A one-and two-dimensional NMR study was performed on three commercial resol phenol-formaldehyde (PF) prepolymer resins. 'H, "C, CSCM and DQF COSY NMR spectral data, in acetoned, , were obtained on each resin and on PF model compounds: phenol, five methylolphenols, four diphenylmethanes, two formals, two dibenzyl ethers and two dibenzylamines. Gated-decoupled "C experiments, using 2,4,6trimethylphenol as internal standard, were used to quantitate the major components present in each of the three resins. The major chemical differences of the three resins were noted. A DQF COSY method was developed that allowed the qualitative identification of most of the major phenolic components present in each of the PF resins.
A total of 13 of the 16 possible methylol derivatives of 2,4 -and 4,4 -dihydroxydiphenylmethane have been synthesized, isolated, and identified. These compounds are found as intermediates in the cure process of resol phenol-formaldehyde (PF) resins. Analysis of the 13 C NMR spectra (in acetone-d 6 ) of these compounds provided a way to evaluate the seven methylolphenol ring types (methylol derivatives of 2-hydroxyphenyl and 4-hydroxyphenyl rings) found in typical resol PF resins using the ipso carbon region from 150 to 160 ppm. A simple diagnostic test was developed using the chemical shift values of the methylol methylene carbon atoms to identify the presence of intermediates containing either a 2-hydroxyphenyl or a 4-hydroxyphenyl ring. Using these data it is now possible to analyze the major components in extracted prepreg PF resins.
Although recent works demonstrated that some potassium compounds that can be converted to KH during ball-milling or heat-treatment have obvious effects on enhancing the dehydrogenation properties of the Li-N-H system, the effect of KH on enhancing the dehydrogenation properties of the Li-N-H system and its catalytic mechanism remain unclear. In this study, the hydrogen desorption properties of the LiNH2-LiH system with alkali metal hydrides (LiH, NaH, or KH) were investigated and discussed. We find that the three types of hydrides are effective for enhancing the hydrogen desorption properties of the LiNH2-LiH system, among which, KH shows the best effect. In comparison with the broad shaped hydrogen desorption curve of the LiNH2-LiH composite without additive, the hydrogen desorption curve of the LiNH2-LiH-0.05KH composite becomes narrow. The dehydrogenation onset temperature of the LiNH2-LiH-0.05KH composite is decreased by approximately 20 °C, and the dehydrogenation peak temperature is lowered by approximately 30 °C. Moreover, the reversibility of the LiNH2-LiH system is enhanced drastically by the addition of KH. On the basis of previous reports and present experimental results, the mechanism for the enhancement of the dehydrogenation properties in the KH-added Li-N-H system is proposed. The reason for the improvement of the hydrogen desorption kinetics is that KH has superior reactivity with NH3 and plays the role of a catalyst to accelerate hydrogen release by cyclic reactions.
The realization of effective CO2 conversion into valuable hydrocarbons is a promising way of addressing the current environmental and energy issues. A convenient, highly selective, and efficient method of CO2 methanation and the synthesis of COx‐free hydrogen/methane fuel mixtures by ball milling‐induced reactions of alkaline carbonates with metal hydrides (MHs) is reported. The natural resources of MgCO3/CaCO3 and MgH2/CaH2 are used as carbon and hydrogen sources, respectively. Mechanochemical investigations of the room‐temperature reactions indicate that some alkaline carbonates can be reduced by MHs under catalyst‐free conditions to selectively afford CH4 as the sole hydrocarbon product in yields of up to 73%. Moreover, the contents of methane in the gaseous products and its yield are shown, which mainly depend on the nature of metal carbonates/hydrides, rate and duration of ball milling, and reaction mixture composition. Thus, this study opens new ways to achieve the CO2 utilization and synthesize of COx‐free hydrogen and methane fuel mixtures.
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