points along with the spinodal temperatures, which are estimated based on the theoretical approach of Ajji and Choplin's mean field theory, shift to higher temperatures by reducing the ramp rate. The detected shifts show a composition dependency. Far away from the critical point, the phase transition temperatures of PCL/SAN blends change more noticeably, which originates from the smaller magnitude of concentration fluctuations in the metastable region and the stronger competition between the phase dissolution and cooling rate. The Flory–Huggins interaction parameter (χ) was appropriately adjusted into the LCST phase boundary as a function of temperature and composition. The results confirmed that the adjusted χ has higher temperature dependency at larger ramp rate of the dynamic measurements. The experimentally combined LCST and UCST phase behavior were also verified by the compressible regular solution model. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47750.     

Two-way reversible shape memory behaviour of crosslinked poly(ε-caprolactone)

Polymers capable of reversible “two-way” shape memory behaviour are of great interest for applications where reversible actuation is demanded, and semicrystalline crosslinked systems have been indicated as an interesting solution towards this end. In this work we have explored the two-way shape memory response of semicrystalline poly(ε-caprolactone)-based polymer networks, prepared with various macromolecular architectures starting from linear, three- and four-arm star poly(ε-caprolactone) functionalized with methacrylate end-groups. All the materials have revealed two-way shape memory capabilities. The effect arises from an elongation process that takes place when the material is cooled under an applied load below the crystallization temperature, and that is completely reversed when heated again above melting temperature, in a manner that strongly depends on the applied load and on the material crosslink density. Two-dimensional XRD analysis, carried out on elongated specimens, shows that the elongation on cooling is accompanied by a change in the crystallinity orientation along the direction of stretch.     

Mg-doped poly(?-caprolactone)/siloxane biohybrids

Ionically conducting materials based on a poly(?-caprolactone) (PCL)/siloxane organic/inorganic host framework doped with magnesium triflate (Mg(CF₃SO₃)₂) were synthesized by the sol-gel process. In this matrix short PCL chains are covalently bonded to the siliceous network via urethane linkages. In this study the salt content of samples was identified using the conventional notation n, where n indicates the number of (C(O)(CH₂)₅O) PCL repeat units per Mg²⁺ ion. Xerogels with compositions ranging from n = ∞ to 1 were prepared. The only composition studied that was not entirely amorphous was that prepared with n = 1. Xerogels with n ≥ 7 are thermally stable up to at least 200 °C. The composition with the highest conductivity of the series is that with n = 34 (5.9 × 10⁻⁹ and 9.8 × 10⁻⁷ S cm⁻¹ at 24 and 104 °C, respectively).     

Nanosized micelles self-assembled from amphiphilic poly(citric acid)–poly(ε-caprolactone)–poly(citric acid) copolymers

In this study, novel ABA-type amphiphilic copolymers consisting of poly(citric acid) (PCA) (A) as hydrophilic segment and poly(ε-caprolactone) (PCL) (B) as hydrophobic block were prepared by an approach in the following two steps: (1) ring-opening polymerization (ROP) of ε-caprolactone with 1,5-pentanediol initiator to obtain a hydroxyl telechelic PCL; (2) melt polycondensation reaction of hydroxyl telechelic PCL and citric acid molecules. The prepared copolymers are capable of self-assembling into nanosized micelles in aqueous solution. The influence of the copolymer composition on the micelle dimensions was investigated. The critical micellar concentration of the copolymers is in the range of 5–6.3 × 10^?2 mg/mL which is determined by the fluorescence probe technique using pyrene. Also the results indicate that CMC of self assembled micelles is influenced by the hydrophilicity of PCA–PCL–PCA copolymers depending on the CA/CP ratio, and these micelles may find great potential as drug carriers in biomedical fields.     

Facile preparation of poly(ε-caprolactone)/Fe3O4@graphene oxide superparamagnetic nanocomposites

The main goal in this work was to prepare and characterize a kind of novel superparamagnetic poly(ε-caprolactone)/Fe₃O₄@graphene oxide (PCL/Fe₃O₄@GO) nanocomposites via facile in situ polymerization. Fabrication procedure included two steps: (1) GO nanosheets were decorated with Fe₃O₄ nanoparticles by an inverse co-precipitation method, which resulted in the production of the magnetite/GO hybrid nanoparticles (Fe₃O₄@GO); (2) incorporation of Fe₃O₄@GO into PCL matrix through in situ polymerization afforded the magnetic nanocomposites (PCL/Fe₃O₄@GO). The microstructure, morphology, crystallization properties, thermal stability and magnetization properties of nanocomposites were investigated with various techniques in detail. Results of wide-angle X-ray diffraction showed that the incorporation of the Fe₃O₄@GO nanoparticles did not affect the crystal structure of PCL. Images of field emission scanning electron microscope and transmission electron microscopy showed Fe₃O₄@GO nanoparticles evenly spread over PCL/Fe₃O₄@GO nanocomposites. Differential scanning calorimeter and polar optical microscopy showed that the crystallization temperature increased and the spherulites size decreased by the presence of Fe₃O₄@GO nanoparticles in the nanocomposites due to the heterogeneous nucleation effect. Thermogravimetric analysis indicated that the addition of Fe₃O₄@GO nanoparticles reduced the thermal stability of PCL in the nanocomposites. The superparamagnetic behavior of the PCL/Fe₃O₄@GO nanocomposites was testified by the superconducting quantum interference device magnetometer analysis. The obtained superparamagnetic nanocomposites present potential applications in tissue engineering and targeted drug delivery.     

Fabrication and characterization of poly(ε-caprolactone)/gelatin nanofibrous scaffolds for retinal tissue engineering

Different ratios of poly(ε-caprolactone) (PCL) and gelatinwere used to fabricate scaffolds for regeneration of retinal pigment epithelium (RPE) layer. Physical and chemical characterizations were performed and the behavior of human RPE cells on the scaffolds was evaluated subsequently. An increase in gelatin content in the scaffold enhanced hydrophilicity, RPE cell attachment, proliferation, and spreading over PCL scaffolds. Granular and cytoplasmic expressions of RPE65 and Cytokeratin 8/18 markers confirmed the presence of RPE cells. It was believed that PCL/gelatin scaffolds could be used as substrates to replace RPE extracellular matrix to facilitate regeneration of RPE layer in retinal diseases.     

Impact of organoclays on the phase morphology and the compatibilization efficiency of immiscible poly(ethylene terephthalate)/poly(ε-caprolactone) blends

Adding nanofillers Cloisite 30B (C30B) and Cloisite 15A (C15A) to poly(ethylene terephthalate) (PET)/poly(ε-caprolactone) (PCL) (70/30, wt/wt) blends via melt blending can improve their phase morphology and change their interface properties. The effects of the different selective localization of clay on the structure and the morphologies are studied and evaluated by theoretical and experimental methods. It is found that C30B is selectively localized in PET and at the PET-PCL interface, whereas C15A is mainly localized at the interface. Moreover, the changes in the rheological behavior of the blends are attributed to the formation of clay network-like structures. X-ray diffraction, scanning electron microscope, and transmission electron micrograph observations also evidenced an exfoliated and/or intercalated structure of C30B, and intercalated structure of C15A in the blend, together with significant morphology changes of the initially immiscible blend. The relative permeability to PET/PCL of the nanocomposites decreased with the increasing of nanoclays content. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48812.     

Synthesis and crystallization kinetics of silsesquioxane-based hybrid star poly(ε-caprolactone)

A series of silsesquioxane-based hybrid star poly(ε-caprolactone) with different arm length (SHPCL-4, SHPCL-10, SHPCL-40) were synthesized from ring-opening polymerisation of ε-caprolactone as a monomer initiated by silsesquioxane-based hybrid polyol (SBOH). Two linear poly(ε-caprolactone)s, LPCL-25 and LPCL-35, were also prepared for comparison. The sequence of LPCL-25<LPCL-35<SHPCL-4<SHPCL-10<SHPCL-40 for total molecular weights (M_n) and the sequence of SHPCL-4<SHPCL-10<LPCL-25<LPCL-35<SHPCL-40 for average molecular weight per arm were determined by ¹H NMR and GPC measurements. The ¹H NMR data also suggested that SHPCLs possess a spheric architecture with 29.2 arms in average. The crystallization kinetics study by non-isothermal DSC showed that the starting temperature of crystallization (T_s), the ending temperature (T_e) and the peak temperature of exothermic curve (T_p) are in the order as: SHPCL-4<SHPCL-10<LPCL-25<SHPCL-40≈LPCL-35, while the crystallinity (X_c) follows the order of SHPCL-4<SHPCL-10<SHPCL-40<LPCL-25<LPCL-35. The corrected overall crystallization rate constant (K_c) calculated from Avrami equation were found to be in the order as: SHPCL-4<SHPCL-10<LPCL-35<LPCL-25≈SHPCL-40, which was further evidenced by the real time morphological observation with polarized light microscopy (POM). It is also found by the POM measurements that the inorganic core and star architecture greatly retards the nucleation of SHPCLs with short arms, while it helps the nucleation of SHPCL with longer arms.     

Disclosing the role of surface and bulk erosion on the viscoelastic behavior of biodegradable poly(ε-caprolactone)/poly(lactic acid)/hydroxyapatite nanocomposites

In this study, biodegradable polymer blends and their nanocomposites were prepared using poly(ε-caprolactone) (PCL) and poly(lactic acid) (PLA) as blending components and hydroxyapatite (HA) nanoparticles as reinforcement. X-ray diffraction spectra showed that the presence of HA nanoparticles enhanced the intensity of the peaks (100) and (200) corresponding to the PCL's crystalline planes. The transmission electron microscopy images confirmed the high tendency of HA nanoparticles to locate in the PLA phase. The water uptake values of samples measured at pH 4 were more than those measured at other pH values. The weight loss behavior of blends in acidic medium was completely different from that in basic and neutral media. The Williams–Landel–Ferry equation and time–temperature superposition principle were applied to the creep compliance of the samples and their master curves were determined at reference temperature of 30 °C, and the mechanical properties of samples were predicted in other conditions. The effect of pH on the creep–recovery response of studied samples was analyzed. From this analysis, it could be found that at pH 4, the creep stain increased, while, at pH 7, there was no a significant change in the viscoelastic property. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47151.     

Advance application of Raman spectroscopy for quantitative analysis of noncrystalline components in thin films of poly(ε-caprolactone)/poly(butadiene) blends

A quantitative analysis method for the distribution of noncrystalline poly(butadiene) component in poly(ε-caprolactone)/poly(butadiene) (PCL/PB) binary blends have been analyzed by advance application of Raman spectroscopy, optical microscopy, and differential scanning calorimetry (DSC) techniques. Thin films of different compositions of PCL/PB binary blends were prepared from solution and isothermally crystallized at a certain temperature. After calibration with real data, quantitative analyses by Raman spectroscopy revealed the amorphous PB are trapped inside the PCL crystals. Polarized optical microscopy and real time atomic force microscopy were used to collect data for the crystal morphology and crystal growth rate. For pure PCL crystals, a morphology of truncated lozenge shape was observed, independent of crystallization temperature and regardless of the blends compositions. For the pure PCL and their blends, almost unique crystal growth rate was found. The miscibility behaviors using DSC were drawn through melting point depression method. The Hoffman-Weeks extrapolations of the blends were found to be linear and identical with those of the neat PCL. The interaction parameter for the blends indicating that the PCL and PB blends have no intermolecular interaction, confirming the blends are immiscible. Despite the immiscibility of the blend, the PCL crystals do not bend during the growth process and do not reduce the growth rate as they do for miscible blend systems.     

Three​-dimensional porous poly(ε-caprolactone)/beta-tricalcium phosphate microsphere-aggregated scaffold for bone tissue engineering

In this study, porous scaffolds made of polycaprolactone (PCL)/β-tricalcium phosphate (BTCP) biocomposite were fabricated for bone tissue engineering (BTE) applications. The microsphere-aggregated scaffolds were prepared with various BTCP concentrations (10wt%, 20wt%, 50wt%) by the freeze-drying method. The porosity of obtained microsphere-aggregated scaffolds with various pore sizes was 80–85%, where this value was about 70% for the PCL/BTCP (50) sample with no microsphere formation. The results indicated that adding BTCP has enhanced mechanical strength, and the mineralization of PCL/BTCP composite scaffolds has been increased compared to the pure PCL scaffolds in simulated body fluid (SBF). The adhesion and proliferation of mouse bone marrow mesenchymal stem cells (mMSCs) seeded onto PCL/BTCP scaffolds were enhanced compared to the PCL. In addition, in terms of differentiation, the incorporation of BTCP led to increasing the mineral deposition and alkaline phosphatase activity of mMSCs. The synergistic effect of using microsphere-aggregated scaffolds along with BTCP as a reinforcing agent in PCL biocomposite showed that these porous biocomposite scaffolds have the potential application in BTE.