Scaffolds with Tunable Properties Constituted by Electrospun Nanofibers of Polyglycolide and Poly(ε‐caprolactone)

Electrospun scaffolds constituted by different mixtures of two biodegradable polyesters are prepared. Specifically, materials with well differentiated properties can be derived from the blending of hydrophilic polyglycolide (PGA) and hydrophobic poly(ε‐caprolactone) (PCL), which are also two of the most applied polymers for biomedical uses. Electrospinning conditions are selected in order to get homogeneous and continuous fibers with diameters in the nano/micrometric range. These conditions are also applied to load the different scaffolds with curcumin (CUR) and polyhexamethylene biguanide (PHMB) as hydrophobic and hydrophilic bactericide compounds, respectively. Physicochemical characterization of both unloaded and loaded scaffolds is performed and involved Fourier transform infrared and ¹H NMR spectroscopies, morphological observations by scanning electron microscopy, study of thermal properties through calorimetry and thermogravimetric analysis, and evaluation of surface characteristics through contact angle measurements. Release behavior of the loaded scaffolds is evaluated in two different media. Results point out a well differentiated behavior where the delivery of CUR and even PHMB are highly dependent on the PGA/PCL ratio, the capability of the medium to swell the polymer matrix, and the diffusion of the selected solvent into the electrospun fibers. All samples show a bactericide effect in both hydrophilic cell culture and hydrophobic agar media.     

Nanoporous Low Dielectric Cyclosiloxane Bearing Polysilsesquioxane Thin Films Templated by Poly(ε‐caprolactone)

Summary: Dielectric cyclosiloxane bearing polysilsesquioxanes (CS‐PSSQs) were prepared by acid catalyzed polymerization using 2,4,6,8‐tetramethyl‐2,4,6,8‐tetra(trimethoxysilylethyl)cyclotetrasiloxane. The molecular weight, and content of the functional end‐groups of the CS‐PSSQs were found to be dependent on the process parameters, such as the molar ratio of water and catalyst to the ? OCH₃ group of the silane monomer, the amount of solvent, and the poly(ε‐caprolactone) (PCL) content, etc. Based on these CS‐PSSQ prepolymers, nanoporous organic/inorganic hybrid thin films were fabricated by spin‐coating mixtures of these prepolymers with star‐shaped PCL on the silicon substrate, and subsequently heating them at 150 and 250 °C for 1 minute each and then at 420 °C for 1 hour. A dielectric constant as low as 2.28 was achieved for the nanoporous PCL/CS‐PSSQ (3:7 v/v) film, along with low moisture absorption in ambient and water conditions, primarily due to the presence of hydrophobic moieties such as ethylene and methyl groups of the polymer and nano‐sized hydrophobic pores inside the matrix, resulting in the film having stable dielectric properties. Moreover, the PCL/CS‐PSSQ (3:7 v/v) nanohybrid film revealed a nanoporous structure containing ca. 1.52 nm of average‐sized mesopores, as measured by the N₂ adsorption method. The CS‐PSSQ‐only film showed high mechanical strengths having an elastic modulus and hardness of 6.64 and 0.88 GPa, respectively, for the 7 500 Å thick film and 2.41 and 0.38 GPa, respectively, for the PCL/CS‐PSSQ (3:7 v/v) film. In addition, the crack velocity of the CS‐PSSQ‐only film was found to be ca. 10^?11 m · s^?1 in ambient conditions and an aqueous environment, probably due to the enhanced hydrophobicity and mechanical toughness of the incorporated methyl group, siloxane unit and ethylene moieties in the polymer matrix.

     

Effect of peroxide crosslinking on thermal and mechanical properties of poly(ε‐caprolactone)

Poly(ε‐caprolactone) (PCL), a saturated polyester, derived from ring‐opening polymerization of ε‐caprolactone, was chemically crosslinked with various amounts of benzoyl peroxide (BPO) by a two‐step method by first evenly dispersing the BPO into the PCL matrix and then crosslinking at elevated temperature. The gel fraction increased with an increase in BPO content. The modified Charlesby–Pinner equation was used to calculate the ratio of chain scission and crosslinking. The results showed that both scission and crosslinking occurred, and that crosslinking predominated over scission. The number‐average molecular weight between the crosslinks determined by the rubber elasticity theory using the hot set test showed a decrease with increasing BPO content. The melting temperature and crystallinity decreased with an increase in BPO content, and the crystallization temperature increased after crosslinking. Dynamic mechanical analysis results showed a decrease in the glass transition temperature as a result of chemical crosslinking of PCL. This was explained by the observed reduction in crystallinity and the increase in free volume due to restrictions in chain packing. Moreover, Young's modulus and elongation at break generally decreased with an increase in BPO content, but the tensile strength first increased with BPO content up to 1.0 wt%, reached a maximum, and then decreased. Copyright © 2007 Society of Chemical Industry     

Synthesis and characterization of fullerene grafted poly(ε‐caprolactone)

The fullerene grafted poly(ε‐caprolactone) (PCL) was successfully synthesized with a graft efficiency of 80%. The fullerene moieties grafted onto the PCL chain aggregate into 1–2 μm particles so that a physical pseudo‐network is formed. Because of the existence of the network structure, the fullerene grafted PCL film can retain its shape at much higher temperatures than that of pure PCL film, as observed in dynamic mechanical tests. It shows a hydrophobic gelling behavior in chloroform solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Toward environment‐friendly composites of poly(ε‐caprolactone) reinforced with stereocomplex‐type poly(l‐lactide)/poly(d‐lactide)

In this work, stereocomplex‐poly(l ‐ and d ‐lactide) (sc‐PLA) was incorporated into poly(ε‐caprolactone) (PCL) to fabricate a novel biodegradable polymer composite. PCL/sc‐PLA composites were prepared by solution casting at sc‐PLA loadings of 5–30 wt %. Differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD) demonstrated the formation of the stereocomplex in the blends. DSC and WAXD curves also indicated that the addition of sc‐PLA did not alter the crystal structure of PCL. Rheology and mechanical properties of neat PCL and the PCL/sc‐PLA composites were investigated in detail. Rheological measurements indicated that the composites exhibited evident solid‐like response in the low frequency region as the sc‐PLA loadings reached up to 20 wt %. Moreover, the long‐range motion of PCL chains was highly restrained. Dynamic mechanical analysis showed that the storage modulus (E′) of PCL in the composites was improved and the glass transition temperature values were hardly changed after the addition of sc‐PLA. Tensile tests showed that the Young's modulus, and yield strength of the composites were enhanced by the addition of sc‐PLA while the tensile strength and elongation at break were reduced. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40208.     

Preparation of poly(ε‐caprolactone)/poly(ε‐caprolactone‐co‐lactide) (PCL/PLCL) blend filament by melt spinning

Poly(ε‐caprolactone)/poly(ε‐caprolactone‐co‐lactide) (PCL/PLCL) blend filaments with various ratios of PCL and PLCL were prepared by melt spinning. The effect of PLCL content on the physical properties of the blended filament was investigated. The melt spinning of the blend was carried out and the as spun filament was subsequently subjected to drawing and heat setting process. The addition of PLCL caused significant changes in the mechanical properties of the filaments. Crystallinity of blend decreased with the addition of PLCL as observed by X‐ray diffraction (XRD) and differential scanning calorimetry (DSC). Scanning electron microscopy (SEM) revealed that the fracture surface becomes rougher at higher PLCL content. It may be proposed that PCL and PLCL show limited interaction within the blend matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Molecular Architecture and Enhanced Thermal Stability of Electrospun Poly(ε‐caprolactone)/Aminopropyl Isobutyl Polyhedral Oligomeric Silsesquioxane Hybrid Fibers

Polymer‐based electrospun fibers have been intensively studied as antimicrobial membranes, drug carriers, and energetic materials. Inorganic fillers or small molecules have been routinely added into polymer matrices in order to enhance product functions. However, the electrospinning process is kinetically controlled and solvent rapidly evaporates due to the large surface‐to‐volume ratio of spinning liquid jet. When electrospinning a multicomponent system, complex phase behavior may occur and give rise to interesting internal structures of resulting products. Such kinetically driven phenomena deserve more attention for optimizing product performance. Here, electrospun poly(ε‐caprolactone)(PCL)/aminopropyl‐heptaisobutyl‐polyhedral oligomeric silsesquioxane (AMPOSS) fibers with AMPOSS content up to 30 wt% are studied as a model system to understand the impact of kinetically controlled phase separation on the fibers' internal structure, properties, and thermal stability. With sufficient AMPOSS loading, the hybrid fibers are found to have an AMPOSS‐shell/PCL‐core structure. The thermal stability of the as‐spun PCL/AMPOSS fibers is therefore greatly enhanced.

     

Evaluation of the thermal and mechanical properties of poly(ε‐caprolactone), low‐density polyethylene,and their blends

The thermal and mechanical properties of low‐density polyethylene (LDPE), poly(ε‐caprolactone) (PCL), and their blends were evaluated. Differential scanning calorimetry showed that increasing the PCL content of the blend did not change the LDPE melting temperature, but reduced the crystallinity by up to 16.8%. This behavior was related to interactions between the PCL chains and the crystalline phase of LDPE. Tensile strength and elongation at break values for the blends were lower than those for the pure polymers, which suggested an incompatibility between the polymers. The values for Young's modulus under tensile increased when PCL was added to LDPE. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91:3909–3914, 2004     

Structure and Mechanical Properties of Poly(lactic acid) Filled with (Starch nanocrystal)‐graft‐poly(ε‐caprolactone)

Poly(ε‐caprolactone) (PCL) was grafted to the surface of starch nanocrystals (StN) via microwave‐assisted ROP. The resultant nanoparticles were then incorporated into a poly(lactic acid) matrix to produce fully‐biodegradable nanocomposites with good mechanical properties. A loading level of 5 wt.‐% StN‐g‐PCL resulted in simultaneous enhancements of strength and elongation. The StN‐g‐PCL self‐aggregated as rubbery microparticles to enhance the elongation by ca. 10‐fold over that of neat PLA. Meanwhile, the grafted PCL chains were miscible with PLA and formed a stress‐transferring interface to the StN, providing a reinforcing function.

     

Biodegradable and photocurable multiblock copolymers with shape‐memory properties from poly(ε‐caprolactone) diol,poly(ethylene glycol), and 5‐cinnamoyloxyisophthalic acid

Biodegradable and photocurable multiblock copolymers of various compositions were synthesized by the high‐temperature solution polycondensation of poly(ε‐caprolactone) (PCL) diols of molecular weight (M_n) = 3000 and poly(ethylene glycol)s (PEG) of M_n = 3000 with a dichloride of 5‐cinnamoyloxyisophthalic acid (ICA) as a chain extender, followed by irradiation by a 400 W high‐pressure mercury lamp (λ > 280 nm) to form a network structure. The gel contents increased with photocuring time, reaching a level of over 90% after 10 min for all copolymers without a photoinitiator. The thermal and mechanical properties of the photocured copolymers were examined by DSC and tensile tests. In cyclic thermomechanical tensile tests, the photocured ICA/PCL/PEG copolymer films showed good shape‐memory properties at 37–60°C, with both shape fixity ratio and shape recovery ratio over 90% at a maximum tensile strain of 100–300%. The water absorption of these copolymers and their rate of degradation in a phosphate buffer solution (pH 7.0) at 37°C increased significantly with increasing PEG content. The novel photocured ICA/PCL/PEG multiblock copolymers are potentially useful in biomedical applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure and mechanical properties of blends of poly(ε‐caprolactone) with a poly(amino ether)

Poly(ε‐caprolactone) (PCL)/poly(amino ether) (PAE) blends were obtained by injection molding without any previous extrusion step in an attempt to (i) contribute to the knowledge of the relation between structure and mechanical properties in these type of blends composed of a rubbery and a glassy polymer and (ii) to find out to which extent are the PCL/PAE blends compatible, and therefore whether the biodegradability of PCL can be added as a characteristic of PAE‐based applications. PCL/PAE blends are composed of a crystalline PCL phase, a pure amorphous PCL phase, and a PAE‐rich phase where some PCL is present. The presence of some dissolved and probably unreacted PCL in the PAE‐rich phase led to a low interfacial tension as observed by the small size of the dispersed particles and the large interfacial area. The dependence on composition of both the modulus of elasticity and the yield stress of the blends was parallel to that of the orientation level. The elongation at break showed values similar to those of PAE in PAE‐rich blends, and was slightly synergistic in very rich PCL compositions; this behavior reflects a change in the nature of the matrix, from glassy to rubbery. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of polyurethane elastomers based on chitosan and poly(ε‐caprolactone)

Biodegradable polyurethane (PU) elastomers with potential for biomedical and industrial applications were synthesized by the reaction of poly(ε‐caprolactone) (PCL) and isophorone diisocyanate (IPDI), extended with different mass ratio of chitosan and 1,4‐butane diol (BDO). Their chemical structures were characterized using FTIR, ¹HNMR, and ¹³CNMR, and thermal properties were determined by TGA and DMTA. Incorporation of chitosan contents into the polyurethane backbone caused improvement in thermal stability and thermal degradation rate. Optimum thermal properties and degradation profile were obtained from elastomer extended with chitosan. The crystallinity and hydrophilicity of the prepared polymers were also examined by X‐ray and contact angle measurements. The results showed that hydrophilicity decreased and crystallinity increased with increasing of chitosan content in polyurethane backbone. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nonisothermal crystallization kinetics and thermomechanical properties of multiwalled carbon nanotube‐reinforced poly(ε‐caprolactone) composites

BACKGROUND: The technological development of poly(ε‐caprolactone) (PCL) is limited by its short useful lifespan, low modulus and high crystallinity. There are a few papers dealing with the crystallization behavior of carbon nanotube‐reinforced PCL composites. However, little work has been done on the crystallization kinetics of melt‐compounded PCL/multiwalled carbon nanotube (MWNT) nanocomposites. In this study, PCL/MWNT nanocomposites were successfully prepared by a simple melt‐compounding method, and their morphology and mechanical properties as well as their crystallization kinetics were studied. RESULTS: The MWNTs were observed to be homogeneously dispersed throughout the PCL matrix. The incorporation of a very small quantity of MWNTs significantly improved the storage modulus and loss modulus of the PCL/MWNT nanocomposites. The nonisothermal crystallization behavior of the PCL/MWNT nanocomposites exhibits strong dependencies of the degree of crystallinity (X_c), peak crystallization temperature (T_p), half‐time of crystallization (t_1/2) and Avrami exponent (n) on the MWNT content and cooling rate. The MWNTs in the PCL/MWNT nanocomposites exhibit a higher nucleation activity. The crystallization activation energy (E_a) calculated with the Kissinger model is higher when a small amount of MWNTs is added, then gradually decreases; all the E_a values are higher than that of pure PCL. CONCLUSION: This paper reports for the first time the preparation of high‐performance biopolymer PCL/MWNT nanocomposites prepared by a simple melt‐compounding method. The results show that the PCL/MWNT nanocomposites can broaden the applications of PCL. Copyright © 2008 Society of Chemical Industry     

Kenaf fiber/poly(ε‐caprolactone) biocomposite with enhanced crystallization rate and mechanical properties

Plant‐derived kenaf fiber (KF)‐reinforced poly(ε‐caprolactone) (PCL) biocomposites were successfully fabricated by the melt mixing technique. The crystallization behavior, morphology, and mechanical and dynamic mechanical properties of PCL/KF composites with various KF weight contents were investigated. The crystallization rate, tensile and storage moduli significantly improved as compared to the virgin polymer. The half times of PCL/KF composite (20 wt % fiber content) in isothermal crystallization at 40°C and 45°C reduced to 31.6% and 42.0% of the neat PCL, respectively. Moreover, the tensile and storage modulus of the composite are improved by 146% and 223%, respectively, by the reinforcement with 30% KF. The morphology evaluated by SEM indicates good dispersion and adhesion between KF and PCL. Overall, these findings reveal that KF can be a potential reinforcement for the biodegradable polymer composites owing to its good ability to improve the mechanical properties as well as crystallization rate. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Hydrolytic Degradation of Amorphous Films of L‐Lactide Copolymers with Glycolide and D‐Lactide

Summary: Films of poly(L ‐lactic acid) (PLLA) and copolymers of L ‐lactide (LLA) with either glycolide [P(LLA‐GA)](81/19) or D ‐lactide [P(LLA‐DLA)](77/23) were prepared and an effect of comonomer type on the hydrolytic degradation of the films was studied in phosphate‐buffered solutions at 37 °C. The degraded films were investigated using gravimetry (weight loss and water absorption), gel permeation chromatography, DSC, X‐ray diffractometry, tensile testing and polarization optical microscopy. To exclude the effects of molecular weight and crystallinity on hydrolytic degradation, the films were prepared from polymers with similar molecular weights and were made amorphous by melt quenching. It was found that the hydrolytic degradation rate decreased in the order P(LLA‐GA) > P(LLA‐DLA) > PLLA. The hydrolytic degradation rate constant of PLLA and LLA copolymer films increased with increasing the water absorption (hydrophilicity), or with decreasing the initial glass transition temperature or the L ‐lactyl unit sequence length, indicating that the hydrolytic degradation rate of the copolymers was closely related to these three parameters. The crystallization of P(LLA‐GA) film occurred within hydrolytic degradation for 20 weeks.

M_n of PLLA and LLA copolymer films as a function of hydrolytic degradation time.     

Poly(vinyl pyrrolidone‐co‐vinyl acetate)‐graft‐poly(ε‐caprolactone) as a compatibilizer for cellulose acetate/poly(ε‐caprolactone) blends

Poly(vinyl pyrrolidone‐co‐vinyl acetate)‐graft‐poly(ε‐caprolactone) (PVPVAc‐g‐PCL) was synthesized by radical copolymerization of N‐vinyl‐2‐pyrrolidone (VP)/vinyl acetate (VAc) comonomer and PCL macromonomer containing a reactive 2‐hydroxyethyl methacrylate terminal. The graft copolymer was designed in order to improve the interfacial adhesiveness of an immiscible blend system composed of cellulose acetate/poly(ε‐caprolactone) (CA/PCL). Adequate selections of preparation conditions led to successful acquisition of a series of graft copolymer samples with different values of molecular weight ( ), number of grafts (n), and segmental molecular weight of PVPVAc between adjacent grafts (M_n (between grafts)). Differential scanning calorimetry measurements gave a still immiscible indication for all of the ternary blends of CA/PCL/PVPVAc‐g‐PCL (72 : 18 : 10 in weight) that were prepared by using any of the copolymer samples as a compatibilizer. However, the incorporation enabled the CA/PCL (4 : 1) blend to be easily melt‐molded to give a visually homogeneous film sheet. This compatibilizing effect was found to be drastically enhanced when PVPVAc‐g‐PCLs of higher and M_n (between grafts) and lower n were employed. Scanning electron microscopy revealed that a uniform dispersion of the respective ingredients in the ternary blends was attainable with an assurance of the mixing scale of several hundreds of nanometers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electrospun PLA/PCL fibers with tubular nanoclay: Morphological and structural analysis

Biodegradable polymers are good candidates for a wide range of applications in tissue engineering and drug delivery because of their biocompatibility, their degradation, mechanical properties, and offer a sustained release of encapsulated drugs. The electrospun polymer nanofibrous materials can be used as carriers for hydrophobic and hydrophilic drugs. This research work focused on poly(lactic acid) (PLA) and blends of PLA with poly (ε‐caprolactone) (PCL) that are reinforced with different concentrations of halloysite nanotubes (HNTs) and various cosolvents for electrospinning including chloroform : acetone, chloroform : methanol, and dichloromethane (DCM) : N,N, dimethylformamide (DFM). The fibers produced from the DCM : DMF system without HNTs were more uniform resulting in smaller fiber diameters as compared to the chloroform: methanol system due to the increased solution conductivity. The addition of HNT nanoparticles produced electrospun fibers with large diameters because the viscosity of the solution increased. Cosolvent was important in determining fiber diameters because it strongly influenced the solution viscosity and conductivity. HNTs had relatively small impact on the growth of a crystalline morphology in PCL–HNT composites. The solvent mixture of chloroform : methanol was better for PLA‐based systems since PLA was found to have slightly higher crystallinity and larger enthalpy value indicating the improved structural orderness in the PLA polymer matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of PEG–PCL–PEG triblock copolymers as carriers of doxorubicin for the treatment of breast cancer

Triblock copolymers of monomethoxy poly(ethylene glycol) (mPEG) and ε‐caprolactone (CL) were prepared with varying lengths of poly(ε‐caprolactone) (PCL) compositions and a fixed length of mPEG segment. The molecular characteristics of triblock copolymers were characterized by ¹H NMR, gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), and differential scanning calorimetry (DSC). These amphiphilic linear copolymers based on PCL hydrophobic chain and hydrophilic mPEG ending, which can self‐assemble into nanoscopic micelles with their hydrophobic cores, encapsulated doxorubicin (DOX) in an aqueous solution. The particle size of prepared micelles was around 40–92 nm. The DOX loading content and DOX loading efficiency were from 3.7–7.4% to 26–49%, respectively. DOX‐released profile was pH‐dependent and faster at pH 5.4 than pH 7.4. Additionally, the cytotoxicity of DOX‐loaded micelles was found to be similar with free DOX in drug‐resistant cells (MCF‐7/adr). The great amounts of DOX and fast uptake accumulated into the MCF‐7/adr cells from DOX‐loaded micelles suggest a potential application in cancer chemotherapy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and Characterization of Biodegradable Poly(ε‐caprolactone)‐Polyglycolide‐Poly(ethylene glycol) Monomethyl Ether Random Copolymer

Summary: Poly(ε‐caprolactone)‐polyglycolide‐poly(ethylene glycol) monomethyl ether random copolymers were synthesized from ε‐caprolactone (ε‐CL), glycolide (GA) and poly(ethylene glycol) monomethyl ether (MPEG) using stannous octoate as catalyst at 160 °C by bulk polymerization. The copolymers with different composition were synthesized by adjusting the weight ration of reaction mixture. The resultant copolymer with a weight ratio (10:15:75) of MPEG2000, GA, and CL was characterized by IR, ¹H NMR, GPC and DSC. The new biodegradable copolymer has potential for medical applications since it is combined with properties of PCL, PGA and MPEG.

     

Effect of thermal aging on the biodegradation of PCL,PHB‐V,and their blends with starch in soil compost

Different proportions of starch were blended with poly(β‐hydroxybutyrate)‐co‐poly(β‐hydroxyvalerate) (PHB‐V) or poly(ε‐caprolactone) (PCL) by extrusion, and the mechanical (maximum tensile strength, elongation at break and Young's modulus) and thermal properties (by differential scanning calorimetry) were determined. The biodegradability of the blends in soil compost was also assessed after thermal aging for 192, 425, and 600 h at different temperatures. The maximum tensile strength of the PCL50 blend (containing 50% starch) was 35% lower than that of PCL and that of the PHB‐V50 blend was 60% lower than that of PHB‐V without thermal aging. PHB‐V blends were more biodegradable than PCL blends. For the blends prepared, only the biodegradation of PHB‐V25 was affected by thermal aging. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3539–3546, 2003