The method of producing methylenediamine

 

(57) Abstract:

Use: receive methylenediamine with plasticizing and antiseptic properties. The inventive spend acetoxysilane of trioxane acetic anhydride at a molar ratio of trioxane-anhydride 1:(1,1-1,3), at 100-120C and using as a catalyst sulfonic cation exchanger in acid form.

The invention relates to the field of organic chemistry, more specifically to a method of obtaining methylenediamine, which are used as plasticizing agents for polyformaldehyde, and antifungal agents.

A known method of producing methylenediamine boiling of paraform with acetanhydride in the presence of concentrated sulfuric acid as a catalyst [1] because of the presence in the reaction mass of concentrated sulfuric acid allocation of the target product is accompanied by a significant resin formation. In addition, corrosive environment caused by the contamination of the product and expensive instrumentation process.

These drawbacks are partially removed in another known method in which to obtain a mixture of mono - and diethylenediamine is at 60aboutC for 10 min, the molar ratio of trioxane-acetanhydride is 1:4,5. The output of equimolar mixture of mono - and diethylenediamine 58%

The process under more mild conditions than in the method [1] allows to significantly reduce the impact of corrosion on the purity of the products, and the material of the apparatus, however, significantly complicates the task allocation methylenediamine, badly divided distillation with diethylenediamine, probably due to the formation of associates. The output of this product in the most favorable case does not exceed 29% of the Homogeneous catalyst used in this method cannot be selected for re-engaging in the process and, as a consequence, it is impossible to organize the process in a continuous pattern.

The objective of the invention was to increase the yield and purity of methylenediamine while simplifying the process.

The problem is solved in this invention by using a method of obtaining methylenediamine by the interaction of trioxane with acetanhydride in the presence of an acid catalyst, wherein the process is carried out at a molar ratio of trioxane-acetanhydride 1:1,1-1,3, the temperature of 100-120aboutSince, in the presence accordance with the invention allows selective process, which are not formed difficultly separating impurities with high yield (87% or more). The selection of the target product of this reaction mass is achieved by a simple distillation, and the product thus receive high purity (97%). The catalyst is separated by filtration and re-use. It is possible to organize a continuous process.

Thus, the method in accordance with the invention is manufacturable and cost-effective, technically feasible, does not require specially corrosion resistant equipment.

P R I m m e R. In a three-neck flask equipped with stirrer, reflux condenser and thermometer, download 19.5 g (of 0.65 mol) of trioxane, 3.4 g of sulfonic cation exchanger KU-2-FRR N+form and of 80.1 g (74 ml) (0.78 mol) of acetanhydride, heated to 120aboutWith and with constant stirring is maintained at these conditions for 5 hours Then the reaction mixture is cooled, the catalyst is separated by filtration, the filtrate is analyzed by GLC. According to the analysis, the yield of the target product methylenediamine ranges 86-88% Methylundecanal allocate by distillation, extracting the fraction 62-64about/11 mm RT.article get 73-75 g, which is 85-86% of theoretical. The purity of the selected single evaporation Metis-acetanhydride in the presence of an acid catalyst, characterized in that the process is carried out at a molar ratio of trioxane acetanhydride equal to 1 (1,1 1,3), a temperature of 100 120oIn the presence of sulfonic cation exchanger in the H+-form.

 

Same patents:
The invention relates to an improved method for producing a 2-ethoxyethyl ether acetic acid (AEA), which finds extensive use as a solvent for the polyurethane, epoxy,alkyd, acrylic and other film-forming materials

The invention relates to the field of organic synthesis, particularly to a method of obtaining monopropylene esters of carboxylic (fatty, naphthenic, aromatic) acids

The invention relates to acrylic esters, in particular to an improved process for the preparation of acrylate used in organic synthesis

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to methods of preparing catalysts based on sulfurized styrene/divinylbenzene copolymer and thermoplastic polymer material, which are used in processes for preparing alkyl tert-alkyl ethers, hydration of olefins, dehydration of alcohols, preparation of esters, and the like. Invention provides molded ionite catalyst consisted of sulfurized styrene/divinylbenzene copolymer in the form of mixture of powdered copolymers with macroporous and gel structure and, as thermoplastic material, propylene polymers and propylene/ethylene copolymers. Preparation of catalyst is accomplished by extrusion at temperature of heating extruder cylinder 140-200°C and temperature of forming head equal to temperature of the last heated zone of heating cylinder.

EFFECT: increased catalytic activity.

10 cl, 3 tbl, 15 ex

FIELD: polymer production.

SUBSTANCE: title oligomers are prepared via reaction of diphenylolpropane with paraform in organic solvent under basic catalysis conditions followed by polycondensation and etherification in presence of organic solvent added and acid catalyst, particularly ion-exchange resins (sulfo-cationites) with moisture content 40-65%. Proportion of dry-weight cationite to condensation product varies between 2 and 30 wt %.

EFFECT: reduced production cost and reduced amount of waste in production of butanolyzed oligomers.

4 ex

FIELD: chemistry.

SUBSTANCE: invention claims modified ion exchange resin, where at least one compound selected out of the following (A) and (B) compounds is linked by ion link to functional acid group of acid ion exchange resin, so that compound is linked by ion link to 0.1-50 mol % of total functional acid group number present in acid ion exchange resin: compound (A) is represented by formula 1, where P is phosphor atom; S is sulfur atom; H is hydrogen atom; R1 is alkylene group including 1 to 6 carbon atoms, where one fragment can include phenylene group; and each R2, R3 and R4 are independently (1) alkyl group including 1 to 6 carbon atoms, or (3) aryl group including 5 to 10 carbon atoms; and compound (B) is represented by formula 2, where P is phosphor atom; S is sulfur atom; H is hydrogen atom; each of R1 and R2 is alkylene group including 1 to 6 carbon atoms, where one fragment can include phenylene group; and each R3 and R4 are independently an aryl group including 5 to 10 carbon atoms. Also invention claims catalyst for obtaining bisphenols, based on this resin, and method of bisphenol obtaining. Invention claims methods of obtaining modified ion exchange resin (versions).

EFFECT: obtained catalyst with high selectivity to bisphenols, obtaining of bisphenol A with high acetone conversion grade.

9 cl, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to improved method of obtaining (meth)acrylic ester including stage of etherification of (meth)acrylic acid with C1-C4alcohol in presence of catalyst from highly acidic cation-exchange resin in form of immovable layer for obtaining (meth)acrylic ester; addition of polymerisation inhibitor into reactor or into distillation column for isolation; stage of isolation, at which (meth)acrylic acid that did not react is separated from reaction solution, obtained at reaction stage, where temperature in distillation column still is in the range from 60 to 100C, and pressure at the top of distillation column is in the range from 1.33 to 26.7 kPa; and recirculation stage in order to return thus obtained (meth)acrylic acid, that did not react, to reaction stage, where solid substances, contained in isolated (meth)acrylic acid that did not react and is returned to reaction stage, are isolated from it. In industry used method of obtaining (meth)acrylic esters is improved in such way as to prolong service life of used in it catalyst from highly acidic cation-exchange resin.

EFFECT: elaboration of improved method of obtaining (meth)acrylic ester.

5 cl, 2 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention refers to making heat-resistant sulphocation catalysts. There is disclosed method for making heat-resistant sulphocation catalysts containing aromatic rings chemically combined with solid polymer base, at least two groups -SO2OH, by sulphonation of aromatic rings of polymer base followed by desulfonation at higher temperature of those aromatic rings having only one group -SO2OH whereat heat-resistant polymer base is sulphonated, while aromatic rings are sulphonated in two or more stages with gradually increasing sulphonation hardness. The first stage involves soft sulphonation with aqueous sulphuric acid solution concentrated 95 wt % and more at temperature 90C and less, preferentially 70C and less. The last stage implies sulphonation with aqueous sulphuric acid solution concentrated 90 wt % and more or with oleum with SO3 concentrated 1 to 30 wt % higher than chemically combined in acid. The catalyst is sequentially washed by dissolved sulphuric acid solution, then by water. Thereafter it contacts at temperature 150 to 200C with an inert solvent not containing groups neutralising -SO3OH groups and introduced in amount required to remove groups -SO2OH from the aromatic rings containing one group -SO2OH only.

EFFECT: making heat-resistant catalyst of required dimension and/or shape.

8 cl, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a bisphenol synthesis catalyst. The method of producing a bisphenol synthesis catalyst, which contains an acidic cation-exchange resin on which a sulphur-containing amine compound is adsorbed, involves bringing the acidic cation-exchange resin into contact with acidic waste water, which contains a sulphur-containing amine compound, released from the catalyst synthesis stage. The waste water has initial concentration of the said sulphur-containing amine compound equal to or less than 170 parts per million (wt) and contact with the said circulating resin is done until the said concentration falls to 5 parts per million (wt) or less.

EFFECT: considerable removal of sulphur-containing amine compound from waste water after catalyst synthesis.

3 cl

FIELD: chemistry.

SUBSTANCE: description is given of use of a catalyst system for (co)oligomerisation of lactide or glycolide with ring opening. The catalyst system is formed by a polymer catalyst based on a strongly acidic ion-exchange resin (1) and a (co)oligomerisation additive of formula (2) R1-E-R2, in which E is an element of the 16th group, R1 is a hydrogen or deuterium atom, R2 is a hydrogen or deuterium atom or a group in formula - E14(R14)(R'14)(R"14), where E14 is an element of the 14th group, R14, R'14, R"14 - represent a hydrogen atom, a deuterium atom, substituted or unsubstituted alkyl, cycloalkyl or aryl.

EFFECT: proposed catalyst system allows for controlling chain length and nature of terminal groups of compounds, separate compounds from a catalyst using a simple and efficient method and prevent loss of catalyst activity.

14 cl, 8 ex

FIELD: chemistry.

SUBSTANCE: apparatus for re-esterification of organic acid with ester has a fixed-bed catalytic reactor and a distillation column, where the pipe between the reactor and the distillation column is fitted with pressure increasing apparatus, and the head of the distillation column is connected to a phase separator which is in turn connected to said reactor, and flow to the reactor passes through a heat exchanger for regulating reaction temperature. The re-esterification method involves the following steps: A) mixing organic acid a) with ester b) and B) transfer of the alcohol residue of the ester b) to the acid a), accompanied by formation of an ester of acid a) and an acid of ester b), where the transfer of the alcohol residue of the ester b) to the acid a) at step B) is carried out in the apparatus described in claim 1. Reactants are fed into the distillation column to carry out re-esterification in the fixed-bed catalytic reactor lying outside the column; a portion of the liquid phase flowing downwards inside the distillation column is trapped and output from the column in form of a separate stream whose pressure is raised using the pressure increasing apparatus and its temperature is controlled in the heat exchanger before being fed into the reactor; the stream coming out of the reactor is fed into the distillation column where the mixture of reaction products is separated and the stream coming out of the top of the column is separated in the phase separator.

EFFECT: reduced expenses.

11 cl, 1 dwg, 2 tbl, 38 ex

FIELD: chemistry.

SUBSTANCE: invention relates to production of ion-exchange moulded catalysts. Described is an ion-exchange moulded catalyst for organic synthesis, which contains a mixture of copolymers with a macroporous and gel structure, a sulphonated copolymer of styrene and divinyl benzene, and a thermoplastic binding component - polypropylene, wherein the weight ratio of the gel and macroposous components is equal to (3.7-14.0):1, respectively, with respect to the dry catalyst, the amount of the binding component is equal to 20-30 wt % with respect to the dry catalyst, the starting components are taken with residual moisture content of not more than 10 wt % and fractional composition of not less than 95% of a fraction of particles with size in the range of 50-200 mcm. Described is a method of producing said catalyst.

EFFECT: obtaining a catalyst in which there is no blocking of the adsorption space of the catalyst and premature evaporation of water.

4 cl, 2 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing an acrylic ester of formula CH2=CH-COO-R, in which R denotes an alky radical, straight or branched, containing 1-18 carbon atoms and optionally a nitrogen heteratom, wherein at the first step glycerine CH2OH-CHOH-CH2OH is dehydrated in the presence of an acid catalyst to obtain acrolein of formula CH2=CH-CHO, then a second step where the obtained acrolein is converted via catalytic oxidation to acrylic acid CH2=CH-COOH, a third step where the acid obtained at the second step is either esterified with an alcohol R0OH, wherein R0 is CH3, C2H5, C3H7 or C4H9, followed by re-esterification of the obtained ester with an alcohol ROH, wherein R assumes the value given above, or esterified with an alcohol ROH, wherein R assumes said value, where content of furfural in the acrylic ester is less than 3 ppm.

EFFECT: high efficiency of the method.

15 cl, 4 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing dimethyl-1,5-naphthalene dicarboxylate that is used in preparing polymers based on thereof and articles made of these polymers. The economic and effective method involves the following stages: (1) dehydrogenation of 1,5-dimethyltetraline to yield 1,5-dimethylnaphthalene; (2) oxidation of 1,5-dimethylnaphthalene prepared at dehydrogenation stage to yield 1,5-naphthalene dicarboxylic acid being without accompanying isomerization stage, and (3) esterification of 1,5-naphthalene dicarboxylic acid prepared at oxidation stage in the presence of methanol to yield the final dimethyl-1,5-naphthalene dicarboxylate.

EFFECT: improved preparing method.

9 cl, 3 dwg, 5 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for synthesis of carboxylic acid esters that are used as components of lacquered resins and components of paint-and varnish materials, especially, as plasticizer for plastics. Method involves interaction of di- or polycarboxylic acids or their anhydrides with alcohols wherein reaction water is removed by azeotropic distillation with alcohol, and liquid removed from reaction by azeotropic distillation is replaced with alcohol completely again. The improvement of periodic method used in synthesis of esters provides enhancing yield of the end product and reducing the reaction process time.

EFFECT: improved method of synthesis.

5 cl, 4 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of saturated aliphatic carboxylic acids with stable carbon isotopes (1-13C). Method involves the hydrocarboxylation reaction of α-olefins with carbon monoxide (13CO) and water at temperature 100-170°C and under pressure not exceeding 5 MPa in the presence of a solvent and catalytic system containing palladium compound as complex PdCl2(PPh3)2 and triphenylphosphine PPh3 taken in the ratio from 1:2 to 1:100, respectively. Synthesized carboxylic acids can be used as diagnostic test-preparations in medicine practice and in criminology, scientific investigations and in other fields. Invention provides synthesis of enanthic acid and caprylic acid labeled by stable carbon isotope 13C at position 1 for a single step, to increase yield of acids as measured for isotope raw, to decrease cost price of acids and to obtain derivatives of (1-13C)-caprylic acid - (1-13C0-caprylate sodium and (carboxy-13C)-trioctanoine.

EFFECT: improved methods of synthesis.

9 cl, 6 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of chlorine-substituted phenoxyacetic acid esters by the esterification reaction of corresponding acid with (C7-C9)-alcohol of normal structure of isomers, or in the combination. The esterification reaction is carried out in the mole ratio alcohol : acid = (1.1-1.75):1.0 by step-by-step increasing the temperature process. At the first step the process is carried out at the boiling point of azeotrope alcohol : water depending on the residual pressure value generated in the system for separation of the main mass of formed reaction water followed by increasing temperature by 20-60°C for the complete termination of the esterification reaction. The process can be carried out in the presence of catalytic amounts of mineral acids 0.01-0.03 wt.-% of the reaction mass. Invention provides high quality and high yield of the end product.

EFFECT: improved method of synthesis.

Catalyst and method // 2316396

FIELD: organic synthesis and catalysts.

SUBSTANCE: invention relates to esterification method utilizing organotitanium or organozirconium catalyst and provides catalytic composition useful in preparation of esters, including polyesters, which contains (i) product of reaction between metal M alcoholate or condensed alcoholate selected from titanium, zirconium, and hafnium alcoholates, (ii) alcohols containing at least two hydroxy groups, (iii) 2-hydroxycarboxylic acid, and (iv) base, wherein molar ratio of base to hydroxycarboxylic acid is within the range between 0.01:1 and 0.79:1. Esterification reaction in presence of above catalyst is also described.

EFFECT: avoided yellowness in final product, raised temperature for the beginning of crystallization and crystallization temperature of polyester.

14 cl, 4 tbl, 20 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method, by which the carboxylic acid/diol mixture, that is suitable as the initial substance for the manufacture of polyester, obtained from the decolourised solution of carboxylic acid without actually isolating the solid dry carboxylic acid. More specifically, the invention relates to the method of manufacturing a mixture of carboxylic acid/diol, where the said method includes the addition of diol to the decolourised solution of carboxylic acid, which includes carboxylic acid and water, in the zone of the reactor etherification, where diol is located at a temperature sufficient for evaporating part of the water in order to become the basic suspending liquid with the formation of the specified carboxylic acid/diol mixture; where the said carboxylic acid and diol enter into a reaction in the zone of etherification with the formation of a flow of a complex hydroxyalkyl ether. The invention also relates to the following variants of the method: the method of manufacture of the carboxylic acid/diol mixture, where the said method includes the following stages: (a) mixing of the powder of damp carboxylic acid with water in the zone for mixing with the formation of the solution of damp carboxylic acid; where the said carboxylic acid is selected from the group, which includes terephthalic acid, isophthatic acid, naphthalenedicarboxylic acid and their mixtures; (b) discolourisation of aforesaid solution of damp carboxylic acid in the zone for reaction obtaining the decolourised solution of carboxylic acid; (c) not necessarily, instantaneous evaporation of the said decolourised solution of carboxylic acid in the zone of instantaneous evaporation for the removal of part of the water from the decolourised solution of carboxylic acid; and (d) addition of diol to the decolourised solution of carboxylic acid in the zone of the reactor of the etherification, where the said diol is located at a temperature, sufficient for the evaporation of part of the water in order to become the basic suspending liquid with the formation of the carboxylic acid/diol mixture; where the aforesaid carboxylic acid and diol then enter the zone of etherification with the formation of the flow of complex hydroxyalkyl ether; and relates to the method of manufacture of carboxylic acid/diol, where the said method includes the following stages: (a) the mixing of the powder of damp carboxylic acid with water in the zone for mixing with the formation of the solution of carboxylic acid; (b) discolourisation of the said solution of damp carboxylic acid in the reactor core with the formation of the decolourised solution of carboxylic acid; (c) crystallisation of the said decolourised solution of carboxylic acid in the zone of crystallisation with the formation of an aqueous suspension; and (d) removal of part of the contaminated water in the aforesaid aqueous solution and addition of diol into the zone of the removal of liquid with the obtaining of the said carboxylic acid/diol mixture, where diol is located at a temperature sufficient for evaporating part of the contaminated water from the said aqueous suspension in order to become the basic suspending liquid.

EFFECT: obtaining mixture of carboxylic acid/diol.

29 cl, 4 dwg

Up!