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Diphosphabenzenes. VII. Reactions of 1,1,3,3‐Tetrakis(dimethylamino)‐1 λ5, 3 λ5‐diphosphete with 5‐Cyano‐1‐pentine and 2‐(Cyanomethyl)‐1‐methylpyrrol 5‐Cyano‐1‐pentine reacts with the equimolar amount of the λ5‐diphosphete 1 to give the λ5‐diphosphinine (λ5‐diphosphabenzene) ( 3 ), while reaction with the double equimolar amount of 1 yields the λ5‐diphosphinine ( 4 ). The acyclic compount 6 is the main product of the reaction between 1 and 2‐(cyanomethyl)‐1‐methylpyrrol, 5 . Melting points of 4 · CH3CN and 6 , and mass, nmr and ir spectra of 3 , 4 , and 6 are reported. The crystal structure of 4 · CH3CN shows an open‐chain ylidic CPCP‐sequence, which is linked to a λ5‐diphosphinine via an ethylene bridge. The X‐ray structure analysis of 6 confirms the existence as an acyclic conjugated double ylid. 相似文献
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Effect of organo-modified clay on accelerated aging resistance of hydrogenated nitrile rubber nanocomposites and their life time prediction 总被引:1,自引:0,他引:1
Organically modified clay - reinforced hydrogenated nitrile rubber vulcanizate was subjected to accelerated heat aging to estimate its long-term thermo-oxidative stability and its useful lifetime was compared with that of the virgin polymer for the first time. Changes in technical properties such as tensile strength, modulus and elongation at break were studied as a function of time and temperature of aging. The infrared spectroscopic analysis of the degraded products revealed that under aerobic hot aging conditions, hydrogenated nitrile rubber (HNBR) compounds undergo cross-linking reactions that lead to embrittlement and ultimately failure. Incorporation of clay filler, however, resulted in significant improvement of the degradation profile of the nanocomposite at elevated temperatures. Loss of ductility during aging of the nanocomposite was also milder, relative to the unfilled polymer, indicating a restricted degradation by the clay filled rubber, thus prolonging the durability. From the scanning electron microscopy and atomic force microscopy studies, it was found that nanofillers protected the elastomer from surface rupture that took place on oxidation. Life prediction of both virgin elastomer and the nanocomposite indicated a three-fold increase in the effective service temperature range of the HNBR using 8 parts organically modified nanoclay. 相似文献
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Mitsutoshi Jikei Hideaki Itoh Norihiro Yoshida Yosuke Inai Teruaki Hayakawa Masa‐Aki Kakimoto 《Journal of polymer science. Part A, Polymer chemistry》2009,47(21):5835-5844
Hyperbranched poly(ether nitrile)s were prepared from a novel AB2 type monomer, 2‐chloro‐4‐(3,5‐dihydroxyphenoxy)benzonitrile, via nucleophilic aromatic substitution. Soluble and low‐viscous hyperbranched polymers with molecular weights upto 233,600 (Mw) were isolated. According to the 1H NMR and GPC data, the unique polymerization behavior was observed, which implies that the weight average molecular weight increased after the number average molecular weight reached plateau region. Model compounds were prepared to characterize the branching structure. Spectroscopic measurements of the model compounds and the resulting polymers, such as 1H, DEPT 13C NMR, and MS, strongly suggest that the ether exchange reaction and cyclization are involved in the propagation reaction. The side reactions would affect the unique polymerization behavior. The resulting polymers showed a good solubility in organic solvents similar to other hyperbranched aromatic polymers. The hydroxy‐terminated polymer was even soluble in basic water. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5835–5844, 2009 相似文献
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Nitriles pose an interesting problem to the explanatory powers of organic chemistry because, despite the favorable overall thermodynamics of hydrolysis to the corresponding amides, the reactions are inherently slow. The rate determining step is hydration of the nitrile to give the imidic acid, which quickly tautomerizes to the amide. In terms of Marcus Theory, the intrinsic barriers for acid and base‐catalyzed hydration are higher for nitriles than for amides, which are themselves slow reactions. It is remarkable that hydration of a nitrile, for which the free energy change is close to zero except for polyhaloacetonitriles, is much slower than hydration of an amide, which is energetically unfavorable. This can be explained by No Barrier Theory in terms of the high energetic cost of the geometrical distortions in “one thing at a time” corner species. There are no experimental equilibrium constants for this initial hydration step, so we have determined them computationally. The free energy change for the initial hydration is small; it is the fast and energetically downhill second step, tautomerization to the amide, which makes the overall hydrolysis of nitrile to amide thermodynamically favorable. Very few of the pKa values needed in the acid and base‐catalyzed mechanisms are known, so we used linear free energy relations and treat the parent pKa values as adjustable parameters. This procedure leads to pKa values in accord with expectation based on such data as are available and permits calculation of rate constants in satisfactory agreement with experiment. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
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A facile one‐pot synthesis of nitriles via a ring‐opening reaction of cyclobutanone adducts with hydroxylamine hydrochloride was developed. 相似文献