Poly(arylether amides) and poly(aryletherketone amides) via aromatic nucleophilic substitution reactions of self‐polymerizable AB and AB2 monomers

Two new extended self‐polymerizable AB monomers, N‐(4‐fluorobenzoyl)‐4‐amino‐4′‐hydroxydiphenylether and N‐(4‐fluorobenzoyl)‐4‐amino‐4′‐hydroxybiphenyl, were prepared. The monomers were homopolymerized and copolymerized to high‐molecular‐weight, linear poly(arylether amides) in N‐methylpyrrolidone (NMP)/toluene in the presence of potassium carbonate at elevated temperature. The polymers retained NMP up to 200 °C. Samples containing small amounts of the solvent (5–10 wt %) were soluble in polar aprotic solvents. However, after complete removal of the NMP, the polymers were only soluble in strong acids such as sulfuric acid and methanesulfonic acid (MSA). The polymers, which had intrinsic viscosities of 0.57–1.49 dL/g (30.1 ± 0.1 °C in MSA), were semicrystalline with melting temperatures above 400 °C. Two new self‐polymerizable AB₂ amide monomers, N,N′‐bis(4‐fluorobenzoyl)‐3,4‐diamino‐4′‐hydroxydiphenylether and N,N′‐bis(4‐fluorobenzoyl)‐3,5‐diamino‐4′‐hydroxybenzophenone, were also prepared and polymerized to give a hyperbranched poly(arylether amide) and a hyperbranched poly(aryletherketone) amide. The arylfluoride‐terminated, amorphous polymers had intrinsic viscosities of 0.34 and 0.24 dL/g (30.0 ± 0.1 °C in m‐cresol), glass‐transition temperatures of 210–269 °C, and were soluble in a wide variety of organic solvents. Matrix‐assisted laser desorption/ionization time‐of‐flight analysis indicated that the components of the low‐molecular‐weight fractions contained cyclic structures. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2374–2389, 2003     

Synthesis and properties of block poly(styrene amides) and poly(styrene esters)

Three series of block copolymers, namely, polystyrenecaproamide (I), polystyrenehexamethyleneadipamide (II), and poly(styreneethylene terephthalate) (III), were prepared, and the properties of the copolymers in relation to the block sequence lengths and the compositions were studied. Styrene was polymerized in the presence of aluminum chloride and thionyl chloride to give ω,ω′-dichloropolystyrenes of various degrees of polymerization from 12.0 to 51.0, which were either ammonolyzed to ω,ω′-diaminopolystyrene or hydrolyzed to ω,ω′-dihydroxypolystyrene. ω,ω′-Diaminopolystyre was treated with adipic acid to give the corresponding salts, namely, ω,ω′-diammoniumpolystyrene adipate, which was melt-polymerized either with ε-amino-n-caproic acid to give polystyrenecaproamide (I) or with hexamethylenediammonium adipate to give polystyrenehexamethyleneadipamide (II). ω,ω′-Dihydroxypolystyrene was melt-polymerized with dimethyl terephthalate and ethylene glycol to give poly(styreneethylene terephthalate) (III). All the block copolymers were of high enough molecular weight to be cast or spun into films or filaments. Upon polymerization, the increase of the block sequence of PSt units increased the amide content but decreased the ester content of the resulting copolymers. Also, an increase in n decreased the inherent viscosities of the copolymers at a constant monomer feed f_c counted by the polymer equivalent of PSt but increased the inherent viscosities at a constant monomer feed r_c counted by the monomer equivalent of PSt. The melting points of the copolymers decreased with increasing n values. Also, an increase in n decreased the densities of I and III but increased the density of II at a constant amide or ester composition F_c counted by polymer units but increased the densities of I, II, and III at a constant amide or ester composition R_c counted by the monomer unit.     

Electric birefringence of solutions of aromatic poly(amide hydrazide) in dimethyl sulphoxide

Birefringence in a pulsed electric field has been investigated for solutions of para-aromatic polyamid hydrazide (PAH) in dimethyl sulphoxide. The values of the specific Kerr constant K extrapolated to zero concentration have been determined. The experimental data are adequately described by the theoretical dependence of K on the contour length of the PAH molecules for kinetically rigid wormlike chains. The angle formed by the dipole moment of the monomer unit and the direction of the PAH chain was found to be 61.5 ± 1.5°. Comparison between relaxation times obtained from the curves of the decay of birefringence after the end of the electric pulse and the intrinsic viscosities of some PAH samples confirm the conclusion about high kinetic rigidity of PAH macromolecules.     

Injection molded hybrid composites based on corn fibers and poly(vinyl alcohol)

Ongoing research cooperation between USDA and the University of Pisa, Italy has yielded several composite blends of poly(vinyl alcohol) (PVA) and corn fibers (CF). The USA is the largest producer of ethanol from cereal grains. Composites based on natural fibers alone are extremely sensitive to water. Their mechanical properties deteriorated upon the absorption of water, thus suggesting a limited usefulness of such formulations in practical applications. In this study, corn-fibers produced during the wet milling process of corn for fuel ethanol were used to prepare composites. CF and PVA were processed in variable amounts in the presence of both dry/fluid plasticizers, such as glycerol and pentaerythritol. Composites prepared from CF in combination with PVA showed little change in their mechanical properties even after conditioning at variable relative humidities, as well as complete soaking in water. Composites tested after storage for one year under 50% relative humidity and 23°C exhibited mechanical properties similar to those of freshly prepared composites. Cornstarch was introduced in the formulation for the purpose of reducing the cost of the final product and to further increase the composition of natural components in the composites. Addition of starch moderately reduced the mechanical properties of the composites.     

Enzymatic degradation of poly(L-lactide) and poly(epsilon-caprolactone) electrospun fibers

Poly(L-lactide) (PLLA) and poly(epsilon-caprolactone) (PCL) ultrafine fibers were prepared by electrospinning. The influence of cationic and anionic surfactants on their enzymatic degradation behavior was investigated by measuring weight loss, molecular weight, crystallinity, and melting temperature of the fibers as a function of degradation time. Under the catalysis of proteinase K, the PLLA fibers containing the anionic surfactant sodium docecyl sulfate (SDS) exhibited a faster degradation rate than those containing cationic surfactant triethylbenzylammonium chloride (TEBAC), indicating that surface electric charge on the fibers is a critical factor for an enzymatic degradation. Similarly, TEBAC-containing PCL fibers exhibited a 47% weight loss within 8.5 h whereas SDS-containing PCL fibers showed little degradation in the presence of lipase PS. By analyzing the charge status of proteinase K and lipase PS under the experimental conditions, the importance of the surface charges of the fibers and their interactions with the charges on the enzymes were revealed. Consequently, a "two-step" degradation mechanism was proposed: (1) the enzyme approaches the fiber surface; (2) the enzyme initiates hydrolysis of the polymer. By means of differential scanning calorimetry and wide-angle X-ray diffraction, the crystallinity and orientation changes in the PLLA and PCL fibers during the enzymatic degradation were investigated, respectively.     

Synthesis and properties of new poly(ether sulfone)amides

High molecular-weight aromatic polyamides were obtained from 1,5- and 2,6-bis-(4′-carboxy-4-phenylenoxy-sulfonyl)naphthalene by direct polycondensation reaction in N-methyl-2-pyrrolidone with various aromatic diamines, using triphenyl phosphite and pyridine as condensing agents. The polymers were characterized by elemental analysis, thermogravimetric analysis, differential scanning calorimetry, and infrared analysis. The polyamides, obtained in quantitative yield, possessed inherent viscosities in the range 0.42–1.70 dL/g, glass transition temperatures between 245–310°C, and 10% weight loss temperatures in nitrogen and air above 435 and 424°C, respectively. Most of the polymers were soluble in aprotic solvents. The effect of the structure on properties, such as solubility, T_g, and thermal behavior, were also studied. © 1996 John Wiley & Sons, Inc.     

Foamed articles based on potato starch, corn fibers and poly(vinyl alcohol)

Single-use packaging materials made of expanded polystyrene (EPS) have been identified as suitable items to be replaced by biodegradable materials. Plates made with EPS represent a source of non-degradable waste that is difficult to collect and to recycle. Potato starch based foamed plates have been prepared by a baking process. Presently, foam plates have been prepared by baking aqueous mixtures of potato starch, corn fibers, and poly(vinyl alcohol) (PVA) inside a hot mold. The effects of the addition of corn fibers, a co-product of bio-ethanol production, on mechanical properties and moisture resistance of potato starch based foamed plates were investigated. The addition of corn fiber to potato starch batter increased baking time and an increased batter volume is needed to form a complete tray. The mechanical properties of the trays decreased with added corn fiber. In previous studies PVA has been added as aqueous solution to improve strength, flexibility, and water resistance of baked starch trays. In this study, 88% hydrolyzed PVA was added as a powder in the mixture, avoiding the time consuming and costly step of pre-dissolving the PVA. The addition of PVA to potato starch batters containing corn fiber mitigated the reduction in tensile properties seen in trays with added corn fiber. Starch-based trays produced with a high fiber ratio and PVA, showed improved water resistance.     

The thermal transformation of an aromatic poly (amide), poly (ortho-oxyamide) and poly (benzoxazole)

The thermal behaviour of three aromatic polymers, poly(3,3-dioxy-4,4-diphenylmethane) (POA), poly(2,2-m-phenylene-5,5-dibenzoxazolemethane) (PBO) and a commercial poly-(phenyleneisophthalamide) (Phenylon) was studied by thermal analysis, i.e. DSC and TG. PBO was formed by the progressive thermocyclization of POA. By transforming POA into PBO the thermal stability was increased proportionally to the degree of cyclization, due to the stiffening of the polymer chain. PBO was found to be more thermally stable than Phenylon. The activation energies of the desorption of moisture, cyclization and thermal degradation of the polymers in both nitrogen and air were determined from non-isothermal TG data.     

Structure of oriented fibers based on poly(vinyl alcohol) modified by detonation nanodiamonds

A comparative study of the structure and mechanical and thermal characteristics of nanocomposite oriented fibers based on poly(vinyl alcohol) impregnated with the nanodiamonds prepared by detonation synthesis and fibers based on the initial unmodified polymer has been performed. The conditions and regimes of gel spinning of the nanocomposite fibers containing highly dispersed nanosized filler without its aggregation are defined. The introduction of nanosized filler particles up to 7 vol % is found to entail no marked changes in the temperature intervals of glass transition and melting in the corresponding DSC thermograms. In this case, the amorphous-crystalline structure of the matrix polymer likewise remains practically unchanged. Under the selected conditions of gel spinning, the resultant nanocomposite fibers with comparable draw ratios are characterized by a higher longitudinal elastic modulus, close values of breaking strength, and lower values of elongation at break as compared with those observed for the fibers based on the initial unmodified polymer. The nanomodified fibers show promise as reinforcing elements in construction materials for various purposes.     

Synthesis of aromatic poly(thioether ketone)

Aromatic poly(thioether ketone)s were prepared by the direct polycondensation of aromatic dicarboxylic acids with aryl compounds containing ether or sulfide structures using phosphorus pentoxide/methanesulfonic acid (PPMA) as a condensing agent and solvent. Polycondensation proceeded smoothly and produced aromatic poly(thioether ketone)s with inherent viscosities up to 0.73 dL/g. The synthesis of substituted aryl ketones by the reaction of substituted benzoic acids with aryl compounds in PMMA was studied in detail to demonstrate the feasibility of the reaction for polymer formation. The thermogravimetry of the aromatic poly(thioether ketone)s showed a 10% weight loss in air and nitrogen at around 450 and 460°C, respectively. © 1992 John Wiley & Sons, Inc.     

Morphology of poly(p-phenylene terephthalamide) fibers

Fibers of poly(p-phenylene terephthalamide) (PPTA) have a fibrillar morphology, the individual fibrils having a high proportion of extended chains passing through periodic defect layers. A pleat structure is superimposed. The fibers are fully crystalline (within the limits of determination) with a small fraction of randomly oriented crystalline material. The major distinction between PPTA and conventional fibers lies in the high level of extended chains passing through the defect layers of the former structure. These extended chains result in crystallographic register being maintained between adjacent ordered zones. Quantitatively, a measure of this order is obtained from a comparison of the correlation length, obtained from meridional x-ray peak widths, and the defect spacing. In conventional fibers the defect spacing, i.e., long period, is longer than the correlation length (i.e., crystal size). In PPTA, the analog of the long period, the defect spacing (about 35 nm) is smaller than the correlation length, which is over 80 nm.     

Effect of urea on poly(methacrylic acid) and poly(acrylic acid) aqueous solutions

The effects of urea on aqueous solutions of both poly(methacrylic acid (PMA) and poly(acrylic acid) (PAA) have been investigated by using potentiometry, viscometry and study of the fluorescence of Auramine O, a cationic dye. The viscosity behaviour of unionized PMA obtained from direct dissolution of solid powder shows that the unneutralized macromolecules can be associated in water. The stability of such “aggregates” seems weak as indicated by their disappearance as soon as the charge density is very low. For PMA salt solution percolated through a cation (H⁺) exchange resin column, no association is observed. The pH-dependent conformational behaviour of PMA which, contrary to PAA, presents compact conformations in water at low charge density is discussed in terms of solvophobic/solvophilic interactions. It is shown that, even for urea concentration up to 8 M, the compact conformations of PMA are not completely destroyed. The formation of H⁺/urea complex is taken into account.     

Electrospun fibers of poly(ethylene terephthalate) blended with poly(lactic acid)

Fibrous blends of polyethylene terephthalate (PET) and polylactic acid (PLA) were fabricated by electrospinning (ES) from a common solvent, at concentrations of PET/PLA = 100/0, 70/30, 50/50, 30/70, and 0/100. Oriented fiber mats were studied either as-spun, or after a cold-crystallization treatment. Scanning electron microscopy of as-spun amorphous fibers showed that addition of PLA into the ES solution prevents occurrence of beads. In some compositions, two glass transitions were observed by temperature-modulated differential scanning calorimetry indicating that the two components in the ES fibers were phase separated. Thermogravimetric analysis was used to study thermal degradation at high temperatures. PLA degrades at a temperature about 100 °C lower than that of PET, and holding or cycling the blends to high temperature can result in the degradation of PLA. Degree of crystallinity was determined using DSC for as-spun and cold-crystallized ES blend fibers. The degree of crystallinity of each blend component is reduced by the presence of the other blend component, and the overall crystallinity of the blend fibers is less than that of the homopolymer fibers. Wide-angle X-ray scattering results show that oriented crystals were formed in the blended electrospun fibers collected on a rotating collector. The cold-crystallization process leads to both PET and PLA crystallizations. Oriented crystallites form even when the fiber is crystallized with its ends free to shrink.     

Mesoscopic simulation of an ionomeric membrane based on sulfonated aromatic poly(ether ether ketone)

Mesoscopic simulation in the framework of the mesoscopic dynamics method (a version of the dynamic density functional method) was performed for a proton conducting membrane based on sulfonated aromatic poly(ether ether ketone) in a wide range of water content in the system. For the selected parametric field, the model demonstrates microphase separation of hydrophilic and hydrophobic segments of the polymer. In the bulk of the membrane, a spatial network of water channels forms, whose walls consist of polar (sulfonated) units of the macromolecule. Independent molecular dynamics simulation for one set of parameters gives close values of the structural characteristics of the membrane, which confirms the correctness of the mesoscopic model.     

Biocomposites based on ramie fibers and poly(L‐lactic acid) (PLLA): morphology and properties

We herein report effects of morphology of PLLA and natural fiber on combination properties of biocomposites based on PLLA and ramie fibers. For this purpose, short ramie fiber (FIB), ramie fabric (FAB), PLLA film (FPLLA), and PLLA powder (PPLLA) were used to investigate the structure–property relationship of PLLA biocomposites with 30 wt% ramie fiber prepared by hot compression molding. It is revealed that mechanical properties of biocomposites are strongly dependent on the morphology of PLLA and FAB. DMA test shows that the improved storage modulus was due to the better dispersion of FIB. DSC and POM tests show that PLLA/FIB biocomposites have the highest spherulite growth rate. TGA test shows that char residue at high temperature is affected by the dispersion of PLLA and ramie fiber. SEM images exhibit the different interfacial adhesion character of FIB and FAB in the PLLA matrix after the ramie fiber treated with alkali and silane. PLLA/FAB biocomposites have not only better anti‐dripping properties when burning but also better aging resistance in UV‐irradiation hydrothermal aging, and which can be attributed to fiber bundle and laminated PLLA biocomposites structure. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and surface characterization of a new multiblock copolymer based on poly(dimethylsiloxane) and aromatic polysulfone

A new alternating block copolymer was synthesized from dihydroxy-terminated poly-(ether ketone sulfone) and bis(dimethylamino)-terminated polydimethylsiloxane oligomers. The chemistry and the thermal properties are discussed. Surface chemical composition of films was analyzed by ESCA. Quantitative calculations showed a noticeable siloxane enrichment at the surface.     

Electrospun chitosan-coated fibers of poly(L-lactide) and poly(L-lactide)/poly(ethylene glycol): preparation and characterization

Fibrous poly(L-lactide) (PLLA) and bicomponent PLLA/poly(ethylene glycol) mats were prepared by electrospinning and then were coated with chitosan. The presence of chitosan coating was proved by scanning electron microscopy and by fluorescence microscopy. On contact with blood, the chitosan coating led to changes in erythrocyte shape and in their aggregation. The haemostatic activity of the mats increased with increasing chitosan content. Microbiological studies against Staphylococcus aureus revealed that the chitosan coating imparts antibacterial activity to the hybrid mats. The combined haemostatic and antibacterial activities render these novel materials suitable for wound-healing applications.     

Lattice defects in poly(p-phenylene-terephthalamide) fibers

The lattice defects in PPTA fibers were studied by line profile analysis. The results indicate that lattice distortions are produced by local defects, probably chain ends incorporated into the crystalline lattice. The disorder is strongly anisotropic. There are indications for the existence of small domains of higher disorder which do not disappear on annealing.Dedicated to Professor Dr. R. Bonart on the occasion of his 60th birthday.     

Synthesis and properties of aromatic poly (ether sulfone)s and poly (ether ketone)s based on methyl-substituted biphenyl-4,4′-diols

Novel methyl-substituted aromatic poly (ether sulfone)s and poly (ether ketone)s were synthesized from combinations of 3,3′,5,5′-tetramethylbipheny-4,4′-diol and 2,2′,3,3′,5,5′-hexamethylbiphenyl-4,4′-diol, and 4,4′-dichlorodiphenyl sulfone and 4,4′-difluorobenzo-phenone by nucleophilic aromatic substitution polycondensation. The polycondensations proceeded quantitatively in a N-methyl-2-pyrrolidone-toluene solvent system in the presence of anhydrous potassium carbonate to afford the polymers with inherent viscosities between 0.86 and 1.55 dL/g. The methyl-substituted poly (ether sulfone)s and poly (ether ketone)s showed good solubility in common organic solvents such as chloroform, tetrahydrofuran, pyridine, m-cresol, and N,N-dimethylacetamide. The tetramethyl- and hexamethyl-substituted aromatic polyethers had higher glass transition temperatures than the corresponding unsubstituted polymers, and did not decompose below 350°C in both air and nitrogen atmospheres. The films of the methyl-substituted poly (ether ketone)s became insoluble in chloroform by the irradiation of ultraviolet light, indicating the occurrence of photochemical crosslinking reactions. © 1994 John Wiley & Sons, Inc.