Poly(vinyl chloride) stabilization with organo-tin compounds: Part VII—Dibutyl tin maleate: Model compound studies

The reaction between dibutyl tin maleate or dibutyl tin bisbutylmaleate and chlorohexene as a model compound for allylic chloride in PVC was studied at 80°C in dichlorobutane solution. From kinetic studies by gas chromatographic analysis of the reaction medium, and also spectroscopic data (infra-red and ¹H NMR) it may be concluded that the main reaction is the substitution reaction which produces mono- and dihexenyl esters, as well as mixed diesters of maleic acid. The elimination reaction plays a minor rôle. Both activities are related to their Lewis acidities. The Diels-Alder condensation between maleates and hexadiene is not observed as a side reaction in these conditions; the main side reaction is the decomposition of monoesters of maleic acid (which is produced by the elimination reaction after one or two steps) into an alcohol and maleic anhydride—a reaction which can be catalysed by organo-tin chlorides. A Diels-Alder reaction between maleic anhydride and hexadiene takes place. The alcohol produced in the side reaction mentioned above may take part in a transesterification reaction with the organo-tin maleate and that reaction probably provides the best explanation of the earlier observation of Frye et al.,¹ according to which there is at least temporary retention of reactivity of tin labelled organo-tin maleate by PVC.     

Computational study of the catalytic synthesis of 5‐nitro‐1,2,4‐triazol‐3‐one

In this study, 5‐nitro‐1,2,4‐triazol‐3‐one (NTO) was theoretically synthesized from urea via chlorination followed by amination, formylation, and nitration under aqueous and gaseous environments based on experience of experimental methods, and metal chlorides and metal oxides were used as catalysts to promote reaction. Reaction routes closely related to experimental processes were successfully constructed, and the corresponding energy barriers were estimated for each elementary reaction. Reaction conditions distinct from those reported in the literature (including the adoption of aluminum chloride, ferric chloride, aluminum oxide, ferrous oxide, and chromium oxide catalysts, the use of nitric acid and dinitrogen pentoxide as nitration agents, and adjustment of the reaction temperature) were used in corresponding reaction systems, and the modeling results suggested that ferric chloride is a good catalyst for the chlorination reaction, ferrous oxide is suitable for catalyzing amination, formylation, and nitration, and nitric acid is the better agent for nitration. Estimates of the comparable energy barriers for each reaction stage were considered to imply more feasible pathways for NTO synthesis. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Reaction of sulphuryl chlorofluoride with a few metals and metal oxides

Sulphuryl chlorofluoride has no observable reaction with metals and metal oxides at room temperature. Metals like copper, silver, iron, and zinc react with the chlorofluoride in the temperature range 200–400°C. Metal chlorides, metal fluorides and sulphur dioxide are the main products of these reactions. With the corresponding metal oxides, on the other hand, the respective metal sulphates are formed in addition to the metal chlorides and fluorides. In the case of lead and lead oxide, lead chlorofluoride is formed instead of lead chloride and lead fluoride. Sulphuryl fluoride is formed in small quantities in all these reactions by the decomposition of the chlorofluoride. Glass is not attacked by sulphuryl chlorofluoride below 500°C.During the course of our investigations on the reactivity of sulphuryl chlorofluoride, it is observed that sulphuryl chlorofluoride does not react with glass up to 500° C. However, it reacts with metals and metal oxides between 200° to 400° C. The reaction products with metals are the corresponding metal chlorides, metal fluorides and sulphur dioxide. With the oxides, in addition to the metal chlorides and metal fluorides, metal sulphates are formed. The results of these investigations are presented in this communication.     

Acyl and Sulfonyl Derivatives of 3,5-Diamino-1-R-1,2,4-triazoles

3-Acylamino-5-amino-1-R-1,2,4-triazoles are formed regioselectively on acylating 3,5-diamino-1-R-1,2,4-triazoles with an equimolar amount of anhydrides, carboxylic acid chlorides, and sulfonyl chlorides. With an excess of anhydride and carboxylic acid chloride 3,5-diacylamino-1-R-1,2,4-triazoles are formed. 3-Acylamino-5-amino-1-R-1,2,4-triazoles do not interact with sulfonyl chlorides. The higher reactivity of the 3-amino group towards acylating agents is determined by electronic and not steric factors. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1342–1350, September, 2005.     

The reaction of diphenyl carbonate with amines and its application to polymer synthesis

Selective formation of biscarbamates from diphenyl carbonate (DPC) and diamines and the preparation of polyurethanes from the carbamates and diols under mild conditions were studied. The reaction of DPC and diamines was significantly affected by catalysts, biscarbamates being exclusively prepared in high yields in the presence of 2-hydroxypyridine. The polycondensation reaction of the biscarbamates with diols was facilitated by catalysts such as metal salts; among the catalysts examined magnesium chloride in pyridine gave the best results. Metal chlorides in pyridine also promoted the reaction of DPC with aromatic amines to give the corresponding ureas, and the direct synthesis of polyureas was achieved by the polycondensation of DPC with diamines in the presence of the chloride.     

Synthesis of cellulose benzoates under homogeneous conditions in an ionic liquid

The ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) as a reaction medium was studied for the synthesis of cellulose benzoates by homogeneous acylation of dissolved cellulose with benzoyl chlorides in the absence of any catalysts. Cellulose benzoates with a degree of substitution (DS) in the range from about 1 to 3.0 were accessible under mild conditions. The DS of cellulose derivatives increased with the increase of the molar ratio of benzoyl chloride/anhydroglucose unit (AGU) in cellulose, reaction time, and reaction temperature. Benzoylation of cellulose with some 4-substituted benzoyl chlorides including 4-toluoyl chloride, 4-chlorobenzoyl chloride and 4-nitrobenzoyl chloride was also readily carried out under mild conditions. Furthermore, regioselectively substituted mixed cellulose esters were synthesized in this work. All products were characterized by means of FT-IR, ¹H-NMR, and ¹³C-NMR spectroscopy. In addition, at the end of benzoylation of cellulose, the ionic liquid AmimCl was easily recycled. When the recycled AmimCl was used as the reaction media, the cellulose benzoate with a similar DS was obtained under comparable reaction conditions.     

A Visible Light Driven Nickel Carbonylation Catalyst: The Synthesis of Acid Chlorides from Alkyl Halides

We describe here the development of a visible light driven nickel carbonylation catalyst. The combination of the large bite-angle Xantphos ligand with nickel(0) generates a catalyst capable of activating alkyl halides toward carbonylation at ambient temperature in the presence of blue light irradiation, and the reductive elimination of high energy acid chloride products. Unlike classical carbonylations, where the coordination of carbon monoxide inhibits the reactivity of earth abundant nickel catalysts, a CO-associated nickel is found to be the active catalyst in the reaction. Coupling the build-up of acid chlorides with nucleophile addition can be used to access various amides, esters and thioesters, including those of sterically encumbered substrates or with metal-reactive functionalities.     

微波辅助的金属氯化物Lewis酸催化纤维素水解

研究了微波辐射下四种金属氯化物Lewis酸的催化纤维素酸水解反应性能,发现CuCl₂的催化性能最好。反应温度、反应时间、微波功率、催化剂用量和酸种类对纤维素水解转化率、葡萄糖和5-羟甲基糠醛(5-HMF)的选择性均有明显影响。与传统热反应相比,微波辐射明显加快纤维素酸水解速率,提高葡萄糖的选择性。0.5g纤维素和15g水,在微波功率800W,温度到达225℃时立即停止反应的条件下,当CuCl₂用量为0.05mmol时,纤维素转化率和葡萄糖选择性达72.6%和62.3%;当CuCl₂用量为0.15mmol时,5-HMF的选择性最高为13.2%;当CuCl₂用量为0.30mmol时,纤维素的转化率高达90.6%,但葡萄糖选择性只有6.7%。     

Synergistic effect of ferric chloride and silicon mixtures on the thermal stabilization enhancement of ABS

A previous study from this laboratory has shown that Lewis acid-type transition metal chlorides (NiCl₂, CoCl₂, ZnCl₂, and FeCl₃) are effective char forming catalysts for ABS terpolymer in an inert atmosphere [Jang J, Kim JH, Bae JY. Polym Degrad Stab 2005;88(2):324.]. However, transition metal chloride catalysed char formation (and flame-retardance enhancement) of ABS in air was unsuccessful due to the oxidative degradation of the char at a higher temperature. In order to overcome these undesirable phenomena, we incorporated silicon with transition metal chlorides as co-catalyst and a series of ABS/transition metal chloride/silicon compounds were made from them and their flame retardancy was evaluated by measuring the limiting oxygen index (LOI) values. Our results showed that among various transition metal chloride/silicon catalyst systems the incorporated mixture of ferric chloride and silicon is very effective in enhancing the thermal stabilization of ABS and LOI value as high as 33 is obtained. The reason for this synergistic effect by ferric chloride and silicon was postulated to come from the interaction between ferric chloride and silicon at elevated temperatures, probably generating silicon tetrachloride and hydrogen chloride.     

Synthesis and reactivity of amino-substituted BEDT-TTF donors as building blocks for bifunctional materials

The first two amino-substituted BEDT-TTF derivatives, aminomethyl-ET (AMET) and aminoethyl-ET (AEET), have been prepared; the critical step in both cases was a hetero Diels-Alder reaction with 1,3-dithiole-2,4,5-trithione. AEET shows expected reactivity towards electrophiles whereas AMET will not react with aryl acid chlorides or sulfonyl chlorides, but amides of AMET can be produced by DCC coupling and mixed anhydride methods.     

Stabilization of poly(vinyl chloride) with organotin compounds: Part VIII—Catalytic action of organic acids and anhydrides with organotin carboxylate

When maleic acid or maleic anhydride are added to a dichlorobutane solution of chlorohexene (as a model compound for allylic chlorides in poly(vinyl chloride)) and organotin carboxylates (maleates or laurate) heated at 80°C, the esterification reaction is strongly accelerated; moreover, the formation of hexadiene, which is the expected product of the competitive elimination reaction, is not observed. The reaction is first order with respect to both chlorohexene and the organic acid or anhydride, and may either be zero or first order with respect to the organotin carboxylate. ¹H-NMR spectra and solubility experiments indicate the formation of complexes between the organotin carboxylate and the organic acid or anhydride. A concerted mechanism between the chlorohexene and these complexes is suggested. A few experiments show that the addition of these organic acids or anhydrides to a PVC formulation leads to improvement of the thermal stability.Finally, other organic acids and anhydrides were also used to complex the organotin carboxylate in order to rule out the complexation mechanism and to discuss the activated complex.     

The effect of temperature on the enthalpy of mixing of polyelectrolyte solutions

The effect of temperature on the enthalpies of mixing of sodium dextran sulphate and sodium alginate with sodium chloride has been determined and the results compared with the predictions based on the line charge theory. Better agreement between experimental and calculated values is obtained at the higher reaction temperature, as previously found for the enthalpies of dilution. Measurement of the additional enthalpy changes occurring when different alkali metal chlorides are mixed with the sodium salt of the polyanion gives the sequence Li⁺ > Na⁺ > K⁺ in order of decreasing overall endothermic enthalpies of reaction. The same sequence is observed with polysulphates and polycarboxylates at different temperatures.     

Effects of stirring rate for thermal runaway reaction in cumene hydroperoxide manufacturing process using calorimetric techniques

A high temperature (1000 °C) thermochemical process for heavy metal removal from sewage sludge ash via the chloride pathway was investigated by thermogravimetry/differential thermal analysis (TG/DTA). TG and DTA measurements gave information about secession and evaporation of water, HCl, and heavy metal chlorides at different temperatures. Additionally, gaseous water and hydrochloric acid which occurred in the process were detected by an FT-IR detector that was coupled to the TG/DTA-system. Heavy metal chlorides which were also formed in the process cannot be detected by this technique. For that reason the outlet gas of the TG/DTA-system was discharged into washing flasks filled with water for absorption. The washing flasks were replaced in temperature steps of 50 °C and the heavy metal concentrations of the solutions were determined by ICP-OES. The temperature-dependent formation/evaporation of different heavy metal chlorides was analyzed and compared for two different thermochemical processes using magnesium chloride hydrate or calcium chloride hydrate as Cl-donors. In both cases evaporation of Cd, Cu, Pb, and Zn was observed from 600 °C, whereas As, Cr, and Ni remained in the solid state. The results were discussed against the background of thermodynamic calculations.     

金属化合物催化的1,1′-联二萘酚-4,4′-二乙酸酯和二(2-乙基己醇)碳酸酯的酯交换

芳香族聚碳酸酯性能优良,其中双酚-A型聚碳酸酯是应用广泛的工程塑料,通常采用光气法或酯交换法来制备,但芳香双羟基化合物与二烷基碳酸酯的酯交换反应速度十分缓慢,需要使用催化剂,且反应温度较高,反应过程伴随着复杂的副反应。本文用金属化合物作催化剂进行1,1′-联二萘酚-4,4′-二乙酸酯和二(2-乙基己醇)碳酸酯的酯交换反应,评价了不同金     

TeCl4 as a catalyst in cationic oligomerisations and polymerisations

TeCl₄ catalyses the oligomerisation and polymerisation of certain substituted phenylethylenes and substituted benzyl chlorides. The catalysis is cationic, TeCl₄ acting as a Lewis acid. The termination of polymerisation of the substituted ethylenes is by an internal Friedel-Crafts reaction, whereas that of the substituted benzyl chlorides is by reaction with chloride ions. Contrary to the usual reactivity sequence, stilbene was found to be more reactive than α-methylstyrene in the TeCl₄-catalysed polymerisations.     

Characterizations of modified cassava starch with long chain fatty acid chlorides obtained from esterification under low reaction temperature and its PLA blending

In contrast to typical starch esterification in an aqueous solution, which are carried out at elevated to ambient reaction temperatures, a low reaction temperature was applied in this study to minimize the starch chain hydrolysis. The physical properties of the modified starch, obtained from an esterification of cassava starch with long-chain fatty acid chlorides carried out in aqueous media at 4°C, were characterized using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and contact angle measurements. The modified starches show improvement in thermal stability and hydrophobicity, which can be further optimized by varying the types of acid chlorides and the reaction conditions. The starch products have high potential for use as fillers for biodegradable polymers, especially polylactic acid (PLA), as their tunable hydrophobicity can impose strong effect on controlling of the PLA's hydrolytic degradation rate for specific applications. Results on mechanical properties of the blends between the modified starch and PLA show an improvement in modulus of the polymer.     

Rapid conversion of cellulose to 5-hydroxymethylfurfural using single and combined metal chloride catalysts in ionic liquid

Direct conversion of cellulose into 5-hydroxymethylfurfural(HMF) was performed by using single or combined metal chloride catalysts in 1-ethyl-3-methylimidazolium chloride(Cl) ionic liquid.Our study demonstrated formation of 2-furyl hydroxymethyl ketone(FHMK),and furfural(FF) simultaneously with the formation of HMF.Various reaction parameters were addressed to optimize yields of furan derivatives produced from cellulose by varying reaction temperature,time,and the type of metal chloride catalyst.Catalytic reaction by using FeCl3 resulted in 59.9% total yield of furan derivatives(HMF,FHMK,and FF) from cellulose.CrCl3 was the most effective catalyst for selective conversion of cellulose into HMF(35.6%) with less concentrations of FHMK,and FF.Improving the yields of furans produced from cellulose could be achieved via reactions catalyzed by different combinations of two metal chlorides.Further optimization was carried out to produce total furans yield 75.9% by using FeCl3/CuCl2 combination.CrCl3/CuCl2 was the most selective combination to convert cellulose into HMF(39.9%) with total yield(63.8%) of furans produced from the reaction.The temperature and time of the catalytic reaction played an important role in cellulose conversion,and the yields of products.Increasing the reaction temperature could enhance the cellulose conversion and HMF yield for short reaction time intervals(5~20 min).     

光气法制备酰氯的催化剂研究进展

酰氯是一类用途非常广泛的重要有机合成中间体,在工业上制备酰氯主要使用的氯化剂包括PCl3、PCl5、SOCl2、光气等,充分反应后通过过滤、蒸馏等工艺进行脱色提纯制得酰氯。光气法由于对环境污染较低,是目前最常用的方法。三光气可以分解成光气,其优良的物理、化学性质以及便捷的储存和运输条件是光气的最佳替代化学品。但由于光气活性较低,在使用过程中添加催化剂必不可少,本文将重点介绍目前光气法制备酰氯时所使用的各种催化剂及其性能。     

Enantioselective ester synthesis in the presence of optically active polymers

Enantiomer-differentiating ester syntheses from acid salts, chlorides, and an anhydride were studied in the presence of optically active polyamines. Enantiomer selection occurred in reactions of a racemic salt with an achiral alkyl bromide and vice versa, which is good evidence of the importance of activation of the carboxylate group by complexation of the counterion and activation of alkyl bromide by the formation of a quaternary salt with polyamine under solid–liquid, phase-transfer reaction conditions. Only small optical activity was observed in the products of acid anhydride or chloride with alcohol.     

Solid State Metathesis Reactions in Various Applications

Solid state metathesis reactions have been studied in fused silica tubes, by differential thermal analysis, and by X‐ray powder diffraction. A selection of reactions between metal (La, Nb, and Ni) chlorides and lithium nitride or lithium acetylide were investigated to get more insight into reaction pathways and intermediate reaction stages that may be adopted on course of the formation of metal nitrides or carbides. Intermediate compounds are considered to be important because they can control the reactivity of a system. Such compounds were traced by changing the molar ratios of reaction partners away from the salt‐balanced binary metal nitride or carbide target compositions. New preparative perspectives are discovered when metal chlorides were reacted with lithium nitridoborate or lithium cyanamide. Due to their reductive nature towards several d‐block metal chlorides, (BN₂)^3‐ and (CN₂)^2‐ react to form metals or metal nitrides plus X‐ray amorphous BN, and probably C₃N₄. With lanthanum chloride they can react to form nitridoborates and nitridocarbonates. The metathesis reaction between lithium cyanamide and cyanuric chloride (C₃N₃Cl₃) instead of metal chloride was studied for the synthesis of C₃N₄.