THERMODYNAMICS OF ASPHALTENE PRECIPITATION AND DISSOLUTION INVESTIGATION OF TEMPERATURE AND SOLVENT EFFECTS

Petroleum asphaltenes have been precipitated in solvent mixtures of n-heptane and toluene at various temperatures, likewise n-heptane asphaltenes have been dissolved in under similar conditions. This give added evidence to apparent hysteresis phenomenon between the two processes. The Asphaltenes have been characterized showing that although data is scattered convergence to certain structural parameters as incipient flocculation is approached. The asphaltenes are seen to consist of an associating and a non-associating part. The solubility of asphaltenes has been correlated/modelled using the Flory-Huggins equation using two different terms for the Flory parameter. A process for evaluation of best choice of solubility parameter and molar volume for the asphaltenes is proposed. Dissolution processes are seen to be best fitted by the equations. Based on these findings the asphaltenes are proposed to be formed by a colloidal and a true solution part.     

Reaction rate and MWD changes in crosslinking of PVC,with dithioltriazine

The reaction rate of crosslinking of PVC with dithioltriazine has been studied by following gel formation and changes in the molecular weight distribution (MWD). Compounding was performed on a roll mill at 145°C and crosslinking by heat treatment at 180 or 90°C. In this system crosslinking is executed by the thiolate anion, formed in situ by reaction with MgO. We have studied the catalyzing effect of several polyols in order to achieve a more efficient reaction. Most likely, these catalysts work by chelating the Mg²⁺ ions, thus increasing the nucleophilic character of the thiolate. With the most efficient ones, ditrimethylolpropane and HO(CH₂CH₂)_6-7H, complete crosslinking can be obtained in 3 min at 180°C, i.e., at processing temperatures. We also followed the changes in the MWD before gelation at a considerably lower temperature, 145°C, and found an extensive molecular enlargement even after 5-10 min. Most surprisingly, μM_n increased up to 100% without formation of insoluble material. By ¹H-NMR measurements on low molecular weight extracts, we have shown this to be due to a fast and selective reaction with allylic chlorine in the unsaturated end groups, ～ CH₂? CH?CH? CH₂Cl, formed in the mechanism of chain transfer to monomer. Due to this reaction, formulations with too high reactivity may crosslink during processing, which calls for a careful balancing of the reactivity for each processing case.     

Thermal degradation of EVA and EBA—A comparison. III. Molecular weight changes

This is the third in a series of papers in which the thermal degradation of ethylene-vinyl acetate (EVA) and ethylene-butyl acrylate (EBA) copolymers are compared. The EBA samples contained 0.8, 1.6, and 5.4 mol % butyl acrylate (BA), respectively, and the EVA samples 1.2 and 6.7 mol % vinyl acetate (VA). The samples were heated in nitrogen in a tubular oven at 285–390°C, for 6–120 min. The molecular weight distribution (MWD), long chain branching, and gel content were analyzed with size exclusion chromatography (SEC). The columns were connected to refractive index, viscometric, and light scattering detectors. EVA gave a pronounced molecular enlargement at all degradation temperatures. In EVA-6.7, gel was formed at all degradation levels, whereas the low content sample, EVA-1.2, did not form any visible amount of gel. The strong tendency to molecular enlargement is due to allyl radicals formed after thermal deacetylation and the formation of internal double bonds. These macroradicals will combine or, less frequently, add to double bonds. The EBA copolymers show a more polyethylenelike degradation behavior. At 285°C molecular enlargement dominates, but already at 333°C a net reduction in molecular size is observed. At high temperatures, ester pyrolysis of the BA groups give carboxylic groups and anhydrides. Alkaline treatment will not give any appreciable change in MWD, showing that the anhydride formation is mainly intramolecular. The chain scission increases with the BA content. This is probably due to β-cleavage of tertiary macroradicals formed in the chain at the acrylate or carboxylic side groups.     

四网协同资源配置模型战略分析

四网协同是中国移动3大战略之一。如何通过科学的资源配置,真正实现四网协同发展,是中国移动集团、省市公司和地市公司共同关注的核心议题。在四网大协同的战略背景下,通过研究搭建了一个基于四网协同的闭环、联动、可获取、可评估的资源配置分析模型。一方面,通过体系化的四网资源配置模型,能够有效地支撑中国移动四网战略的落地,保障四网协同战略的有效实施;另一方面,通过闭环的投资策略方案比较分析,支撑中国移动集团公司与各省公司四网投资的精细化管理,提升投资管理效益。同时,还根据大协同分析思路和端管云策略体系,达到提升中国移动的企业综合效益,促进中国移动可持续发展的目标。     

Experimental demonstration of polarization discrimination at the Helstrom bound

Abstract

We present an experimental realization of discrimination between non-orthogonal polarization states at the Helstrom bound for minimum probability of error. The experiment was performed with highly attenuated laser light with a mean number of about 0·1 photons per pulse.     

Identification of the Sex Pheromone of the Currant Shoot Borer Lampronia capitella

Under an artificial light:dark cycle, females of Lampronia capitella were observed calling, with extended terminal abdominal segments, during the first 2 hr of the photoperiod. Extracts of terminal abdominal segments from females elicited large electroantennographic responses from male antennae. Gas chromatography with electroantennographic detection revealed three active peaks. Based on comparison of retention times and mass spectra of synthetic standards, these compounds were identified as (Z,Z)-9,11-tetradecadienol and the corresponding acetate and aldehyde. The electroantennographic activity of the four geometric isomers of all three compounds was investigated, and the respective (Z,Z)-isomer was found to be the most active in all cases. Aldehydes generally elicited larger antennal responses than alcohols, whereas acetates were the least active compounds. A subtractive trapping assay in the field, based on a 13:26:100 micrograms mixture of (Z,Z)-9,11-tetradecadienal, (Z,Z)-9,11-tetradecadienyl acetate, and (Z,Z)-9,11-tetradecadienol confirmed that all three compounds are pheromone components. Subtraction of (Z,Z)-9,11-tetradecadienol from the blend completely eliminated its attractiveness, whereas the other two-component blends showed reduced activity. This is the first pheromone identification from the monotrysian superfamily Incurvarioidea, confirming that the common pheromones among ditrysian moths (long-chain fatty acid derivatives comprising alcohols, acetates, and aldehydes with one or more double bonds) is not an autapomorphy of Ditrysia, but a synapomorphy of the more advanced heteroneuran lineages.     

Adsorption of phenol and 1-naphthol onto XC-72 carbon

XC-72 carbon (XC-72) was characterized by SEM, XPS, N₂ adsorption-desorption, particle size distribution analysis and potentiometric acid-base titration. The adsorption of phenol and 1-naphthol on XC-72 was studied as a function of contact time, pH, adsorbent content and temperature. The kinetic adsorption data were described well by the pseudo-second-order model. The adsorption isotherms of phenol were described well by Freundlich model, while the adsorption isotherms of 1-naphthol were fitted well by Langmuir model. The results demonstrated that XC-72 had much higher adsorption capacity for 1-naphthol than for phenol. The adsorption thermodynamic data were calculated from the temperature-dependent adsorption isotherms at T=293, 313 and 333 K, and the results indicated that the adsorption of phenol was an exothermic process, whereas the adsorption of 1-naphthol was an endothermic process. XC-72 is a suitable material for the preconcentration of phenol and 1-naphthol from large volumes of aqueous solutions.     

Corresponding-states and parachor models for the calculation of interfacial tensions

A generalized corresponding-states model based on two reference fluids and a parachor correlation were developed for the prediction of interfacial tensions for non-polar and weakly polar pure fluids and mixtures. Pure methane and n-octane were chosen as reference fluids of the corresponding-states model. The two models were tested on 86 pure substances, more than 30 binary and multicomponent mixtures, 11 naphtha reformate cuts, 6 petroleum cuts and 2 North Sea oil mixtures. The calculated results were found to be in good agreement with experimental data.     

Oligoaniline intermediates in the aniline-peroxydisulfate system

Chemical oxidative polymerization of aniline using peroxydisulfate oxidant in aqueous pH 2.5–10.0 buffers yields electrically insulating brown powders that are believed to be mixtures of Michael-type adducts of benzoquinone monoimine and aniline at various stages of hydrolysis. A spectroscopically similar product is formed when solid 1,4-benzoquinone is added to an aqueous solution of aniline at room temperature in the absence of peroxydisulfate. This suggests that the peroxydisulfate oxidant in the aniline/S₂O₈^2? system provides a pathway for the formation of benzoquinone monoimine as an intermediate. Benzoquinone monoimine intermediate could be formed as a result of a Boyland–Sims rearrangement of aniline proceeding via the intermediacy of p-aminophenyl sulfate. Benzoquinone monoimine undergoes a series of conjugate 1,4-Michael-type addition/reoxidation/coupling steps with aniline or p-aminophenyl sulfate yielding the oligoaniline product. The precipitate that is isolated is also in the midst of two simultaneous pH dependent hydrolysis reactions: (i) hydrolysis of the imine groups to quinone, and (ii) hydrolysis of arylsulfates to phenols. The ratio of hydrolysis in each case was determined by the C/N ratio and sulfur elemental analysis values yielding analytical data that is consistent with experimentally determined values and also with our proposed reaction scheme. These findings offer a rationale for the high C/N ratios (>6.0) frequently observed in these systems while tracing the genesis of the residual sulfur in the product to unhydrolyzed arylsulfate. The oligoaniline product has previously been reported to have a novel poly-aza structure consisting of continuously linked –N–N–N– bonds, and alternately also reported to consist of phenazine-type linkages. This study is consistent with the latter and describes a pathway to phenazine coupling through a second and third stage hydrolysis of the arylsulfate and reoxidation with peroxydisulfate. There is no pathway for the formation of linear –N–N–N– linkages in the aniline/benzoquinone adduct and the striking similarity between its spectroscopic properties and the aniline/S₂O₈^2? adduct suggests that it is not a preferred pathway under these experimental conditions.