Method for synthesis of bioresource acrylic esters

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

 

The invention concerns a method for the synthesis of esters of acrylic acid of the formula CH2=CH-COO-R, in which R denotes an alkyl radical, linear or branched, containing from 1 to 18 carbon atoms and containing, perhaps, a heteroatom, such as nitrogen. Esters of acrylic acid, acrylates, widely used in industry. The range of applications for polymers extensive. However, some of them require acrylate, is used as a monomer or as co monomer upon receipt of the copolymer or ternary copolymers, standards of purity of the product. These standards of cleanliness in relation to some of the compounds are specific and directly linked to the polymer of the final application. It is difficult to achieve these standards, without resorting to very expensive methods of fractionation and purification.

Acrylates derived from acrylic acid or a simple esterification or interesterification reaction light acrylate-type methyl-, ethyl-, propyl - or butyl acrylate, gidroksilirovanii connection required for synthesis of the polymer, forming, or forming part of the final broadcast.

As an example, 2-ethyl hexyl acrylate of the formula CH2=CH-COO-CH2-CH(C2H5)-(CH2)3-CH3as usual denoted AGO (AEN), usually get straight what tarificatie acrylic acid of the formula CH 2=CH-COOH 2-ethylhexanol according to the following reaction:

CH2=CH-COOH+CH3-(CH2)3-CH(C2H5)-CH2OH⇒

CH2=CH-COO-CH2-CH(C2H5)-(CH2)3-CH3+H2About

As for complex aminoether formula CH2=CH-COO-CH2-CH2-N(CH3)2, dimethylaminoethylacrylate, usually denoted by DMEA (ADAME), it is usually obtained by transesterification of complex acrylic ester of the formula CH2=CH-COOR0according to the following reaction:

CH2=CH-COOR0+(CH3)2N-CH2-CH2OH⇒CH2=CH-COO-CH2-CH2-N(CH3)2+R0OH,

thus R0means or CH3or2H5or3H7or4H9.

The butyl acrylate BA (ABu), ester of formula CH2=CH-COO-C4H9very often used in ways copolymerized to obtain a copolymer with elastomeric properties, are often synthesized by direct esterification of acrylic acid with n-butanol.

The MA methyl acrylate (S) of the formula CH2=CH-COO-CH3very often used in the methods of copolymerization for producing fibers, most often synthesized by direct esterification of acrylic acid with methanol.

The acrylate EA (AE) of the formula CH2=CH-COO-C2H5very often used in ways the Ah copolymerization to give cohesion textile fibers, most often synthesized by direct esterification of acrylic acid with ethanol.

These monomers with a degree of purity satisfactory for end industrial applications, is often difficult.

On this occasion, mention can be made of French patent No. 2777561 on the name of the applicant company, which describes a particularly difficult way to obtain DMEA, which allows to obtain a product having a content of "pollutants"such as acrylate (EA) and dimethylaminoethanol (DMAE), following a strict limit values.

As for the synthesis AGO, which is catalyzed by acid, the industry uses a heterogeneous catalyst, applying a resin acid character. In General, these resins are strong cation-exchange resins with sulfonic type. The problem when getting AGA, is in the presence of derived complex ester significant amounts of impurities, in particular, compounds of the type maleic that cause the deletion of this last specification, taken to its commercialization in most areas, in particular in the field of adhesives, pressure-sensitive (CDC) (PSA).

Acrylic acid (AA)used as a starting compound in method of this type, essentially, in the industrial plan is produced from propylene. It is subjected to oxidation in the two is Tadei according to the following reaction process:

CH2=CH-CH3+O2⇒CH2=CH-Cho+H2About

2CH2=CH-Cho+O2⇒2CH2=CH-COOH,

or total reaction: CH2=CH-CH3+3/2O2⇒CH2=CH-COOH+H2About

This synthesis of acrylic acid called petrochemical synthesis and, thus, as a starting compound, it uses propylene, which is subjected to two consecutive ocalenia. It has the advantage that it allows to synthesize or acrolein (AKO) (ASO), which is put on sale as such, if you stop at the first stage, or acrylic acid, if the oxidation finish.

This method of oxidation is very effective, has however the disadvantage that it produces by-products, impurities, such as, in particular, furfural, cyclic aldehyde, maleic anhydride or maleic acid, which are very difficult to separate from the main product, even in any way classical cleanup.

In the case of obtaining acrylic acid this reaction is carried out usually in the vapor phase, usually in two stages, which can be carried out in two different reactors or in a single reactor:

∗ the first stage implements a sensitive quantitative oxidation of propylene in mixture, enriched acrolein (AKO), where AK contains the camping in the minority;

∗ the second stage completes the conversion AKO in AK.

The gaseous mixture coming from the second stage of the oxidation reaction, is formed, in addition to acrylic acid:

• easy connections that are not condensable at ordinary temperature and pressure (nitrogen, oxygen and unconverted propylene, propane present in the reacting propylene, monoxide and carbon dioxide formed in small quantities during the last oxidation),

• light condensing connections: in particular, the water resulting from the oxidation of propylene, unconverted acrolein, light aldehydes as formaldehyde and acetaldehyde, and acetic acid, the main impurity arising in the reaction zone,

• heavy compounds: furfuraldehyde, benzaldehyde, maleic anhydride, benzoic acid.

The second stage of receiving is to extract the AK from the gaseous mixture coming from the second stage by introducing this gas into the bottom of absorption column where it meets a counter flow of the solvent introduced into the upper part of the column. In most these methods, the solvent used in this column represents the water and the hydrophobic solvent with a high boiling point.

In the case of absorption methods using water as the absorbent solvent, the hundred and the AI additional purification include stage of dehydration, usually carried out in the presence of a solvent that is not miscible with water, in the extraction column or column heterotetramer distillation, then the stage of removal of light compounds, in particular acetic acid and formic acid, and the stage of removal of heavy compounds.

In the case of methods, which uses a hydrophobic solvent phase is essentially the same, except for the removal of water, which is carried out in the top of the first absorption column. These methods have the major inconvenience that use significant amounts of solvent with a high boiling point that, in addition to the value of the transaction may create problems release products that are harmful to the environment, as well as polymerization in the columns, which contribute imposed by solvent high temperatures in the lower part of the column.

In these ways, except that just mentioned, the separation of heavy compounds is a major problem.

In addition, this method has the disadvantage that uses propylene, which is a fossil source product derived from oil, which, as you know, will eventually disappear and that, whatever it is, will cost more and more expensive.

It was found, for example, that furfural, even p is outstudy in acrylic acid in trace quantities, or in a concentration of more than 0.01 wt. -%, may at some subsequent transformations to present a significant inconvenience, strongly negatively affecting the degree of polymerization required for the product in the intended application. Similarly, it was observed that this method also has the disadvantage that in its implementation as a by-product synthesized also maleic anhydride or maleic acid, at a concentration of more than 0.1% wt., can in some applications create a significant disadvantage because of the acidity generated in the monomer.

The presence of ISO-isomer (isobutylacetate) in BA can modify the Tg (glass transition temperature) of the final polymers.

As for EA, furfuraldehyde is an admixture difficult to obtain DMEA and subsequent use of this monomer as a precursor of the cationic coagulant.

The invention aims to overcome these inconveniences by proposing a new method of synthesis of these esters, using a different method of synthesis of acrylic acid, in an earlier development, using as starting product glycerin instead of propylene. In addition, the use of alcohols, which have their own vegetable and/or animal origin, will allow you to fix "bioresource" the nature of the way the consumption, essentially, renewable source connections.

The method of synthesis of acrylic acid by this route is a two-stage method lies in the dehydration of glycerol to acrolein in the first stage, then, in the second stage, in the oxidation of acrolein in acrylic acid according to the following reaction process:

CH2OH-CHOH-CH2HE←→CH2=CH-Cho+2H2About

CH2=CH-Cho+1/2O2⇒CH2=CH-COOH.

From ancient times it is known that glycerin may result in acrolein. Glycerin is obtained by methanolysis of oils of vegetable and/or animal origin at the same time that the methyl ester, which are used in particular as a fuel or combustible in the gas and home heating oil. Glycerin can also be obtained by hydrolysis of vegetable and/or animal oils, leading to the formation of fatty acids, or the saponification of vegetable and/or animal oils, leading to the formation of Soaps. This is a natural product, which has a green aura, available in large quantities and can be stored and transported without difficulty. Numerous studies dedicated to the valorization of glycerol according to its degree of purity, and the dehydration of glycerol to acrolein is one of the ways.

The above reaction is used to obtain the Acro is Aina, based on glycerol, is an equilibrium reaction. In General, low temperatures favor the hydration reaction, and high temperatures favor the reaction of dehydration. To obtain acrolein, it is necessary, therefore, to apply a sufficient temperature and/or a partial vacuum, to move the reaction. The reaction can be carried out in the liquid phase or in the gas phase. It is known that the reaction of this type is catalyzed by acids. The oxidation reaction of acrolein usually carried out in the gas phase in the presence of the oxidation catalyst.

To illustrate the work done on this subject in the last decades, can be called French patent No. 695931 where to get acrolein, a pair of glycerol was forced to pass at high temperature through acid salts (salts of phosphoric acid). Outputs defined after fractional distillation, were more than 75%. In the patent US 2558520 dehydration reaction was carried out in the gas/liquid phase in the presence of diatomaceous earths impregnated with salts of phosphoric acid, in suspension in an aromatic solvent. In these conditions was obtained the degree of conversion of glycerol into acrolein 72,3%.

Recently in the US patent 5387720 has been described a method of obtaining acrolein dehydration of glycerol in the liquid phase or in the gas phase on solid acid catalysts, designated the x acidity on Hammett. According to this patent, used an aqueous solution containing from 10 to 40% glycerol, and operated at temperatures in the range from 180°C to 340°C in the liquid phase and from 250°C to 340°C in the gas phase. According to the authors of this patent, the reaction in the gas phase is preferred, as it allows you to have a degree of conversion of glycerol, close to 100%. This reaction leads, after condensation, to aqueous solution of acrolein containing by-products such as hydroxypropane, propanidid, acetaldehyde, acetone, addition products acrolein to glycerol. Approximately 10% of the glycerol is converted into hydroxypropane, which is found as the predominant by-product in the solution of acrolein. Acrolein is isolated and purified by fractional distillation or by condensation. For reactions in the liquid phase conversion 15-25% may not be exceeded under fear of side products formation in an unacceptable quantity and the quality of the monomer (acrolein or acrylic acid), are incompatible with the desired quality. In document WO 06/087083 reaction of dehydration of glycerol in the gas phase was carried out in the presence of molecular oxygen.

Document WO 06/087084 discloses the application for the dehydration of glycerol in the gas phase strongly acidic solid catalysts having acidity on Hammett on dasouza in the range from -9 to-18. Usually glycerin, used as starting product for the reaction of dehydration, is an aqueous solution.

To obtain acrylic acid, acrolein is subjected to the second stage of oxidation. In the patent application EP 1710227 the reaction product resulting from the reaction of dehydration of glycerol in the gas phase, is subjected to the subsequent stage of oxidation in the gas phase to obtain acrylic acid. The method is carried out in two reactors in series, each of which contains a catalyst adapted to carry out the reaction. In the application WO 06/092272 described the combination process with its first two stages, dehydration and oxidation, and subsequent stages, to obtain purified acrylic acid.

A preferred variant of the method that contains two stages, described in the patent application FR No. 2909999 from 19 December 2006, is to implement partial condensation of water in the reactive gases leaving the first stage of dehydration of glycerol, before the introduction of gas into the reactor 2nd stage of oxidation to acrylic acid. This additional stage of condensation is cooled gaseous stream to a temperature that some of the water condenses into the liquid phase, and the acrolein remains in gaseous form.

Similarly, it was proposed action is to participate in one stage. In the application WO 06/114506 describes a method for acrylic acid in a single stage reaction of oxodegradable glycerol in the presence of molecular oxygen with 2 consecutive reactions of dehydration and oxidation.

The invention aims to mitigate these inconveniences by proposing to obtain esters to use acrylic acid, obtained by other methods of synthesis, use as a primary source of product glycerin.

The object of the present invention is the method of synthesis of ester of acrylic acid of the formula CH2=CH-COO-R, in which R denotes an alkyl radical, linear or branched, containing from 1 to 18 carbon atoms and containing, perhaps, a heteroatom, nitrogen, characterized in that thethe first stage is subjected to glycerol CH2OH-CHOH-CH2OH dehydration reaction in the presence of an acid catalyst to obtain acrolein formula CH2=CH-CHO, then, in the second phase, catalytic oxidation transform thus obtained acrolein to acrylic acid CH2=CH-COOH, then, at the third stage, is subjected to acid obtained in the second stage, the reaction of esterification alcohol ROH in which R has the value given above.

In one embodiment, the method of the third stage is carried out in two sub-phases, the first is that acrylic colormatrixfilter light alcohol, containing from 1 to 4 carbon atoms, then on the second turn ester selected light alcohol, usually methanol or ethanol, in the desired ester by transesterification with an alcohol ROH. This option is used, in particular, in the case in which the alcohol ROH contains a heteroatom, such as nitrogen.

In another embodiment, the method can be implemented in the same way as it was described in the application WO 06/114506, the first two steps in a single reactor by reaction of oxodegradable glycerol in the presence of molecular oxygen, through 2 consecutive reactions of dehydration and oxidation.

In another embodiment, the method is carried out intermediate stage of condensation of water contained in the stream coming from the first stage of dehydration of glycerol, before introduction into the reactor of the 2nd stage of oxidation to acrylic acid.

The first stage of dehydration of glycerol is carried out in a gas phase reactor in the presence of a catalyst at a temperature varying in the range from 150°C to 500°C, preferably in the range from 250°C to 350°C, and pressure varying in the range from 105to 5.105PA.

Used reactor can operate in a fixed bed, fluidized bed or circulating fluidized bed, or in the configuration of the modules (platesor grid)in the presence of a solid acid can produce the ditch.

Suitable catalysts are homogeneous or multiphase materials, insoluble in the reaction medium, which have the acidity to Gameto, denoted by H0less +2, as described in patent US 5387720, which makes access article Tanabe and co-authors (K. Tanabe et al.) in "Studies in Surface Science and Catalysis", vol 51, 1989, chap 1 et 2; acidity on Gamete determined by amine titration using indicators or by adsorption of bases in the gas phase. Catalysts that meet the criterion of "the acidity of H0less than +2"can be selected from among natural or synthetic calcium silicate materials or acidic zeolites; mineral substrates, such as oxides, coated with inorganic acids, monobasic, dibasic, dragonanime or polybasic acids; oxides or mixed oxides or heteropolyacids.

These catalysts could be a salt of heteroalicyclic, in which the protons of the specified heteroalicyclic exchanged for at least one cation selected among elements belonging to the I-XVI groups of the Periodic system of elements, and these salts of heteropolyacids containing at least one element selected from the group containing W, Mo and V.

Among the mixed oxides can also be called the oxides on the basis of iron and phosphorus and oxides on the basis of the cesium, phosphorus and tungsten.

Preferably, the catalysts choose among zeolites, Nafion composites®(based on sulfonic acid and fluorine-containing polymers), chlorine-containing oxides of aluminum, phosphonoformate and/or kremnipolymer acids and their salts, and various solid substances such as metal oxides, such as tantalum oxide Ta2O5the oxide of niobium Nb2O5aluminium oxide Al2O3, titanium oxide TiO2, zirconium oxide ZrO2the tin oxide SnO2silicon dioxide SiO2or aluminosilicate SiO2-Al2O3saturated acid functional groups, such as borate BO3, sulfate (SO4, wolframate WO3, phosphate PO4silica SiO2or molibdate MoO3.According to literature data, all of these catalysts have the acidity to Gamete H0less than +2.

Previous catalysts, in addition, can include a promoter, such as Au, Ag, Pt, Rh, Pd, Ru, Sm, Ce, Yt, Sc, La, Zn, Mg, Fe, Co, Ni or montmorillonite.

The preferred catalysts are the phosphated Zirconia, wallpaperbase oxides of zirconium, siliconized oxides of zirconium, oxides of titanium or tin, impregnated with tungstate or phospholipases, phosphated aluminum oxide or silica, heteroalicyclic or salt is of heteroalicyclic, the iron phosphate and iron phosphate containing promoter.

The second stage of the method according to the invention is carried out in the following conditions.

The oxidation reaction stream rich in acrolein generated during the first stage (the concentration of acrolein, usually from 2 to 15% by volume), is carried out in the presence of molecular oxygen, which likewise can be introduced in the form of air or in the form of air, enriched, or diluted by molecular oxygen, with the content varying in the range from 1 (the stoichiometric minimum concentration AKO 2% at the reactor inlet) to 20% by volume, relative to the incoming flow, and in the presence of gases that are inert under the reaction conditions, such as the N2, CO2, methane, ethane, propane or other light alkanes and water.Inert gases, necessary way in order to avoid finding reactionmix in thethe field of Flammability,partially or completely represent the gases obtained in the upper part of the separation column below the reactor of the second stage.

The oxidation reaction occurs at a temperature varying in the range from 200°C to 350°C, preferably from 250°C to 320°C and at a pressure varying in the range from 105to 5.105PA.

As the oxidation catalyst used all types of AC is alization, well-known specialists in this field for this reaction. Usually use a solid substance containing at least one element selected from the list: Mo, V, W, Re, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Te, Sb, Bi, Pt, Pd, Ru, Rh, in metallic form or in the form of an oxide, sulfate or phosphate. In particular, use compounds containing in the form of mixed oxides of Mo and/or V and/or W and/or Cu and/or Sb and/or Fe as a main component.

The reactor can operate in a fixed bed, fluidized bed or circulating fluidized bed. You can also use a plate heat exchanger with a modular arrangement of the catalyst, such as heat exchangers described in the patents listed below: EP 995491, EP 1147807 or US 2005/0020851.

The third stage of esterification sold to synthesize esters, such as acrylate, methyl acrylate, and butyl-, propyl - and 2-ethylhexylacrylate, perform the following classical conditions.

The catalytic reaction is carried out in the following conditions of temperature and pressure: temperature from 60 to 90°C and a pressure of from 1.2.105to 2.105PA.

Catalysts for the esterification reaction are acid. They can be selected from among mineral acids such as sulfuric acid, sulfonic and phosphoric acids or their derivatives: p-toluensulfonate, who benzolsulphonate, methansulfonate, dodecylsulfonate..., and the reaction proceedsin a homogeneous single-phase system. The catalysts can also be of solid polymers (ion-exchange resin of acid character, and in this case, the reaction proceeds in a two-phase heterogeneous environment.

These latter catalysts will beusually sulfonated copolymers of styrene and divinylbenzene (DVB) (DVB), called "acidic resins, gel type or macroporous material, the DVB content which can vary from 2 to 25% of the mass. and acidity are expressed in EQ. N+/l is in the range from 1 to 2.

For example, supplied by Lanxess under the name Lewatit, or firm Rohm Haas et under the name Amberlyst.

Used catalysts are preferably ion-exchange resin of acid character type Amberlyst 131 and Lewatit K.

The reaction is carried out in a reactor of a continuous action.

For the variant of the method, which used the etherification slight alcohol as described above, followed by transesterification "target" alcohol for the desired complex ether, interesterification conditions are as follows.

The interesterification reaction is conducted periodically or continuously, as described in patents FR 2617840, FR 2777561 and FR 2876375.

The way interesterification is the introduction of a reaction when praduman the air and in the presence of a catalyst and at least one polymerization inhibitor at a temperature in the interval from 20 to 120°C. and at a pressure equal to the atmospheric pressure or less than atmospheric pressure, lung complex acrylic ester with a "target" alcohol, usually dialkylaminomethyl, in a molar ratio of a light complex acrylic ester/aminoplast being in the range from 1.3 to 5, in the presence of a catalyst, removing the reaction azeotropic mixture of light ester/light alcohol and allocation at the end of the reaction dialkylaminoalkyl, usually by distillation.

Under dialkylaminoalkyl mean dimethylaminoethylacrylate and diethylaminoethylamine.

As a catalyst, you can use alkylsilane, as, for example, utiltity, derivatives of tin, as the oxide dibutylamine or distannoxane, derivatives of zirconium as zirconium acetylacetonate, derivatives of magnesium, as atoxic magnesium derivatives of calcium, as calcium acetylacetonate. These connections involve the rate of 10-3to 5.10-2mole per mole of dialkylaminomethyl, preferably at the rate of 5.10-3to 1.10-2mole per mole of dialkylaminomethyl.

Choose preferably, the molar ratio of a light complex acrylic ester/dialkylamino being in the range from 1.5 to 2.5.

During the reaction support, preferably, the temperature intervals in the e 80 to 120°C. more preferably, from 90 to 115°C. the pressure of the support, preferably in the range from 50 to 85 kPa, i.e. the reaction is carried out at slightly reduced pressure.

Among dialkylaminomethyl suitable for the present invention include Diethylaminoethanol and dimethylaminoethanol with a preference for dimethylaminoethanol.

As the polymerization inhibitor used phenothiazines, simple methyl ether of hydroquinone, hydroquinone, di-tert-butyltetrahydrofuran, 4-hydroxy-TEMPO, alone or in a mixture, at the rate of from 500 to 2500 ppm relative to the total loading.

In the preferred form of the method according to the present invention, the synthesis is aimed at complex aminoether acrylic acid of the formula CH2=CH-COO-CH2-CH2-N(CH3)2in which during the third stage of the acid obtained in the second stage, is subjected to the esterification of a light alcohol, methyl or ethyl, then, finally, subjecting the thus obtained ester of the interesterification reaction under the action of amerosport formula (CH3)2-N-CH2-CH2OH.

The technical problem underlying the resolution is to obtain the esters of acrylic acid having high purity, that is, in this case, the content of furfural<3 ppm, connections, especially Negele is compulsory for subsequent use of the complex ester. In fact, these compounds are, in particular, to become Quaternary salt, called "quaternion DMEA" ("ADAME quats"), under the action of, for example, CH3Cl. These"quaternion DMEA"could be part of coagulants, designed for water purification in the form of copolymers quaternion DMEA/acrylamide. But it was found that the presence in quaternionic DMEAinas an impurity even a very small number of furfural was a very strong influence on the degree of polymerization of the monomer, the resulting molecular weight (Mw), much smaller than the mass, which is necessary for effective product in this application.

Variant of the method is that at the first stage, the glycerol is subjected to dehydration reaction in the presence of an acid catalyst having an acidity on Gamete less than +2, then, in the second stage, oxidize the resulting acrolein to acrylic acid in the presence of a catalyst containing, in the form of mixed oxides of the following metals Mo and/or V and/or W and/or Cu and/or Sb and/or Fe, and then, at the third stage, atrificial acid by light alcohol of formula R0OH, in which R0denotes an alkyl radical containing from 1 to 4 carbon atoms, preferably ethanol, and finally praeteritorum receive the config ester under the action of amerosport formula (CH 3)2-N-CH2-CH2OH.

At the end of the third stage of the transesterification light acrylate-aminosterol formula (CH3)2-N-CH2-CH2OH carried out preferably in the presence of a catalyst comprising tetrabutyltin, tetraethylthiuram or Tetra(2-ethylhexyl)titanate, at a temperature in the range from 90 to 120°C., in a reactor with stirring at a pressure in the range from 0.5.105PA to 105PA.

In the first stage, the content of furfural in acroleine after condensation of water, which constitutes a large part of the reaction medium (it should be recalled that the glycerol is treated in the form of an aqueous solution), before its introduction into the second stage is of the order of several tens of ppm in comparison with several hundred ppm in afluente first stage propylene method.

This content then reduce during the later stages of purification of acrylic acid, the esterification then interesterification acid to achieve a slightly lower concentrations in the technical AK (SO) (AAT), about ten ppm in the acrylate and, finally, less than 3 ppm in the final DMEA, while effluent that go with each stage, purified by distillation. Received DMEA chetvertyy by the action of methyl chloride according to the method described, for example, documents the customers EP 1144356, EP 1144357 or WO 00/43348 that leads to aqueous solution ADAMQUAT MC, containing 80% of active substance. Then ADAMQUAT MC will polymerized with acrylamide, and the resulting polymer is characterized by viscosity measurement at room temperature molar aqueous NaCl solution containing 0.1% of a copolymer obtainedtherefore, as illustrated in the patent FR 2815036.

In another preferred form of the method according to the present invention, synthesis refers to the synthesis of ester of the formula

CH2=CH-COO-CH2-CH(C2H5)-(CH2)3-CH3(AGA) with a low residual content of acid.

Ester of the formula CH2=CH-COO-CH2-CH(C2H5)-(CH2)3-CH3usually referred to AGE, usually obtained by the esterification of acrylic acid formula

CH2=CH-COOH 2-ethylhexanol according to the following reaction:

CH2=CH-COOH+CH3-(CH2)3-CH(C2H5)-CH2OH<==>

CH2=CH-COO-CH2-CH(C2H5)-(CH2)3-CH3+H2About

The equilibrium of this reaction should be shifted towards the formation of ester by the removal of water, usually by entrainment with the aid of a solvent which forms with water heterotetramer mixture, or, easier, and more preferable in the form of a mixture of alcohol, of ester and water, which also obrazovaniya.rabotayu mixture. After decanting, the aqueous phase is removed and the organic phase is returned in the response.

The following stages of purification to obtain pure complex acrylic ester are to implement the removal of light compounds (mainly excessive alcohol, unconverted acrylic acid and residual water from the upper part of the column to remove light connections,then remove heavy compounds from the bottom of the column for removal of heavy compounds, the net product is extracted from the upper part of the column.

The problem when getting complicated acrylic ester AGO, based on acrylic acid, produced according to a conventional method petrochemical type, then tarifitsiruemih 2-ethylhexanol, using a method based on resin acid character is in the presence of derived complex ester of the significant content of certain impurities and, in particular, compounds of the type maleic who are forced to exclude the latter from the specifications that are approved for commercialization in most areas, in particular in the field of adhesives and processing of leather and textiles, in which the presence of acidity slows down the polymerization process.

The residual acidity of the pure monomer may have two main causes: the presence of acrylic acid and the presence of the male is a new anhydride, contained as impurities in the acrylic acid used for esterification. While the removal of residual acrylic acid can be carried out by the destruction of lung connections from the top of the first column to remove light compounds after the reaction, removal of maleic acid or maleic anhydride is much more time consuming, as the maleic anhydride is a compound with a volatile, close to the volatility AGO. Maleic anhydride may occur from incomplete conversion of this compound to mono(2-ethylhexyl)maleate, di(2-ethylhexyl)maleate in the esterification of the alcohol. In fact, mono(2-ethylhexyl)maleate is a connection with low resistance, which is subjected to purification columns dismutation in the anhydride and di(2-ethylhexyl)maleate. While maleic anhydride resulting from the reaction of dismutation and/or present as an impurity acrylic acid is not converted by esterification cannot be easily removed by distillation, taking into account its boiling temperature close to the boiling point of the monomer, and is the cause of the acidity of the synthesized complex ether, which is a nuisance for polymers on the basis of this complex ether.

Get this product with a satisfactory degree of purity in PR the industrial plan is particularly difficult, as it is emphasized in the French patent No. 2818639 mentioned above.

The only solution to solve this problem are removing maleic anhydride from a raw material that is, or to use what is called an ice acrylic acid, or to provide additional stages of the removal of manumaleuna, which is formed from maleic anhydride raw materials during the stage of esterification, for example, by neutralization with sodium hydroxide. Unfortunately, these two solutions are industrial unsuitable for reasons of additional value.

One of the objects of the invention is the smoothing of these disadvantages, offering a new way of synthesis AGO, which used the method of synthesis of acrylic acid, using as starting compound glycerin instead of propylene.

The aim of the invention is a method for the synthesis of ester of acrylic acid of the formula CH2=CH-COO-CH2-CH(C2H5)-(CH2)3-CH3, characterized in that thethe first stage is subjected to glycerol CH2OH-CHOH-CH2OH dehydration reaction in the presence of an acid catalyst to obtain acrolein formula CH2=CH-CHO, then, in the second phase, catalytic oxidation transform obtained acrolein to acrylic acid CH2=CH-COOH and, finally, on the third one hundred the AI is subjected to acid, obtained in the second stage, the esterification reaction with an alcohol of the formula CH3-(CH2)3-CH(C2H5)-CH2OH by acid catalysis.

The content of maleic anhydride in the reactor exit oxidation acrolein in AK, on the basis of propylene is about 1 wt. -%, after cleaning up the stage AK, called technical (SO) (AAT), its content is very usually is, in the order of magnitude, from 1000 to 1500 h/million Maleic anhydride, present in SO, will, unfortunately, remain in the reaction medium during stage SO esterification of 2-ethylhexanol and to form esters, monomaniac 2-ethylhexanol and mostly (ten times more) demolet this alcohol. The separation of this latter, which is a heavy product, by distillation, is relatively easy. Unfortunately, the firm-applicant, it was found that during the distillation monomaniac will dismutase in demolet, which is easily separated and, therefore, is not an inconvenience, but also maleic anhydride, which will be present in the received AGE, and that the contents are much higher threshold (<40 ppm), adopted in the industrial specifications.

The first two stages, dehydration and oxidation, carried out as described above, and the esterification reaction is carried out in the liquid phase at the temperature, the finding is the action scene in the interval from 50 to 150°C. in the presence of a solid acid catalyst, for example, the type of resin Lewatit K or Amberlyst 15 at a pressure in the range from 1 to 3.105PA.

One of the main objects of the invention is the use of raw materials of natural origin and renewable, that is, bioresource.Regardless of obtaining acrylic acid from"natural"glycerin invention extends to the use, in the course of the esterification of alcohols ROH renewable natural origin or derived from biomass, differently called bioresource. If light alcohols are in the industrial plan often segobiano origin, it will be different for higher alcohols. As examples, butanol, which is obtained by propylene hydroformylation in n-Butyraldehyde with subsequent hydrogenation to n-butanol. Not to mention the fact that this method uses another natural source connection, it should be noted that this method of synthesis leads to n-butanol, containing trace amounts of ISO-butanol, about 1000 ppm, which is entirely found in the butyl acrylate in the form of isobutylacetate.

The object of the invention is also a method for the synthesis of butyl acrylate, in which acrylic acid is obtained as described above, based on glycerol, and then atrificial n-butanol obtained by the fermentation of biomass in risotti bacteria.

Fermentation of renewable products, leading to producing butanol, usually with the presence of acetone is carried out in the presence of one or more related microorganisms, the microorganism may be naturally modified by chemical or physical tension or genetically, in this case we speak of the mutant. The most commonly used microorganism is aClostridiumpreferably it is aClostridiumacetobutylicumor one of its mutants. The lists above are not limiting.

Stage fermentation may also be preceded by a stage of initial hydrolysis products using enzyme type cellulase or a complex of several enzymes of type cellulase.

As a renewable source compounds can be used plant compounds; compounds of animal origin or compounds derived from the recycled materials of vegetable or animal origin (recycled materials).

As plant compounds considered, in particular, sugars, starches, and any plant compound that contains sugar, cellulose, hemicellulose and/or starches.

As compounds derived from recycled materials, can be called, in castnet is, vegetable or organic waste containing sugars and/or starches, and also any fermentable waste.

Preferably, could be used the raw materials of low quality, such as potatoes, which can be frozen, grains contaminated with mycotoxins, or the remains of the sugar beet, or whey with serveren.

Preferably, renewable source compounds are plant compounds.

By stage of fermentation is usually followed by stage selection butanol.

This selection of butanol is to separate the reaction products, for example, heterotetrameric distillation. This separation may also be accompanied by distillation to obtain butanol in a more concentrated form.

Equally can be provided by phase separation of n-butanol from the other isomers. However, fermentation leads to a more limited number of isomers of butanol than the chemical path of propylene hydroformylation. The table below illustrates the analysis of butanol obtained by fermentation of renewable starting materials, and butanol obtained from a natural source connections.

Butanol obtained by fermentation resume aamah
original products
(analysis before cleaning)
(%)
Butanol derived from fossil source products
(analysis of post-treatment)
(%)
Butanol0,0037

Butanol-20,0113<0,0010
n-butyl acetate0,0009
Isobutanol0,06620,0960
n-butanol99,599,8
2-butene-1-ol0,1112
1,1-dibutoxy0,0139

n-butanol obtained by fermentation of renewable raw materials, has isobutyl alcohol/n-butanol is less than that of the pure butanol produced from natural raw materials, and it is even possible to stage the allocation of n-butanol. Isobutanol and n-butanol have very similar physical-chemical properties, so that the separation of these p is the FL is expensive. The use of n-butanol with a low content of Isobutanol and other by-products represents thus an extremely important economic advantage of the method which is the object of the invention, since it allows to obtain an acrylate higher degree of purity than the degree of purity BA obtained using petrochemical butanol, with less cost.

The use of carbon-containing source compounds of natural origin and renewable can be detected thanks to the carbon atoms forming part of the final product. In fact, unlike products derived from natural materials, products made from renewable raw materials, bioresource contain14C.

All samples of carbon, extracted from living organisms (animals or plants), actually represent a mixture of 3 isotopes:12With (approximately 98,892%),13With (~1,108%) and14(Tracks: 1,2.10-10%). Ratio14C/12In living tissues is identical to this ratio in the atmosphere. In the environment14With exists in two predominant forms: in mineral form, i.e. carbon dioxide (CO2), and in organic form, that is, carbon is included in an organic molecule.

In living organisms ratio14C/12is maintained constant by the metabolism, since carbon is continually exchanged with the environment. Since the content of14With in the atmosphere is sensitive constant, it remains constant in the body while he was alive, because he absorbs this14With, as if he absorbs12C. Average ratio14C/12With equal 1,2.10-12.

Isotope12Since is stable, this means that the number of atoms12With this sample is constant over time. Isotope14With is radioactive (each area of the carbon to be alive, contains enough of the isotope14With to give 13.6 disintegrations per minute), and the number of such atoms in the sample decreases over time (t) according to the law:

n=n0exp(-at)

where:

- n0indicates the number of14From the beginning (before the death of the creature, animal or plant),

n denotes the number of14With that remaining after time t,

-andrepresents the rate constant of decay (or constant radioactive decay); it is associated with a half-life time.

Half-life time (or half-life) is a period of time, at the end of which any number of radioactive nuclei or unstable particles of a given substance is reduced by half as a result of disintegration; the half-life of T1/2bound by konstanty the rate of decay andformulaandT1/2=ln 2. The half-life of14C is 5730 years.

Whereas the half-life (T1/2)14To believe that the contents of the14With is sensitive constant, starting from the extraction of vegetable raw materials to manufacturing the final product, polymer, for example, and even to the end of its use.

Firm-applicant believes that the compound or the polymer comes from a renewable source product, if it contains at least 15% (0,2.10-12/1,2.10-12) masses. With renewable origin in relation to the total weight of carbon, preferably at least 50 wt%. With renewable origin relative to the total mass of carbon.

In other words, the product or the polymer comes from a renewable source connections, you have a product or polymer is bereturned if it contains at least 0,2.10-10%mass.14With, preferably, 0.6 to.10-10%mass.14With respect to the total mass of carbon. In particular, the compound or polymer is bioresource if it contains from 0.2.10-10%1.2.10-10%mass.14C.

Currentlythere are at least two different methods of measuring the content of14With the sample.

- Liquid Scintilla the ion spectrometry: this method is the expense of beta-particles, the resulting decay of14C. Measure beta radiation emitted by a sample of known mass (the number of carbon atoms known) for a certain period of time. This radioactivity is proportional to the number of atoms14With, which can thus be determined. Isotope14With present in the sample emits β-rays, which are in contact with scintillation fluid (scintillator) generate photons. These photons have different energies (in the range from 0 to 156 Kev) and form what is called the range of14C. According to two variants of this method, the analysis is carried out either by CO2previously obtained by the combustion of carbon-containing sample in a suitable absorbent solution, or benzene, after preliminary conversion of carbonaceous sample in benzene.

- Mass spectrometry: sample restore in graphite or in gaseous CO2analyzed in the mass spectrometer. In this method, use the accelerator mass spectrometer to separate ions14C and12With and, therefore, to determine the ratio of the two isotopes.

These methods of measuring the content of14Since the products are precisely described in ASTM D 6866 (in particular, D6866-06) and the standards ASTM d 7026 (in particular, 7026-04). These methods compare the data measured on the test specimen, with the data of the coupon sample 100% bioresource origin, to give the relative percentage bioresource carbon in the sample. Ratio14C/12With or mass content of14With respect to the total mass of carbon can then be calculated for the analyzed sample.

Preferably used method is mass spectrometry, as described in standard ASTM D6866-06 ("accelerator mass spectrometry").

The object of the invention is also the use of esters containing at least 0,2.10-10%mass.14With that obtained by the process according to the invention in its various embodiments, as monomers or comonomers to obtain polymers or copolymers industrial polymerization.

The object of the present invention are polymers or copolymers derived from esters synthesized by the methods according to the invention.

EXAMPLES

The method according to the invention is illustrated by the following examples

Example 1 (comparative):Synthesis of DMEA based on petrochemical

The method consists in the fact that in the first phase synthesized acrolein by oxidation of propylene. This stage was carried out in the gas phase in the presence of a catalyst based on oxides of molybdenum and bismuth at a temperature close to 320°C and at atmospheric pressure. On the second studiesuniversity effluent, enriched with acrolein coming from the first stage, was subjected to the reaction of selective oxidation to acrylic acid in the presence of molecular oxygen and a catalyst, representing a mixed oxide of molybdenum-vanadium containing copper and antimony, at a temperature of about 260°C and at atmospheric pressure.

Reactions were carried out in a laboratory reactor with a fixed bed. The first oxidation reactor was a reaction tube with a diameter of 22 mm, filled with 500 ml of catalyst for the oxidation of propylene to acrolein, immersed in a salt bath(eutectic mixture of KNO3, NaNO3, NaNO2maintained at a temperature of 320°C. was fed with a gas mixture consisting of 8 mol%. propylene, 8 mol%. water, air, in the quantity necessary to obtain a molar ratio of About2/propylene 1,8/1, and nitrogen in addition.

Facing the gas mixture is then sent to power the second oxidation reactor acrolein in acrylic acid, representing a reaction tube with a diameter of 30 mm, filled with 500 ml of the catalyst is immersed in the cooling salt bath of the same type that bath first reaction stage, supported at a temperature of 260°C.

At the outlet of the second reactor, the gaseous mixture is introduced into the lower part of the absorption column in countercurrent to a stream of water introduced into the upper part is th column. In the lower part of the column, filled with nozzle ProPack, was equipped with a condensing section, in the upper part of which is recycled part of the condensed mixture to be extracted from the bottom of the column, after cooling in an external heat exchanger.

The next phase was the purification of acrylic acid with the aim of obtaining acrylic acid technical quality. This used a series of successive distillations, well-known experts in this field. The resulting aqueous solution was subjected to distillation in the presence of solvent mixture (MIBK), which allowed to remove the water from the upper part of the column after decanting heterotetramer mixture MIBK-water and returning the solvent in the upper part of the column. Digidratirovannogo acrylic acid, extracted from the bottom of the column, was sent to supply the column to remove low-boiling products, which could remove from the top of the light compounds, mainly acetic acid. Finally released from the lungsimpurityproducts : acrylic acid, which was extracted from the bottom of this column, was sent to supply the column to remove high-boiling products,which could remove heavy compounds from the bottom. Acrylic acid is obtained in the upper part of the column, was a t the ical acrylic acid (SO).

At the third stage of technical acrylic acid was atrificial ethanol in the presence of a catalyst, representing an acidic resin Lewatit K1461, the following conditions of temperature and pressure: T:80°C and P:1,5.105PA. The reaction was carried out continuously feeding the reagents (ethanol) in the first reaction stage, which consists of two reactors, placed in parallel containing resin. The stream coming from the first stage had been transferred to the second reaction stage, consisting of a reactor containing the resin. Two reaction stages were connected in series. At the input of the first stage operated under conditions of excess ethanol with a molar ratio ethanol/AK 2, at the input of the second stage operated under conditions of excess SO, through the injection box SO that originate from the bottom of the first distillation column, which was isolated from a mixture of EA/ethanol/water (in this case, the molar ratio of SO/ethanol was equal to 2). The flow at the outlet from the second reaction stage was purified by distillation and liquid-phase extraction. In addition to the first column 1 mentioned before, the chain distillation contained 4 other distillation columns and the column of liquid-phase extraction.

The head fraction of the first column containing a mixture of EA/ethanol/water, was sent to a distillation column, which was concentrated the I of this mixture in the upper part to the amount as it is possible more close to theoretical azeotropic mixtures EA/ethanol/water. From the bottom of this column was removed stream containing mostly water. The head fraction of the column was directed to the column liquid-liquid extraction,allowingto distinguish EA from a mixture of ethanol/water. This mixture was processed in the distillation column to extract:

- from the top of a concentrated mixture of ethanol/water, which is returned in the response.

- from the bottom of the water, which was again directed to the extraction column.

Head fraction extraction columns, representing a mixture of EA/light connection/heavy compounds were sent to a distillation column which would get:

from the upper part of the light compounds (mainly acetate)

from the lower part of the EA and heavy compounds (furfural, various additives as stabilizers...).

The bottom product of column 5 is sent to a distillation column 6, which is the output:

from the top of a clean EA

- from the bottom of the heavy compounds.

Finally, the last stage was carried out by the transesterification of ethyl acrylate by aminosterol formula (CH3)2-N-CH2-CH2OH in the presence of a catalyst, which was tetraethylsilane, at a temperature of 115°C. in a reactor with stirring at a pressure of 8,67.10 PA.

Content of furfural measured by spectrophotometry in the UV and visible regions in the presence of aniline (threshold 0.5 h/million) during the various stages were 300 ppm in acroleine in the first stage, 120 ppm in 10 ppm in the acrylate and, finally, 3 ppm in the final complex ether.

Example 2:Synthesis of DMEA from and glycerin

Reproduced the experiment according to example 1, using as starting product during the first two stages of glycerin, which is first subjected to dehydration to acrolein,then the last one was oxidized to acrylic acid, while the last two stages were identical.

The dehydration reaction was carried out in the gas phase in the reactor with a fixed bed in the presence of the solid catalyst, representing wallpaperjohnnyzirconium oxide ZrO2-WO3at a temperature of 320°C at atmospheric pressure. A mixture of glycerol (20% wt.) and water (80% of the mass.) sent to the evaporator in the presence of air in a molar ratio of About2/glycerin, equal to 0.6/1. The gaseous mixture leaving the evaporator at 290°C, was injected into the reactor, representing a tube 30 mm in diameter, filled with 400 ml of the catalyst is immersed in a salt bath (eutectic mixture of KNO3, NaNO3, NaNO2maintained at a temperature of 320°C. At the outlet and the reactor gaseous reaction mixture is sent to the bottom of the condensation column. This column consisted of the lower section filled with rings process (Raschig), on which was mounted a condenser in which the circulated cold heat-transfer fluid.The temperature of the cooling in heat exchangers were selected in such a way as to obtain in the upper part of the column the temperature of the vapors 72°C at atmospheric pressure. In these circumstances, the loss of acrolein in the lower part of the condensation columnwas less than 5%.

This gaseous mixture was introduced after adding air (molar ratio About2/acrolein is 0.8/1) and nitrogen in an amount necessary to obtain the concentration of acrolein of 6.5 mol%, at the entrance of the reactor oxidation acrolein in acrylic acid. This oxidation reactor was a tube 30 mm in diameter, filled with 480 ml of the catalyst based on a mixed oxide of Mo/V, immersed in a salt bath, identical to the bath described before, supported at 250°C. Before introduction on the catalytic layer of the gaseous mixture is pre-heated in the tube, too immersed in the salt bath.

At the outlet of the reaction gas mixture was subjected to cleaning processing identical to the processing of comparative example 1.

Thirdand the fourth stage of esterification and interesterification was carried out in the conditions of example 1.

Content of furfural measured in flux is Oh by spectrophotometry in the UV and visible regions during different stages of were such that the mass ratio of furfural to acrolein was 70 ppm at the inlet of the oxidation reactor acrolein in acrylic acid, after condensation of water, 30 ppm to 3 ppm in the acrylate and, finally, <0.5 h/million in the final complex ether.

These measurements of very small quantities are delicate and subject to risks in these operating conditions. Much more revealing are the results obtained during the polymerization of these molecules after their quaternization. In fact, the viscosity of the polymer derived from a molecule according to example 1 was 3.6 JV, while the viscosity of the polymer derived from a molecule according to example 2, was 4.5 SP, which means that the molecular weight of this polymer is clearly higher than the viscosity of the polymer according to example 1.

Example 3 (comparative):Synthesis AGO based on petrochemical

Repeated the first two stages according to example 1, andtechnical acrylic acid obtained after stages of purification described in example 1 was subjected to esterification with an alcohol of the formula CH3-(CH2)3-CH(C2H5)-CH2OH, which was conducted in the following conditions.

The esterification reaction was carried out in liquid phase at a temperature of 95°C with a light excess and in the presence of resin Lewatit K2621 at a pressure of 0.65 .105PA.

In each of effluents the content of maleic anhydride was measured using high-performance obremeniaet liquid chromatography. Used chromatographic column Lichrosphere 100 RP 18, 250 mm in length with an inner diameter of 4 mm as eluent used a mixture of water/methanol. Used UV detector, worked at 225 nm.

The output from the first stage acrylic acid had a content of maleic anhydride 1% of the mass. After cleaning SO was the content of maleic anhydride 1500 ppm; and after the stage of esterification and subsequent purification by distillation acidity of the pure product was lowered to 150 h/million

Example 4:Synthesis AGO from and glycerin

Repeated the first two stages according to example 2 andreceived technical acrylic acid were subjected to esterification with an alcohol of the formula CH3-(CH2)3-CH(C2H5)-CH2OH that was conducted under the conditions described in example 3.

Mass concentration of maleic anhydride, referred to acrolein, at the entrancein the second stage of the reaction was less than 1 wt. -%, after condensation of the water content in the technical acrylic acid was about 500 ppm, and the final acidity in AGE was <40 hours/million

1. A method of obtaining a complex ester of acrylic acid of the formula CH2=CH-COO-R, in which the Oh R denotes an alkyl radical, linear or branched, containing from 1 to 18 carbon atoms and containing, possibly, nitrogen heteroatom,
characterized in that the first stage is subjected to glycerol CH2OH-SEN-CH2OH dehydration reaction in the presence of an acid catalyst to obtain acrolein formula CH2=SN-SNO, then, in the second phase, catalytic oxidation transform thus obtained acrolein to acrylic acid CH2=CH-COOH, then, at the third stage, is subjected to acid obtained in the second stage,
or esterification reaction with an alcohol R0OH, in which R0represents CH3With2H5With3H7or4H9with subsequent reaction of transesterification of ester obtained by the alcohol ROH in which R has the meaning given above,
either the esterification reaction of the alcohol ROH, in which R has the meaning given above,
where the content of furfural in a complex ester of acrylic acid is less than 3 h/million

2. The method according to claim 1, characterized in that the first stage is carried out in the gas phase in the reactor at a temperature varying in the range from 150°C to 500°C, preferably in the range from 250°C to 350°C, and a pressure in the range from 105up to 5·105PA, and in the presence of a solid acid catalyst having an acidity on Gamete, bonachea H 0less +2.

3. The method according to one of items 1 and 2, characterized in that the second stage is performed by the oxidation reaction of the obtained acrolein at temperatures varying in the range from 200°C to 350°C, preferably from 250°C. to 320°C., at a pressure varying in the range from 105up to 5·105PA, and in the presence of a solid oxidation catalyst containing at least one element selected from the list: Mo, V, W, Re, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Te, Sb, Bi, Pt, Pd, Ru, Rh, in metallic form or in the form of an oxide, sulfate or phosphate.

4. The method according to one of claims 1 to 2, characterized in that the third stage of esterification is carried out at a temperature from 60°C to 90°C and at a pressure of from 105up to 5·105PA in the presence of an acid catalyst such as sulfuric acid, sulfonic acid, phosphate, or their derivatives, paratoluenesulfonyl, benzosulfimide, methansulfonate, dodecylsulfonate, while the reaction proceeds in a homogeneous single-phase medium, or a solid acid catalyst, such as a solid polymer ion exchange resin of acid character, sulfonated copolymers of styrene with divinylbenzene (DVB), in particular, and in this case, the reaction proceeds in a two-phase heterogeneous environment.

5. The method according to claim 1, characterized in that the last stage is carried out in two sub-phases, the first, sakluchala is camping in the esterification, such esterification according to claim 4, but carried out with a slight alcohol of the formula CH2=CH-COOR0where R0is a or CH3or2H5or3H7or4H9and the second, consisting of transesterification of ester thus obtained, the alcohol ROH, the target for the desired ether complex.

6. The method according to claim 5, characterized in that the transesterification is carried out in the presence of a catalyst and at least one polymerization inhibitor at a temperature in the range from 20°C to 120°C, preferably from 80°C to 120°C and the pressure is equal to atmospheric pressure or less than atmospheric pressure, preferably in the range from 50 to 85 kPa, and the catalyst chosen among alkylsilanes, as, for example, utiltity, derivatives of tin, as the oxide dibutylamine or distannoxane, derivatives of zirconium as zirconium acetylacetonate, derivatives of magnesium, as atoxic magnesium derivatives of calcium, as calcium acetylacetonate.

7. The method of synthesis of ester of acrylic acid of the formula CH2=CH-COO-CH2-CH(C2H5)-(CH2)3-CH3, characterized in that the first stage is subjected to glycerol CH2HE IS NON-CH2OH dehydration reaction in the presence of an acid catalyst to obtain acrolein formula is CH 2=SN-SNO, then, in the second phase, catalytic oxidation transform obtained acrolein to acrylic acid CH2=CH-COOH, and, finally, in the third stage, is subjected to acid obtained in the second stage, the esterification reaction with an alcohol of the formula CH3-(CH2)3-CH(C2H5)-CH2OH by acid catalysis,
where the content of furfural in a complex ester of acrylic acid is less than 3 h/million

8. The method of synthesis according to claim 7, characterized in that the first stage is carried out in a gas phase reactor in the presence of a catalyst at a temperature varying in the range from 150°C to 500°C, preferably in the range from 250°C to 350°C, and a pressure in the range from 105up to 5·105PA, in the presence of a solid acid catalyst having an acidity on Gamete, denoted by H0less +2.

9. The method of synthesis according to one of claim 7 or 8, characterized in that the second stage is performed by the oxidation reaction of the obtained acrolein, which is carried out at temperatures varying in the range from 200°C to 350°C, preferably from 250°C. to 320°C., at a pressure varying in the range from 105up to 5·105PA, and in the presence of a solid oxidation catalyst containing at least one element selected from the list: Mo, V, W, Re, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Te, Sb, Bi, Pt, Pd, Ru, Rh, is Academica in the metallic form or in the form of oxide, sulfate or phosphate.

10. The method according to one of claims 7 to 8, characterized in that the third stage of esterification is carried out at a temperature from 60°C to 90°C and at a pressure of 1.2·105up to 2·105PA in the presence of an acid catalyst such as sulfuric acid, sulfonic acid, phosphoric or their derivatives paratoluenesulfonyl, benzosulfimide, methansulfonate, dodecylsulfonate, while the reaction proceeds in a homogeneous single-phase medium, or a solid acid catalyst, such as a solid polymer ion exchange resin of acid character, sulfonated copolymers of styrene with divinylbenzene (DVB), in particular, and in this case, the reaction proceeds in a two-phase heterogeneous environment.

11. The method of obtaining complex aminoether acrylic acid of the formula CH2=CH-COO-CH2-CH2-N(CH3)2, characterized in that the first stage is subjected to glycerol CH2OH-SEN-CH2OH dehydration in the presence of an acid catalyst to obtain acrolein formula CH2=SN-SNO, which in the second stage oxidation converted into acrylic acid CH2=CH-COOH, then the third stage is subjected to the acid obtained in the second stage, the esterification of the alcohol of formula R0OH, with R0is a or CH3or2H5or3H7, the I 4H9and, finally, in the fourth stage is subjected to the obtained ester of the interesterification reaction under the action of amerosport formula (CH3)2-N-CH2-CH2OH,
where the content of furfural in a complex ester of acrylic acid is less than 3 h/million

12. The method of synthesis according to claim 11, characterized in that the first stage is carried out in a gas phase reactor in the presence of a catalyst at a temperature varying in the range from 150°C to 500°C, preferably in the range from 250°C to 350°C, and a pressure in the range from 105up to 5·105PA, in the presence of a solid acid catalyst having an acidity on Gamete, denoted by H0less +2.

13. The method according to one of claim 11 or 12, characterized in that the second stage is performed by the oxidation reaction of the obtained acrolein, which is carried out at temperatures varying in the range from 200°C to 350°C, preferably from 250°C. to 320°C., at a pressure varying in the range from 105up to 5·105PA, and in the presence of a solid oxidation catalyst containing at least one element selected from the group of Mo, V, W, Re, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Te, Sb, Bi, Pt, Pd, Ru, Rh, in the form of metal or in the form of an oxide, sulfate or phosphate.

14. The method according to one of § § 11 and 12, characterized in that the third stage of esterification carry Speer is om formula R 0OH, with R0is a or CH3or2H5or3H7or4H9at a temperature from 60°C to 90°C and at a pressure of 1.2·105up to 2·105PA in the presence of an acid catalyst such as sulfuric acid, sulfonic acid, phosphoric or their derivatives paratoluenesulfonyl, benzosulfimide, methansulfonate, dodecylsulfonate, while the reaction proceeds in a homogeneous single-phase medium, or a solid acid catalyst, such as a solid polymer ion exchange resin of acid character, sulfonated copolymers of styrene with divinylbenzene (DVB), in particular, and in this case, the reaction proceeds in a two-phase heterogeneous environment.

15. The method according to one of § § 11 and 12, characterized in that the fourth stage of the transesterification is carried out in the presence of a catalyst and at least one polymerization inhibitor at a temperature in the range from 20°C to 120°C, preferably from 80°C to 120°C and the pressure is equal to atmospheric pressure or less than atmospheric pressure, preferably in the range from 50 to 85 kPa, and the catalyst chosen among alkylsilanes, as, for example, utiltity, derivatives of tin, as the oxide dibutylamine or distannoxane, derivatives of zirconium, as acetylacetonate, zirconium, etc is svodnik magnesium, as atoxic magnesium derivatives of calcium, as calcium acetylacetonate.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to method of reverse splitting of Michael adducts, contained in fluid F with weight part ≥ 10 wt %, counted per liquid F weight, which were formed in the process of obtaining acrylic acid or its esters, in installation of reverse splitting, which includes, at least, one pump P, separation column C, which from bottom to top consists of bottom part, separating part, which is adjacent to bottom part and contains internal devices with separating effect, and head part, which follows it, in which pressure in gaseous phase decreases from bottom to top, as well as indirect heat exchanger with circulation of heat carrier UW, which has, at least, one secondary volume and, at least, one primary volume, separated from said, at least, one secondary volume by means of real separating wall D, in which fluid F with supply temperature TZ is continuously introduced into separation column C in point of supply I, which is located in said separation column C above the lowest internal device with separating effect; expenditure flow M˙ of fluid F with temperature TSU, flowing into bottom part through internal devices with separating effect, containing Michael adducts, is continuously taken away in located at the lowest level of bottom part of column C by means of pump P, in such a way that in bottom part as bottom fluid set is level S of fluid, flowing into it, which constitutes less than half of distance A, measured from point of separating column C, located at the lowest level, to lower surface of the lowest internal device with separating effect in separation column C, while in the remaining volume of bottom part, located above said level of fluid, pressure of gas GD exists, as well as, at least, one partial flow I from expenditure flow M˙* is passed through, at least, one secondary volume of indirect heat exchanger with circulation of heat carrier UW, and by indirect heat exchange with liquid heat carrier, passed simultaneously through, at least, one primary volume of said indirect heat exchanger with circulation of heat carrier UW, is heated to temperature of reverse splitting TRS, which is above temperature TSU; and from removed from, at least, one secondary volume of indirect heat exchanger with circulation of heat carrier UW with temperature TRS flow of substance M˙ in point of supply II, which is below the lowest internal element with separating effect of separation column C and above level S of bottom fluid, at least, one partial flow II is supplied back into bottom part of separation column C in such a way that said, at least, one partial flow II in bottom part of separation column C is not directed on bottom fluid, and, at least, from one of two flows M˙, M˙* discharged is partial flow as residual flow on condition that temperature of reverse splitting TRS is set in such a way that, on one hand, in the process of passage of, at least, one secondary volume of indirect heat exchanger with circulation of heat carrier UW, at least, part of Michael adducts, contained in, at least, one partial flow I, are split with formation of respective to them products of reverse splitting, as well as, on the other hand, at least, one partial flow II, supplied back into separation column C, under existing in bottom part in point of supply II gas pressure GD, is boiling, and gaseous phase, which is formed in the process of boiling, containing, at least, partial amount of product of reverse splitting, is supplied into head part of column C as gas flow G, containing product of reverse splitting, following decreasing towards head part of column C gas pressure, and said gas flow G by direct and/or indirect cooling is partially condensed still in head part of separation column C and/or being discharged from head part of separation column C, condensate, formed in this process is, at least, partially returned to separation column C as reflux fluid, and gas flow, remaining in the process of partial condensation, is discharged, with pump P representing radial centrifugal pump with semi-open radial working wheel. Coefficient of efficiency Q of claimed method constitutes at least 20%.

EFFECT: improvement of method.

14 cl, 9 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing higher alkyl(meth)acrylates which are used in synthesis of polymer depressor additives intended to prevent setting and reduction of low-temperature viscosity of paraffin-base oil. The method involves esterification of acrylic acid or a mixture of acrylic acid and methacrylic acid with higher fatty alcohols C16-C26 in a medium of a hydrocarbon solvent in the presence of an acid catalyst and a radical polymerisation inhibitor, followed by neutralisation of the acidic reaction mass using higher primary amines C8-C14 at temperature of 20-90°C and molar ratio of amine groups to free acid groups of (1.0-1.3):1.0. After said neutralisation, the solution of higher alkyl(meth)acrylates can be used to produce polymer depressor additives without further purification.

EFFECT: avoiding formation of wastes in form of salts of salt-containing waste water, high output of products owing to reduced loss of monomers at the neutralisation step, and simple technique of producing the monomer mixture for synthesis of depressor additives for paraffin-base oil.

2 tbl, 23 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing ethylenically unsaturated acids and esters thereof of the following formula: R3-C(=(CH2)m)-COOR4 , where R3 and R4 each independently represent hydrogen or an alkyl group, and m equals 1, by reacting alkanoic acid or an alkanoic acid ester of formula R3-CH2-COOR4, where R3 and R4 each independently represent hydrogen or an alkyl group with a methylene or ethylene source of formula , where R5 and R6 are independently selected from C1-C12 hydrocarbon groups or H; X is O or S; n is an integer from 1 to 100; and m equals 1, in the presence of a catalyst system to an ethylenically unsaturated acid or ester as a product, where the product in form of an acid or ester is then brought into contact with a dienophile to eliminate the undesirable colour of the product, where the dienophile is a compound of formula: where Z is selected from a group consisting of -C(O)Y, -CN, -NO2 or halogen; Y is selected from a group consisting of hydrogen, alkyl, hetero, -OR, halogen or aryl; R, R1 and R2 independently denote hydrogen, alkyl or aryl, and hetero denotes N, S or O. The heteroatoms can be unsubstituted or substituted with one or more groups consisting of hydrogen, alkyl, -OR, aryl, aralkyl or alkaryl, where R is as defined for Y; Z' can denote any group selected above for Z, or can also denote hydrogen, alkyl, aryl or hetero; or Z and Z1 together can form a -C(O)Y(O)C- group so that the dienophile forms a cyclic group of formula , where R1 and R2 are as defined above, Y is hetero as defined above, or Y is an alkylene group of formula -(CH2)s-, where s equals 1, 2 or 3.

EFFECT: obtained products comes into contact with a dienophile to eliminate the undesirable colour of the product.

37 cl, 2 dwg, 10 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to improved method of obtaining aminoacrylates (dimethylaminoethylacrylate and dimethylaminoethylmethacrylate) by transesterification of methylacrylate or methylmethacrylate by dimethylethanolamine at increased temperature in presence of Ti-containing liquid-phase catalyst. Synthesis is realised in two successive reactors: first, which works without methanol distillation, to conversion of DMAE 30-40% and second, from which distillation of methanol is carried out continuously to complete conversion of initial DMAE, with recycle of unreacted acrylate into first reactor and recycle of DMAE into second reactor.

EFFECT: method makes it possible to simplify reactor unit, increase specific productivity with preservation of high selectivity of process.

1 dwg, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing acetone cyanohydrin. The disclosed method comprises the following steps: A) reacting acetone and hydrogen cyanide in a reactor to obtain a reaction mixture, wherein the reaction mixture is subjected to circulation and acetone cyanohydrin is obtained; B) cooling at least a portion of the reaction mixture; C) removing at least a portion of the obtained acetone cyanohydrin from the reactor; D) continuous distillation of the removed acetone cyanohydrin to obtain a bottom product of acetone cyanohydrin and an overhead product of acetone in a distillation column; E) returning at least a portion of the overhead product of acetone to step A, wherein during returning, the overhead product of acetone is kept at temperature lower than 60°C, and the reaction to produce acetone cyanohydrin is carried out in the presence of a base catalyst. The invention also relates to methods of producing an alkyl ester of methacrylic acid and methacrylic acid which, as one of the steps, include producing acetone cyanohydrin using the disclosed method, a method of producing polymers based at least in part on alkyl esters of methacrylic acid, an apparatus for producing alkyl esters of methacrylic acid and use thereof.

EFFECT: method enables to prevent splitting of the overhead product of acetone and, as a result, reduces formation of deposits in the system when producing acetone cyanohydrin.

19 cl, 7 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of purifying unsaturated compounds from a group of glycol esters, wherein purification is carried out in an apparatus which is equipped with at least two evaporators, the evaporators being connected such that a portion of an unsaturated compound circulates on a loop, wherein vapours condensed after evaporation in a first evaporator are removed and vapours condensed after evaporation in a second evaporator are fed into the first evaporator, the method being characterised by that mass flow with which vapours condensed after evaporation in the first evaporator are removed from the mixture to be purified is less than the mass flow with which vapours condensed after evaporation from the second evaporator enter the first evaporator.

EFFECT: purification method enables to obtain especially pure product with high output.

23 cl, 1 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing acetone cyanohydrin. The method involves step A) of reacting acetone and a strong acid in the presence of a base catalyst in a reactor to obtain a reaction mixture, wherein the reaction mixture circulates, and acetone cyanohydrin is obtained; B) cooling at least 70 wt % of the reaction mixture by flowing in the cooling region of a cooler with dwell time in the cooler of 0.1-2 hours, wherein the cooler contains one cooling element or at least two cooling elements; C) removing at least a portion of the obtained acetone cyanohydrin from the reactor. In terms of the total internal volume of the cooler, the volume of the cooling region of the cooler is larger than the volume of the cooling element or at least two cooling elements of the cooler. The invention also relates to methods of producing an alkyl ester of methacrylic acid and methacrylic acid, which includes as one of the steps, production of acetone cyanohydrin using the disclosed method, as well as an apparatus for producing alkyl esters of methacrylic acid and use thereof.

EFFECT: method increases output of acetone cyanohydrin.

19 cl, 8 dwg, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to improved methods of producing alkyl esters of methacrylic acid as a reaction product, particularly to a method in which a) a reaction mixture which contains an amide of methacrylic acid, water, sulphuric acid and at least one alkanol undergoes esterification in one or more reaction spaces, b) the crude reaction product, in at least one fractionation column, is subjected to a separation process to obtain a reaction product which contains water, alkyl methacrylate and alkanol, c) the reaction product obtained at step b) is condensed in one or more heat-exchangers, d) the condensate is separated in at least one separation device into an organic phase and an aqueous phase, e) the organic phase is washed with water to obtain a washed organic phased and flush water and f) the separated aqueous phase, along with the flush water, is returned to at least one reaction space. The invention also relates to an apparatus for producing alkyl esters of methacrylic acid, at least having i) one or more reaction spaces in which a reaction mixture, which contains an amide of methacrylic acid, water, sulphuric acid and alkanol, undergoes esterification, ii) at least one fractionation column in which the reaction product is subjected to separation, iii) one or more heat-exchangers in which the reaction product subjected to separation is condensed, iv) at least one separation device in which the condensate is separated into an organic phase and an aqueous phase, v) at least one washing column in which the organic phase is washed with water, vi) at least one liquid-conducting connection between the separation device and at least one reaction space, through which the separated aqueous phase, optionally along with flush water, is returned to at least one reaction space.

EFFECT: high efficiency.

18 cl, 11 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing allyl methacrylate, which involves reaction of allyl alcohol with a methacrylic ester formed from an alcohol having 1-4 carbon atoms, where the reaction is carried out at temperature in the region of 80°C to 120°C in the presence of a polymerisation inhibitor and wherein the alcohol, which is released from the methacrylic ester used, is separated, wherein the reaction is carried out in the presence of zirconium acetyl acetonate as a catalyst and in conditions of feeding an oxygen-containing gas.

EFFECT: method makes production of allyl methacrylate with very high purity especially favourable.

17 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for producing ethylene glycol dimethacrylate, involving transesterification of an ester of methacrylic acid with ethylene glycol, where methacylate is formed by an alcohol containing 1-4 carbon atoms, at temperature ranging from 90°C to 130°C in the presence of lithium chloride in a combination with another chemically active compound as a catalyst and a polymerisation inhibitor and separating alcohol released from the ester of methacrylic acid used, the other chemically active compound used being lithium amide (LiNH2).

EFFECT: method according to the invention enables to obtain ethylene glycol dimethacrylate at a very low cost and having very high purity.

22 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing pure methacrylic acid, which involves: a) gas-phase oxidation of a C4 compound to obtain a methacrylic acid-containing gas phase, b) condensing the methacrylic acid-containing gas phase to obtain an aqueous methacrylic acid solution, c) separating at least a portion of the methacrylic acid from the aqueous methacrylic acid solution to obtain at least one methacrylic acid-containing raw product, d) separating at least a portion of methacrylic acid from the at least one methacrylic acid-containing raw product by thermal separation to obtain pure methacrylic acid, wherein at step (d), methacrylic acid is separated from at least a portion of at least one methacrylic acid-containing raw product by fractionation, and wherein the pure methacrylic acid is collected through a side outlet used for the fractionation column, and the amount of pure methacrylic acid collected over a certain time interval ranges from 40% to 80% of the amount of the methacrylic acid-containing raw product fed into the fractionation column over the same time interval. The invention also relates to an apparatus for producing methacrylic acid using said method, the apparatus comprising: a1) a gas-phase oxidation unit, b1) an absorption unit, c1) a separation unit, and d1) a purification unit, wherein the purification unit has at least one distillation column, wherein the at least one distillation column has at least one side outlet for pure methacrylic acid. The invention also relates to a method of producing methacrylic esters, polymethacrylate, polymethacrylic esters, which includes a step for said production of pure methacrylic acid.

EFFECT: obtaining an end product with fewer by-products while simplifying the process.

32 cl, 3 tbl, 4 dwg, 6 ex

FIELD: machine building.

SUBSTANCE: invention refers to a method for obtaining an ether additive, which involves mixing of dicarboxylic acid with ether so that water, ether and excess alcohol is obtained with further separation of water and alcohol from ether by rectification; at that, as an acid there used is oxalic acid, and as alcohol - n-butanol or 2-ethylhexanol. Cyclohexane used as a solvent is supplied for mixing of oxalic acid with alcohol, and rectification is performed in two columns so that cyclohexane (solvent) is obtained in the first column, which is returned to the stage of mixing with oxalic acid and alcohol and supply of residue of the first column to the second one so that alcohol and target product (ether additive) are obtained in it.

EFFECT: method allows simplifying the process and making it more economic by excluding the use of a catalyser, processing stages of reaction mass with an agent decomposing the catalyser, and reaction mass sorption and filtration stages.

2 cl, 2 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to chemical engineering and specifically to processing fusel oil, which is a large-tonnage waste in the alcohol industry. Fusel oil from production of ethyl alcohol is processed by esterification with glacial acetic acid in the presence of a sulphuric acid catalyst, and neutralisation, wherein esterification is carried out while boiling the reaction mixture and continuously separating water using a separating flask. The obtained product is separated from the catalyst under a vacuum at temperature not higher than 110°C. The obtained product and the catalyst are separately neutralised and the obtained product is additionally dried.

EFFECT: method enables to process fusel oil into a highly efficient component of mixed solvents of high quality with low cost of production and high output of the product.

4 cl

FIELD: chemistry.

SUBSTANCE: invention relates to novel dimethacrylic esters of dimerised fatty acid used as binding materials when producing various composite materials, in filling compounds and anaerobic sealants. Dimethacrylic esters of dimerised fatty acid have the structural formula: in which R=CH2CH2OCH2CH2; СН2СН2ОСН2СН2ОСН2СН2; (СН2)4; СН2СН2;

EFFECT: improved method.

2 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing alkoxy-polyoxyalkylene(meth)acrylates. Described is a method of producing alkoxy-polyoxyalkylene(meth)acrylate, in which: a) at least one metal compound of formula MetOR10 is taken, where Met denotes lithium, sodium, potassium, rubidium or caesium, and where R10 denotes hydrogen or a straight or branched alkyl residue, b) at least one alcohol R12OH is added, where R12 denotes a straight alkyl residue, with 1-18 carbon atoms or 2-(2-(2-methoxyethoxy)ethoxy)ethyl, where the molar mass of R12 is less than that of alkoxy-polyoxyalkylenes, c) at least one alkylene oxide of formula (VI) is added and reacts with the metal compound of formula MetOR10, where residues R11 denote, in each case independently from each other, hydrogen or a straight alkyl residue, and d) (meth)acrylic acid anhydride is directly added and reacts with the product from step c) in the presence of a stabiliser or a mixture of stabilisers.

EFFECT: simple and improved method of producing alkoxy-polyoxyalkylene(meth)acrylates.

9 cl, 16 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing (meth)acrylic esters (F) based on alcohols having at least one carbon-carbon triple bond, characterised by that at least one alcohol having at least one carbon-carbon triple bond of formula (1) where R1 denotes hydrogen, alkyl having 1-18 carbon atoms; alkyl having 2-18 carbon atoms, aryl having 6-12 carbon atoms, cycloalkyl having 5-12 carbon atoms, interrupted, if necessary, by one or more oxygen and/or sulphur atoms and/or one or more substituted or unsubstituted amino groups, or a 5-6-member heterocycl having oxygen, nitrogen and/or sulphur atoms, wherein said residues can be substituted with aryl, alkyl, aryloxy, alkyloxy, heteroatoms/or heterocycles, respectively, and R2 denotes alkylene having 1-20 carbon atoms, cycloalkylene having 5-12 carbon atoms, arylene having 6-12 carbon atoms, or alkylene having 2-20 carbon atoms interrupted by one or more oxygen and/or sulphur atoms and/or one or more substituted or unsubstituted amino groups and/or one or more cycloalkyl groups, -(CO)-, -O(CO)O, -(NH)(CO)O-, -O(CO)(NH)-, -O(CO)- or -(CO)O, where the names of the residues can be replaced with aryl, alkyl, aryloxy, alkyloxy, heteroatoms and/or heterocycles respectively, n is a whole number from 0 to 3, preferably from 0 to 2 and more preferably from 1 to 2 and X; for each i=0 to n can be independently selected from a group comprising -CH2-CH2-O-, -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2-C(CH3)2-O-, -C(CH3)2-CH2-O-, -CH2-CHVin-O-, -CHVin-CH2-O-, -CH2-CHPh-O- and -CHPh-CH2-O-, preferably from a group comprising -CH2-CH2-O-, -CH2-CH(CH3)-O- and -CH(CH3)-CH2-O-, and more preferably CH2-CH2-O-, where Ph denotes phenyl and Vin denotes vinyl, wherein the hydroxy groups of the alcohol are primary or secondary, esterified in the presence of at least one enzyme (E) with (meth)acrylic acid or re-esterified with at least one (meth)acrylic ester (D).

EFFECT: use of the present method enables to obtain esters of an acid based on alcohols which have carbon-carbon triple bonds with good output and low colour indices.

5 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing 11(E)-tetradecen-1-ylacetate, which is sex pheromone of sod webworms, the basic component of pheromones of omnivorous leaf-roller moths, stem moths, fir leaf-roller moths and certain other types of dangerous pests, involving a Grignard reaction of acrolein with ethylmagnesium bromide to obtain 1-penten-3-ol, ortho-ether Claisen rearrangement with participation of 1-penten-3-ol and triethyl ortho-acetate to obtain ethyl ether of 4(E)-heptenoic acid, reduction of the ethyl ether of 4(E)-heptenoic acid to obtain 4(E)-hepten-1-ol, substitution of the hydroxyl group of 4(E)-hepten-1-ol with Br to obtain 1-bromo-4(E)-heptene, cross-coupling reaction of 1-bromo-4(E)-heptene with 7-[(tetrahydro-2H-pyran-2-yl)oxy]heptylmagnesium bromide in the presence of a catalyst to obtain 11(E)-tetradecen-1-ol, acetylation of 11(E)-tetradecen-1-ol to obtain 11(E)-tetradecen-1-ylacetate, in which cross-coupling of 1-bromo-4(E)-heptene with 7-[(tetrahydro-2H-pyran-2-yl)oxy]heptylmagnesium bromide to obtain 11(E)-tetradecen-1-ol is carried out in the presence of a Li2CuCl4 in the medium of tetrahydrofuran in the following molar ratio [1-bromo-4(E)-heptene]: [7-[(tetrahydro-2H-pyran-2-yl)oxy]heptylmagnesium bromide]:[ Li2CuCl4]:[tetrahydrofuran]=1:1.2:0.03:20 for 1 hour at temperature of minus 75°C, then for 1 hour at temperature ranging from minus 75°C to 20°C and for 10 hours at 20°C. Since the 1-2% content of the (Z)-isomer already inhibits attractive properties of 11(E)-tetradecen-1-ylacetate, existing methods are not suitable for practical application.

EFFECT: method is distinguished by stereoselectivity.

2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel compounds of formula (I), where each R1, R2 and R3 is independently selected from a group comprising H, OH, F, Cl, Br, a methoxy group and an ethoxy group; or R1 and R2 together form -OCH2O-, and R3 is selected from a group comprising H, OH, methoxy group, ethoxy group and halogens; R4 denotes OH or o-acetoxybenzoyloxy nicotinoyloxy or iso-nicotinoyloxy; R5 denotes or , and at least one of R1, R2 and R3 is not hydrogen.

EFFECT: method for synthesis of a compound of formula (I) and use of the compound of formula (I) in preparing medicinal agents for preventing or treating cerebrovascular diseases.

17 cl, 14 tbl, 5 dwg, 12 ex

FIELD: chemistry.

SUBSTANCE: method involves reaction of a polyatomic alcohol - neopentyl glycol, trimethylol propane, pentaerythritol with trialkylacetic acid in molar ratio 1:1 in the presence of an acid catalyst which is a sulphonic acid derivative having pKa between -2 and +2, carried out at temperature 180°C or lower.

EFFECT: invention enables to obtain hydrolysis-resistant esters.

8 cl, 3 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing dialkyl ether of naphthalene dicarboxylic acid used in production of different polymer materials such as polyesters or polyamides from a liquid-phase reaction mixture containing low-molecular alcohol, naphthalene dicarboxylic acid, and material which contains polyethylene naphthalate, in mass ratio of alcohol to acid between 1:1 and 10:1, at temperature between 260°C and 370°C and pressure between 5 and 250 absolute atmospheres.

EFFECT: method enables production of highly pure NDC.

6 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: described is a method of producing acrolein by dehydrating glycerol in the presence of tungsten compound-containing solid-phase catalysts with Hammett acidity H0 less than +2, which contain palladium as a promoter.

EFFECT: high output and enabling catalyst regeneration without loss of properties thereof.

23 cl, 3 ex

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