Preparation and Degradation Behaviors of Poly(L-lactide-co-glycolide-co-ε-caprolactone)/1,4-butanediamine Modified Poly(lactic-co-glycolic acid) Blend Film

Abstract

Polymer blending is an attractive method for producing new polymer materials with excellent properties. In this work the blended polymers were prepared from poly(L-lactide-co-glycolide-co-ε-caprolactone) and 1,4-butanediamine modified poly(lactic-co-glycolic acid) (PLLGC/BMPLGA). The hydrophilicity was studied by static water contact angle tests. The in-vitro degradation behaviors of the PLLGC/BMPLGA blended films were investigated during various degradation periods. The results showed that the introduction of the PLLGC reduced the hydrophilicity and degradation rate of the blended polymers while improved the tensile strength and elongation percentage. Therefore, we suggest the blends of the PLLGC and BMPLGA could supply a potential biomaterial for application in the medical field for use as tissue engineering scaffolds or drug delivery.     

Preparation and Characterization of Poly(L-lactide-co-glycolide-co-ε-caprolactone) Scaffolds by Thermally Induced Phase Separation

Abstract

The technique of thermally induced phase separation (TIPS) is favorable for the fabrication of a porous scaffold due to a number of advantages. In this work the poly(L-lactide-co-glycolide-co-ε-caprolactone) (PLLGC) terpolymer was synthesized by melt copolymerization and porous scaffolds thereof from its solution in 1,4-dioxane were fabricated by using the TIPS method. The effects of fabrication parameters, including polymer concentration and freezing temperature, on the morphology, pore size and mechanical properties were studied. The results showed that the average pore size of the PLLGC porous scaffold increased with a decrease in PLLGC concentration and the pore size resulting from freezing at 4?°C (about 20–100?μm) was significantly larger than for other samples (20–50?μm) frozen at lower temperatures. The porosity of the scaffolds decreased with increasing PLLGC concentration or decreasing freezing temperature. On the other hand, the compressive strength of the scaffolds increased with the increase of PLLGC concentration or the decrease of freezing temperature, as would be expected. The present results can be applied in design to control the processing parameters of TIPS for a scaffold with desired pore morphology.     

Preparation and Characterization of Poly(L-lactide-co-glycolide-co-ε-caprolactone)/Nano-biaoactive Glass-Nano-β-tricalcium Phosphate Composite Scaffolds

Abstract

Polymeric/ceramic composite scaffolds that are biocompatible and biodegradable are widely used for tissue engineering applications. In this work a series of poly(L-lactide-co-glycolide-co-ε-caprolactone)/nano-biaoactive glass-nano-β-tricalcium phosphate composite scaffolds were successfully fabricated and the influences of the inorganic content and freezing temperature on the physical properties were studied. The composite scaffolds with various inorganic contents showed an interconnected pore structure with irregular shapes. The composite scaffolds had a porosity that was reduced with increasing inorganic content and decreasing freezing temperature. The incorporation of inorganic fillers and decreasing freezing temperature improved the mechanical properties of the hybrid scaffolds. By appropriate control of these two factors (10.0?wt% content of NBAG and β-TCP with freezing at ?30?°C) a suitable composite scaffold was prepared as a potential bone tissue engineering implant.     

Preparation and characterization of biodegradable poly(ε-caprolactone)-based gel polymer electrolyte films

Biodegradable polymer electrolyte films based on poly(ε-caprolactone) (PCL) in conjunction with lithium tetrafluoroborate (LiBF₄) salt and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF₄) ionic liquid were prepared by solution cast technique. The structural, morphological, thermal, and electrical properties of these films were examined using X-ray diffraction (XRD), optical microscopy (OM), differential scanning calorimetry (DSC), and impedance spectroscopy. The XRD and OM results reveal that the pure PCL possesses a semi-crystalline nature and its degree of crystallinity decreases with the addition of LiBF₄ salt and EMIMBF₄ ionic liquid. DSC analysis indicates that the melting temperature and enthalpy are apparently lower for the 40 wt% EMIMBF₄ gel polymer electrolyte as compared with the others. The ambient temperature electrical conductivity increases with increasing EMIMBF₄ concentration and reaches a high value of ～2.83?×?10^?4 S cm^?1 for the 85 PCL:15 LiBF₄ + 40 wt% EMIMBF₄ gel polymer electrolyte. The dielectric constant and ionic conductivity follow the same trend with increasing EMIMBF₄ concentration. The dominant conducting species in the 40 wt% EMIMBF₄ gel polymer electrolyte determined by Wagner’s polarization technique are ions. The ionic conductivity of this polymer electrolyte (～2.83?×?10^?4 S cm^?1) should be high enough for practical applications.     

Synthesis and Characterization of Terpolymers of poly(L-lactide-glycolide-ε-caprolactone)

Random terpolymers of poly(L-lactide-glycolide-ε-caprolactone) (PLLGC) was prepared by ring-opening polymerization of L-lactide, glycolide and ε-caprolactone monomers initiated with stannous octanoate. Fourier transform infrared spectra, nuclear magnetic resonance and gel permeation chromatography were employed to characterize the obtained PLLGC terpolymers. The effects of polymerization temperature, reaction time, the amount of initiator and the polymerization pressure on the weight average molecular mass and polydispersity index of the PLLGC were investigated. In addition, the water contact angle of the PLLGC was also tested. The characterization of chemical structure showed that the PLLGC was successfully synthesized. For instance, a PLLGC terpolymer with a weight average molecular mass of about 12.435?×?10⁴?Da and a polydispersity index of 1.28 was obtained when the polymerization was conducted with a molar ratio of monomer to initiator ([M]/[I]) of 2000, polymerization temperature of 140?°C, polymerization pressure of 5.0?Pa and reaction time of 24?h. The random incorporation of ε-CL monomer units decreased the wettability of the PLGA copolymers.     

Relationship Between Interfacial Adhesion and Viscosity of Cellulose Fiber Filled Polypropylene and Poly(ε-caprolactone): A Review

The relationship between interfacial adhesion and dynamic viscosity of regenerated cellulose fiber (CF) filled in poly(ε-caprolactone) (PCL) and polypropylene (PP) matrix is compared. The rate of viscosity rise from its virgin polymer of the PCL/CF compounds shows higher than that of the PP/CF ones at the same CF loadings. The interfacial adhesion of the CF surface with the PCL matrix is better than with the PP due to polar characteristic of the PCL. Striking differences are observed in the PCL compounds. As the concentration of the particles increases, the crystalline temperature, the spherulite formation, the elongation modulus and the yield stress of the PCL/CF compounds are significantly higher than those of the PP/CF compounds. More spherulites are locally developed on the CF surface in the PCL/CF compounds than in the PP/CF ones. The higher rate of viscosity rise of the PCL/CF compounds than the PP/CF compounds is due to higher interfacial adhesion of the CF surface with the PCL than with the PP.     

Miscibility Determination in Poly(ε-caprolactone)/Poly(Vinyl Formal) Blend by Equilibrium Melting Temperature and Spherulite Morphology

Miscibility of poly(ε-caprolactone), (PCL), containing 1, 5, and 10 wt.% poly(vinyl formal) (PVF) blends was investigated by polarized optical microscopy (POM), atomic force microscopy (AFM), and differential scanning calorimetry (DSC) for spherulitic morphology and equilibrium melting temperature (T°_m, via Hoffman-Weeks plot). The T°_m of PCL in the blends was similar to that of pure PCL, indicating immiscibility. Isothermally, melt crystallized virgin PCL between 30°C and 50°C showed spherulitic morphology with negative birefringence, Maltese cross, and without extinction rings. The nucleation and growth rates of PCL spherulites were found to be dramatically reduced with the addition of PVF. Extinction rings and a change in the sign of the birefringence of the PCL spherulites were observed and were found to be dependent on blend composition and crystallization temperature. The presence of a ring pattern in spherulites was an indication of miscibility between the two polymers that had failed to be detected by thermal methods. The formation of a ring pattern is discussed in terms of lamella twisting originating from a change in the crystallization mechanism.     

Preparation and Characterization of Gelatin–Poly(L-lactic) Acid/Poly(hydroxybutyrate-co-hydroxyvalerate) Composite Nanofibrous Scaffolds

Poly(L-lactic) acid (PLLA) scaffolds, prepared by electrospinning technology, have been suggested for use in tissue engineering. They remain a challenge for application in biological fields due to PLLA's slow degradation and hydrophobic nature. We describe PLLA, PLLA/poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV), and PLLA/PHBV/gelatin (Gt) composite nanofiberous scaffolds (Gt–PLLA/PHBV) electrospun by changing the electrospinning technology. The morphologies and hydrophilicity of these fibers were characterized by scanning electron microscopy (SEM) and water contact angle measurement. The results showed that the addition of PHBV and Gt resulted in a decrease in the diameters and their distribution and greatly improved the hydrophilicity. The in-vitro degradation test indicated that GT–PLLA/PHBV composite scaffolds exhibited a faster degradation rate than PLLA and PLLA/PHBV scaffolds. Dermal fibroblasts viabilities on nanofibrous scaffolds were characterized by [3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide] (MTT) assay and cell morphologies after 7 days culture. Results indicated that the GT–PLLA/PHBV composite nanofibers showed the highest bioactivity among the three scaffolds and increased with increasing time. The SEM images of cells/scaffolds composite materials showed the GT–PLLA/PHBV composite nanofibers enhanced the dermal fibroblasts's adhesion, proliferation, and spreading. It is suggested that the nanofibrous composite scaffolds of GT–PLLA/PHBV composites would be a promising candidate for tissue engineering scaffolds.     

Micromechanical Behavior and Glass Transition Temperature of Poly(Methyl Methacrylate)–Rubber Blends

Abstract

The microhardness of transparent rubber‐toughened poly(methyl methacrylate) (RTPMMA) was investigated by means of the microindentation technique. Core‐shell particles (CSP) with a rubbery shell were used as reinforcing material for the production of RTPMMA. The increasing volume fraction of CSP within the poly(methyl methacrylate) (PMMA) matrix is shown to soften the material, diminishing the hardness (H) value of RTPMMA of about 40% of the initial value at 35 vol% CSP content. Creep experiments under the indenter are reported. The creep constant is found to increase by adding CSP up to a leveling‐off value. On the other hand, the thermal variation of the creep constant for the blends shows a maximum. Results reveal a good correlation of the glass transition temperature (T _g) value deduced from microindentation, and the values obtained from differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) techniques. Contrary to expectation H is shown to decrease with increasing glass transition temperature. In the case of the drawn materials, the indentation anisotropy is shown to gradually increase with draw ratio and CSP content. This finding is explained on the basis of the higher orientation of the PMMA molecules near the periphery of CSP.     

Thermal Behavior of Polyamide‐12 and Poly (Styrene‐Co‐Acrylonitrile) Blend

In this work, an unusual morphology of a mixture of polyamide‐12 (PA‐12) with a series of poly (styrene‐co‐acrylonitrile) (SAN) was obtained by solution casting and fast solvent evaporation. The prepared film was transparent although it contained many crystals. These crystals apparently prevented phase separation despite the instability of the PA‐12 and SAN mixtures below 180°C. In isothermal experiments, once the crystals were melted, phase separation began and the scattered intensity fit the Cahn–Hilliard theory. When the AN content in the SAN copolymer was less than 5%, the phase separation took place when only part of the crystals were melted at 180°C. However, due to the constraint of unmelted crystals, the growth rate of phase separation at this temperature was much slower.     

Preparation and properties of a gel polymer electrolyte system based on poly-ε-caprolactone containing 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Gel polymer electrolytes (GPE) obtained by immobilizing a solution of zinc triflate (ZnTr) in an ionic liquid, namely 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [emim][Tf₂N] within a biodegradable polymeric matrix of poly-ε-caprolactone (PCL) were prepared by a simple solvent cast technique for different concentrations of the ionic liquid. The electrolyte with the composition 75 wt% PCL: 25 wt% ZnTr+100 wt% [emim][Tf₂N] showed the highest ionic conductivity of 1.1×10⁻⁴ S cm⁻¹ at 25 °C and favored by the rich amorphous phase of the GPE as confirmed from room temperature X-ray diffraction analysis (XRD). The morphology of the GPE was examined using scanning electron microscopy (SEM) which revealed the homogeneity of the prepared GPE system. The temperature dependence of electrical conductivity of the GPE followed the Arrhenius behavior. The Zn²⁺ ionic transport number has been determined to be ~0.62 which denotes the predominant contribution of zinc ion towards total ionic conductivity. The electrochemical stability window of GPE is found to be 2.5 V with a thermal stability upto 200 °C. This eco-friendly and safe electrolyte may be used to fabricate compostable batteries, in future, with a suitable selection of other components of the battery system.     

Effects of Molecular Weight on Thermal Degradation of Poly(α-methyl styrene) in Nitrogen

The effects of molecular weight on the thermal degradation behavior of poly(α-methyl styrene) (PAMS) was investigated by pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) and thermogravimetric analysis (TGA). The Py-GC/MS analysis results showed that the degradation of PAMS with different molecular weights in nitrogen produced only the monomer, alpha-methylstyrene. The TGA results showed a pronounced reduction in the decomposition temperature with increasing molecular weight. The degradation kinetic parameters, calculated by the Kissinger and the Coats–Redfern methods, further revealed that the activation energy and the pre-exponential factor decreased with increasing molecular weight. Most importantly, the degradation order of the PAMS in nitrogen remained around 1, independent of the molecular weight, suggesting the maintenance of the depolymerization mechanism. All the above results provided an insight into the effects of molecular weight on the thermal degradation behavior of PAMS.     

Lactone polymers. V. Viscoelastic properties of poly-ε-caprolactone and poly-ε-thiocaprolactone

The viscoelastic properties of crystalline poly-ε-caprolactone and poly-ε-thiocaprolactone have been characterized and compared by stress relaxation and dynamic mechanical studies. The glass transition temperature of poly-ε-thiocaprolactone was shown to be -40°C at 1 Hz and appeared to be independent of the degree of crystallinity. The rate of viscoelastic relaxation for each polymer was independent of linear strain rate of a decade range. The density of each polymer over a wide temperature range was used to reduce the individual time-dependent modulus values to an arbitrary reference temperature. This reduction of stress relaxation data to a standard mechanical state obviated the requirement of vertical shift factors for construction of the respective master curves. The distribution of relaxation times was correlated with the glass transition and the crystalline melt temperature range for each polymer.     

Effect of lithium thiocyanate addition on the structural and electrical properties of biodegradable poly(ε-caprolactone) polymer films

Polymer electrolyte films of biodegradable poly(ε-caprolactone) (PCL) doped with LiSCN salt in different weight ratios were prepared using solution cast technique. The effect of crystallinity and interaction between lithium ions and carbonyl groups of PCL on the ionic conduction of PCL:LiSCN polymer electrolytes was characterized by X-ray diffraction (XRD), optical microscopy, Fourier transform infrared spectroscopy (FTIR) and AC impedance analysis. The XRD results revealed that the crystallinity of the PCL polymer matrix decreased with an increase in LiSCN salt concentration. The complexation of the salt with the polymer and the interaction of lithium ions with carbonyl groups of PCL were confirmed by FTIR. The ionic conductivity was found to increase with increasing salt concentration until 15 wt% and then to decrease with further increasing salt concentration. In addition, the ionic conductivity of the polymer electrolyte films followed an Arrhenius relation and the activation energy for conduction decreased with increasing LiSCN concentration up to 15 wt%. UV–vis absorption spectra were used to evaluate the optical energy band gaps of the materials. The optical energy band gap shifted to lower energies with increasing LiSCN salt concentration.     

Cure Behavior and Thermal Properties of Poly (Amide-Amidic Acid) Modified Diglycidyl Ether of Bisphenol-A/4,4′-Diaminodiphenylsulfone

Poly (amide-amidic acid) (PAA) was selected to modify diglycidyl ether of bisphenol-A (DGEBA)/4,4′-diaminodiphenylsulfone (DDS). The cure behavior was studied by means of nonisothermal differential scanning calorimeter (DSC) analysis, indicating that PAA played a role of catalyst during the process of the curing reaction. Results of Fourier transform infrared spectroscopy (FT-IR) analysis showed that the PAA acted as a co-curing agent when the PAA content was 3.2–38.4 phr and also as a modifier when the PAA content was 12.8–38.4 phr. The glass transition temperature (T_g ) decreased with the increase of PAA content. The thermal stability improved when the PAA content was 3.2–6.4 phr because of the catalytic effect of PAA. The flexural strength improved for the varying PAA content studied in this work, with the highest flexural strength being obtained when the PAA content was 6.4 phr. The fracture surface morphology was observed using scanning electron microscopy (SEM); the morphologies varied with changing content of PAA.     

Curing Behavior and Mechanism of Diglycidyl Ether of Bisphenol-A in the Presence of Poly (Amide–Amidic Acid) and 4,4′-Diaminodiphenylsulfone

Poly (amide-amidic acid) (PAA) and 4, 4′-diaminodiphenylsulfone (DDS) with varying molar ratios were used as co-curing agents to cure diglycidyl ether of bisphenol-A (DGEBA). The curing process was investigated. The differences between PAA and the conventional curing agents are discussed relative to the curing behavior and mechanism when cured with DGEBA. It was found that a lower temperature was needed to cure DGEBA when PAA was used as co-curing agent with DDS. There was only one step during the curing process of DGEBA and PAA, compared with the conventional curing agents (two steps). The activation energy (E) of the curing process of DGEBA with the co-curing agents, computed using model free estimations, was lower than that with DDS and PAA individually.     

Designing and Characterization of Poly(L-Lactide)/Poly(ϵ-Caprolactone) Multiblock Copolymers

A series of poly(L-lactide)/poly(?-caprolactone) (PLA/PCL) biodegradable multiblock copolymers was synthesized by a two-step process and characterized. Ring-opening polymerization was used to prepare a series of HO-PLA-PCL-PLA-OH copolymers initiated by hydroxyl-terminated PCL. Then the triblock copolymers and 1,6-hexamethylene diisocyanate (HDI) were reacted with different copolymer/HDI weight ratios. Consequently, a series of PLA/PCL multiblock copolymers with designed molecular chain structure was obtained. Gel permeation chromatography (GPC), Fourier transform infrared (FTIR) spectroscopy, and ¹H NMR were used to characterize these copolymers and the results showed that the designed PLA/PCL copolymers had been synthesized. Dynamic mechanical analysis (DMA) was applied to characterize their thermal properties. Stress–strain curves showed that a PLA/PCL copolymer with adjustable mechanical properties had been achieved.     

Viscoelastic and Dielectric Behavior of Poly(1‐Butene)/Multiwalled Carbon Nanotube Nanocomposites

Linear viscoelastic properties and dielectric behavior of poly(1‐butene)/multiwalled carbon nanotube (MWCNT) nanocomposites were investigated. Dynamic mechanical analysis showed significant increase in storage modulus in the rubbery regime. The tan δ peak temperature remained constant; however, the peak intensity was lowered for the nanocomposites. In melt rheological studies the nanocomposites showed a shift in crossover frequency to the lower side, suggesting delayed relaxation of the molecular chains in the presence of MWCNT and this shift was found to depend on the content of MWCNT. The dielectric constant increased from 2.2 to 70 for the nanocomposite with 7 wt. % MWCNT. The electrical conductivity increased significantly, from 10^?15 to 10^?3 S/cm. The results of rheology and dielectric studies indicate that a percolation network is formed that is responsible for the observed changes.     

Preparation and Properties of 2, 4-2-Isocyanic Acid Methyl Ester/Poly(ϵ-caprolactone)/Diethylene Glycol Hydrogels

The hydrophilic polyurethane (PU) hydrogels have become attractive in the biomedical field for drug delivery. In this work 2, 4-2-isocyanic acid methyl ester (TDI), poly(?-caprolactone) (PCL), and poly(ethylene glycol) (PEG) were used to prepare a prepolymer and then diethylene glycol (DEG) was used as a chain extender to prepare a novel hydrophilic polyurethane, TDI/PCL-PEG/DEG. The obtained PU hydrogels were characterized by Fourier transform infrared (FT-IR) spectroscopy and scanning electronic microscopy (SEM). By varying the ratio of PCL to PEG in the copolymer, modulations of hydrophilicity and drug release behavior were observed. FT-IR analysis confirmed the successful synthesis of the TDI/PCL-PEG/DEG hydrogels. The introduction of PEG into the PU hydrogels led to a porous structure. The water contact angle and swelling ratio results confirmed that the hydrophilicity increased with increasing amounts of the PEG segments. The introduction of PEG also increased the release rate of chloramphenicol, used as model drug, from the PU hydrogels.