Ionic miscibility enhancement via microion elimination in sulfonated polystyrene/poly(ethyl-acrylate-co-4-vinyl pyridine) ionomer blends

Miscibility enhancement of ionomer/ionomer and ionomer/polymeric acid systems is studied on the polymer pairs of poly(styrene-co-tetramethyl ammonium styrenesulfonate)/poly(ethyl acrylate-co-N-methyl-4-vinylpyridinium iodide) and poly(styrene-co-styrenesulfonic acid)/poly(ethyl acrylate-co-N-methyl-4-vinylpyridinium iodide). NMR and dynamic mechanical results show that in these blends direct macroion–macroion interaction can be achieved with the elimination of microcounterions from the polymer chains. Ion-ion attraction leads to a miscibility enhancement comparable to that of the previously reported proton transfer blends; a miscible blend is obtained with ca. 5 mol% of ions in the polymers.     

Degradable polymer blends. I. Screening of miscible polymers

Blends of biodegradable polymers having properties distinct from the individual polymer components, and that are suitable for use as carriers of pharmaceutically active agents, were prepared from two or more polyanhydrides, polyesters, and mixtures of polyanhydrides and low molecular weight polyesters. The blends have different properties than the original polymers, providing a mean for altering the characteristics of the polymeric matrix without altering the chemical structure of the component polymers. Aliphatic, aromatic, and copolymers of polyanhydrides were miscible in each other and formed less crystalline compositions with a single melting point which was lower than the melting point of the starting polymers. The polyesters: poly(lactide-glycolide), poly(caprolactone), and poly(hydroxybutyric acid) presented some miscibility in each other. However, the polyanhydrides were immiscible with the polyesters resulting in a complete phase separation both in solution or in melt mixing. Only low molecular weight polyesters (in the range of 2000) of lactide and glycolide, mandelic acid, propylenefumarate, and caprolactone presented some miscibility with polyanhydrides. Similarly, poly(orthoester) and hydroxybutyric acid polymers formed a uniform mixture with the anhydride polymers which had the two melting points of the original polymers. Drug release from polymer blends composed of poly(hydroxybutyric acid) or low molecular weight poly(lactic acid) with poly(sebacic anhydride) (PSA) showed a constant release of drug for periods from 2 weeks to several months as a function of the PSA content in the blend. Increasing the content of PSA, a fast degrading polymer, increases the release rate from the blend. © 1993 John Wiley & Sons, Inc.     

Synthesis and Characterization of a Branched Poly(Methacrylamide): Thermal Stability and Molecular Simulation Studies of Their Blends With Vinylic Polymers

The synthesis of a poly(diethylaminoethyl methacrylamide) (BP), based on a lineal methacrylamide with diethylaminoethyl branches was carried out. Thermal behavior was studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Relatively high thermal stability is found. Blends with poly(methylmethacrylate) (PMMA), poly(acrylic acid) (PAA) and poly(monomethyl itaconate) (PMMI) were prepared. Their thermal properties in blends were studied together with miscibility, in order to improve thermal properties of vinylic polymer blends. An increase of thermal stability was found for certain blend compositions. By FTIR analysis, higher band displacements were found for low BP compositions. AFM and molecular simulation analysis were carried out in order to elucidate the structural origin leading to thermal stability and miscibility increases. Hydrophobic interactions among methyl end groups of BP and methylene groups of vinylic polymers should be the responsible of miscibility and thermal stability increases.     

Thermal analysis of polysiloxanes, aromatic polyimide and their blends

Low molecular weight poly(dimethylsiloxane) and poly(methylphenylsiloxane) were synthesized and blended with polyimide (PI) at its precursor poly(amic acid) stage. FTIR analysis has proven the retention of polysiloxanes in polyimide after the ultimate curing of blends. Differential scanning calorimetric analysis was performed on polysiloxanes to elucidate the structures present in polymers while thermogravimetric analysis (TGA) was performed on polysiloxanes, polyimide as well as their blends to evaluate the thermal stability and to analyze the effect of polysiloxane incorporation in blends. Blends have shown synergistic improvement as compared to neat polyimide.     

Solubility and miscibility of poly(ethyl oxazoline)

The solubility of poly(ethyl oxazoline) in aqueous solutions was studied. The cloud point temperatures decreased in the presence of sodium chloride but increased by the addition of tetrabutylammonium bromide or dioxane. Solution-cast films of blends of the polymer and poly(acrylic acid) were miscible, but mutual precipitation occurred in water, methanol, and dioxane. The compositions of the complexes correspond in most cases to simple molar ratios of the interacting groups. The glass transition temperatures of the complexes are higher than the values for blends of the same compositions, and the high values are attributed to hydrogen bonds acting as physical crosslinks. Complex formation also occurs when the polymer is mixed with a styrene-acrylic acid copolymer and with low weight polymers containing phenol groups.     

pH effects on the complexation, miscibility and radiation-induced crosslinking in poly(acrylic acid)-poly(vinyl alcohol) blends

The effect of pH on the complexation of poly(acrylic acid) with poly(vinyl alcohol) in aqueous solution, the miscibility of these polymers in the solid state and the possibility for crosslinking the blends using gamma radiation has been studied. It is demonstrated that the complexation ability of poly(vinyl alcohol) with respect to poly(acrylic acid) is relatively low in comparison with some other synthetic non-ionic polymers. The precipitation of interpolymer complexes was observed below the critical pH of complexation (pH(crit1)), which characterizes the transition between a compact hydrophobic polycomplex and an extended hydrophilic interpolymer associate. Films prepared by casting from aqueous solutions at different pH values exhibited a transition from miscibility to immiscibility at a certain critical pH, pH(crit2), above which hydrogen bonding is prevented. It is shown here that gamma radiation crosslinking of solid blends is efficient and only results in the formation of hydrogel films for blends prepared between pH(crit1) and pH(crit2). The yield of the gel fraction and the swelling properties of the films depended on the absorbed radiation dose and the polymer ratio. [Diagram: see text] SEM image of an equimolar PAA-PVA blend cast from a pH 4.6 solution.     

由分子间氢键导致的丝素构象转变的FT-IR研究

用FT－IR研究发现，在丙烯腈与丙烯酸甲酯的共聚物（PANMA）与聚L-丙氨酸（PLAL）的共混体系中，丝素（SF）与PANMA的共混体系及SF与聚丙烯酸钠（NA）的共混体系中，含有羰基或其它极性基团的高分子与SF形成强弱不等的氢键．由于氢键的形成,使SF分子不得不调整自身的构象，从而引起其构象转变．讨论了可能的分子间氢键的结构．     

Chromatic changes in the blends of electroactive polymers with comb-shaped flexible polymers

The effect of blending of alkylated polymers, which have different backbone structures, was investigated in order to improve the electronic properties of conducting polymers. Comb-shaped flexible polymer, poly(octadecyl acrylate) (PODA), was blended with rigid alkylated conducting polymers, poly(3-dodecyl-thiophene)(PDDT), and polyaniline emeraldine base (PANI)/p-dodecyl-benzenesulfonic acid (DBSA) complex, respectively, to investigate the effect of long alkyl chain of flexible polymer on the conformational mode change of rigid backbones and the effect of intermolecular interaction between these alkylated polymers. Optical microscopy was applied to observe the morphology change and obtain the phase diagrams of these blends. The intermolecular interactions that occurred in these blends were explained for each different characteristic peak obtained with FT-IR spectra. Solvatochromism (red-shift) of PDDT/PODA binary blends in solid state due to the planarity change of rigid backbone in the presence of PODA and electrochromism of PANI(DBSA)₄/PODA ternary blends due to the hydrogen bonding between the nitrogen cation of PANI complex and carbonyl group of PODA are observed in UV-Vis-NIR spectra. Interestingly, the increase of conductivity was observed in the presence of 5 wt% of PODA in PDDT/PODA binary blends and a homogeneous smectic liquid crystalline structure was clearly confirmed by cross polarized optical microscopy in PANI(DBSA)₄/PODA ternary blends.     

Stereocomplex formation in AB DI-block copolymers of poly(ϵ-caprolactone) (a) and poly(lactide)(B)

The thermal properties of two series of AB di-block copolymers of poly(ϵ-caprolactone) (A) and poly(lactide) (B) and their blends were studied. Each series contained poly(lactide) blocks of opposite chirality. The length of the poly(ϵ-caprolactone) blocks was not varied (DP = 70), whereas the poly(lactide) blocks were of varying length (DP = 5 − 80). Blends of polymers containing blocks of opposite chirality were prepared by mixing in solution. The melting temperature of the PLA phase was raised by approximately 55 °C in the blends due to stereocomplex formation. The melting temperatures of the crystalline PCL and PLA phases strongly depended on the composition of the block copolymers.     

Electroluminescence and charge photogeneration in poly(9,9-dihexadecylfluorene-2,7-diyl) and its blends

Photoluminescence, electroluminescence (EL), charge photogeneration and transport were studied in poly(9,9-dihexadecylfluorene-2,7-diyl) (PFC16), poly[(2,5-dihexadecyl-1,4-phenylene)(1,4-phenylene)] (PPPC16) and their blends. Blending of PFC16 with PPPC16 led to a significant improvement of the EL efficiency and stability compared with the devices fabricated from the neat polymers. Efficient blue and white light-emitting devices (LEDs) were fabricated using the blends. The increase in the EL efficiency was attributed to modification of the charge injection, transport and recombination properties in the blend.     

Structure and interactions in homopolymers and blends as studied by the methods of vibrational and nmr spectroscopy

The combination of IR, Raman and NMR spectroscopy was used in the study of the blends of semicrystalline and amorphous polymers with considerably different strength of intermolecular interactions: poly(ϵ-caprolactam)/polystyrene (PCL/PS), poly(ethylene oxide)/poly(methyl methacrylate) (PEO/PMMA) and poly(N-methyllaurolactam)/poly(4-vinylphenol) (PNMLL/PVPh). In the vibrational and NMR spectra of the blends composed of non-interacting polymers (PCL/PS) and weakly interacting polymers (PEO/PMMA), no band changes were observed which would indicate changes of the conformational structures. ¹H NMR relaxation of the PCL and PS components in the blends is the same as in the respective homopolymers similarly treated. In the blends of weakly interacting polymers (PEO/PMMA), the crystallinity of PEO is influenced by the presence of PMMA and is negligible in the blends with less than 30 wt.-% of PEO. The rotating-frame spin-lattice relaxation time for protons T^H_1p of PMMA indicates close contact of the PMMA and PEO chains. In the blends PNMLL/PVPh with strong hydrogen-bonding interactions, both components are intimately mixed on a scale of 3–4 nm and significant shifts of some bands both in vibrational and in NMR spectra reveal changes of structure.     

Mesophase structure and some properties of liquid-crystalline organoelement polymers

The structure and physico-mechanical properties of polyphosphazene, poly(trimethylvinylsilane) and blends of polyphosphazene with polyethylene were studied. It was shown that these organoelement homopolymers form mesophase structure which can be described as condis-crystal, and mesophase polymers are effective modifiers when mixed as blends with polyethylene, allowing to make processing more effective and obtain composites with improved mechanical properties.     

Specific interactions in blends of poly(ethylene oxide) and poly(bisphenol A-co-epichlorohydrin): FTIR and thermal study

Blends of poly(ethylene oxide) (PEO) of high molecular weight with poly(bisphenol A-co-epichlorohydrin) (PBE) with high epoxy equivalent were studied spectroscopically, thermally and morphologically. As similar systems of low molecular weight, a single T_g was observed for all blends, indicating miscibility. A progressive decrease in the degree of crystallinity and in the size of the PEO spherulites as the PBE is added is also observed. Quantitative analysis from FTIR spectra provided determination of specific interactions between the constituents and their variation with PEO content. Simulations were performed utilising the spectra of the pure polymers to confirm that the observed changes in the experimental spectra of the blends were due to interaction between the polymers.     

Blends of synthetic and natural polymers as special performance materials

The interest for blends of synthetic and natural polymers is growing and several applications in many different fields are now becoming evident. The biological-synthetic polymers interactions play a relevant role in controlling the mechanism that constitutes the basis of biocompatibility of materials used in medicine. This work concerns with the preparation and chemico-physical and mechanical characterization of blends in which the biological component is hyaluronic acid or its benzyl ester derivatives, and the synthetic component is poly(vinyl alcohol) or ethylene-vinyl alcohol copolymers.     

PH effects in the complex formation and blending of poly(acrylic acid) with poly(ethylene oxide)

The effect of pH on the complex formation between poly(acrylic acid) (PAA) and poly(ethylene oxide) (PEO) has been studied in aqueous solutions by turbidimetric and fluorescent methods. It was shown that the formation of insoluble interpolymer complexes is observed below a certain critical pH of complexation (pH(crit1)). The formation of hydrophilic interpolymer associates is possible above pH(crit1) and below a certain pH(crit2). The effects of polymer concentrations in solution and PEO molecular weight as well as inorganic salt addition on these critical pH values were studied. The polymeric films based on blends of PAA and PEO were prepared by casting from aqueous solutions with different pHs. These films were characterized by light transmittance measurements and differential scanning calorimetry. The existence of the pH value above which the polymers form an immiscible blend was demonstrated. The transitions between the interpolymer complex, miscible blend, and immiscible blend caused by pH changes are discussed. The recommendations for preparation of homogeneous miscible films based on compositions of poly(carboxylic acids) and various nonionic water-soluble polymers are presented.     

Morphology and properties of super-toughened bio-based poly(lactic acid)/poly(ethylene-co-vinyl acetate) blends by peroxide-induced dynamic vulcanization and interfacial compatibilization

Super-toughened poly(lactic acid) (PLA)/poly(ethylene-co-vinyl acetate) (EVA) blends were prepared via 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (AD) induced dynamic vulcanization and in situ interfacial compatibilization. The effects of AD on the morphology and properties of PLA/EVA blends were studied using a Brabender torque rheometer, gel content test, scanning electron microscopy (SEM), differential scanning calorimetry (DSC) thermogravimetric analysis (TGA) and mechanical properties test. The torque and gel content demonstrated that EVA and PLA was successfully vulcanized in the presence of free radicals obtained by the decomposition of the 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (AD). Additionally, the gel content results indicated that, compared with PLA, EVA is more aggressive with free radicals. The SEM revealed that a relatively uniform phase morphology and good interfacial compatibilization were achieved in the dynamically vulcanized PLA/EVA/AD blends. The interfacial reaction and compatibilization between the component polymers resulted in the formation of super-toughened PLA/EVA blended materials.     

Thermal degradation of bromine-containing polymers: Part 11—Blends of poly(2,3-dibromopropyl methacrylate) and poly(2,3-dibromopropyl acrylate) with poly(methyl methacrylate) and poly(methyl acrylate)

The products of degradation of blends of poly(2,3-dibromopropyl methacrylate) and poly(2,3-dibromopropyl acrylate) with poly(methyl methacrylate) and poly(methyl acrylate) are predominantly those to be expected from the degradation of the individual polymers. However, the appearance of methyl bromide and methanol from all four blends indicates that some interaction does occur across the phase boundary between the two constituent polymers. This is presumed to consist of the reaction of hydrogen bromide, formed by decomposition of the brominated polymers with the methyl groups of the acrylate and methacrylate polymers.     

Fracture evaluation of plasticized polylactic acid / poly (3-HYDROXYBUTYRATE) blends for commodities replacement in packaging applications

Nowadays, scientific and technological efforts are being carried out to diminish serious ecological problems caused by indiscriminate use of non-biocompostable polymers in the packaging industry. In this sense, novel biodegradable blends of different composition based on poly(lactic acid) (PLA), poly(3-hydroxybutyrate) (PHB) and tributyrin (TB) are developed and here proposed as an eco-friendly alternative. Materials are characterized by fracture experiments under quasi-static and biaxial impact loading. Fracture behavior is analyzed together with thermal, tensile and water permeation properties to evaluate their potential in-service performance. TB_PLA/PHB blends with 15 wt% TB exhibit better permeation and fracture toughness than currently used bio-based polymers, being in the range of polyethylene properties. Results highlight the potential of these new blends broadening the current application field of PLA.     

Amphiphilic segmented polyurethanes as surface modifying additives

Amphiphilic segmented polyetherurethanes were prepared from methylene diphenylene diisocyanate (MDI), poly(ethylene glycol) 1500 (PEG), and a fatty acid monoglyceride as a chain extender. The polymers were not soluble in water or methanol, but dissolved readily in organic solvents. The amphiphilic properties were demonstrated as a large hysteresis in the water contact angles, exceeding 110°. The amphiphilic polymers were shown to modify the surface properties of a poly(ether urethane) (PEU) and a poly(ether urethane urea) (PEUU) when added in 1–10 wt %, presumably due to migration of the additive to the surface. The surfaces of particularly the PEU blends became highly amphiphilic, exhibiting contact angles hystereses up to 90–100°. A surface saturation effect was observed at 5% added amphiphilic polymer. A difference in the behavior of PEU and PEUU was ascribed to differences in solubility of the additive in the matrix. On long-term exposure to water the PEUU blends increased their amphiphilic behavior.