Microwave‐assisted synthesis of optically active poly(amide imide)s derived from diacid chloride containing epiclon and L‐leucine with aromatic diamines

Epiclon [3a,4,5,7a‐tetrahydro‐7‐methyl‐5‐(tetrahydro‐2,5‐dioxo‐3‐furanyl)‐1,3‐isobenzofurandione or 5‐(2,5‐dioxotetrahydrofurfuryl)‐3‐methyl‐3‐cyclohexyl‐1,2‐dicarboxylic acid anhydride] was reacted with L ‐leucine in acetic acid, and the resulting imide acid ( 3 ) was obtained in a high yield. The diacid chloride ( 4 ) was obtained from its diacid derivative 3 by a reaction with oxalyl chloride in dry carbon tetrachloride. The polycondensation reaction of 4 with several aromatic diamines, such as 4,4′‐sulfonyldianiline, 4,4′‐diaminodiphenylmethane, 4,4′‐diaminodiphenylether, p‐phenylenediamine, m‐phenylenediamine, 2,4‐diaminotoluene, and 1,5‐diaminonaphthalene, was developed with a domestic microwave oven in the presence of a small amount of a polar organic medium such as N‐methylpyrrolidone. The polymerization reactions were also performed with two other methods: low‐temperature solution polycondensation in the presence of trimethylsilyl chloride and reflux conditions. A series of optically active poly(amide imide)s with moderate yields and inherent viscosities of 0.12–0.19 dL/g were obtained. All of these polymers were fully characterized by IR, elemental analysis, and specific rotation techniques. Some structural characterizations and physical properties of these optically active poly(amide imide)s are reported. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1077–1090, 2003     

Use of ionic liquid and microwave irradiation as a convenient, rapid and eco-friendly method for synthesis of novel optically active and thermally stable aromatic polyamides containing N-phthaloyl-l-alanine pendent group

An efficient, fast and easy method for synthesis of new optically active and thermally stable aromatic polyamides (PAs) containing pendent phthalimide group and l-alanine flexible side spacer using room temperature ionic liquid (RTIL) by microwave irradiation has been investigated. The results found that RTIL efficiently absorb microwave energy, thus leading to a very high heating rate. All the PAs showed excellent solubility and readily dissolved in various organic solvents. Thermogravimetric analysis (TGA) exhibited that polymers were stable, with 10% weight loss recorded above 373 and 418 °C in the nitrogen atmosphere. In order to see the efficiency of microwave irradiation, this method was compared with polycondensation of the same monomers in RTILs using conventional heating.     

Highly sensitive voltammetric sensor based on catechol-derivative-multiwall carbon nanotubes for the catalytic determination of captopril in patient human urine samples

A new catechol-derivative compound, N-(3,4-dihydroxyphenethyl)-3,5-dinitrobenzamide, was synthesized and used to construct a modified-carbon nanotubes paste electrode. The electro-oxidation of captopril at the surface of the modified electrode was studied using cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy. Under the optimized conditions, the differential pulse voltammetric peak current of captopril increased linearly with captopril concentration in the ranges of 6.4×10(-8) to 3.2×10(-48) mol L(-1). The detection limit was 3.4×10(-8) mol L(-1) captopril. The diffusion coefficient and kinetic parameters (such as electron transfer coefficient and the heterogeneous rate constant) for captopril oxidation were also determined. The RSD% for 0.5 and 10.0 μmol L(-1) captopril were 2.1% and 1.6%, respectively. The proposed sensor was successfully applied for the determination of captopril in human patient urine and tablet samples.     

Optically active poly(amide-imide)/zinc oxide hybrid nanocomposites based on hydroxyphenyl benzamide segments: Compatibility by using 3-methacryloxypropyltrimethoxysilane coupling agent

In this study, a new series of optically active poly(amide-imide)/zinc oxide hybrid nanocomposites were fabricated by the sonication-assisted method. The compatibility of the organic and inorganic parts was effectively improved by reducing in aggregation of nanoparticles by surface modification using the coupling agent. The coupling agent 3-methacryloxypropyltrimethoxysilane was selected to improve the compatibility between the polymer matrix and ZnO nanoparticles. Characterizations with FTIR spectroscopy, FE-SEM, X-ray diffraction and AFM confirm the success in synthesis of nanocomposites.     

Poly(vinyl alcohol) Chains Grafted onto the Surface of Copper Oxide Nanoparticles: Application in Synthesis and Characterization of Novel Optically Active and Thermally Stable Nanocomposites Based on Poly(amide-imide) Containing N-trimellitylimido-L-valine Linkage

Green polymer nanocomposites (NCs) show unique properties of combining the advantages of nanofillers and organic polymers. In this study, in order to control the dispersion of nanoparticles (NPs) in a polymer matrix, first, poly(vinyl alcohol) (PVA) as a green modifier was grafted on the surface of the CuO NPs to obtain CuO-PVA nanohybrid. Then poly(amide-imide) (PAI) was synthesized by the direct step growth polymerization of N-trimellitylimido-L-valine and 4,4′-methylenebis(3-chloro-2,6-diethylaniline) in ionic liquid medium. Finally, CuO-PVA hybrids were incorporated into the PAI matrix using ultrasonic technique for the preparation of PAI/CuO-PVA NCs. The obtained PAI/CuO-PVA NCs were characterized by different methods. The results of thermogravimetric analysis showed that thermal stability of the NCs was enhanced by incorporation of CuO-PVA nanohybrid compared to the pure PAI.     

Microwave-promoted synthesis of new optically active poly(ester-imide)s derived from N,N-(pyromellitoyl)-bis-l-leucine diacid chloride and aromatic diols

Pyromellitic dianhydride (benzene-1,2,4,5-tetracarboxylic dianhydride) (1) was reacted with l-leucine (2) in a mixture of acetic acid and pyridine (3:2) and the resulting imide-acid [N,N^′-(pyromellitoyl)-bis-l-leucine diacid] (4) was obtained in quantitative yield. The compound (4) was converted to the N,N^′-(pyromellitoyl)-bis-l-leucine diacid chloride (5) by reaction with thionyl chloride. A new facile and rapid polycondensation reaction of this diacid chloride (5) with several aromatic diols such as phenol phthalein (6a), bisphenol-A (6b), 4,4^′-hydroquinone (6c), 1,8-dihydroxyanthraquinone (6d), 1,5-dihydroxy naphthalene (6e), 4,4-dihydroxy biphenyl (6f), and 2,4-dihydroxyacetophenone (6g) was developed by using a domestic microwave oven in the presence of a small amount of a polar organic medium such as o-cresol. The polymerization reactions proceeded rapidly and are completed within 10 min, producing a series of optically active poly(ester-imide)s (PEIs) with good yield and moderate inherent viscosity of 0.10-0.27 dl/g. All of the above polymers were fully characterized by IR, elemental analyses and specific rotation. Some structural characterization and physical properties of these optically active PEIs are reported.     

Novel optically active poly(amide-imide)s from N,N-(4,4-carbonyldiphthaloyl)-bis-l-phenylalanine diacid chloride and aromatic diamines by microwave irradiation

3,3^′,4,4^′-benzophenonetetracarboxylic dianhydride (4,4^′-carbonyldiphthalic anhydride) (1) was reacted with l-phenylalanine (2) in a mixture of acetic acid and pyridine (3:2) and the resulting imide-acid [N,N^′-(4,4^′-carbonyldiphthaloyl)-bis-l-phenylalanine diacid] (4) was obtained in high yield. The compound (4) was converted to the N,N^′-(4,4^′-carbonyldiphthaloyl)-bis-l-phenylalanine diacid chloride (5) by reaction with thionyl chloride. A new facile and rapid polycondensation reaction of this diacid chloride (5) with several aromatic diamines such as 4,4^′-diaminodiphenyl methane (6a), 2,4-diaminotoluene (6b), 4,4^′-sulfonyldianiline (6c), p-phenylenediamine (6d), 4,4^′-diaminodiphenylether (6e), m-phenylenediamine (6f), benzidine (6g) and 2,6-diaminopyridine (6h) was developed by using a domestic microwave oven in the presence of a small amount of a polar organic medium such as o-cresol. The polymerization reactions proceeded rapidly, compared with the conventional solution polycondensation, and was completed within 7 min, producing a series of optically active poly(amide-imide)s with high yield and inherent viscosity of 0.22-0.52 dl/g. All of the above polymers were fully characterized by IR, elemental analyses and specific rotation. Some structural characterization and physical properties of this optically active poly(amide-imide)s are reported.     

Studies on synthesis and in vitro biodegradability of novel optically active nanostructure poly(ester-imide)s containing <Emphasis Type="SmallCaps">l</Emphasis>-phenylalanine and <Emphasis Type="SmallCaps">l</Emphasis>-isoleucine linkages

A series of biodegradable functional amino-acid-based poly(ester-imide)s (PEI)s were designed and synthesized by the direct polycondensation reaction of chiral diacids composed of naturally occurring α-amino acids with 4,4′-thiobis(2-tert-butyl-5-methylphenol) in the presence of tosyl chloride, pyridine, and N,N-dimethylformamide as a condensing agent. These new chiral polymers were characterized with respect to chemical structure and purity using specific rotation experiments, FT-IR, ¹H-NMR, techniques, and elemental analysis. The surface morphology of these polymers was investigated by field emission scanning electron microscopy. The result indicated nanoscale morphology of the obtained polymers. Thermal stability and the weight loss behavior of the resulting PEIs were studied by TGA techniques. All PEIs showed no significant weight loss below 400 °C in a N₂ environment. The monomers and prepared polymers were co-cultivated with airborne fungal spores in culture media to study their biological activity. Soil burial test was also used for evaluation of their biodegradation behavior. The results showed that the synthesized monomers and their derived polymers are biologically active and that their degradation products are probably nontoxic to microbial growth.     

New cohort of optically active nanostructure poly(amideimide)s: Production and properties

Novel aromatic-aliphatic poly(amide-imide)s containing chiral units in the main chain and hydroxyl benzamide units in the side chain have been obtained from the step-growth polymerization of 3,5-diamino-N-(4-hydroxyphenyl) benzamide(2) with different chiral diacid chlorides(1a-1e).Theoretical calculations were done by means of computational chemistry methods to narrate the stable conformation and orientation of each diacid chloride monomers under reaction conditions.These polymers were characterized by conventional techniques.The resulting polymers show good thermal stability.Other physical properties of polymers including crystallinity,inherent viscosity and morphological characteristics were also studied.