A new class of aromatic polyetheraroylhydrazides. I. Synthesis and chemical–physical characterization

A series of new aromatic polyetheraroylhydrazides incorporating 4-oxybenzoyl units has been synthesized, whose general formula was [CONHNHCO? O? O–(CH₂)_x? O? phenyl O-CONHNHCOO]_n with x values in the range of 2 to 12. The increasing number of methylene units in the backbone gave rise to polymers which melted before the hydrazidic linkage underwent thermal cyclation to oxadiazole. Moreover, many polymers showed multiple endotherms on melting. X-ray diffraction studies confirmed a crystalline organization of polyhydrazides for methylene units above 4. © 1993 John Wiley & Sons, Inc.     

Synthesis and characterization of new epoxy and cyanate ester resins

New epoxide and cyanate ester resins with an aromatic ester backbone namely 1,3-[di-(4-glycidyloxy diphenyl-2,2^′-propane)]-isophthalate (DGDPI) and 1,4-[di-(4-cyanato diphenyl-2,2^′-propane)]-terephthalate (DCDPT) were synthesized and the intermediates were characterized by IR, 1H-/¹³C-NMR spectroscopic methods. The cured products from DGDPI and DHDPI exhibited higher T_g compared with standard epoxy system. The increase in the T_g may be due to the cyanate ester and rigid aromatic backbones present in the curing system.     

Ascorbic Acid Oxidation at Nonmodified and Copper‐Modified Polyaniline and Poly‐ortho‐methoxyaniline Coated Electrodes

The electrochemical oxidation of ascorbate ions is comparatively studied at polyaniline (PANI) and poly‐ortho‐methoxyaniline (POMA) layers in absence and presence of electrodeposited copper species. In comparison to PANI, POMA layers allow decreasing the overpotential necessary for driving the ascorbate oxidation reaction. A nonlinear dependence of the ascorbate oxidation current on the polymer layer redox charge is found. Copper electrodeposited in PANI and POMA layers is electrocatalytically active for the investigated reaction. Two separate oxidation waves are observed in the case of Cu‐PANI whereas a single ascorbate oxidation wave and enhanced currents are found in the Cu‐POMA case.     

The phases of polymers as determined by NMR

Nuclear magnetic resonance (NMR) spectroscopy has been used to study the morphology and dynamics in semicrystalline polymers. Dynamics may be observed through NMR relaxation rates that are sensitive to motions in the 1–10⁸ Hz range, or through modulation of anisotropic magnetic interactions, such as the chemical shift and dipole-dipole interactions. Morphological structure may be inferred through NMR measurements of polymer dynamics or investigated directly through studies of the magnetic interactions. Here, we discuss the study of morphological structure in semicrystalline polymers using NMR, and review results on poly(ethylene terephthalate) that address the question of the number of phases in this semicrystalline polymer.This work was funded by the Office of Naval Research.     

Analysis of NAD(P) and NAD(P)H cofactors by means of imprinted polymers associated with Au surfaces:: A surface plasmon resonance study

Crosslinked films consisting of the acrylamide-acrylamidophenylboronic acid copolymer that are imprinted with recognition sites for β-nicotinamide adenine dinucleotide (NAD⁺), β-nicotinamide adenine dinucleotide phosphate NADP⁺, and their reduced forms (NAD(P)H), are assembled on Au-coated glass supports. The binding of the oxidized cofactors NAD⁺ or NADP⁺ or the reduced cofactors NADH or NADPH to the respective imprinted sites results in the swelling of the polymer films through the uptake of water. Surface plasmon resonance (SPR) spectroscopy is employed to follow the binding of the different cofactors to the respective imprinted sites. The imprinted recognition sites reveal selectivity towards the association of the imprinted cofactors. The method enables the analysis of the NAD(P)⁺ and NAD(P)H cofactors in the concentration range of 1×10⁻⁶ to 1×10⁻³ M. The cofactor-imprinted films associated with the Au-coated glass supports act as active interfaces for the characterization of biocatalyzed transformations that involve the cofactor-dependent enzymes. This is exemplified with the characterization of the biocatalyzed oxidation of lactate to pyruvate in the presence of NAD⁺ and lactate dehydrogenase using the NADH-imprinted polymer film.     

Viscosity of aqueous solutions of polysaccharides and hydrophobically modified polysaccharides: Application of Fedors equation

Amphiphilic polysaccharides have been obtained by hydrophobic modification of a neutral bacterial polysaccharide, dextran. Various amounts and types of aliphatic hydrocarbon groups have been attached to dextran.The solution behaviour of unmodified dextran samples and amphiphilic dextran derivatives is characterized by viscometric measurements. The overall viscosity behaviour of unmodified polysaccharides is described up to C × [η] = 3, using the equation of Fedors [Fedors RF. Polymer 1979;20:225] which involves only a concentration parameter. The latter is shown to depend on the hydrodynamic volume of the macromolecules in solution.The equation of Fedors is shown to conveniently estimate the viscosity behaviour of amphiphilic dextran derivatives up to C × [η] = 1. The interdependence between Fedors parameter and other viscometric characteristics (intrinsic viscosity, Huggins coefficient) is evidenced. These results are extended to the data of other authors.     

Study and characterization of virgin and recycled LDPE/PP blends

Recycling of mixed plastic wastes composed of low-density polyethylene (LDPE) matrix and polypropylene (PP) was carried out by compounding using single-screw or twin-screw extruders. Blends of virgin polymers have been prepared to compare mechanical properties of both virgin and regenerated materials. First, a model composition of virgin LDPE/PP blend was prepared to study the effect of process parameters and that of different types of compatibilizers. Second, the results were applied to plastic wastes coming from industrial post-consumer plastic wastes. By adding compatibilizing agents such as ethylene-propylene-diene monomer, ethylene-propylene monomer, or PE-g-(2-methyl-1,3-butadiene) graft copolymer, elongation at break and impact strength were improved for all blends. The effect of these various copolymers is quite different and is in relation with their chemical structure. The recycled blends exhibit suitable properties leading to applications that require good mechanical properties.     

Functionalization of montmorillonite by acrylamide polymers containing side-chain ammonium cations

Stable polyacrylamide (polyAA)–montmorillonite adducts were prepared by two distinct processes: (1) free radical copolymerization of AA with alkaline clay previously treated with 2-(N-methyl-N,N-diethyl ammonium iodide)ethylacrylate (QD1) and (2) direct interactions of alkaline montmorillonite with various preformed copolymers of AA with QD1. The structure of the adducts as determined by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry and X-ray diffraction was shown to consist of AA macromolecules inserted between lamellar layers whose spacing was larger than in the polymer-free clay. The polymer was strongly attached to the inorganic surfaces, probably due to cooperative formation of electrostatic bonding. The thermal stability of the organic polymers in the resulting complexes was substantially enhanced while the mobility of macromolecules decreased.     

Synthesis and properties of novel poly(amide-imide)s containing pendent diphenylamino groups

A new dicarboxylic acid, 2,4-bis(N-trimellitoyl)triphenylamine, bearing two preformed imide rings was synthesized from the condensation of 2,4-diaminotriphenylamine and trimellitic anhydride at 1:2 molar ratio. A series of poly(amide-imide)s (PAIs) with inherent viscosities of 0.38-0.66 dl/g were prepared by triphenyl phosphite-activated polycondensation from the diimide-dicarboxylic acid with various aromatic diamines. All the resulting PAIs were readily soluble in a variety of organic solvents and formed strong and tough films via solution casting. These PAIs have useful levels of thermal stability associated with moderately high glass-transition temperatures (259-314 °C) and 10% weight loss temperatures in excess of 530 °C in nitrogen or in air.     

A New Chemo‐Enzymatic Route to Side‐Chain Liquid‐Crystalline Polymers: The Synthesis and Polymerization of 6‐(4‐Methoxybiphenyl‐4′‐oxy)hexyl Vinyl Hexanedioate

A novel synthetic method combining chemo and enzymatic synthesis strategies was employed to prepare a vinyl acetate type monomer, 6‐(4‐methoxybiphenyl‐4′‐oxy)hexyl vinyl hexanedioate (VA‐LC). Homo‐ and copolymers of VA‐LC with maleic anhydride (MAn) were prepared by conventional free radical polymerization using 2,2′‐azobisisobutyronitrile (AIBN) and 1,1′‐azobis (cyclohexane carbonitrile) (AHCN) as an initiator at 95 and 60 °C, respectively. The thermal properties of the generated polymeric material were investigated by differential scanning calorimetry (DSC), and the optical texture was inspected by polarizing optical microscopy (POM). While the monomer VA‐LC does not exhibit liquid‐crystalline properties, poly(VA‐LC), and the alternating copolymer of VA‐LC with maleic anhydride both displayed such properties.