SU538661A3 - Urethane production method - Google Patents

Description

(54) Process for the preparation of urethanes oksimegilen, dimegilensulfon or osgago Dime tilenke rutting, jR may be an alkyl, CEC loalkil, alkylene, cycloalkylene or aralkyl which may contain a chain oxygen atom, nitrogen or sulfur, sulfoxide, sul background, amine, amide carbonyl or cyclocarboxylic ester groups. In addition, R may be substituted with alkyl, aryl, alkoxy or aryloxyl with at least 10 carbon atoms. Most often of alcohols, methyl, ethyl, n and sec-propyl, nizo and tert-butyl, amyl, hexyl, lauryl, cetyl, benzyl, chlorobeneyl, methoxybenzyl alcohols, ethylene, diethylene, propyl- and dipropy / tenglycol, glyderol, trimethylolpropane, hexanetriol, pentaerythritol, and also polyols, glyders, trimethylol propane, hexanetriol, pentaerythritol, and also esters, and polymers, glyderol, trimethylolpropane, hexanetriol, pentaerythritol, and also esters, glyderol, glyderol, glyderol, trimethylolpropane, hexanetriol, pentaerythritol, and also polymers, glyderol, glyderol remains unesterified, esterified The group in such ether alcohols usually contains up to 10 carbon atoms and is preferably alkyl, cycloalkyl or apajt kil, which can be substituted by halo id. Phenols may contain substituents in the benzoid rings, for example alkyl or alkoxy with 1-10 carbon atoms and halogen. Of the mono- and polyatomic phenols used, phenol, chlorine alkylphenols, catechin, resorcinol, hydroquinone, 4,4-dihydroxydiphenylmethane, naphthols, chlorine, methyl-, these, butyl- and octylnaphols, antranols, methyl, ethyl -, buty # and octyl anthro- nols, phenanthrols, chlorine, methy-n-, these # -, butyl and octylphenanthrols, pyrogallol, phloroglucin and polyhydroxyphenol ethers, provided that in Kpai, at least one hydroxyl group is with non-esterified, The esterifying group in such esters usually contains up to 10 carbon atoms and represents L is preferably an alkyl, cycloalkyl or apaj keel, which may be substituted, for example halo. An example of a nitrogen-containing compound is one that contains at least one non-cyclic group in which the nitrogen atom is directly bonded to one carbon atom and through a double bond to an oxygen atom or another nitrogen atom. Such compounds include organic nitro, nitroso, azo, and azoxy. Compounds containing up to 24 carbon atoms, preferably nitroaromatic and tertiary nitroaliphatic compounds. As nitro compounds, mononitro compounds are used, such as nitrobenz sol, alkyl- and alkoxynitrobenzenes, in which atzhil contains 1-1O carbon atoms, aryl- and aryloxynitrobenols, in which aryl represents unsubstituted or substituted for chlorine, phenyl, tolyl, xylyl, naphthyl, chloronitrobenzene and dinitro compounds, such as o-, m- and p-dinitrobenzenes, alkyl- and alkoxy-dinitrobenzenes, chlorodinitrobenzenes, trinitro compounds, such as trinitrobenzene, alkyl-, alkoxo-N, aroyl- and aryloxitrin-nitrobenzene, alkyl-, alkoxy-N, nitro-nitro, and aryloxy-nitrobenzenes; olinitro derivatives of naphthalene, diphenyl, diphenylmethane, anthracene and phenanthrene. Substituted or unsubstituted Alifa .ticheskie nitro compounds such as mononitroproizvodnye methane, ethane, propane, butane, cyclopentane, cyclohexane, cyclobutane, octadecane, 2,2 dimetilnitrobutan 3-methane tilnitrobutan, Z-1-nitropropene, fenilnitrometan n bromo- , p-nitro and p-methoxyphenylnitromethane, dinitro derivatives of ethane, propane, butane hexane, decane, cyclohexane, methylcyclohexane, di- (nitrocyclohexyl) methane - can also be used. However, when using primary, secondary and cycloaliphatic compounds, the yield of urethanes is reduced. Aromatic nitro compounds are best taken nitrobenzene, nitrotoluene, dinitrobe№zol, dinitrotoluene, trinitrobenzene, 4,4 -dinitrodifenilmetan, p-nigroanizol, p- and o-nitroetoksibenzol, 2,4-dinitroanizol, 2,4-dinitroetoksibenzol, 3, 5-dinitrobenzyl acetate, 1-chloro 2,4-dimethox-5-nitrobenzene, 1,4-dimethoxy-2-nitrobenzene, p-nitrophenyl nitromethane and tertiary aliphatic nitro compounds, such as 2-methyl-2-nitropropane and 1-methyl -1-nitrocyclohexane. Most preferably, 2,4-, 2,5-, and 2,6-dinitrotoluenes, m- and p-dinitrobenzenes, and 4,4-dinitrodiphenylmethane are used. Among the nitro compounds, we can mention mono dinitrose derivatives of benzene and toluene, nitrosobutane, nitrosocyclohexane, and diniosemethylcyclohexane. As azo compounds, compounds of the general formula can be used, where R and R are the same or different unsubstituted or substituted alkyls or aryls, for example azobenol, nitrosobenzene, chloroisobenzene, alkyl- or ril-substituted azobenzenes. Of the azoxy compounds of the general formula (0) K, as shown above, the most preferred are azoxybenol, nitro and chloro-oxybenol, alkyl or aryl-substituted azoxybenzenes. In order to obtain ureganes, it is possible to omit mixtures of nitro, nitroso, azo or azoxy compounds with a mixture of hydroxyl containing compounds, as well as compounds containing both functional groups, i.e. hydroxy-nitro, hydroxy-nitro-, hydroxy-azo- and hydroxy-azoxy compounds, such as 2-hydroxy-synthroethane, 2. piproxynitrozo-ethane, nitrobenzenes, nitrosophenols, nitro- and nitro-naphthols, hydroxy-azo and hydroxyazoxybenzenes However, the highest yield of urethanes was observed. Metallic selenium can be used as a catalyst, especially in powder form, and its derivatives, such as selenium dioxide and trioxide, selenium oxide mixtures, selenium chloroxide, titanium diselide, titanium disulfide selenium, sodium and zinc selenides, zinc and tungsten selenides, selenium sulfide, selenic acid, dimethicN-, diethyl-, diphenylselenide, diethyldiselenide, carbonyl; selenide, diethylpolyselenide, dibutylpolyselenide; elemental sulfur and. its derivatives, for example, hydrogen sulfide, carbon dioxide, carbon disulfide, sodium and potassium sulfides, sulfur dioxide, polysulfides, mercaptans, thioethers containing up to 20 atoms of a genus, or mixtures thereof. The catalyst can be used on its own or applied to an inert carrier such as alumina, silica, coal, barium sulphate, calcium carbonate, asbestos, bentonite, infusorna earth, fuller's earth, organic ion exchange resins. Organic bases, for example, triethylamine, pyridine, quinoline, N, N-dimethyl aniline, diethylamine, treg-butylamine, 1,4-di azobicyclo (2.2,2) -octane, N, N, N, N,

- tetramethylethylenediamine, getramethylenediamine, ethylenediamine, polyvinylpyridine, and salts of metals carboxylic, sulfonic and phosphoric acids, such as lithium, sodium, potassium, calcium acetates, palladium and ruthenium acetates, p-toluenesulfonates, methylsulfonates, acidic phosphates, lituritans, lit-vitae, lit-vitae, lit-vitae, lit-vitae, lit-vitae, lit-vitae, lit-vitae, lit-vitae, lit-vitae, lit-vitae, lit-vitae, lit-vitae, lit-vitae, lit-vitae, litolite, citrate, borate; antimony triacetate. These salts can be directly introduced into the reaction mixture or obtained from the appropriate reagents during the experiment.

The reaction can be carried out without using the base in the presence of water only. However, it is better to use the base in combination with water.

the course of the reaction.

The amount of carbon monoxide is usually 3-50, preferably 8-15 mol, per non-cyclic group, in which the nitrogen atom of the nitrogen-containing compound is directly bonded to one carbon atom and through a double bond to an oxygen atom or another nitrogen atom. Carbon monoxide can be fed to the reactor continuously or intermittently. With the continuous introduction of carbon monoxide and the recycling of unreacted carbon monoxide, the consumption of the carbon monoxide is significantly reduced.

Reaction temperature 100-2OO C, carbon monoxide pressure 1О-1ОО ATA. With more, the process can be carried out in the presence of a solvent, such as benzene, toluene, xylene, aceto and benzonitrile; N, N - dimethylformamide and N, N dimethylacetamide; dimethyl sulfoxide; 1,1,2-trichloro-1, 2,2-trifluoroethane; mono-, di, and trichlorobenzene; tetrahydrofuran (THF), 1,4-dioxane, 1,2-dime toxet ta n. At elevated temperatures and pressures, the reaction can be carried out in an inert diluent medium, for example, an aliphatic or aromatic hydrocarbon, such as n-pentane, toluene, ethers, esters, ketones. The molar ratio between the catalyst and the nitrogen-containing organic compound is 1: 1 O - 1: 1000. In determining the molar ratio, it is based on the content of elemental selenium or sulfur and the active aero-containing groups, for example, not a group. The molar ratio between the nitrogen-containing compound and the base is 50: 1 - 1:10, and between the water and the catalyst 0.5: 1 - 1000: 1, preferably 1; 1 - 200: 1, at the reaction temperature more, only water without a base can be used. At lower temperatures, the use of a base in combination with minimal amounts of water to achieve a high yield of the desired products is necessary. The water needed for the reaction can be separated when the salt used as a base is obtained from the corresponding acid and metal oxide hydroxide. During the reaction, a certain amount of by-products, mainly amines, can form along with the urethanes, especially when using a sulfur catalyst and / or more water. The order of reagent displacement depends on the design features of the equipment used and does not significantly affect the high temperature; decomposition of the initial or resulting substances is possible. The process of urethane production proceeding in mass can be carried out in a semicontinuous or continuous FW method. For a continuous method, especially suitable Ion exchange type catalysts. The reaction time depends on the nature of the reactants, temperature, pressure, type of catalyst and type of equipment used. It is usually less than 180 minutes, e.g. 10-75 minutes. Target products are isolated by known methods. The resulting urethanes contain one or more urethane groups and, by their nature, can be monomeric or polymeric. From urethanes containing no more than three urethane groups per molecule, one can obtain the corresponding isocyanates using thermal and catalytic treatment. Linear polyurethanes used in the production of fibers or elastomers can be mo- gous (googled directly from diols, dinitrocompounds and carbon monoxide, or from hydroxy compounds and carbon monoxide, while polyurethanes used as flexible or solid, PLASTIC materials can be obtained from mixtures of diols or polynitro compounds of diols or polyols and carbon monoxide.In all examples, the conversion and yield of the target products are determined by gas chromatography, Examples 1-11, Nitrobenzene, m Tyl alcohol, selenium and base are loaded into a 110 ml rotating autoclave withstand the required time at a certain temperature and pressure of carbon monoxide and the resulting urethane is separated. The results of the experiments are shown in Table 1, Example 12 of nitrobenzene. , 0.5 g of selenium, 45–35 ml of THF and 1 or 2 g of sodium acetate trihydrate are maintained at an initial pressure of 56.2 kg / cm carbon monoxide and a temperature of 200 ° C in a 110 ml rotating autoclave. After 10 minutes, the conversion of 50 nitrobenzene reaches 64 or 70%, and the yield of urethane is 74 or 63%, respectively. When carrying out the reaction at 170 ° C after 6O, the conversion of nitrobenzene is 72 or 100%, and the yield of the target product is 55% 7O or 74 %, respectively, Example 13, From 5 ml of nitrobenzene, 30 ml of methyl alcohol, 35 ml of THF, O, OO8 mol of lithium acetate monohydrate and 0.5 g of selenium by analogy to example 12 (60 5 , 2 kg / cm, temperature 170 ° C) after 10 minutes after receiving the south of the desired product with a yield of 68%, Conversion of nitrobenzene 94%, When carrying out the reaction at 170 or within 60 minutes or at 13 ° C for 140 minutes, the conversion of nitrobenzene is 100, 87 or 71%, and the yield is 3 85 or 71% respectively, Example 14, As in example 13, but using 0 as catalyst , 1 g of titanium disulfide and carrying out the reaction at 150 ° C after 60 min get a “spruce product with 88% srsodam. Conversion of nitrobenzene 86%. In the absence of acetate monohydrate, lithium nitrobenzene does not react. Examples, O, 29 g of lithium hydroxide, 0.72 g of acetic acid, nitrobenzene, methyl alcohol, 15 ml of dioxane and a catalyst are placed in a 110 ml autoclave and kept at a certain temperature and initial pressure - carbon monoxide. The results of the experiments are given in the table. 2 Example 20, 10 ml of nitrobenzene, 65 ml of methyl alcohol, 2, 1 or 0.5 g of seoi, 1.6 ml of pyridine and 1 g of trihydroxybenzene; c r nv Rut is pumped into sodium acetate cell and loaded into a 300 ml autoclave and held at an initial pressure of carbon monoxide of 183 kg / cm and a temperature of 200 C for 45 minutes. Conversion of nitrobenzene 94, 83 or 46%, the output of urethane 33. 38 or 32% respectively Example 21, In an autoclave with a capacity of ZOO ml load Yu ml of nitrobenzene. Methyl alcohol, 35 ml of 1,4-diode, 0.5 g of metallic selenium alkaline bases, is kept for 30 minutes at a temperature of 20 ° C and an initial pressure of carbon monoxide of 183 kg / cm and the desired product is isolated. When used as a base, 1 g sodium trihydrach acetate; 1 g of sodium acetate (molten); 1 g sodium acetate (molten) in the presence of 0.2 g water; sodium acetate, psnluchennoy of 0.48 g of sodium hydroxide and 0.72 g of acetic acid in the reaction mixture; 1 g of anhydrous potassium acetate and 1 g of anhydrous potassium acetate in the presence of 0.2 g of water, the conversion of nitrobenzene is 100, 8, 100, 91, 50 and 100%, respectively. In the presence of 0.2 g of water, the conversion of nitrobenzote reaches 64%, and in the absence of water and a base, only 9%, Example 22, 0.29 g of lithium hydroxide, 0.72 g of acetic acid, 0.50 g of selenium, 1 O, 7 g of nigrobenol or 19.8 g of aoxybenzene, 30 ml of methyl and 35 ml of dioxane load and autoclave with a capacity of 300 ml and hold for 30 minutes at a temperature of 200 ° C and an initial pressure of carbon monoxide of 183 kg / cm, Conversion of nitrogen-containing compounds Neither reaches 100 or 86%, and the output of the urethane is 7O or 69%, respectively. Examples 23-27. 10.9 g of 2,4-dinitrotoluene, ethyl alcohol, potassium hydroxide, acetic acid, base, and powdered metallic selenium are loaded into a 300 ml autoclave and carbon monoxide is fed into it to a pressure of 56.2 kg / cm and held at a certain temperature. . In all experiments, the results of which are given in Table. 3, the conversion of 2,4-dinitrotol ol is 10 O%, Example 28. In a pilot plant, including a reactor, equipped with a stirrer, a liquid mixture is fed containing (in wt.%): 1O industrial dinitrotoluene (80% 2,4-dinitrotoluene and 20% 2,6-dinitrotoluene), 87 industrial ethanol (denatured ethanol containing 2% benzene), 1 acetic acid, 1 potassium hydroxide and 1 selenium dioxide, together with a stoichiometric excess of carbon monoxide. Optimal reaction conditions: temperature 177 ° С, contact time 30 min, pressure 71 kg / cm. Under these conditions, the conversion of dinitrotoluene is 100%, the yield of diurethane is 90-95%. At a temperature of 152 ° C and a contact time of 6O, 30, and 15 min, the conversion is 100%, 90%, and 76%, respectively. When the process is carried out at a temperature below 177 and a contact time of 30 minutes, the yield of diurethanes decreases with a simultaneous increase in the yield of monourethanes. When re-conducting is performed at a temperature above 177 ° C and a contact time of more than 30 minutes, the output of diurethanes usually decreases. Under optimal conditions, the reaction proceeds rapidly even with a low concentration of catalyst, for example, conversion reaches 90% at a concentration of selenium catalyst of 0.07 wt.%.

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table 2

The reactions were carried out in 35 ml of THF in a 300 ml bottle.

Ky

The test was conducted in a 300 ml autoclave.

1920

Formula iaobregeni selenium, sulfur, selenium compounds, compounds

1. A method of producing uahanes of vaimod-base and / or water, with a hydroxyl-containing organic 2. Method pop, 1, distinguishing compounds with carbon monoxide and azo-coder, with the fact that the reactivity is carried out at a pressure of an organic compound in the presence of carbon monoxide 10-100 per day and temperature and pressure in the presence of 100-200 C,

VII catalyst followed by separation-3, The method according to PP, 1 and 2, distinguishes the target product by known methods, y and the fact that the process is carried out in distinction with the fact that, for the purpose of a yuli ratio between the catalyst

to increase the yield and purity of the target pro- and nitrogen-containing organic compounds, as the catalyst we use 1: 1O - 1: 1000,

538661

sulfur or their mixtures and the process Vedug in