Preparation of redox fibers containing hydroxy‐alkyl amino groups and their adsorptive properties toward Au(III)

Three kinds of redox fibers (fibers II, III, and IV) are prepared by amination of the reactive chloromethylated poly(vinyl acetate) grafting polystyrene‐divinylbenzene fiber (fiber I) with diethanolamine, ethanolamine, or triethanolamine. The N‐content of the fibers is 2.26, 2.71, and 1.86 mmol g⁻¹, respectively. Results of static adsorption experiments show that the adsorption amount of fibers II, III, and IV toward Au(III) reaches 550 mg g⁻¹, 620 mg g⁻¹, and 409 mg g⁻¹, respectively, between pH 2.0 and pH 3.0. Some adsorbed Au(III) can be reduced to Au(0). The reduction percentage of Au(III) adsorbed by fiber II increases with rising pH value of the solution and can be as high as 87% at pH 5.0. The amount of Au(III) adsorbed by fiber II increases with solution temperature, but decreases with ionic strength of the solution. The adsorption amount of fibers II and III toward Au(III) is less in ethanol or in acetacetate medium than in water. Kinetic adsorption data indicates that 50 min is needed for fiber II to adsorb half of its saturate adsorption amount of Au(III). It was proved by elemental analysis, infrared spectroscopy, nuclear magnetic resonance, and electron spectroscopy for chemical analysis determinations that the carbon atoms connecting with the hydroxy groups near the nitrogen atoms were easily oxidized into carbonyl ones during redox adsorption reaction of fibers II, III, and IV with Au(III). Some grains of gold adsorbed on fiber II were discovered under scanning electron microscopy. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 47–54, 1999     

Coloration properties and clearability of phthalimide‐derived monoazo disperse dyes containing ester groups

The coloration properties and clearability of disperse dyes prepared from phthalimide‐derived diazo components and a coupling component containing two carboxylic acid ester groups have been investigated. Members of the series featured C₂–C₄ alkyl substituents on their phthalimidyl nitrogen atom. The nature of the N‐alkyl group made no consistent difference to dye uptake on polyester. No correlation was found between percentage exhaustion and calculated solubility parameters. Wash fastness was extremely good. Comparison with analogues indicated that the diester motif was of significant extra benefit to wash fastness for phthalimide‐derived dyes, but did not increase photostability above the lower range of commercial acceptability. Clearability was compared with that of dyes lacking one or both hydrolysable structural features, as well as with that of some industrial dyes. The novel dyes exhibited a greater tendency to be solubilised, consistent with hydrolysis of their ester and/or phthalimide functionalities.     

Synthesis and properties of novel poly(meth)‐acrylates containing tricyanocyclopropyl groups for piezoelectric applications

o‐(2,2,3‐Tricyano‐3‐carbomethoxycyclopropyl)phenoxyethyl acrylate ( 5a ) and o‐(2,2,3‐tricyano‐3‐carbomethoxycyclopropyl)phenoxyethyl methacrylate ( 5b ) were prepared by reactions of bromomalononitrile with methyl o‐(2‐acryloyloxyethoxy)benzylidenecyanoacetate and methyl o‐(2‐methacryloyloxyethoxy)benzylidenecyanoacetate respectively. The dipole moments of 5a and 5b , calculated by atom superposition and electron delocalization molecular orbital method, were 2.75–3.47 D. Monomers 5a and 5b were polymerized with free‐radical initiators to obtain the polymers with tricyanocyclopropane ring as a piezoelectric chromophore in the pendant group. The resulting polymers 6a and 6b were soluble in common organic solvents such as acetone and DMF. Polymers 6a and b showed thermal stability up to 280 °C in TGA thermograms. T_g values obtained from DSC thermograms were in the range 125–140 °C. Piezoelectric coefficients (d₃₁) of the poled films were 1.2–1.4 pC N^?1. These polymers showed good temporal and long‐term thermal stabilities which are acceptable for piezoelectric device applications. Copyright © 2003 Society of Chemical Industry     

Synthesis and spectroscopic properties of novel phthalimide‐derived monoazo disperse dyes containing ester groups

The synthesis and spectroscopic properties of monoazo dye series, whose members consist of N‐alkylphthalimide diazo components combined with a coupling component containing two ester groups, are reported. Such colourants are potentially alkali‐clearable as a consequence not only of the presence of diester functionality on the coupler, but also through use of the base‐sensitive phthalimide system. Shortening the N‐alkyl group by removing one or two methylene units from a butyl chain made little difference to absorption properties, as would be expected given the relatively minor differences in inductive character produced. Shifts in the absorption maximum of the dyes associated with dibromination of the phthalimidylazo motif and its subsequent cyanodehalogenation were in agreement with theory and literature data for related series. Diester substitution on the coupling component brought about hypsochromism and hypochromism.     

Synthesis and properties of polytriazoleimide containing anthracene,pyridine and 1, 2, 3‐triazole groups and their nanocomposites with titanium dioxide

A novel anthracene, pyridine and 1, 2, 3‐triazole containing diamine was synthesized by copper catalyst 1, 3‐dipolar cycloaddition of azides and alkynes groups (Click reaction). A series of polytriazoleimide (PTAI) nanocomposites were successfully prepared by condensation polymerization between the synthesized diamine monomer and commercially available pyromellitic dianhydride with different weight percentage of titanium dioxide (TiO₂). The structure of the monomer and polymer were confirmed by the fourier transform infrared and nuclear magnetic resonance spectroscopy. The synthesized PTAI is readily soluble in common polar solvents. The PTAIs naocomposites exhibited high thermal stability, the temperature corresponding to a 5% weight loss in the range of 495°C–555°C, excellent flame retardancy (char yield were found to be in the range of 48.1–66.4) and high glass transition temperature (T_g) at (267°C–294°C). Furthermore incorporation of TiO₂ into the PTAI matrix significantly improve the dielectric constant (2.70–4.75 at 1MHz) and dielectric loss (0.06–0.46 at 1 MHz). POLYM. ENG. SCI., 59:129–138, 2019. © 2018 Society of Plastics Engineers     

Preparation and surface- active properties of new amphipathic compounds with two phosphate groups and two long- chain alkyl groups

New compounds bearing two dihydrogen phosphate groups and two long- chain alkyl groups (octyl or decyl) were prepared in good yields by the reaction of 1,ω-bis(alkyloxymethyl)- oligo (ethylene glycol)s with polyphosphoric acid. Amphipathic di- or tetrasodium phosphates were obtained by neutralization of the free acids with sodium hydroxide, and their surface- active properties in water were measured. Almost all these di- or tetrasodium phosphates showed good water solubility. Their abilities to form micelles and to lower surface tension were fairly good as compared with general monoalkyl phosphates consisting of one longer alkyl chain and one hydrophilic group. The foaming property of aqueous solutions of the tetrasodium salts was different from that of the disodium salts. The former showed very low foaming ability.     

Synthesis and thermal properties of randomly branched poly(butylene isophthalate) containing sodium sulfonate groups

Randomly branched poly(butylene isophthalate) samples containing sodium sulfonate groups were prepared from dimethyl isophthalate, 3,5‐bis(carbomethoxycarbonyl) benzene sulfonate, tris(hydroxyethyl) isocyanurate, and 1,4‐butanediol, according to the well‐known two‐stage polycondensation procedure. The polymers, containing various amounts of branching units and ionic groups, demonstrated to be soluble in the most common organic solvents, an evidence that gelation was not reached under the polymerization conditions adopted. The thermal behavior was examined by thermogravimetric analysis and differential scanning calorimetry. The sulfonate as well as the branching units had only a limited effect on the thermal stability, which slightly decreased with respect to pure poly(butylene isophthalate). The analysis carried out using DSC technique showed that the T_m of the copolymers decreased with increasing counit content, differently from T_g, which, on the contrary, increased. Baur's equation was found to describe well the T_m‐composition data. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1374–1379, 2006     

The properties of epoxy–imide resin cured by phosphorylated diamines containing different alkyl groups on phosphorus

Cured networks of epoxy–imide resin cured with four types of phosphorylated diamine curing agents that contained different alkyl groups on phosphorus were studied. The structures of these novel phosphorus‐containing curing agents were confirmed by Mass, EA, IR, and ¹H‐NMR and ¹³C‐NMR spectra characterization. The reactivities were measured by differential scanning calorimetry (DSC). It is found that the reactivities were not affected by the types of alkyl groups in the curing agents. In thermal gravimetric analysis (TGA), those polymers that were obtained through the curing reactions between epoxy–imide resin and four curing agents (BAMP, BAEP, BAPP, and BABP) also demonstrated excellent thermal properties as well as a high char yield. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 141–147, 2002     

Preparation and surface active properties of amphipathic compounds with two sulfate groups and two lipophilic alkyl chains

These compounds with various connecting groups between the two lipophilic groups were prepared by the reaction of glycol diglycidyl ethers with long-chain alcohols, followed by sulfation with chlorosulfonic acid or with a mixture of chlorosulfonic acid and acetic acid. The Krafft point of all these new amphipathic compounds was below 0°C, and they had good water solubility. These compounds were superior in surface active properties to general anionic surfactants with one lipophilic chain and one hydrophilic group, such as sodium dodecylsulfate. The effect of the structure of the connecting group on CMC, γ_CMC, foaming properties and wetting ability was investigated. They also showed excellent lime-soap dispersing ability.     

Solid fuels, their properties, and applications

Future studies in the area of mixed solid fuels for rocket motors are predicted. It is expected the promising fuels will consist of an “active” binder and a high enthalpy oxidant, but will not contain metallic fuel. The energy indices of these fuels ensure an effective specific impulse ≈50 (kg·sec)/kg higher than that of those in use today. Ways of reducing the temperature of the gaseous combustion products of solid fuels to 300–330 K are examined, which will allow these fuels to be used in systems with traditional materials (metal, plastic, rubber, etc.). The prospects for using solid fuels with elevated combustion temperatures are studied, as well as the possibility of using the principles employed in establishing the composition of solid fuels in the synthesis of various materials. Translated fromFizika Goreniya i Vzryva, Vol. 35, No. 2, pp. 30–34, March–April 1999.     

Thermal and electrical properties of copoly(1,3,4‐oxadiazole‐ethers) containing fluorene groups

A series of aromatic copolyethers containing 1,3,4‐oxadiazole rings and fluorene groups was prepared by nucleophilic substitution polymerization technique of 9,9‐bis(4‐hydroxyphenyl)fluorene, 1 , or of different amounts of 1 and an aromatic bisphenol, such as 4,4′‐isopropylidenediphenol or phenolphthalein, with 2,5‐bis(p‐fluorophenyl)‐1,3,4‐oxadiazole. The polymers were easily soluble in polar solvents like N‐methylpyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, and chloroform and can be cast from solutions into thin flexible films. They showed high thermal stability, with decomposition temperature being above 425°C. The polymers exhibited a glass‐transition temperature in the range of 195–295°C, with a reasonable interval between glass‐transition and decomposition temperature. Electrical insulating properties of some polymer films were evaluated on the basis of dielectric constant and dielectric loss and their variation with frequency and temperature. The values of the dielectric constant at 10 kHz and 20°C were in the range of 3.16–3.25. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Compared properties of aromatic polyisophthalamides containing 5‐(4‐acetoxy‐benzamido) pendent groups

A series of aromatic polyamides containing 5‐(4‐acetoxy‐benzamido) pendent groups have been synthesized and their properties have been characterized and compared with those of related polyamides. The polyamides have weight‐ and number‐average molecular weights in the range of 36,680–65,700 and 12,685–35,490, respectively, and polydispersities in the range of 1.82–3.66. These polymers show good thermal stability comparable to traditional aromatic polyisophthalamides, with initial decomposition temperature between 270–320°C and glass transition temperature in the range of 230–270°C. Compared with related polyisophthalamides without any pendent groups, the present polymers show better solubility in certain solvents such as N‐methylpyrrolidinone and dimethylacetamide and can be cast from solutions into thin transparent flexible films having dielectric constants in the range of 3.42–4.27. The polymer films display remarkable hydrophilicity, which makes them potential candidates for use as advanced materials in humidity sensors. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 650–657, 2001     

Synthesis of water‐insoluble functional copolymers containing amide,amine, and carboxylic acid groups and their metal‐ion‐uptake properties

The crosslinked poly[N‐(3‐dimethylamino)propylmethacrylamide] [P(NDAPA)] and poly[N‐(3‐dimethylamino)propylmethacrylamide‐co‐acrylic acid] [P(NDAPA‐co‐AA)] were synthesized by radical polymerization. The resins were completely insoluble in water. The metal‐ion‐uptake properties were studied by a batch equilibrium procedure for the following metal ions: silver(I), copper(II), cadmium(II), zinc(II), lead(II), mercury(II), chromium(III), and aluminum(III). The P(NDAPA‐co‐AA) resin showed a lower metal‐ion affinity than P(NDAPA), except for Hg(II), which was retained at 71% at pH 2. At pH 5, the resin showed a higher affinity for Pb(II) (80%) and Cu(II) (60%), but its affinity was very low for Zn(II) and Cr(III). The polymer ligand–metal‐ion equilibrium was achieved during the first 20 min. By changing the pH, we found it possible to remove between 60 and 70% of Cd(II) and Zn(II) ions with (1M, 4M) HClO₄ and (1M, 4M) HNO₃. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5232–5239, 2006     

Preparation and thermal properties of liquid crystalline ionomers having mesogenic ester side chains containing three phenyl groups

A series of liquid crystalline (LC) copolymers having both the repeat units of mesogenic ester side chains containing three phenyl groups and the repeat units possessing an acid group were prepared. The acid groups of the LC copolymers were neutralized with sodium acetate to give a varying degree of neutralization. It was found that the LC properties of the ionomers depended strongly on both the relative amount of the units having the mesogenic side chains and the amount of ionic units. It was also observed that the formation of the nematic phase of the LC ionomers was suppressed by the increase in ion contents. After the analysis of the thermal data of the phase transitions, it was suggested that the transition temperatures of the LC phases of the copolymers and their ionomer forms, and the temperature ranges for the LC phases were affected by the relative amounts of both mesogenic and acidic units and by the degree of neutralization, simultaneously.     

Surface activities,biodegradability and antimicrobial properties of glucosamine derivatives containing alkyl chains

Three series of D-glucosamine derivatives containing an alkyl chain with 8 to 14 atoms, methyl 2-acylamino-2-deoxy-D-glucopyranosides,n-alkyl 2-acetylamino-2-deoxy-D-glucopyranosides andn-alkyl 2-amino-2-deoxy-D-glucopyranoside hydrochlorides, were synthesized, and their surface properties (such as surface tension, critical micelle concentration (CMC), dynamic surface tension and foaming properties), biodegradability and antimicrobial activities were evaluated.n-Alkyl 2-amino-2-deoxy-D-glucopyranoside hydrochlorides containing C8 to C12 carbon chains showed surface activities, a CMC and excellent foaming properties. The α-anomers showed a slightly lower CMC than the β-anomers, indicating less hydrophilicity of the α-anomers. On the other hand, glucosamine derivatives containing amide groups showed poor surface activities in water due to their lower solubilities in water. All glucosamine derivatives containing alkyl chains were biodegraded as well as conventional ethoxylated nonionics by activated sludge from the municipal sewage treatment plant. Methyl 2-acylamino-2-deoxy-D-glucopyranosides andn-alkyl 2-amino-2-deoxy-D-glucopyranoside hydrochlorides showed a broader spectrum of antimicrobial activity than the correspondingn-alkyl glucopyranosides. Among them the C12 derivatives showed the best results.     

The introduction of alkyl,ester, carboxylate,amino, hydroxyl,and phosphate functional groups to the surface of polyethylene

The surface of polyethylene was derivatized with ester, carboxylate, amino, hydroxyl, and phosphate functional groups. α, ω bifunctional alkanes, containing on one end a primary amine, were coupled to oxidized polyethylene through an amide linkage. Polyethylene was first oxidized with chromic acid, the carboxylate groups were converted to the acyl chloride with phosphorus pentachloride, and then reacted with a primary amine to give the covalently bound amide. The copposing ends of the bifunctional alkanes were the methyl, tertiary amine, ester, and hydroxyl groups. The ester was converted to the carboxylate by acid cleavage and the hydroxyl group converted to the phosphate by treatment first with phosphorus oxychloride and then aqueous base. Attenuated total reflection FTIR, XPS, and pH-dependent contact angle wetting were used to characterize the surfaces. The FTIR data were used to confirm the formation of the amide and to detect an undesired carboxylate/ammonium ion complex formed in the presence of trace amounts of water. XPS data were used to confirm expected changes in elemental composition and to provide quantitative estimates of the yields. Oxidation of the polyethylene introduced 5 × 10¹⁴ carboxylate groups/cm² in the 25 Å XPS sampling depth. Of these, up to 98% could be converted to the amide. The advancing contact angle data confirmed the acid/base behavior of the functional groups.     

Synthesis and properties of an alkoxysilane dye containing three electronic donor groups for nonlinear optical applications

In order to obtain an efficient hybrid inorganic–organic nonlinear optical (NLO) materials, an azo-dye containing three electronic donor groups 2,5-dimethyl-4-(4′-nitrophenylazo)phenol (DMNPAP) was synthesized and reacted with 3-isocyanatopropyl triethoxysilane (ICTES) to give an alkoxysilane dye (ICTES–DMNPAP). Molecular structural characterizations for DMNPAP and ICTES–DMNPAP were investigated by elemental analysis, ¹H NMR, FTIR, UV–visible spectra and differential scanning calorimetry (DSC). The alkoxysilane dye could be hydrolyzed and polymerized in the presence of water, and then transparent hybrid films could be fabricated by spin coating on the indium–tin-oxide (ITO) glass substrates. Compared with the dye 4-nitro-4′-hydroxy-azobenzene (NHA) containing only one hydroxyl as donor group, DMNPAP exhibited larger β_CTμ_g value measured by solvatochromic method, and second harmonic generation (SHG) measurement of the hybrid films was in agreement with the result.