Aromatic nitrations by mixed acid. Slow liquid-liquid reaction regime

Aromatic nitrations by mixed acid have been selected as a specific case of a heterogeneous liquid-liquid reaction. An extensive experimental programme has been followed using adiabatic and heat-flow calorimetry and pilot reactor experiments, supported by chemical analysis. A series of nitration experiments has been carried out to study the influences of different initial and operating conditions such as temperature, stirring speed and sulphuric acid concentration. In parallel, a mathematical model to predict the overall conversion rate has been developed. In this paper the mathematical modelling and the implementation and experimental validation for benzene, toluene and chlorobenzene mononitration in the kinetic control regime (slow liquid-liquid reaction) are presented and discussed.     

氧气液相氧化一元取代甲苯制备芳香醛

研究了在酸碱不同体系下气氛液相氧化对氯甲苯、邻硝基甲苯制取相应芳香醛的反应 ,比较了反应温度、反应时间、氧气流量、底物浓度对各自反应的影响。初步研究了反应在酸碱不同条件下的反应机理 ,认为在醋酸体系下是自由基反应 ,而在有机胺体系下应是碳负离子反应。     

Study of the coupling reactions between electrochemically generated aromatic radical anions and methyl, alkyl and benzyl radicals

Alkyl radicals produced in the indirect reduction of alkyl halides or alkyldimethylsulfonium salts by electrochemically generated aromatic radical anions couple fast with the latter and alkylated or dialkylated dihydro compounds are formed. Rate constants measured for the coupling reaction between on one hand methyl, primary, secondary and tertiary alkyl radicals as well as benzyl and cumyl radicals and on the other hand a wide spectrum of electrochemically generated aromatic radical anions are found to be about 1×10⁹ M⁻¹ s⁻¹. Previous measurements of coupling rate constants for primary alkyl radicals have been re-evaluated since they were affected by the presence of an S_N2 reaction occurring between the alkyl halides used as radical precursors and the aromatic radical anions. New experiments are also included using alkyldimethylsulfonium salts as precursors in order to prevent such S_N2 artefacts. It is concluded that sterical hindrance does not play a significant role for the radical-radical anion coupling reactions. In general the rate constants for the coupling reactions are all close to 10⁹ M⁻¹ s⁻¹.     

煤焦油改性酚醛树脂研究

引入含有多环芳烃煤焦油组分来改性酚醛树脂,在反应釜中按一定比例加入苯酚、甲醛、氢氧化钠和煤焦油.在碱性催化剂作用下反应4～7 h,真空脱水,得到了煤焦油改性热固性酚醛树脂.对改性后树脂的固含量、残炭值测定和热失重-差热分析,结果表明煤焦油加入量为苯酚质量的15%时改性树脂具有较大的固含量和残炭值,耐热性也得到了显著提高.     

Aerobic selective oxidation of (hetero)aromatic primary alcohols to aldehydes or carboxylic acids over carbon supported platinum

The synthesis of substituted benzaldehydes, benzoic acids, heterocyclic aromatic aldehydes and acids has been studied via the oxidation of the aromatic alcohols with air under mild pressure (<20 bar) at 100 °C, in the presence of a 1.95 wt.% Pt/C catalyst. The solvent was found to play the most important role in determining the selectivity of the oxidation products. Changing the solvent enabled tuning the reaction either to the aldehyde (pure dioxane), or the carboxylic acid (dioxane/aqueous solution without or with addition of sodium hydroxide). This oxidation method allowed to effectively oxidize many substituted benzylalcohols with various electron-releasing or -attracting groups (NO₂, Me, OMe, Cl, Br, OH, phenyl, …) and heterocyclic alcohols including nitrogen and sulphur atoms (2-thiophenemethanol, 2- and 4-pyridine methanol compounds).     

EFFECT OF NONSOLVENT ADDITIVES ON THE PORE SIZE AND THE PORE SIZE DISTRIBUTION OF AROMATIC POLYAMIDE RO MEMBRANES

In this paper discussions are made on the effect of nonsolvent swelling agents on the average pore size and pore size distributions at the surface of polyamide membranes which result from casting solutions involving above nonsolvent swelling agents.

The size of the polymer aggregate in the film casting solution and the size of polymer network pores are correlated to physicochemical data of ions which constitute the electrolytes used as nonsolvent swelling agents. As such ionic properties the charge density and the free energy of transition of ions from polyamide phase to water phase were considered. The validity of the correlation is limited in a range of casting solution composition where the polymer concentration in the casting solution is close to the limiting concentration of polymer at the phase boundary and the molar ratio of the nonsolvent swelling agent to the amide group involved in the polyamide polymer is equal to or slightly more than 0.7.     

CONCENTRATION POLARIZATION OCCURRING INSIDE THE MEMBRANE DURING STEADY STATE PERVAPORATION

Experimental profiles of a single penetrant (water) across the membrane have been established at different downstream pressures during steady state pervaporation. The profiles ofacetic acid-water binary penetrant system across the membrane were also measured at different downstream pressures, temperatures and compositions during steady state pervaporation. A stack of identical pre-characterized symmetric aromatic polyamide membranes was used for the profile study. The theoretical prediction of concentration polarization from mathematical equations has been confirmed by the experimental profile data for a binary penetrant system.     

Soluble aromatic polyamides bearing asymmetrical diaryl ether groups

A series of novel aromatic polyamides containing asymmetrical diaryl ether structure were synthesized by the phosphorylation polyamidation of 5-(4-aminophenoxy)-1-naphthylamine with various dicarboxylic acids. The polymers were obtained in high yields and moderately high inherent viscosities (0.74-1.36 dl/g). Except for one example, all the polyamides were amorphous and readily soluble in many organic solvents and could afford flexible and tough films via solution casting. The cast films exhibited good mechanical properties with tensile strengths of 90-128 MPa, elongations at break of 9-64%, and initial moduli of 2.08-3.08 GPa. Glass-transition temperatures ranged from 222 to 288 °C by DSC. Thermal stabilities by TGA for the polymer series ranged from 462 to 517 °C in air at the point of 10% weight loss. These polyamides displayed a lower crystallinity and better solubility and film-forming capability than the corresponding analogues derived from symmetrical 1,5-diaminonaphthalene and 1,5-bis(4-aminophenoxy)naphthalene.     

Studies on the synthesis and properties of poly(amide-azomethine)

Homopolymer and copolymer of poly(amide-azomethine) were synthesized from the corresponding diamines and dialdehydes. The polymerization was proceeded in the mixed solvent of o-chlorophenol and m-cresol (1: I by volume) at 0 °C for I S h. The inherent viscosities of the new aromatic poly(amide-azomethine)s are in the range of 0.51 to 2.31 dl/g. These polymers were soluble in sulfuric and formic acid. The TGA results show that no weight loss up to 400 °C under nitrogen atmosphere, which suggests the relatively good thermal stabilities.