Radiopaque,barium sulfate‐filled biomedical compounds of a poly(ether‐block‐amide) copolymer

Various radiopaque compounds of a poly (ether‐block‐amide) copolymer resin filled with fine barium sulfate particles were prepared by melt mixing. Material properties of the filled compounds were investigated using various material characterization techniques, including thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic rheometry, uniaxial tensile test, and dynamic mechanical thermal analysis (DMTA). The effects of the filler and its concentration on the measured material properties are evaluated. It has been found that in addition to its well‐known X‐ray radiopacity, the filler is quite effective in reinforcing some mechanical properties of the copolymer, including modulus of elasticity and yield strength. More interestingly, it has been observed that at low loading concentrations near 10 wt %, the filler may also act as a rigid, inorganic toughener for the copolymer by improving the postyield material extensibility of strain hardening against ultimate material fracture. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal properties and dielectric relaxation of a multi‐component poly(ether‐co‐amide) based on polyamide‐12

DSC, dielectric relaxation and dynamic mechanical thermal analysis (DMTA) were carried out on two multi‐component poly(ether‐co‐amide) samples having different weight ratios of polyamide prepared by condensation polymerization with 12‐aminododecanoic acid, adipic acid and polyetherdiamine consisting of poly(tetramethylene oxide) and poly(propylene oxide). The melting temperature was lowered by an increase in the weight ratio of the polyamide segment. Three relaxation modes, α′, α_s and β, were found from dielectric relaxation measurements in different temperature ranges. The high temperature relaxation mode, α′, has a large dielectric constant, which disappears at the melting temperature of the polyamide crystal in the sample. The relaxation times for the segmental motion, α_s, were different for the samples, which is attributed to the difference in the composition of the uncrystallized polyamide segments in the amorphous domain. The glass transition temperature estimated from DMTA is located between those of constituting polymers. On the other hand, the activation energy of β‐mode observed at low temperatures is the same for samples with different polyamide ratios, which is attributed to the local motion of the polyether segments. The uncrystallized polyamide segments are miscible with the polyether segments, which results in a lowering of the glass transition temperature of the amorphous domain and enlarges the temperature range of the rubber state of the copolymer due to the high melting temperature of the polyamide segments. © 2016 Society of Chemical Industry     

Study on the synthesis of poly(ether‐block‐amide) copolymer based on nylon6 and poly(ethylene oxide) with various block lengths

Various segmented block copolyetheramides based on nylon6 (N6) and poly(ethylene oxide) (PEO) with different compositions and block length of the hard and soft segments were synthesized. The effect of composition of the hard and soft segments was studied via FTIR spectroscopy based on the characteristic peak of ester group at wave number of 1730 cm^?1. The average block length of the hard and soft segments in block copolymers was determined from H‐NMR analysis. Differential thermal analysis thermograms confirmed a microphase separated morphology over a broad range of temperature, leading to two separated crystalline domains. An increase in the interconnectivity of the polyamide segments controlled by chain extension, greatly improved the formation of polyamide lamellae crystals determined by X‐ray diffractometry. Atomic force microscopy images indicated different morphologies of dispersed phase in the dominant phase, which plays an important role in their performance for membrane processes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of thermomechanical history on the crystallization of poly(ether‐block‐amide)

The quiescent and flow‐induced crystallization of a poly(ether‐block‐amide) is studied by means of rheo‐optical methods. Both optical microscopy and small angle light scattering have been used. The multiblock copolymer has a microphase‐separated structure with an order–disorder transition at 180–185°C, as measured with rheometry and SAXS. The number of nuclei, spherulitic growth rates, and the characteristic time scale for crystallization are compared with that of a polyamide of similar molar mass. For the poly(ether‐block‐amide)—containing a majority of amide segments—the growth rates of the spherulites during quiescent crystallization are similar for the block copolymer and the homopolymer, even if the spherulitic structures are not the same. When flow is applied, the two materials behave differently. The flow increased the nucleation density in the homopolymer but not in the block copolymer. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Copolymers based on poly(butylene terephthalate) and polycaprolactone‐block‐polydimethylsiloxane‐block‐polycaprolactone

A series of novel thermoplastic elastomers, based on poly(butylene terephthalate) (PBT) and polycaprolactone‐block‐polydimethylsiloxane‐block‐polycaprolactone (PCL‐PDMS‐PCL), with various mass fractions, were synthesized through melt polycondensation. In the synthesis of the poly(ester‐siloxane)s, the PCL blocks served as a compatibilizer for the non‐polar PDMS blocks and the polar comonomers dimethyl terephthalate and 1,4‐butanediol. The introduction of PCL‐PDMS‐PCL soft segments resulted in an improvement of the miscibility of the reaction mixture and therefore in higher molecular weight polymers. The content of hard PBT segments in the polymer chains was varied from 10 to 80 mass%. The degree of crystallinity of the poly(ester‐siloxane)s was determined using differential scanning calorimetry and wide‐angle X‐ray scattering. The introduction of PCL‐PDMS‐PCL soft segments into the polymer main chains reduced the crystallinity of the hard segments and altered related properties such as melting temperature and storage modulus, and also modified the surface properties. The thermal stability of the poly(ester‐siloxane)s was higher than that of the PBT homopolymer. The inclusion of the siloxane prepolymer with terminal PCL into the macromolecular chains increased the molecular weight of the copolymers, the homogeneity of the samples in terms of composition and structure and the thermal stability. It also resulted in mechanical properties which could be tailored. Copyright © 2010 Society of Chemical Industry     

Semiquantitative FTIR Analysis of the Crosslinking Density of Poly(ester amide)‐Based Thermoset Elastomers

Thermoset elastomers represent a class of polymers for a wide range of biomedical applications. Crosslinking density of thermoset elastomers is considered as an important parameter. In this study, semiquantitative Fourier transform infrared (FTIR) analysis is developed as a novel method to determine crosslinking density of poly (ester amide) thermoset elastomers. Poly(1,3‐diamino‐2‐hydroxypropane‐co‐polyol sebacate) (APS) is an example of poly(ester amide) thermoset elastomer. Polyethylene glycol (PEG) has been recently incorporated into APS polymer structure to obtain novel PEGylated APS‐based elastomers with tunable properties. The crosslinking densities of different APS and APS‐co‐PEG films are determined by the theory of rubber elasticity and FTIR. These results show that the intensity ratios between amide and carbonyl peak correlate well with the calculated crosslinking density from the elastic modulus. Thus, semiquantitative FTIR analysis offers a direct, facile, and less variable method to determine the crosslinking density and guide the consistent synthesis of poly(ester amide) thermoset elastomers.

     

Compatibility,crystallinity and mechanical properties of poly(lactic acid)‐poly(ether‐block‐amide) based copper nanocomposites

Binary and ternary composites of poly(lactic acid) (PLA), poly(ether‐block‐amide) (PEBAX) and copper nanoparticles were prepared by melt blending in an internal mixer. Compatibility and molecular interactions between the three components of the nanocomposites were evaluated using scanning electron microscopy and Fourier transform infrared spectroscopy. It was found that the carbonyl groups of the PLA and copper nanoparticles interact. Also, PLA and PEBAX are compatible and develop molecular interactions between the C=O of PLA and the C=O and NH of PEBAX, forming dipole–dipole bonds and hydrogen bonds. The compatibility and molecular interaction between PLA and PEBAX are reduced by copper nanoparticles. The reduction of compatibility between PLA and PEBAX produced a lower storage modulus and lower strain at break in the ternary systems than in the blend PLA‐PEBAX. Copper nanoparticles enhanced the crystallinity of PLA. PLA responded more strongly to the nucleating effect of copper when PEBAX was added indicating a synergistic effect. The strain at break of PLA was enhanced by the addition of PEBAX but was severely reduced by the presence of nanoparticles. © 2020 Society of Chemical Industry     

Partially Sulfonated Poly(1,4‐phenylene ether‐ether‐sulfone) and Poly(vinylidene fluoride) Blend Membranes for Fuel Cells

Blend membranes based on high conductive sulfonated poly(1,4‐phenylene ether‐ether‐sulfone) (SPEES) and poly(vinylidene fluoride) (PVDF) having excellent chemical stability were prepared and characterized for direct methanol fuel cells. The effects of PVDF content on the proton conductivity, water uptake, and chemical stability of SPEES/PVDF blend membranes were investigated. The morphology, miscibility, thermal, and mechanical properties of blend membranes were also studied by means of scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA) measurements. The blend membrane containing 90 wt.% SPEES (degree of sulfonation – DS = 72%) and 10 wt.% PVDF (M_w = 180,000) exhibits optimum properties among various SPEES72/PVDF membranes. Addition of PVDF enhanced resistance of the SPEES membrane against peroxide radicals and methanol significantly without deterioration of its proton conductivity. It's proton conductivity at 80 °C and 100% relative humidity is higher than Nafion 115 while it's methanol permeability is only half of that of Nafion 115 at 80 °C. The direct methanol fuel cell performance of the SPEES membranes was better than that of Nafion 115 membrane at 80 °C.     

Synthesis and characterization of poly(ether‐block‐amide) membranes for the pervaporation of organic/aqueous mixtures

We made poly(ether‐block‐amide) membranes by casting a solution on a nonsolvent surface. The effects of the solvent ratio (n‐butanol/isopropyl alcohol), temperature, and polymer concentration on the quality of the membranes were studied. The results show that the film quality was enhanced with increasing isopropyl alcohol ratio in the solvent. This behavior was related to the reduction of the solution surface tension and the interfacial tension between the solution and nonsolvent. Uniform films were made at a temperature range of 70–80°C and a polymer concentration of 4–7 wt %. The morphology of the membranes was investigated with scanning electron microscopy. The qualities of the films improved with increasing isopropyl alcohol ratio in the solvent. With these membranes, the pervaporation of ethyl butyrate (ETB)/water and isopropyl alcohol/water mixtures was studied, and high separation performance was achieved. For ETB/water mixtures, with increasing ETB content, both the permeation flux and separation factor increased. However, for isopropyl alcohol/water mixtures, with increasing isopropyl alcohol content, the permeation flux increased, but the separation factor was diminished. Increasing temperature in a limited range resulted in a decreasing separation factor and an increasing permeation flux. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Drug delivery system based on poly(ether‐block‐amide) and acrylic acid for controlled release of vancomycin

Poly(ether‐block‐amide) (PEBA) films were grafted with acrylic acid (AAc) by gamma radiation, using the oxidative pre‐irradiation technique. The effect of dose, monomer concentration, temperature, and reaction time on the graft percentage of AAc onto PEBA was studied. The modified material PEBA‐g‐AAc was characterized by Fourier infrared spectroscopy (FTIR), scanning electron microscopy, and water contact angle. It was found that PEBA films did not suffer degradation at low doses (<30 kGy) during the grafting process. Additionally, PEBA‐g‐AAc was proved as drug delivery system using vancomycin as drug model. The PEBA‐g‐AAc with 39 and 98% of AAc loaded 63 and 98 mg g^?1, respectively. The release profiles showed a sustained delivery by 48 h with a partial retention of drug, which depends of grafting percentage. The microbiological tests showed that PEBA‐g‐AAc was able to inhibit the growing of Staphylococcus aureus in three consecutive challenges. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45745.     

Design and Synthesis of Mechano‐Responsive Color‐Changing Thermoplastic Elastomer Based on Poly(n‐Butyl Acrylate)–Spiropyran‐Polystyrene Comb‐Structured Graft Copolymers

Colorimetric mechanophores like spiropyran (SP) represent an emerging type of interesting signal molecule that can be incorporated into polymers or other materials as a stress transducer. In this work, a new type of spiropyran‐containing inimer molecule MA‐SP‐Br are designed and synthesized, which is incorporated into polybutylacrylate (PBA) chains through reversible addition‐fragmentation chain transfer (RAFT) copolymerization with n‐butyl acrylate (BA). PBA‐SP‐Br is then used as a macro‐initiator to graft polystyrene (PS) side chains from the PBA backbone through atom transfer radical polymerization (ATRP) of styrene. The resulting comb‐structured graft copolymer PBA‐SP‐PS contains 0.15–0.34% SP and exhibits a characteristic feature of thermoplastic elastomers. Under uniaxial stretch, the materials possess an excellent mechano‐responsivity and change color at strains as low as about 14%.     

Biodegradable Poly(ε‐Caprolactone)‐Based Graft Copolymers Via Poly(Linoleic Acid): In Vitro Enzymatic Evaluation

Well‐defined graft copolymers based on poly(ε‐caprolactone) (PCL) via poly(linoleic acid) (PLina), are derived from soybean oil. Poly(linoleic acid)‐g‐poly(ε‐caprolactone) (PLina‐g‐PCL) and poly(linoleic acid)‐g‐poly(styrene)‐g‐poly(ε‐caprolactone) (PLina‐g‐PSt‐g‐PCL) were synthesized by ring‐opening polymerization of ε‐caprolactone initiated by PLina and one‐pot synthesis of graft copolymers, and by ring‐opening polymerization and free radical polymerization by using PLina, respectively. PLina‐g‐PCL, PLina‐g‐PSt‐g‐PCL3, and PLina‐g‐PSt‐g‐PCL4 copolymers containing 96.97, 75.04 and 80.34 mol% CL, respectively, have been investigated regarding their enzymatic degradation properties in the presence of Pseudomonas lipase. In terms of weight loss, after 1 month, 51.5 % of PLina‐g‐PCL, 18.8 % of PLina‐g‐PSt‐g‐PCL3, and 38.4 % of PLina‐g‐PSt‐g‐PCL4 were degraded, leaving remaining copolymers with molecular weights of 16,140, 83,220 and 70,600 Da, respectively. Introducing the PLina unit into the copolymers greatly decreased the degradation rate. The molar ratio of [CL]/[Lina] dramatically decreased, from 21.3 to 8.4, after 30 days of incubation. Moreover, reduced PCL content in PLina‐g‐PSt‐g‐PCL copolymers decreased the degradation rate, probably due to the PSt enrichment within the structure, which blocks lipase contact with PCL units. Thus, copolymerization of PCL with PLina and PSt units leads to a controllable degradation profile, which encourages the use of these polymers as promising biomaterials for tissue engineering applications.     

Modified zeolitic–midazolate framework 8/poly(ether‐block‐amide) mixed‐matrix membrane for propylene and propane separation

In this study, we fabricated a dual‐layer PES–poly(ether‐block‐amide) (PEBA) composite membrane that included zeolitic–midazolate framework 8 (ZIF‐8) particles and evaluated it for propylene and propane separation under pure and mixed feed conditions. To improve the performance, compatibility, and distribution of particles in the polymer matrix, the ZIF‐8 particles were modified by 3‐(triethoxysilyl) propyl amine (APTES) and 3‐(trimethoxysilyl) propyl amine (APTMS) amino silane coupling agents. Particle modification did not have much effect on the structure and particle size and slightly reduced the membrane specific surface area. The modified particles tended to be in the soft section. At the high loading rate of modified particles, their appropriate compatibility increased the membrane gas permeability () and selectivity. APTES with the proper chain length compared with APTMS had a higher and the same selectivity. The best performance (by 32.1 gpu) was found in PES–PEBA–ZIF‐8–APTES 20%. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46273.     

Amide–acid functional SiO2 nanocomposites based on new semi‐crystalline poly(ether‐sulfone‐amide): thermal,combustion and mechanical studies

New amide–acid functional SiO₂ nanoparticle (FSNP)‐reinforced semi‐crystalline aliphatic–aromatic poly(ether‐sulfone‐amide) (PESA) was synthesized using a solution method in dimethylformamide. The surfaces of SiO₂ nanoparticles were functionalized with phthalic anhydride, and subsequently PESA was synthesized using direct polymerization with good yield and desired molar mass. PESA / SiO₂ nanocomposites (PSNCs) were prepared with three different contents of FSNP and the morphology and mechanical, thermal and combustion properties of the PSNCs were studied. The results of X‐ray diffraction, field‐emission scanning electron microscopy and transmission electron microscopy showed a uniform dispersion for FSNP in the PESA matrix. According to the results of mechanical tests, the tensile strength and the Young's modulus of PESA were enhanced by FSNP loading. Thermogravimetric analysis and derivative thermogravimetry results showed a substantial improvement in thermal properties of PESA. The temperature at 5% mass loss was increased from 371.7 to 395.8 °C for the PSNC containing 8 mass% of FSNP, as well as the char yield being enhanced greatly, which was about 30% higher than that of neat PESA. Significant improvements in combustion properties were observed for PSNCs from microscale combustion calorimetry. The peak heat release rate showed an obvious improvement and decreased by about 57% compared to that of neat PESA on 8 mass% loading of FSNP. © 2016 Society of Chemical Industry     

Influence of the incorporation of fine calcium carbonate particles on the impact strength of polypropylene/polystyrene‐block‐poly(ethylene butene)‐block‐polystyrene blends

The Izod impact strength of two kinds of ternary composites was investigated. One consisted of polypropylene (PP), the triblock copolymer polystyrene‐block‐poly(ethylene butene)‐block‐polystyrene (SEBS), and calcium carbonate (CaCO₃) particles, and the other consisted of PP, carboxylated SEBS (C‐SEBS), and CaCO₃ particles. The mean size of the CaCO₃ particles was about 160 nm. According to scanning electron microscopy observations, the composite with SEBS showed a morphology in which SEBS domains and CaCO₃ particles were independently dispersed in the PP matrix. On the other hand, the composite with C‐SEBS showed a morphology in which CaCO₃ particles were encapsulated by C‐SEBS; that is, a core–shell structure was formed. The Izod impact strength of the composite with SEBS was higher than that of the composite with C‐SEBS and the PP/SEBS and PP/C‐SEBS binary blends. According to observations of the fractured surface, the stress‐whitened area was larger in the composite with SEBS than in the composite with C‐SEBS and the PP/SEBS and PP/C‐SEBS binary blends. The toughening mechanism of the composite, using nanometer‐sized CaCO₃ particles in combination with SEBS, was examined. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and mechanical properties of clay/polystyrene‐block‐polybutadiene‐block‐polystyrene triblock copolymer (SBS) intercalated nanocomposites using organoclay containing stearic acid

Organoclays containing various amounts of stearic acid (SA) were synthesized, and clay/polystyrene‐block‐polybutadiene‐block‐polystyrene triblock copolymer (SBS) intercalated nanocomposites were prepared using organoclays containing SA by melt‐blending. Montmorillonite was the clay used, and both stearylamine and SA were used as surface modifiers. The amount of SA added was 0, 20, 50 and 100% of the cation‐exchange capacity (CEC). In this study, the effects of SA on the microstructure and mechanical properties of the clay/SBS nanocomposites were investigated. In clay/SBS with 100% CEC of SA, although no exfoliation of the clay occurred, the stacked clay layers were uniformly dispersed at the nanometer level (100–800 nm) without agglomeration. Clay/SBSs containing SA exhibited superior mechanical properties compared to clay/SBS without SA. It was found that SA effectively improved the clay dispersion in the SBS matrix and the mechanical properties of the clay/SBSs. Copyright © 2006 Society of Chemical Industry     

Release of highly hydrophilic drugs from poly(ϵ‐caprolactone) matrices

We examine the release of two highly hydrophilic drugs, nicotine and caffeine, from poly(ε‐caprolactone) (PCL) matrices. We find that the dominant mechanism for drug release is drug diffusion through the PCL matrices. As a result, the rate of drug release (defined by the amount of drug released per unit time) decreases exponentially with time. Coating the drug‐carrying particles with a drug‐free PCL layer significantly changes the release profile: instead of exponential decay, the release rate exhibits a peak whose location (time) and magnitude vary with the diffusion coefficient of the drug in the polymer and the thickness of the coating. As a result, coating may be used to control the release rate andobtain a relatively constant rate over a period of time. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical,thermal, barrier,and rheological properties of poly(ether‐block‐amide) elastomer/organoclay nanocomposite prepared by melt blending

Polyether block amide (PEBA) elastomer‐organoclay nanocomposites were prepared by a melt mixing technique. The X‐ray diffraction and transmission electron microscope analysis indicated that the nanocomposite formed a partially exfoliated nanostructure in which the organoclay was dispersed uniformly throughout the matrix at the nanometer scale. The effect of organoclay on the melting temperature (T_m), glass transition temperature (T_g), crystallization temperature (T_c), and heat of fusion (ΔH_m) of the PEBA was determined by differential scanning calorimetry. Enhanced mechanical properties of the nanocomposites were observed from tensile and dynamic mechanical analysis. Thermal gravimetric analysis showed that the clay nanoparticles caused an increase in the thermal stability of the PEBA. Measurement of oxygen permeability and the degree of swelling in ASTM #3 oil indicated that the gas barrier properties and solvent resistance were greatly improved by the clay nanoparticles. Melt rheological studies revealed that the nanocomposites exhibited strong shear thinning behavior and a percolated network of the clay particles was formed. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

ZnBr2‐catalyzed chemical effects in poly(acrylonitrile‐ co‐butadiene)

The excellent chemical properties and resistance to oil of poly(acrylonitrile‐co‐butadiene), or nitrile–butadiene rubber (NBR), has led to the extensive use of these elastomers as O‐ring material in the oil extraction industry. The degradation of NBR gaskets is known to occur during the well completion and oil extraction process when they are exposed to bromide fluids such as ZnBr₂‐based completion fluid. Samples of NBR, polyacrylonitrile, and polybutadiene were exposed to ZnBr₂‐based completion fluid and analyzed by attenuated total reflectance (ATR) and diffuse reflectance IR. These analyses showed that the ZnBr₂ completion fluid promoted the hydrolysis of the nitrile group to form amides and carboxylic groups. The carbon–carbon double bonds in NBR were unaffected after short exposure to ZnBr₂‐based completion fluid but were quickly hydrated in acidic bromide mixtures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1250–1257, 2003