Effect of structure on properties of aromatic-aliphatic polybenzimidazoles

Homopolymers and copolymers containing the polybenzimidazoles ring were prepared from terephthalic acid (T), fumaric acid (F), and 3,3′-diaminobenzidine tetrachloride (DAB) in polyphosphoric acid. The polymers were characterized by viscometry, infrared spectroscopy, and nitrogen analyses. The effect of copolymer composition on the ultraviolet and visible spectra, solubility in various solvents, and density was also investigated. The relative thermal stability of the various polybenzimidazoles was investigated by using dynamic thermogravimetry in air. Polybenzimidazole derived from terephthalic acid was most stable, and the introduction of aliphatic residues resulted in a decrease in thermal stability. However, the homopolymer of fumaric acid was more stable than the copolymers of fumaric acid and terephthalic acid.     

Effect of structure on properties of aromatic-aliphatic polybenzimidazoles. II

Polybenzimidazoles (PBI) with p-phenylene and/or cis-vinylene groups in the backbone were prepared from terephthalic acid (T), maleic acid (M), and 3,3′ diamino-benzidine tetrahydrochloride dihydrate (DAB) in poly(phosphoric acid) (PPA). Five polymer samples were prepared by varying the M:T molar ratios in the following order: 1:0, 1:1, 2:1, 1:2, and 1:4. The polymers were characterized by intrinsic viscosity, density, electronic fluorescence, and IR spectra. The effect of composition on the solubility of the polymers in various organic solvents was also investigated. The relative thermal stability of the polymers was evaluated by dynamic thermogravimetry in air and polybenzimidazoles (PBI) with cis-vinylene groups were found to be less stable.     

Synthesis and properties of new polybenzimidazoles and N-phenyl polybenzimidazoles with flexibilizing spacers on the polymer backbone

Several new polybenzimidazoles (PBIs) and N-phenyl PBIs were synthesized by high temperature solution polycondensation techniques. Three different tetramine hydrochlorides and one N-phenyl tetramine hydrochloride were condensed independently with p-phenylenedioxydiacetic acid (PDDA), 2,2′-[isopropylidene bis(p-phenyleneoxy)] diacetic acid (bisacid A₂) and 2,2′-[sulfonyl bis(p-phenyleneoxy)] diacetic acid (bisacid S) in polyphosphoric acid (PPA) at high temperatures. The polymers were obtained in 55–65% yield with inherent viscosities in the range 0.58–0.96 dL/g. Four model benzimidazoles (MBI) were also synthesized to confirm the formation of polybenzimidazoles. The PBIs and MBIs were characterized by infrared spectroscopy and elemental analysis. The properties of the polymers such as solubility, density, crystallinity, and thermal, thermoxidative, and isothermal stabilities were studied.     

TGA–MS degradation studies of some new aliphatic–aromatic polybenzimidazoles

The degradation of a series of polybenzimidazoles containing metylene groups in the chain was studied by TGA and MS. On heating the polymer derived from m-phenylenediacetic acid and 3,3′-diaminobenzidine to about 560°C in argon, partial fast decomposition into a solid sublimate was observed. The sublimate consisted of a mixture of fractions derived from the breaking of the chain at the methylene bonds. These methylene groups can be preoxidized at 250°C to carbonyl groups, eliminating thereby this mode of decomposition. At temperature higher than 560°C, gaseous products similar to those of the corresponding all-aromatic PBI are obtained.     

Synthesis,structure and some properties of a new polyalcohol

A new polyalcohol (CH₂CH₂CH(OH))_n was synthesized from 1:1 ethylene/carbon monoxide alternating copolymer (polyketone) by reduction with sodium borohydride. Some structural and chemical properties are described.     

Soluble polybenzimidazoles with intrinsic porosity: Synthesis,structure, properties and processability

We have explored two novel comonomers, namely, 4,16‐dicarboxyl[2.2]paracyclophane and 5,5′,6,6′‐tetraamino‐3,3,3′,3′‐tetramethyl‐1,1′‐spirobi[indane], for the synthesis of co‐polybenzimidazoles (co‐PBIs) with intrinsic porosity. Both these monomers possess twisted structures that can lead to “awkward” macromolecular shapes that cannot pack efficiently. The consequences of introducing these two monomers on the structure and properties of PBIs are reported. The random copolymers synthesized are amorphous and possess glass transition temperatures (T_gs) greater than 400 °C. T_g decreases with increasing comonomer content indicating an increase in fractional free volume. The copolymers have low surface area. TEM and BET measurements show evidence of mesopore formation. The copolymers show significant carbon dioxide adsorption. Single chain molecular dynamics simulation of 24‐mer repeat units shows intramolecular void spaces arising as a result of distorted polymer chain with reduced conformational mobility. These studies define a new synthetic strategy for “bottoms‐up” synthesis of PBIs with intrinsic porosity. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1046–1057     

Study of the ultraviolet spectra of some new polybenzimidazoles and model compounds of the benzimidazole series

Summary A study was made of the ultraviolet absorption spectra of some new polybenzimidazoles, containing either aromatic or aliphatic dicarboxylic acid moieties, and also of their model compounds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 184–187, January, 1965     

Preparation and properties of polybenzimidazoles containing cardo groups

Several polybenzimidazoles containing cardo groups were prepared: A cardodicarboxylic acid, 9,9-bis(4-carboxyphenyl)fluorene, and two cardotetramines, 9,9-bis(3,4-diaminophenyl)fluorene and 9,9-bis(3,4-diaminophenyl)10-anthrone. The cardodicarboxylic acid was condensed with aromatic tetramines and the cardotetramines were condensed with aromatic dicarboxylic acids. Prior to polymer synthesis two model compounds, 9,9-bis[4,(2-benzimidazolyl)phenyl]fluorene and 2,2′-diphenyl-5,5′-(9,9-fluorenediyl)-bibenzimidazole were prepared and characterized by spectral methods. The polymers were obtained in 60–70% yield and showed reduced viscosity in the range of 0.7–1.1 dL/g. They were soluble in dimethyl formamide (DMF) and chlorinated solvents like tetrachlorethane. The thermal stabilities of these cardopolymers were superior to noncardopoly-benzimidazoles.     

Molecular mass characteristics and solution behavior of some cardo polybenzimidazoles

The behavior of dilute solutions of cardo polybenzimidazoles based on 3,3′4,4′-tetraaminodiphenyl ether; 3,3′,4,4′-tetraaminodiphenyl sulfone; and 4,4′-diphenylphthalidedicarboxylic acid in solvents of various natures has been studied by the methods of dynamic light scattering, sedimentation, and viscometry. All of the polymers have been found to contain a microgel fraction. For each fraction, the diffusion coefficient and the particle size are determined. The experimental characteristics of macromolecules correspond to the conformational rigidity calculated by a computer simulation procedure.     

Effects of adjacent groups of benzimidazole on antioxidation of polybenzimidazoles

The chemical oxidative stabilities of poly(2,2-(m-phenylene)-5,5-bibenzimidazole) (PBI-ph), poly(2,5-benzimidazole) (ABPBI), poly(2,2′-hexyl-5,5′-bibenzimidazole) (PBI-hex), and poly(2,2′-imidazole-5,5′-bibenzimidazole) (PBI-imi) are studied. By means of FTIR and ¹HNMR analysis, more information about the degradation process of PBI-ph is found as: CH₂ groups are left in the residual polymers; after the N-H bond and the trisubstituted benzene ring are oxidized by oxidative free radicals, the meta-phenylene is relatively stable. Through Fenton tests, the chemical oxidative stabilities of these PBIs are compared and results show that PBI-ph is the stablest material while PBI-imi is the unstablest one. Through FTIR analysis, the structure changes to those degraded PBIs are compared. The conjugated structure formed between meta-phenyl and benzimidazole can protect the main chain of PBI-ph from the attack of oxidative free radicals. Additionally, effects of acid on PBI-ph degradation rate are evaluated and the results show that phosphoric acid can slow down the chemical oxidative degradation.     

Synthesis and properties of some new polyazomethine-urethanes

Two new bisazomethine diols were prepared from terephthalaldehyde and aromatic or aliphatic aminoalcohols. The structure of the diols with bisazomethine moieties was confirmed by ¹H-NMR, IR, UV spectroscopy and elemental analysis. Bisazomethine aliphatic diol exhibited a smectic phase that has been identified by means of polarizing microscopy and differential scanning calorimetry. By using these diols as partners in polyaddition reaction between poly(tetramethylene oxide)diol of 2000 average molecular weight, tolylene-2,4-diisocyanate (as 2,4- and 2,6-TDI, 80:20 v/v isomers mixture) and bisazomethine diol (1:3:2 molar ratio), two polyazomethine-urethanes were synthesized. Polyazomethine-urethanes with a higher concentration of poly-Schiff's base units were also obtained by reacting the above bisazomethine diols with the same diisocyanate (1:1 molar ratio). All polymers were characterized by viscometry, elemental analysis, IR, UV, ¹H-NMR spectroscopy and TGA techniques.     

Molecular properties of some new cyclic ethynylsilanes

Summary The question about conjugation between -CC- and -SiMe ₂- groups in [-CC-SiMe ₂-] _n withn=4 and 5 has been investigated by AM 1 calculations which show strong conjugation. In the structure determination (AM 1, X-ray) and in the Raman spectra no significant differences to normal values are observed. The NMR Si-Ccoupling constant and UV spectra are presented.This paper is dedicated to Professor Dr. mult. Victor Gutmann on the occasion of his 70th birthday with warmest personal wishes     

N-substitution of polybenzimidazoles: Synthesis and evaluation of physical properties

Series of N-substituted polybenzimidazoles (PBI) were synthesized using selective alkyl groups with varying bulk and flexibility, viz., methyl, n-butyl, methylene trimethylsilane and 4-tert-butylbenzyl. PBI-I based on 3,3′-diaminobenzidine (DAB) and isophthalic acid and PBI-BuI based on DAB and 5-tert-butyl isophthalic acid were chosen for N-substitution. Structural characterizations of substituted polymers by FT-IR and ¹H NMR revealed elimination of hydrogen bonding. Evaluation of their physical properties revealed that N-substitution rendered better solvent solubility in common organic solvents, more open polymer matrix, but reduced thermal properties in comparison to their respective parent PBI. 4-tert-butylbenzyl, methylene trimethylsilane or n-butyl group substituted polymers were soluble even in chlorinated solvents (CHCl₃ and TCE). Substantial variations in gas permeability of inert gases, He and Ar and attractive P_He/P_Ar selectivity, especially after methyl group substitution depicted potential of these materials for gas separation.     

Synthesis,characterization, optical,thermal and electrical properties of polybenzimidazoles

The variation of dielectric constant and dielectric loss of two novel polybenzimidazole (PBI) were studied at constant temperature with variable frequency. The polymers have shown maximum dielectric constant at low applied frequency 50 Hz at 393 K due to the space charge polarization. The AC conductivity and activation energy of polymers were arrived from dielectric constant and dielectric loss values. PBIs were synthesized by the oxidative polycondensation of benzimidazole monomers, 2-(1H-benzo [d] imidazole-2-yl)-4-bromophenol (BIBP), and 2-(1H-benzo [d] imidazole-2-yl)-6-methoxyphenol (BIMP) in an aqueous alkaline medium using NaOCl as oxidant. The monomers and polymers were characterized by various spectroscopic techniques. Fluorescence spectra of monomers and polymers showed their λ _max emission in the region of 472–479 and 463–472 nm respectively. The electrical conductivities of iodine doped polybenzimidazoles were measured by four-point probe technique and it increases with increase in iodine vapour contact time. The electrical conductivity values were correlated with the charge density on imidazole nitrogen obtained from Huckel calculation method. Both the PBI are having reasonably good thermal stability and are shown by high carbines residues of around 40% at 500°C in thermogravimetric analysis.     

Thermodynamic and adsorption properties of semiinterpenetrating polymer networks based on polybenzimidazoles and polyaminoimide resin

Thermodynamic characteristics of adsorption of organic compounds on semiinterpenetrating networks based on polybenzimidazoles and polyaminoimide resin with different compositions were studied at small coverages using inverse gas chromatography. The following characteristics were determined: adsorption equilibrium constants (specific retention volumes) of substances of different classes (n-alkanes, aromatic hydrocarbons, ethers, ketones, alcohols, and nitrogen- and halogen-containing compounds), appropriate changes in differential molar internal energy and Helmholtz potential, and changes in standard molar entropy of the sorbates. The contributions of the molecular fragments to the heat of adsorption were calculated. The adsorption properties of the semiinterpenetrating networks based on polybenzimidazoles and polyaminoimide resin differ from those of the starting polymeric materials and their physical mixtures with the similar composition. Unlike graphitized thermal carbon black (nonspecific adsorbent), the network and starting materials manifest the specific properties (electron-donating and electron-accepting). The difference in the thermodynamic characteristics of adsorption on the semiinterpenetrating polymeric networks with different compositions is determined by the size and geometry of interphase regions.