Ferromagnetic Intermolecular Interaction of N-Protonated Pyridylphenylcarbene

Abstract

The HCl and DCl salts of pheny1-4-pyridyldiazomethane were prepared and irradiated at 6 K to generate the carbenes. Their ESR spectra indicated presence of plural triplet carbenes with slightly-different zero-field splitting constants. Besides the triplet species, we found a quintet species whose signal intensity decreases with increasing temperature. The quintet spin state was concluded to be a ground state which was produced by an intermolecular ferromagnetic interaction of the triplet carbenes. The ferromagnetic interaction would be explained by the McConnell mechanism, judging from the crystal structure of the HCl salt of phenyl-4-pyridylketone.     

Gamma irradiation of cholesteric products: Effect of the presence of organic solvents

The shift δT of the selective reflection temperature due to an exposure to γ-rays is studied for a mixture of cholesteric substances dissolved in various organic solvents. Values of δT such as 0.2°C per krad can be obtained. The influence of the solvent nature (carbon tetrachloride, chloroform, trichloroethylene, …) is also discussed. It is shown that the shift δT is due to the presence of radiolysis products of the solvent; this effect is more specially studied in the case of carbon tetrachloride containing a radical scavenger.     

Molecular Packing in Crystalline Domains of Unsymmetrical Poly(benzoxazole-imide): Investigation using Modeling of a Model Compound

To probe the molecular packing in crystalline domains of an unsymmetrical poly(benzoxazole-imide) (BPDA-BOA) introduced alternating phenylbenzoxazole and bisphthalimide units via the two-step polymerization of 5-amino-2-(4- aminophenyl)benzoxazole (BOA) and 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), the crystal structure of its model compound, 5-phthalimido-2-(4-phthalimidophenyl)benzoxazole (PA-BOA), was investigated using powder wide-angle X-ray diffraction (WAXD) combined with molecular modeling using a Materials Studio program. Powder WAXD pattern of the model compound can be well indexed in terms of amonoclinic unit cell with parameters of a = 12.005 Å, b = 3.837 Å, c = 23.562 Å, β = 96.711°. There are two molecules in the unit cell with the space group of P2 (3). Based on the crystal structure of the model compound powders and the WAXD analysis of poly(benzoxazole-imide) film, it can be concluded that the projection of the monomer repeat length of the poly(benzoxazole-imide) chains in the chain directionis around 19.0 Å, and the interchain side-by-side distance and face-to-face distance between the centroids of two neighboring BPDA-BOA chains are around 6.10 and 4.01 Å, respectively. The difference of molecular packing between the poly(benzoxazole-imide) chains in their crystalline domains and the model compounds in their crystals are also presented. Both the side-by-side and face-to-face π-π stacking distances between two neighboring polymer chains in the poly(benzoxazole-imide) crystalline domains are significantly larger than the corresponding values between two neighboring molecules in the model compound crystals due to a more kinked and twisted conformation.     

聚酰亚胺复合材料的摩擦性能及其机理研究

研究了含有固体润滑剂的炭纤维增强 PI复合材料在干摩擦和水润滑 2种状态下的摩擦磨损性能及其磨损机理 .结果表明 ,在水润滑条件下 ,摩擦系数和磨损率都有不同程度的降低 ,其中含 PTFE的炭纤维增强 PI复合材料的耐磨性最佳 ,最低磨损率为 9.9× 10 - 7mm3/ N· m.其主要原因可能与材料存在极性酰胺基团有关 ,酰胺基易通过氢键与水分子结合 ,在摩擦表面形成水吸附膜 ,使摩擦表面直接接触减少 ,从而改善材料的摩擦磨损性能     

Thermo-oxidatively stable polyimides and their chemical structures

A series of aromatic diamines having ether and/or carbonyl moieties in their structures were synthesized. By using these synthesized diamines and commercially available tetracarboxylic dianhydrides, various kinds of polyimides having ether and/or carbonyl moieties were synthesized. The thermo-oxidative stability of the obtained polyimides was investigated by focusing on the chemical structures of their repeating structure units. The reason for the improved thermo-oxidative stability of the ether–carbonyl polyimide structure was explained by an electronically balanced condition, i.e., the balance of electron donor moiety (—O—) and electron acceptor moiety (—CO—) in a chemical structure, and the degree of electron deficiency of the benzene–imide ring structure. The possibility of the formation of a charge transfer complex (CT-complex) was also mentioned as an explanation of the improved thermo-oxidative stability of ether–carbonyl polyimide structures. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1717–1723, 1998     

Imidization and interdiffusion of poly(amic ethyl ester) precursors of PMDA/3,4′-ODA

Para-, meta-, and mixed isomeric poly(amic ethyl ester) precursors of the polyimide based on pyromellitic dianhydride (PMDA) and 3,4′-oxydianiline (3,4′-ODA) were synthesized. The intrinsic viscosity of each of the isomers was measured in an NMP solution and found to be less than corresponding isomers derived from PMDA and 4,4′-oxydianiline (4,4′-ODA) precursors with comparable molecular weight. The imidization and solvent retention were measured as a function of imidization temperatures, T_i using forward recoil spectrometry (FRES). For samples cast from a single solvent, either N-methyl pyrrolidone (NMP) or dimethyl sulfoxide (DMSO), no difference was observed in the temperature-dependent imidization behavior between the isomers. In all cases the imide fraction f increased as T_i increased, and reached a value of unity, i.e., full conversion at 400°C. At the same T_i, samples cast from DMSO showed a slightly higher f than samples cast from NMP. FRES and time of flight FRES (TOF-FRES) were used to measure the interdiffusion distance, w, of deuterium-labeled tracers into nondeuterated base layers of the polyimide of PMDA/3,4′-ODA treated at various T_i. The primary determinant of w for all isomers was T_i, and the particular isomer used as either the base or the tracer molecule did not seem to affect w. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2247–2258, 1998     

Diffusion in gas separation membrane materials: A comparison and analysis of experimental characterization techniques

Typically, materials with high-performance transport properties such as zeolites, carbon molecular sieves, or hyper rigid polymers are inherently difficult or impossible to characterize by steady-state membrane permeation experiments used for conventional polymers. Diffusion coefficients determined by transient sorption, a measurement easily performed on brittle media, are analyzed here and compared to those determined by steady-state permeation/sorption and transient permeation for a glassy polymer and a carbon molecular sieve. Average and local diffusion coefficients are extrapolated to zero upstream partial pressure to eliminate effects caused by concentration dependence. Good agreement between the techniques was observed for the glassy polymer. On the other hand, carbon molecular sieves, possessing a more complex morphology, exhibit a greater difference in diffusion coefficients determined by the various techniques. Nevertheless, comparison of the analysis techniques is shown to provide potentially valuable insights into the morphological features of such carbon molecular sieves. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1747–1755, 1998     

Synthesis and properties of polyimide-clay hybrid films

Polyimide-clay hybrid films with four different sizes of clay minerals have been synthesized to investigate the effect of the size of clay minerals to the properties of the hybrids. Hectrite, saponite, montmorillonite, and synthetic mica were used as clay minerals. Those clays consist of stacked silicate sheets about 460 Å (hectrite), 1650 Å (saponite), 2180 Å (montmorillonite), and 12300 Å (synthetic mica) in length, 10 Å in thickness. The longer the length of clay mineral was, the more effectively properties of polyimide were improved. In the case of polyimide-mica hybrid, only 2 wt % addition of synthetic mica brought permeability coefficients of water vapor to value less than one-tenth of that of ordinary unfilled polyimide, and thermal expansion coefficient was lowered at the level of 60% of the original one. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2289–2294, 1997     

Investigation of microwave energy to cure carbon fiber reinforced phenylethynyl-terminated polyimide composites,PETI-5/IM7

The application of microwave energy to the processing of carbon fiber reinforced phenylethynyl-terminated polyimide composites (PETI-5/IM7) was investigated and evaluated with a variable-frequency microwave furnace. The thermal and physical properties of the composites were measured by dynamic mechanical thermal analysis, thermogravimetric analysis, thermomechanical analysis, and density and composition tests. The mechanical properties were determined by 3-point-bending and short-beam-shear tests at both room temperature and 177 °C. The shear failure surfaces of both microwave- and thermally cured composites were detected with environmental scanning electron microscopy. A comparison of the thermal and microwave processes was conducted to evaluate the advantage of the microwave process. Microwave-cured composites, fabricated under various pressures at the fixed process temperatures, also were investigated. From these studies, it was concluded that microwave energy successfully was used to fabricate PETI-5/IM7 composites with higher glass-transition temperatures (by 11–16 °C) and higher retention in flexural strength, flexural modulus, and shear strength at 177 °C than those fabricated by the thermal process. Furthermore, the microwave processes required only half the time used for the standard thermal process. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4616–4628, 1999