Molecular orbital conformational energy calculations of the aromatic heterocyclic poly(5,5′-bibenzoxazole-2,2′ diyl-1,4-phenylene) and poly(2,5-benzoxazole)

Interest in potential high-performance polymers, leading to characterization and development of the rodlike poly(p-phenylene benzobisoxazoles) (PBO) and poly(p-phenylene benzobisthiazoles) (PBT), has recently been extended to a related group of polymers referred to as AAPBO, ABPBO, AAPBT, and ABPBT. In this study, geometry-optimized CNDO/2 molecular orbital calculations have been carried out on AAPBO and ABPBO model compounds to determine conformational energies as a function of rotation about each type of rotatable bond within the repeat units. For AAPBO, which contains two types of rotatable bonds per repeat unit, the bond between the benzoxazole group and p-phenylene group prefers the coplanar conformation with a barrier to free rotation of 2.1 kcal mol^?1, while the bond between the benzoxazole groups prefers a conformation approximately 60 degrees away from coplanarity with a barrier to coplanarity and to free rotation of 3.6 kcal mol^?1. For ABPBO, which contains only the former type of rotatable bond per repeat unit, the coplanar conformations were preferred with a barrier to free rotation of 1.6 kcal mol^?1. These results are in excellent agreement with the results of both theoretical and experimental studies on the structurally analogous PBO. They are also consistent with the liquid crystalline behavior found for ABPBO but not for AAPBO.     

Fabrication of uvioresistant poly(p-phenylene benzobisoxazole) fibers based on hydrogen bond

The poly(p-phenylene benzobisoxazole) (PBO) fiber with excellent performance is vulnerable to the irradiation of UV light, which significantly limits their application in advanced composites. Therefore, finding feasible and efficient ways to improve the uvioresistant properties of PBO fiber is of significance. In this work, a facile one-pot method is developed for continuously preparing the PBO/poly(2,5-dihydroxy-1, 4-phenylpyridimidazole) (PIPD) copolymer fiber to greatly enhance the anti-UV properties of PBO fibers. The experimental results demonstrate that the fabricated PBO/PIPD copolymer fiber (molar ratio of 7:1) with greatly improved surface wetting properties (the maximum increase can reach about 179%) possesses satisfactory and desired uvioresistant performance, which is 30.8% higher than that of pure PBO fibers after 480 h UV aging irradiation. The fabricated PBO/PIPD copolymer fiber with improved UV stability has the potential to be applied to many important application areas even in a severe and harsh environment. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48432.     

Synthesis and characterization of a rigid-rod dihydroxy poly(<Emphasis Type="Italic">p</Emphasis>-phenylene benzobisoxazole) fiber with excellent surface and axial compression properties

A series of dihydroxy poly(p-phenylene benzobisoxazole) (DHPBO) were prepared by introducing binary hydroxyl polar groups into poly(p-phenylene benzoxazole) PBO macromolecular chains and the effects of hydroxyl polar groups on surface wettability, interfacial adhesion and axial compression property of PBO fiber were investigated. Contact angle measurement showed that the wetting process both for water and for ethanol on DHPBO fibers were obviously shorter than that on PBO fibers, implying DHPBO fibers have a higher surface free energy. Meanwhile, single fiber pull-out test showed that DHPBO fibers had higher interfacial shear strength than that of PBO fibers. Scanning electron microscope proved that there was more resin remained on the surface of DHPBO fibers than on PBO fibers after pull-out test. Furthermore, axial compression bending test showed that the introduction of binary hydroxyl groups into macromolecular chains apparently improved the equivalent bending modulus of DHPBO fibers.     

Microstructural investigations of PBT/nylon 6,6 composites

The microstructure of composites made from blends of poly(p-phenylene benzobisthiazole) [PBT] and nylon 6,6 has been investigated with wide-angle X-ray diffraction, selected area electron diffraction, and small-angle X-ray scattering techniques. The composite samples investigated were spun in both fiber and film forms dilute solutions of methane sulfonic acid. The structure of the composites was found to be a microfibrillar network of PBT in a matrix of partially crystalline nylon 6,6. The diameters of the PBT microfibrils were in the range of 30 to 70 Å.     

Synthesis of novel single-walled carbon nanotubes/poly (<Emphasis Type="Italic">p</Emphasis>-phenylene benzobisoxazole) nanocomposite

Poly (p-phenylene benzobisoxazole) (PBO) fibers are some of the strongest organic polymer fibers. However, the introduction of single-walled carbon nanotubes (SWNT) into the PBO backbone might lead to improvements in their alignment and physical properties. Therefore, SWNT was cut and functionalized by three oxidative cutting methods. After cutting, three different types of SWNT were obtained. Furthermore, copolymerization of SWNTs with PBO polymer was successfully carried out in a mixed solvent of polyphosphoric acid and methanesulfonic acid. The SWNTs were homogeneously distributed throughout the films of copolymerized products, as determined by Raman spectroscopy. The benzoxazole moieties could be formed between the carboxyl of SWNTs and o-aminophenol derivatives of PBO polymer. The length of SWNTs affected the dispersion and reaction activity. Short SWNTs could react with the PBO polymer more easily and form more covalent bonds.     

Compressive behaviour of rigid rod polymer fibres and their adhesion to composite matrixes

Abstract

The deformation behaviour of the new high performance polymer fibres, poly(p-phenylene benzobisoxazole) (PBO) and polypyridobisimidazole (PIPD) and their adhesion to an epoxy composite matrix have been investigated. Both fibres give well defined Raman spectra, and the deformation micromechanics of PBO and PIPD single fibres and composites were studied from stress induced Raman band shifts. Single fibre stress-strain curves were determined in both tension and compression, thus providing an estimate of the compressive strength of these fibres. It was found that the PIPD fibre has a higher compressive strength (~1 GPa) than PBO (~0·3 GPa) and other high performance polymer fibres, because hydrogen bond formation is possible between PIPD molecules. It has been shown that when PBO and PIPD fibres are incorporated into an epoxy resin matrix, the resulting composites show very different interfacial failure mechanisms. The fibre strain distribution in the PBO-epoxy composites follows that predicted by the full bonding, shear lag model at low matrix strains, but deviations occur at higher matrix strains due to debonding at the fibre/matrix interface. For PIPD-epoxy composites, however, no debonding was observed before fibre fragmentation, indicating better adhesion than for PBO as a result of reactive groups on the PIPD fibre surface.     

Semi-empirical calculation and spectroscopic study of protonated poly(p-phenylene benzobisoxazole) models

The characters of poly(p-phenylene benzobisoxazole) (PBO) in methanesulfonic acid (MSA) are strongly influenced by the protonation effect. Due to such protonation effect, the experimental optical absorption spectrum was red shifted from the optical absorption spectrum predicted by AM1/ZINDO–CI (Austin Method 1/Zerner's intermediate neglect of differential overlap coupled to single configuration interaction) method. Further studies on AM1-optimized geometries of PBO showed that the final minimized torsion angle of benzoxazole and phenylene rings increased from 0.04° for the neutral molecule to 18.53° for protonated form at N atom. Moreover, the repulsive Coulombic interactions originated from protonation tend to stiffen the PBO chain. The AM1/ZINDO–CI calculation also indicated that the strongest UV absorption peak of PBO was blue shifted with increasing torsion angle.     

Heat resistance properties of poly(p-phenylene-2,6-benzobisoxazole) fiber

The high temperature properties of Poly(p-phenylene-2,6-benzobisoxazole) (PBO) fiber are examined and compared with those of the p-Aramid fiber. In particular, the temperature dependence of tensile strength of the PBO fiber is reported for the first time. The PBO fiber has 100°C higher decomposition temperature than the p-Aramid fiber, and the amount of toxic gases in combustion is much smaller than the p-Aramid fiber. Although the relative strength decreased proportionally in the range of room temperature to 500°C, the PBO fiber has 40% of the strength at room temperature even at a temperature of 500°C. After thermal treatment at 500°C for 60 s, the PBO fiber retained 90% of its original strength. The PBO fiber is expected to substitute for asbestos, which is still used as a heat resistant cushion material. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1031–1036, 1997     

Mechanism of degradation of poly(p‐phenylene benzobisoxazole) under hydrolytic conditions

Poly(p‐phenylene benzobisoxazole) (PBO) fiber has received great interest because of its excellent mechanical properties and good thermal stability. The objective of this study was to expose degradation mechanism of PBO under neutral and acidic conditions by molecular mass and Fourier transform infrared (FTIR) spectroscopy. Results were not consistent with the classic degradation mechanism, which indicates that degradation should occur through the ring opening and chain scission of the benzoxazole ring. The FTIR absorption spectra of PBO suggested that the o‐hydroxy amide linkage (the open ring structure) was present in the PBO molecule chain to some extent because of the incomplete polymerization. Further investigation showed that hydrolysis might occur in the open ring section during hydrolytic degradation. Based on the experimental data, a new degradation mechanism was proposed. It suggests that, in the early and middle stages, hydrolysis occurred primarily in the o‐hydroxy amide linkage of the open ring. The concentration of the o‐hydroxy amide structure determined the speed of degradation of PBO. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Deformation studies of single rigid-rod polymer-based fibres. Part 1. Determination of crystal modulus

This series of papers covers several aspects related to the influence of external stresses on the crystalline microstructure of rigid-rod polymer-based fibres. For the study, the main three fibres of this type have been selected, namely poly(p-phenylenebenzobisoxazole) (PBO fibres), poly(p-phenylenebenzobisthiazole) (PBT or PBZT fibres) and the novel poly{2,6-diimidazo[4,5-b:4′-5′-e]pyridinylene-1,4(2,5-dihydroxy)phenylene} (PIPD or M5 fibres). Synchrotron radiation was employed to record high-quality wide-angle X-ray scattering patterns from single fibres. The present paper deals mainly with the evaluation of lattice strain along the fibre axis (c-)direction. Crystal moduli of the different fibres were calculated from the variation with stress of the lattice strain determined from the shift of the major meridional (00l) reflections. This procedure rendered values of approximately 440 GPa for the crystal modulus of PIPD and PBO fibres, and 350 GPa for the PBT one. The difference between these two values was explained in terms of specific molecular conformation of the monomers in the unit cell. Discrepancies between the crystal and macroscopic (calculated from tensile tests) moduli are due to imperfections generated during the manufacture of the fibres.     

Processing and properties of poly(p-phenylene benzobisthiazole)/nylon fibers

Composite fibers of poly(p-phenylene benzobisthiazole) (PBT) with nylons were spun from dilute acid solutions. The effects of wet-stretching, heat treatment time, tension, and temperature on the tensile properties are reported. Nylon 6,6 and nylon 6 at several molecular weights were studied. Moduli of 40 GPa and tensile strengths of 375 MPa were achieved for 30/70 PBT/nylon composites. Heat treatment of the nylon/PBT fibers at 160–225°C for 12–19 h increased the tensile modulus by 20–50% and the tensile strength by a smaller amount. At the same time, the intrinsic viscosity of the nylons increased as much as 100%, indicating the solid-state polymerization of the nylon. The largest tensile modulus attained is less than half the theoretical value predicted by a linear “rule of mixtures” as might be expected for an oriented molecular composite. Although differential scanning calorimetry shows a melting transition at temperatures 5–10°C higher than the pure nylons, the composite does not flow at temperatures above this transition. Sulfuric acid dissolves most of the nylon, but does not destroy the mechanical integrity of the fibers; differential scanning calorimetry indicates that the remaining fiber contains little or no nylon. The results are consistent with a microstructure consisting of a microfibrillar network of PBT, surrounded by a separate nylon phase.     

Effect of MWCNTs irradiation grafting treatment on the surface properties of PBO fiber

The aim of this article is improved the surface properties of Poly[p‐phenylenebenzobisoxazole] (PBO) fiber with epichlorohydrin hybridized carboxylic multi walled carbon nanotubes (MWCNTs‐Ecp) grafting by using γ‐ray irradiation technology. The surface chemical properties, the surface morphology, the amount of the grafted MWCNTs on PBO fiber and the surface free energy of PBO fibers have been analyzed. The results show that MWCNTs‐Ecp have been grafted on the surface of PBO fiber by γ‐ray irradiation treatment. The surface chemical inertness and the surface smoothness of PBO fiber are significantly improved by grafting MWCNTs‐Ecp chains, the amount of the grafted MWCNTs on PBO fiber is about 11.9%, and the surface free energy of PBO fiber has an increase of 42.6% by generating some active groups such as ? COOH, ? OH, and ? C? Cl on the surface of PBO fiber. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of protonation on the conformational characteristics and geometry of the rod-like benzobisoxazole polymers

Recent experiments on model compounds suggest that rodlike polybenzobisoxazole (PBO) and polybenzobisthiazole (PBT) chains are protonated when dissolved in highly acidic solvent. The PBO model compound can exist as a 2H⁺ ion, with one proton on each nitrogen atom, or (depending on the acidity of the medium) as a 4H⁺ ion, with two additional protons on the oxygen atoms. The PBT model compounds generally form 2H⁺ ions, owing to the lower basicity of sulfur atoms relative to oxygen atoms. In the present study, geometry-optimized CNDO/2 calculations have been carried out in an attempt of predict the effect of protonation on the conformational characteristics and geometry of PBO model compounds. Values of the conformational energy vs. rotation of the endphenylenes about the heterocyclic group are calculated for cis-PBO model compounds in the unprotonated form and as 2H⁺ and 4H⁺ ions. All three species prefer the coplanar conformation with maximum barriers, occurring at the perpendicular conformation, of approximately 8.4, 33.6, and 84.0 kJ mol^?1 for the unprotonated form, the 2H⁺ ion, and the 4H⁺ ion, respectively. Steric arguments would suggest that repulsions between the acidic protons and the ortho hydrogens on the phenylenes would render the coplanar conformation more repulsive than other orientations. However, detailed analysis of the optimized geometries reveals that the rotatable bond shortens with protonation, indicating an increased bond strength and, hence, increased conjugation energy.     

In situ polymerization and photophysical properties of poly(p‐phenylene benzobisoxazole)/multiwalled carbon nanotubes composites

Poly(p‐phenylene benzobisoxazole)/multiwalled carbon nanotubes (PBO‐MWCNT) composites with different MWCNT compositions were prepared through in situ polymerization of PBO in the presence of carboxylated MWCNTs. The nanocomposite's structure, thermal and photophysical properties were investigated and compared with their blend counterparts (PBO/MWCNT) using Fourier transform infrared spectra, Raman spectra, Wide‐angle X‐ray diffraction, thermogravimetric analysis, UV‐vis absorption, and photoluminescence. The results showed that MWCNTs had a strong interaction with PBO through covalent bonding. The incorporation of MWCNTs increased the distance between two neighboring PBO chains and also improved the thermal resistance of PBO. The investigation of UV‐vis absorption and fluorescence emission spectra exhibited that in situ PBO‐MWCNT composites had a stronger absorbance and obvious trend of red‐shift compared with blend PBO/MWCNT composites for all compositions. This behavior can be attributed to the efficient energy transfer through forming conjugated bonding interactions in the PBO‐MWCNT composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis,structure and properties of carbon nanotube/poly(p‐phenylene benzobisoxazole) composite fibres

Carbon nanotube/poly(p‐phenylene benzobisoxazole) (CNT/PBO) composite fibres were prepared by in situ polymerization and dry‐jet wet spinning. The structure and properties of the CNT/PBO fibres were investigated. FTIR and viscosity measurements showed that the functional groups on the CNT surface took part in the polymerization and affected the chemical structure and molecular weight of the composite. CNT/PBO composites with high molecular weight could be obtained by controlling the amount and addition time of CNTs. Compared with PBO fibres containing no CNTs prepared under the same conditions, the thermal resistance of the CNT (2 wt%)/PBO fibres was higher and the tensile strength was also improved by 20–50%. WAXD and SEM measurements indicated that the orientation degree of the CNT (2 wt%)/PBO fibres was smaller than that of PBO fibres. The fracture surfaces of these two fibres were also different. CNT dispersion in the CNT (2 wt%)/PBO fibres was examined by TEM. A model of the interactions between CNTs and PBO is proposed, based on these results. Copyright © 2006 Society of Chemical Industry     

Electrically conductive composite of polyaniline and poly (p-phenylene/diphenyl ether-terephthalamide)

In order to improve the flexibility and the anti-static properties of poly-(p-phenylene-terephthalamide) (PPTA), the copolymer of p-phenylene diamine, p,p′-diaminodiphenyl ether and terephthaloyl chloride (PPDTA) was synthesized. This copolyamide PPDTA was mixed with electrically conductive polyaniline (PAn) in concentrated sulphuric acid solution, and was processed to form film, or fibre, of the new composite PAn/PPDTA with high strength and good electrical conductivity. The composite is a lyotropic liquid crystalline polymer with electrical conductivity 10^?1 S/cm. The surface morphology of the PAn/PPDTA composite consists of an oriented fibre-like texture.     

Thermal degradation of poly(p‐phenylenebenzobisoxazole) and poly(p‐phenylenediamine terephthalamide) fibres

This study investigates the thermal stability of poly(p‐phenylenediamine‐terephtalamide) (PPT) and poly(p‐phenylenebenzobisoxazole) (PBO) fibres. Excellent behaviour of PBO is shown in comparison to that of PPT. The thermal stability (under pyrolytic or thermo‐oxidative conditions) of PBO is 150 °C higher than that of PPT. Moreover, the strong influence of oxygen, which plays the role of an initiator of degradation, on the degradation of fibres is shown. Using the invariant kinetic parameter (IKP) method, it is shown that the degradation rate of PBO is strongly reduced in comparison with that of PPT. It provides a simulation of the ‘fuel flow’ able to feed the flames, which can explain the high fire performance of PBO compared to PPT. © 2001 Society of Chemical Industry     

Thermal behavior of aryl-aliphatic polyamides

Low molecular weight poly(p-phenylene sebacamides) and (m-phenylene sebacamides) were prepared by interfacial polycondensation by varying the concentration of p-and m-phenylenediamine in the initial feed. The polymers were characterized by intrinsic viscosity measurement and IR spectra. The relative thermal stability was evaluated by differential thermal analysis and dynamic thermogravimetry in air and nitrogen atmospheres. A systematic dependence of stability on intrinsic viscosity of poly(m-phenylene sebacamide) was observed indicating an endgroup initiation of degradation. No such dependence was observed in poly(p-phenylene sebacamide). A probable mechanism for the thermal degradation has been proposed.     

Complementary X-ray scattering and high resolution imaging of nanostructure development in thermally treated PBO fibers

Structural changes in poly(p-phenylene benzobisoxazole) (PBO) derived carbon fibres (CFs), treated in the range 900 °C ? T ? 2700 °C, are investigated by small- and wide-angle X-ray scattering (SAXS and WAXS), and by high-resolution transmission electron microscopy (HRTEM). SAXS detects rough interfaces within the fibres, normal to the fibre axis and belonging to a fibril structure. HRTEM and SAXS also reveal nanometre-sized elongated voids spaced semi-regularly along the fibre axis. With increasing temperature, longitudinal packing becomes denser and the broad reflections in the WAXS region sharpen into the reflections characteristic of graphite. Preferential axial orientation of the graphitic layers is due to the internal fibril structure of the fibre, which itself is governed by the draw axis of the parent PBO fibre and improves substantially on going from 2400 °C to 2700 °C. In-plane reflections in the parallel direction are well resolved, demonstrating tri-periodic ordering within the graphitic sheets (“true” graphitization, with hkl reflections in place of the hk bands of bi-periodic turbostratic carbons). This study of PBO-based CFs is the first detailed analysis of the nanostructural changes that occur during the graphitization process of 1D carbons.     

X‐ray scattering study on the damage in fibers used in soft body armor after folding

The goals of the research effort described in this article are to develop a framework to evaluate improvements in next‐generation fibers used in soft body armor and to anticipate long‐term performance and potential fiber deterioration. This effort to date has included the effect of folding on the fibers and exploring the interaction between the specific fiber strain energy and their sound velocity. Previous work in this lab noted a severe drop‐off of tensile strength and strain‐to‐failure in poly(p‐phenylene benzobisoxazole) (PBO) fibers when subjected to repeated folding. Subsequent work on poly(p‐phenylene terephthalamide) (PPTA) fibers showed at most a slight drop‐off in these mechanical properties. Results from wide angle X‐ray diffraction indicated that both PPTA and PBO fibers showed no significant changes in the d‐spacing and the apparent crystal size. However, with small angle X‐ray scattering, it was found that the void and fibril sizes within PBO fibers may decrease after folding. Environmental scanning electron microscopy showed no damage to the fiber surfaces upon folding, and confocal microscopy revealed extensive internal damage to the PBO fibers that tracks well with the SAXS and mechanical testing results. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers