A copolymer of poly[2,2′‐(m‐phenylene)‐5,5′‐ bibenzimidazole] and poly(2,5‐benzimidazole) for high‐temperature proton‐conducting membranes

A novel copolymer of polybenzimidazoles was prepared by copolymerization of 3,3′‐diaminobenzidine tetrahydrochloride, 3,4‐diaminobenzoic acid and isophthalic acid in polyphosphoric acid at 200 °C. The polymerization could be performed within 90–110 min with the assistance of microwave irradiation. The solubility of the copolymer obtained in N,N‐dimethylacetamide (DMAc) was improved compared with those of poly[2,2′‐(m‐phenylene)‐5,5′‐bibenzimidazole] and poly(2,5‐benzimidazole). Thus copolymer membranes could be readily prepared by dissolving the copolymer powders in DMAc with refluxing under ambient pressure. The decomposition temperature of the copolymer was about 520 °C in air according to thermogravimetric analysis data. The proton conductivity and mechanical strength of the phosphoric acid‐doped copolymer membranes were investigated at elevated temperatures. A conductivity of 0.09 S cm^?1 at 180 °C and a tensile stress at break of 5.9 MPa at 120 °C were achieved for the acid‐doped copolymer membranes by doping acids in a 75 wt% H₃PO₄ solution. Copyright © 2010 Society of Chemical Industry     

Preparation of polyamides containing para-linked dimethylbiphenylene moieties

A series of wholly aromatic polyamides containing 3,3′-dimethylbiphenyl-4,4′-dicarboxylic acid (P-DMBA) and 3,4′-dimethylbiphenyl-4,3′-dicarboxylic acid (Q-DMBA) was prepared by the direct polycondensation method using triphenylphosphite and pyridine. Most of the polymers are readily soluble in polar aprotic solvents such as N-methyl-2-pyrrolidone (NMP), N,N′-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), pyridine (py), and m-cresol and could be cast into tough and flexible films. The solubilities of copolyamides containing P-DMBA and Q-DMBA as acid components were remarkably improved. These were characterized by inherent viscosity, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical spectrometry (DMS) measurements. The glass transition temperatures of these polymers were in the range of 200–300°C and the 5% weight loss temperatures were 430–470°C. Films prepared by casting from polymer solutions exhibited good tensile properties. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:847–853, 1998     

Poly(P-benzoquinono)diimidazoles from two-ring aromatic dicarboxylic acids

New poly(p-benzoquinono)diimidazoles have been synthesized by one-stage polycondensation in polyphosphoric acid of 2,3,5,6-tetraamino-p-benzoquinone with diphenyl-4,4′-dicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid, 4,4′-oxydibenzoic acid, and 4,4′-sulfonyldibenzoic acid. The polymers were characterized by infrared and ultraviolet spectral study, viscometric measurements, and thermal analysis. The effects of introducing flexibilizing links such as ? CH₂? ,? O? , and ? SO₂? in the backbone of the polymers, on their thermal stability and solubility were studied.     

Poly(benzoxazinone-imide)s and poly(benzoxazinone-phenylquinoxaline-imide-amide)s containing hexafluoroisopropylidene units

Fluorine-containing poly(benzoxazinone-imide)s and poly(benzoxazinone-phenyl-quinoxaline-imide-amide)s have been synthesized by solution polycondensation of di-acid dichlorides containing imide and hexafluoroisopropylidene groups with 4,4′-di-aminodiphenylmethane-3,3′-dicarboxylic acid or with mixtures of the latter with a di-amino phenylquinoxaline. These polymers show high thermal stability, the decomposition temperatures being in the range of 450–470°C. Transparent flexible films were cast from the solutions of the corresponding polyamidic acid intermediates that after thermal cyclization showed low dielectric constant which recommends them for future applications in microelectronics.     

联苯-4,4′-二甲酸合成研究

研究联苯-4,4′-二甲酸的合成工艺,以对硝基甲苯为原料,经氧化、还原和重氮化-偶联反应制备联苯-4,4′-二甲酸。重点研究了重氮反应中滴加亚硝酸对反应的影响。以对硝基甲苯计,总收率为66.6%,联苯-4,4′-二甲酸的(HPLC)纯度为98.7%。     

Electrochemical study on the effect of bipyridine dicarboxylic acid and its cobalt complex on the corrosion behaviour of carbon steel in acidic medium

The 2,2′-bipyridine-3,3′-dicarboxylic acid (bida) and its cobalt complex (Co-bida) were tested as corrosion inhibitors for N80 carbon steel in sulphuric acid solution by electrochemical polarization and electrochemical impedance spectroscopy method. The results indicate that the complex and ligand inhibit the corrosion of mild steel in H₂SO₄ solutions and the extent of inhibition increases with inhibitor concentration and decreases with temperature. The inhibition efficiency of the inhibitors follows the trend Co-bida > bida. A mixed-inhibition mechanism is proposed for the inhibitive effects of the compounds. The adsorption characteristics of the inhibitors were approximated by Temkin isotherm. Morphological study of the carbon steel electrode surface was undertaken by scanning electron microscope and the interfacial species formed on the surface in the presence of inhibitors analyzed by infrared spectroscopy.     

Resin. III. Synthesis,characterization, and ion-exchange properties of a 2,2′-dihydroxybiphenyl–formaldehyde copolymer resin

A 2,2′-dihydroxybiphenyl–formaldehyde copolymer, synthesized by the condensation of 2,2′-dihydroxybiphenyl with CH₂O in the presence of an acid catalyst, proved to be a selective chelating ion-exchange copolymer for certain metals. The chelating ion-exchange properties of this copolymer were studied for Fe(III), Cu(II), Ni(II), Zn(II), Cd(II), and Pb(II) ions. A batch equilibrium method was employed in the study of the selectivity of metal ion uptake, involving the measurements of the distribution of a given metal ion between the copolymer sample and the solution containing the metal ion. The study was carried out over a wide pH range and in media of various ionic strengths. The copolymer showed a higher selectivity for Fe(III), Cu(II), and Ni(II) ions than for Co(II), Zn(II), Cd(II), and Pb(II) ions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

制备手性联萘二甲酸的工艺改进

从手性联萘酚原料出发,通过3步反应合成标题化合物,总收率62%,产品光学纯度>99%。其中关键反应手性2,2’-二(三氟甲磺酸基)-1,1’-联萘与CO的直接羰基化反应,经过条件优化,可使用CO气袋完成,避免了昂贵的高压反应设备的使用。各步反应操作简便,条件温和,适合工业化生产。     

Structure and properties of ethylene—methacrylic acid copolymers and their sodium salts: Dielectric and proton magnetic relaxation studies

Dielectric and proton magnetic relaxation data have been obtained for an ethylene-methacrylic acid copolymer (containing about 4 mole% methacrylic acid units) and its 53% ionised sodium salt. The degrees of crystallinity and percentage ionisation of the samples investigated were estimated by infra-red methods. The dielectric results were obtained principally in the frequency range 100 Hz to 10 kHz and at temperatures ranging from 80° to – 120°. A few results are also reported at frequencies down to 0·1 Hz and up to 100 MHz. For the acid copolymer, two dielectric loss regions are observed and these are correlated with the reported mechanical β′- and γa-processes respectively. The partly ionised copolymer exhibits three dielectric relaxation regions which correlate with the mechanical α-, β- and γa-relaxations respectively. In addition, a dielectric peak appears at about —40° in the presence of absorbed water, a result similar to that found in the polyamides. The proton magnetic relaxation results were obtained by pulse methods which yielded the spin-lattice relaxation times T₁ (at 30 MHz) and T_1p (at kilohertz frequencies) as a function of temperature from ?180° to 100°. Two components were generally observed for T_1p. For the acid copolymer the β′- and γ-processes have been observed from these results, as well as a lower-temperature (δ) process which has not been detected by the mechanical or dielectric methods. For the sodium salt the γ- and δ-processes are also found, in addition to a high-temperature process in the region of the merged α- and β-processes. The present data are consistent with previous assignments for the β′-, α-, β- and γ-processes. The ‘water’ relaxation appears to involve some rotation of water molecules, or of ionic segments to which water molecules are attached, in the proposed ionic domains. The δ-process is ascribed to the rotations of methyl groups present in the methacrylic acid units.     

PHOTO-DEGRADATION OF HYDROPHOBIC DERIVATIVES OF PYRIDINECARBOXYLIC ACID AS COPPER EXTRACTANTS FROM CHLORIDE MEDIA

ABSTRACT

The photo-stability of 2-ethylhexyl pyridine-3-carboxylate and N,N′-di(2-ethylhexyl)pyridine-3,5-dicarboxamide as the model extractants of copper from chloride media were studied and compared with the photo-stability of di(2-ethylhexyl) pyridine-3,5-dicarboxylate, N,N,N′,N′-tetrahexylpyridine-3,5-dicarboxamide and the hydroxyoxime copper extractants. Also the resistance against the UV light the copper(II) complexes of tested extractants were done. The obtained results of photo-degradation indicate that the UV light degraded amide derivatives and esters of pyridine-3,5-dicarboxylic acid and pyridine-3-carboxylic acid. A comparison of the photo-stability of oximes and derivatives of pyridine-3,5-dicarboxylic acid and pyridine-3-carboxylic acid indicates that all tested derivatives of pyridinecarboxylic acid are more stable than hydroxyoxime copper extractants. The copper complexes of derivatives of pyridinecarboxylic acid are less stable than the copper complexes of hydroxyoxime.     

Copolyimides new polybenzoxazinone-imides

New polybenzoxazinone-imides have been synthesized by cyclopolycondensation reaction of 4,4′-diaminodiphenylmethane-3,3′-dicarboxylic acid with diacid chlorides containing preformed imide rings. The low temperature solution polycondensation technique, used in these experiments, afforded poly(amic acids) of high molecular weight in the first step, which subsequently underwent thermal cyclodehydration at 200–300°C to give polybenzoxazinone-imides in the second step. The obtained polymers have been characterized by IR absorption, elemental and thermogravimetric analyses. From 10% polymer solution flexible and transparent films have been cast with good mechanical and insulating properties.     

Tris(3-aminophenyl)Phosphine oxide-based nadimide resins. II

A series of phosphorus-containing nadimide end-capped resins having different backbones was prepared by reacting endo-5-norbornene-2-3-dicarboxylic acid anhydride (nadic anhydride), pyromellitic dianhydride (PMDA)/3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride (BTDA)/2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6F) and tris(3-aminophenyl)phosphine oxide (TAP) in glacial acetic acid/acetone. Structural characterization of the resins was done by elemental analysis, FTIR, and ¹H-NMR. Thermogravimetric studies revealed a multistep decomposition reaction for uncured resins. Residual weight at 800°C in nitrogen was found to be 50–60%. Resins cured at 300°C for 1 h in air atmosphere were stable up to 440 ± 20°C and decomposed in a single step above this temperature. The char yields of cured resins were in the range 63–71.5%. © 1992 John Wiley & Sons, Inc.     

Silatrane based imide resins: synthesis and characterization

A series of silatrane based imide resins having different end-caps were prepared by reacting 1-(3-aminopropyl)silatrane with 5-norbornene-endo-2,3-dicarboxylic anhydride (nadic anhydride), 5-methyl-5-norbornene-2,3-dicarboxylic anhydride (methyl nadic anhydride), hexachloronadic anhydride, maleic anhydride, benzophenone-3,3′,4,4′-tetracarboxylic dianhydride or pyromellitic dianhydride in dimethylacetamide. Structural characterisation of the resins was done by elemental analysis and IR. In DSC traces of these resins, an exothermic transition associated with crosslinking was observed above 230°C. Thermogravimetric studies revealed a multistep decomposition reaction. Residual weight at 800°C in nitrogen was found to depend on the backbone structure and ranged from 32–60%.     

Conjugates of poly(N‐isopropyl acrylamide‐co‐acrylic acid) with alanine monopeptide,dipeptide, and tripeptide

A random copolymer of N‐isopropyl acrylamide (NIPAAm) and acrylic acid (AAc) with an AAc content of 3.1 ± 0.19 mmol of carboxylic acid groups per gram of the copolymer and with a number‐average molecular weight of 1400 was synthesized by free‐radical polymerization with 2,2′‐azoisobutyronitrile in dimethylformamide. Then, monopeptide, dipeptide, and tripeptide (i.e., alanine) conjugates of this copolymer were prepared with their carboxyl‐end‐protected (with methyl ester hydrochloride) form of alanine, with a water‐soluble carbodiimide. Of the carboxylic acids, 93, 69, and 57% were conjugated (loaded) with alanine at the monopeptide, dipeptide, and tripeptide conjugation steps, respectively. The chemical structures of the copolymer and conjugates were analyzed by Fourier transform infrared and ¹H‐NMR, which revealed the conjugate formation. Amino acid conjugation caused significant decreases in the lower critical solution temperatures (LCST) of the copolymer, especially at pH 7.4. The LCST values of the dipeptide and tripeptide conjugates of poly(NIPAAm‐co‐AAc) at both pH 4.0 and 7.4 shifted to significantly higher temperatures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2012–2019, 2003     

Synthesis and characterization of new sulfonated copolytriazoles and their proton exchange membrane properties

This work reports the synthesis and characterization of a series of new sulfonated copolytriazoles. The polymers were prepared by CuI catalyzed 1,3-cycloaddition reaction of an equimolar amount of a dialkyne monomer, 1,3-diethynylbenzene and a mixture of two diazide monomers, namely, 4,4′-diazidodiphenyl ether and 4,4′-diazido-2,2′-stilbenedisulfonic acid disodium salt. The copolymers showed high inherent viscosity indicating the formation of high molar mass product. The copolymers were characterized by Fourier transform infrared and proton nuclear magnetic resonance spectroscopic techniques. The copolymer membranes displayed moderate water uptake, high dimensional, mechanical, and thermal stability. Transmission electron microscopy micrographs displayed excellent phase-separated morphology along with very fine ionic clusters. The copolymer PTEOSH-90 (90% degree of sulfonation) showed much higher proton conductivity value which is up to 196 mS cm⁻¹ at 80 °C in completely hydrated condition compared to that of Nafion (165 mS cm⁻¹). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48514.     

2，2＇-二羟基-1，1-联萘-4，4＇-二羧酸的合成

BINOL类配体是一类重要的具有C2轴、不含手性中心的不对称联芳香化合物。文章将3-硝基-1-萘酸用亚硫酸铁还原成胺,并生成稳定的硫酸盐,之后重氮化,用沸腾的稀硫酸水解成酚,再成酯,最后用三氯化铁在水中偶联合成化合物2,2’-二羟基-1,1＇-联二萘-4,4’-二羧酸。并探讨了各反应过程中的影响因素。     

Physical and relaxation properties of flame-sprayed ethylene-methacrylic acid copolymer

A range of physical and chemical properties of flame-sprayed ethylenemethacrylic acid copolymer (EMAA) were assessed, following different processing conditions. Coatings were produced at a range of specific temperatures by varying the propane flow rate and gun traverse rate. The flame spraying process oxidizes the EMAA copolymer during processing, the extent of oxidation increasing with greater deposition temperatures. Coatings were scanned using dielectric relaxation spectroscopy at a frequency range from 10² to 10⁶ Hz over a temperature interval of -20 to 85°C. The glass transition temperature (usually denoted as the β′ relaxation in this system), is attributed to the microBrownian motion of long chain segments in the amorphous phase and is found to decrease with increasing deposit temperature. The oxidation process appears to reduce the position of the β relaxation due to chain scission. The molecular weight for the EMAA powder was reduced from 22,693 g/mol to 9302 g/mol when deposited at 271°C as shown by gel permeation chromatography. Despite the decrease in chain length, the activation energies for β′ relaxation increased with increasing coating temperatures. This is attributed to the increased polarity of the oxidized coatings resulting in greater intermolecular association, which outweighs the decreased chain length.     

Forced torsional properties of PMR composites with varying nadic ester concentrations and processing histories

PMR polyimide resin was prepared from 4,4′-methylenedianiline (MDA), the dimethyl ester of 3,3′,4,4′- benzophenonetetracarboxylic acid (BTDE) and the monomethyl ester of 5-norbornene-2,3-dicarboxylic acid (NE). The NE group serves as a chain terminator and crosslinking site. PMR/Celion 6000 composites were fabricated from resins having varying NE concentrations using two molding processes, and the laminates characterized in forced torsion. Glass transition temperatures (T_g) of 360–390°C were observed in the crosslinked resins, as compared with the literature value of 284°C reported for the uncrosslinked systemT_g did not decrease with decreasing NE concentrations over the range from 2.0 to 1.25 moles. Stoichiometry, within the range studied, showed little influence on shear properties; however, a 25% variation in matrix shear modulus with processing was observed. The G₁₂ values determined in forced torsion were in excellent agreement with those reported from tensile tests of ±45° laminates. A branching and possible secondary crosslink mechanism is proposed based on dynamic mechanical behavior and infrared spectra of the composites.     

POSS-enhanced shape-memory copolymer of polynorbornene derivate and polycyclooctene through ring-opening metathesis polymerization

A copolymer consisting of polycyclooctene (PCOE) and poly(5-norbornene-exo,exo-2,3-dicarboxylic anhydride) (PNBEDCA) was firstly synthesized through ring-opening metathesis polymerization, and then the obtained copolymer P(COE-co-NBEDCA) was readily modified by grafting reaction of NBEDCA units with polyhedral oligomeric silsesquioxanes (POSS) to afford a novel functionalized copolymer P(COE-co-NBEDCA-g-POSS), in which carboxyl and POSS as side chains attached to polynorbornene backbones. The copolymers were characterized by means of thermogravimetry, wide-angle X-ray diffraction, and stress–strain measurements. The shape memory effect of the copolymer was evaluated by dynamical mechanical analysis and shape recovery speed. Having the properties of the good shape fixity and the large shape recovery, the POSS-enhanced copolymer is expected to use as a potential shape memory material.     

The STOBBE Condensation,Part IX. The cyclisation of (E)-3-Methoxycarbonyl-4-(5′-methyl-2′-thienyl)-but-3-enoic acid,and α,β-bis-(5-methyl thenylidene)-succinic anhydride,to benzothiophen derivatives

The condensation of 5-methyl-thiophen-2-aldehyde with dimethyl succinate in the presence of potassium t-butoxide or sodium hydride gave predominantly (E)-3-methoxy-carbonyl-4-(5′-methyl-2′-thienyl)-but-3-enoic acid 1a , whose configuration is proved by cyclisation with sodium acetate in acetic anhydride to the corresponding benzothiophen derivatives 2 . Alcoholysis of the derived (E)-carboxy-4-(5′-methyl-2′-thienyl)-but-3-enoic anhydride 3 gives the half-ester 1c which is isomeric with the half-ester 1a . Condensation also gave the α,β-bis-(5-methyl thenylidene)-succinic acid 4a in small amounts. The derived anhydride 5 yields on pyrolysis 4-(5′methyl-2′-thienyl)-2-methyl-benzothiophen-5,6-dicarboxylic anhydride 6 .