SK126599A3 - Method for producing at least one alkylvinylether and/or alkenyl vinylether - Google Patents

Abstract

A method for producing is carried out in the liquid reaction medium at a pressure of 0.05 to 0.3 Mpa under the catalytic action of superalkaline catalytic system generated in situ in the vinylation reaction medium of alcohol or acetylene alcohols containing gas at a temperature of 60 to 140 °C, or separately, at least from one alkali metal compound and at least one aprotic polar to bipolar solvent in from 5 to 40 mol. surplus for mol of alkali metal compound, by synergism of gas containing acetylene and at least one aliphatic alcohol. Optionally the catalytic system is preparing separately and it is adding to the vinylation medium, in which the molar ration of alkali metal compound or compounds to alcohol or to water/alcohols mixtures is maintaining 1 : 0.001 to 2 (1 : 0.05 to 1.2), by taking away of generated vinyl ether or mixture of vinyl ether as azeotropic mixture with at least one alcohol and/or water, and/or solvent carrying especially the water and alcohol. Raw product is dividing, chief product is isolating, unconverted acetylene and alcohols are recycling, whereby the part of catalytic system is also discontinually or continually taking away and regenerating. Chief reaction mixture may be stabilized by inhibitors and retarders of subsequent and side reaction.

Description

Technical field

The present invention provides a method of manufacture of at least one alkyl vinyl ether and / or the superbase alkenylvinyléteru catalyzed addition of alcohols, saturated or unsaturated Cl to _Cg, respectively. C ₃ to C 1 to acetylene, under mild reaction conditions allowing high selectivity to the corresponding ethers, as well as safety of the vinylation stage of the process.

BACKGROUND OF THE INVENTION

Recently used processes for the preparation of alkyl vinyl ethers by vinylating aliphatic alcohols with acetylene were carried out under the catalytic action of alkali metal hydrazides or alcoholates at a pressure of 1 to 4 MPa at a temperature of 200 to 250 ° C [Favorskij A.E., Shostakovsky M.F. Obšč. chim. 13. 1943, no. 1, p. 1; CIOS XXIX-62 (1945); Reppe W. Vinylierung Lieb. Ann. Chem. 60, 1956, pp. 81-138; Shostakovsky M.F. Prostye vinilovye efiry, p. 250 Moscow, Izd AN USSR (1952); Femkin O.N., Sixaks G.K., Treger Ju.A .: Acetilen, pp. 143-148, 318-321, Moscow Khimija (1991)]. Thus, for the preparation of isobutyl vinyl ether at said high temperature, a pressure of 0.5 MPa was required and for the synthesis of methyl vinyl ether 2.5 MPa. However, for safety reasons, it is necessary to dilute acetylene with 35 to 50% by volume of nitrogen [Lebedev N.N .: Khimija i technol osnovnogo organičeskogo i neftechimič. sinteza, s 369-372, Moscow Khimiya (1975); UUmans Enzyklopädie der Technischen Chemie, Bd. 23, 579, Verlag Chemie, Weinheim (1983)], which requires higher investment, energy and operating costs at all. Its operational risk is also increasing. Later it turned out [Trofimov B.A .: Uspechi chim., 40, 1981, p. 248; FROM. organ chim., 22, 1986, pp. 199 and 31, 1991, p. 1368; SU 437 737 (1975)] that in a super-basic environment produced e.g. butylated hydroxyl or alcoholate with crown ethers [Steinbam D et al. J. Organometal Chem., 414.1991, p. 45-50], but in particular DMSO with KOH or KOR [Trofimov B.A. et al .: Ž organ chimii, 31. 1991, p. 647], vinylation of alcohols with acetylene, proceeds at a sufficiently rapid temperature of 80-100 ° C,

MOH + CORNER + H ₂ O (A)

THE CORNER

HC = CH-ROM [MCH = CRO] -> ROM + CH ₂ = CHOR (B)

1___!

allowing to operate at substantially lower to atmospheric pressure. However, the reproducibility of the reaction parameters and results for industrial use, despite the evident contribution of the super-basic catalyst system, is problematic. Thus, the vinylation of allyl alcohol with acetylene, catalysed by the DMSO-KOH system at 80 to 100 ° C and mol. ratio of allyl alcohol: KOH = 1: 1 to 2 and allyl alcohol: DMSO = 1:15 to 30 [Trofimov B.A. et al., SU 1 338 327 (1988); FROM. org chim. 26. 1990, p. 725], wherein the yield of allyl vinyl ether and cis-vinyl-1-propenyl ether should be

43.5 to 88.1%. Even such a range of yields suggests that the determined reaction and technological parameters are not sufficient to develop an industrial production technology. This is also related to other reaction conditions for the preparation of the catalyst system itself, the main and side mechanisms, including the subsequent reactions of alkyl vinyl ethers and alkenyl vinyl ethers. Thus, it exploits the disadvantages of the found supercoat catalyst system, eliminates the deficiencies and vinylation problems of aliphatic alcohols than the method.

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION The present invention provides a process for the production of at least one alkyl vinyl ether and / or alkenyl vinyl ether by super-catalyzed addition of at least one saturated aliphatic alcohol having a carbon number of 1 to 8 and / or an unsaturated alcohol having carbon numbers of 3 to 8 with acetylene at 60 to 140. C, wherein the addition is carried out in a liquid reaction medium at a pressure of 0.02 to 0.3 MPa, under the catalytic effect of a super-basic catalyst system formed in situ in the reaction medium of vinylation and / or separately from at least one alkali metal compound and / or an alkali metal and at least one aprotic polar to bipolar solvent in an S to 50 molar excess per mole of the alkali metal compound or compounds, the interaction of the acetylene gas and the at least one aliphatic alcohol, or by adding to the reaction medium vinylation and / or special preparation an catalytic system precursor allytic system and / or finished catalyst system, providing a molar ratio of the alkali metal compound (s) to the alcohol or alcoholic mixture or alcohol / water mixture of 1: 0.01 to 2 in a vinylation environment in the presence of acetylene and alcohol; removing the formed vinyl ether or vinyl ether mixture as an azeotropic mixture with at least one alcohol and / or water and / or a solvent forming an azeotropic mixture with water and / or alcohol, wherein a part of the catalytic system for regeneration is gradually or simultaneously removed from the vinylation environment Fresh catalyst precursor or fresh catalyst system precursors and / or finished catalyst system, wherein the azeotropic mixture of vinyl ether or a mixture of vinyl ethers with at least one alcohol and other volatile constituents of the reaction mixture distilled and / or stripped, isolating the main product the unconverted acetylene is recirculated, the unconverted alcohol or alcohols and / or the solvent is recycled to the reaction medium of the vinylation and / or special catalyst preparation.

The advantage of the process according to the invention is its reproducibility, production reliability, high vinylation rate under mild reaction conditions, while at the same time achieving high selectivity for alkyl vinyl ethers and alkenyl vinyl ethers at low investment, energy and even low operating costs. Last but not least, it is operational safety and virtually wastelessness of the entire production process.

At least one alkali metal is selected from sodium, potassium and rubidium and at least one alkali metal compound is selected from their oxides, hydroxides and especially alcoholates. Because of its low potency, lithium and its compounds are poorly suited, and cesium and its compounds are too low for technical and economic demands. In the case of alcoholates, it is best to ensure that the alkoxy groups of the alcoholates, most preferably potassium, are similar to the alkoxy groups of the vinyl alcohols.

The aprotic polar to bipolar solvent is selected from N-alkyl-2-pyrrolidone, Ν, Ν-dimethylformamide, acetanilide, MNH ₂ amide, wherein M is an alkali metal, sulfanoxide, sulfolaxide, tetraalkylammonium hydroxide, especially dimethylsulfoxide (DMSO) and diethylsulfoxide.

Suitable solvents forming azeotropic mixtures with water, alcohols and optionally vinyl ethers are relatively low boiling hydrocarbon solvents, boiling under normal conditions of 40 to 140 ° C. In this case, however, it should be ensured, if already used, for better separation that the boiling point is quite different from the boiling point of both the vinyl ether produced and the alcohol used.

The catalyst system is prepared in situ in the reaction medium of vinylation from the starting components or precursors of the catalyst system, such as alkali metal alcoholates, especially potassium alcoholate, or alkali metal hydroxide, alcohol, aprotic polar to bipolar solvent, preferably dimethylsulfoxide and acetylene containing gas. For the preparation of the catalyst system, the most suitable temperature is usually 65-75 ° C.

The catalyst system prepared separately as well as the precursors of the catalyst system into the reaction medium are dosed in portions, discontinuously, semi-continuously or continuously. The alkyl or alkenyl vinyl ether formed and the reaction water or even the water supplied with the raw materials are removed from the reaction medium, usually together with the part of the alcohol fed to the vinylation medium. Since the water present, if any, poisones the catalytic system itself, it hydrolyzes with the conjugated isomerization of the alkyl- and / or conjugates. alkenyl vinyl ether, thereby reducing the selectivity of vinyl ether formation, the water from the reaction medium should be removed as thoroughly as possible. Not only alcohol, but all raw materials are most perfectly absolutely dry, anhydrous. For carrying out the process according to the invention, if the raw materials are no longer absolutely dry, the water content thereof must not exceed 0.1% by weight. However, the excess alcohol also retards its own vinylation. It is therefore necessary to maintain the molar ratio of alkali metal compound (s) to alcohol or alcohol mixture 1 in the vinylation environment; 0.001 to 2, preferably 1: 0.05 to 1.2. At a molar ratio of less than 1: 0.001, the production rate of the device is too low, and at greater than 1: 1.2, the vinylation reaction rate decreases.

The gas-containing acetylene for carrying out the process according to the invention is pure acetylene or technical grade acetylene, a mixture of acetylenes with methane or natural gas, optionally with hydrocarbons C ₂ to C ₄ , a mixture of acetylene with inert gases such as nitrogen, argon, carbon dioxide , even with carbon monoxide and hydrogen.

Preferably, the continuously removed vinyl ether, usually in the form of an azeotropic mixture with an alcohol, is further separated by known methods, rectification, extraction, extractive distillation or rectification, e.g. for separating an alcohol from an alkyl or alkenyl vinyl ether using ethylene glycol to polyethylene glycol as an alcohol scavenger extract and permeable vinylether, then propylene glycol, dipropylene glycol, alkanolamines, and the like.

In the regeneration of the catalyst system, higher molecular compounds are removed from it by extraction, in particular with a non-polar solvent, whereby the aprotic polar to bipolar solvent can be separated by distillation under reduced pressure, the entire crude catalyst system is stripped of undissolved impurities and the like.

In order to prevent unwanted side reactions, especially in the vinylation reaction stage, inhibitors or retarders are introduced into the vinylation environment, not only by radical but also by cationic reactions, known inhibitors of oligomerization to polymerization of acetylene, such as bismuth, antimony and the like. the resulting acid catalysts of vinyl ether oligomerization of an organic compound containing tert. amino groups such as tert. alkylamines and the like.

Further details of embodiments of the process according to the invention, as well as other advantages, are apparent from the examples which supplement the description but do not limit the claims.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

A 600 cm ³ , four-necked flask with an elongated bottom portion for longer contact time with the acetylene-containing gas is fed through the bottom frit of acetylene, equipped with a stirrer, by measuring the temperature with a mercury thermometer fitted with a reflux condenser immersed in The oil bath, the temperature of which was controlled to an accuracy of + 2 ° C, was weighed with 280 g of dimethylsulfoxide (DMSO) containing 0.15 wt. water, 85.777 g of potassium butanoate (mol ratio DMSO-butanoate = 1: 6). After heating to 70 + 0.2 ° C, 200 cm ³ / min of acetylene were started. for 30 min. Thereafter, the temperature was raised to 120 ° C and 25 g of n-butanol was added and then 10.6 g / h of n-butanol was continuously fed over 3 h. The formed n-butyl vinyl ether with a portion of n-butanol and water supplied to the reaction medium with raw materials was continuously distilled off. The crude distilled product as well as the reactor contents were weighed and analyzed by GLC. The conversion of n-butanol reached 76.2% and the selectivity to butyl vinyl ether was 87.3%.

Using an equimolar amount of potassium butanolate under otherwise similar conditions, the conversion of butanol is only 54.2% and the selectivity to butyl vinyl ether is 69.7%.

However, using an equimolar amount of sodium and potassium butanolate under otherwise similar conditions, the conversion of n-butanol reached 72.8% and the selectivity to butyl vinyl ether was 84.3%.

However, by increasing the amount of DMSO from 280 to 450 g, the conversion of n-butanol was already 88.3% and the selectivity to butyl vinyl ether was 84.9%. And using an equimolar amount of the n-butanol / isobutanol mixture, the conversion of the butanol mixture was 88.9% and the selectivity to the butyl butyl isobutyl ether mixture was 85.1%. Using allyl alcohol instead of n-butanol in an amount of 44.33 g and potassium allyl alcoholate instead of sodium butanolate, the conversion of allyl alcohol reached 79.3% and the selectivity to allyl vinyl ether was 78.1% and vinyl-Z-isopropyl ether 8.3%.

Under otherwise similar conditions, but by replacing the Liebig cooler with a reflux condenser, i.e. without draining off vinyl ether, water and part of the allyl alcohol, leaving only unconverted acetylene, allyl alcohol conversion reached 74.5% but selectivity to allyl vinyl ether only 56.3% and vinyl- Z-isopropenyl ether 9.7%.

Example 2

In a separate two-necked flask equipped with a Liebig condenser, potassium butanolate is prepared from powdered potassium hydroxide and n-butanol in a molar ratio of potassium hydroxide: n-butanol = 1: 1.5 with stirring at 75-95 ° C. From its synthesis, the reaction water and excess butanol are mainly withdrawn in the form of an azeotropic mixture. The potassium butanolate thus prepared is used to prepare a solution in dimethylsulfoxide (DMSO) in which the molar ratio of potassium n-butanolate: DMSO = 1:28. This is applied by continuous dosing as a precursor of the catalyst system for the continuous vinylation of n-butanol with acetylene, containing as impurities (v / v) 2.7 nitrogen, 5.4 methane, 0.6 oxygen and 0.2 carbon monoxide.

200 g of said potassium butanolate solution in DMSO are initially charged to the reactor specified in Example 1, 20 g of butanol are added and heated to 70 ° C and 200 cm ³ / min of acetylene gas is started. After 30 min, the temperature of the reaction mixture is heated to 100 ° C and n-butanol is continuously metered in in an amount such that the molar ratio of potassium butanolate: butanol in the reaction solution gradually decreases from 1: 1 to 0.5 and after 10 h was only 1: 0.3 as the reaction mixture was gradually withdrawn from the bottom of the reactor to gradually regenerate the catalyst. During the continuous preparation of n-butyl vinyl ether, n-butyl vinyl ether was removed from the reactor mainly in the form of an azeotrope with n-butanol and mixed to the water (reaction and mainly supplied with the feedstock) for separation. Extractive rectification using ethylene glycol gave n-butyl vinyl ether. The n-butanol was separated from the distillation residue, which was reused to produce the alcoholate. Particularly the higher boiling by-products were separated by toluene extraction and after the residue toluene was distilled off, DMSO was distilled off in part of the residue under reduced pressure and the potassium alcoholate mixture after recrystallization was either returned directly to the vinylation reaction medium or dissolved in DMSO. The remainder of the residue, i.e. DMSO, in particular with the potassium compounds, is returned as a precursor of the catalyst system to the vinylation environment.

Acetylene-containing gas leaving the reaction after condensation of the predominantly azeotropic mixture is about 40% by volume for energy combustion, the remainder being recycled together with fresh feed gas containing acetylene.

Similarly, isobutanol is vinylated except that potassium isobutanolate is prepared instead of n-butanolate. Analogously, vinylation of 2-ethylhexanol, only the vinylation temperature was 120 ± 2 ° C, instead of potassium butanolate, potassium 2-ethylhexanolate was applied and the vinylation was carried out under reduced pressure (0.06 ± 0.01 MPa). Furthermore, vinylation of a mixture of allyl alcohol (50% by weight) with 4-octen-1-ol (50% by weight) wherein sodium allyl alcoholate was applied instead of sodium butanolate. Further, a mixture of allyl alcohol, 2-buten-1-ol and 4-octene-1-ol and a similar mixture of allyl alcohol, 2-buten-1-ol and 2-ethylhexanol (33.33% each). The results are summarized in Tab. First

Table 1

Vinylated alcohol Vinyl Alcohol Conversion [%] Selectivity to alkyl vinyl ether (s) [%] n-butanol 59.1 85.6 n-butanol 64.9 84.9 isobutanol 59.5 87.3 2-ethylhexanol 49.9 78.3 n-butanol + isobutanol, mol. 1: 60.2 89.2 allyl alcohol + 4-octen-1-ol, 52.5 88.1 weight. 11 allyl alcohol + 2-buten-1-ol + + 4-Octen-1-ol, wt. 11: 1 54.7 84.2 allyl alcohol + 2-buten-1-ol + + 2-ethylhexanol, wt. 1: 1: 1 53.9 85.2

For the isolation of individual vinyl ethers, such as mixtures of alkyl and alkenyl vinyl ethers containing unconverted alcohols as well as admixtures of unsaturated hydrocarbons and volatile saturated hydrocarbons, extractive distillation, respectively. rectification and used the n-alkanes C _I0, removing hydrocarbons by extractive distillation using a glycol mainly alcohols and other polar compound.

Example 3

On the apparatus specified in Example 1 and under similar conditions, the catalyst system was first formed in said reactor from alkali metal and alcohol hydroxides at 80 ± 0.5 ° C and self-vinylated with pure refined acetylene at a similar flow rate to Example 1, with reaction water mainly from the synthesis of the alcoholate

MOH + ROH-> ROM + H ₂ O was continuously removed with the resulting vinyl ether, the effect of the type of sodium hydroxide as well as the different MOH: DMSO ratio was investigated. The results are summarized in Table 2.

Table 2

Vinylated alcohol MOH / DMSO molar ratio conversion alkanol I 'l% Selectivity to alkyl vinyl ether depending on molar ratio and type of MOH RbOH KOH NaOH LiOH n-butanol 0,333 31.1 20.7 22.1 9.7 - n-butanol 0,125 56.7 23.2 24.2 - 0.9 n-butanol 0,025 62.3 75.1 52.1 13.2 0.8 n-butanol 0,050 69.2 93.3 88.3 26.9 4.1 n-butanol 0,070 65.3 82.1 72.3 15.6 0.3 hexanol 0,050 59.1 90.1 87.4 15.0 0.5 isobutanol + allyl alcohol (mol 1: 1) 0,050 58.2 94.3 89.8 25.3 6.7

Example 4

Following the procedure of Example 1, only the catalyst system was formed from KOH + DMSO + n-butanol in the presence of butanol and examined at the molar ratio of KOH. DMSO = 27 effect of temperature on butanol conversion (after deduction of azeotroped distillate) and selectivity on butyl vinyl ether. At 100, 110, 120 and 140 ° C the butanol conversion was 85 to 99% and the selectivity to butyl vinyl ether was 15, 31, 65.90 and 55%, respectively.

Example 5

To a three-necked 1500 cm ³ flask was charged 225 g of a suspension of potassium isobutanoate in isobutanol (the precursor slurry was prepared using toluene solvent as the water exchanger, equivalent to 39.9 g of KOH) and 1,423 g of DMSO. to 70 ° C and pure acetylene, additionally refined on alumina, was introduced at 14.4 dm ³ / h for 30 min. Thereafter, after the temperature was raised to 110 ° C, isobutanol was metered in at a flow rate of 30 cm ³ / h. All reaction parameters were measured and GLC samples of the distillate and GLC were collected and analyzed at 3 h intervals. the crude product and the residue respectively. worn catalyst as well as gas samples. A sample of crude isobutyl vinyl ether was stabilized by the addition of 1 wt. KOH. The conversion of isobutanol was 85-92%, the selectivity of converted isobutanol to isobutyl vinyl ether from 86 to 100%, ie isobutyl vinyl ether yield 79.5 to 85%.

Example 6

The procedure was similar to that in Example 5, but only the same amounts of DMSO + N-butylvinyl-2-pyrrolidone (I), tetrabutylammonium hydroxide + DMSO (II), Ν, Ν-dimethylformamide + were compared as polar solvents (component of the catalyst system). diethylsulfoxide (III), diethylsulfoxide + N-methyl-2-pyrrolidone (IV), Ν, Ν-dimethylacetamide + DMSO (V), sulfolaxide (VI), sulfolaxide + DMSO (VII), with average isobutyl vinyl ether yields of converted isobutanol ( 74 ± 3 (I), 82 ± 3 (II), 80 ± 3 (III), 75 ± 3 (IV), 85 ± 3 (V). In addition, in addition, inhibitors and retarders of ionic and radical reactions are added to the vinylation environment at 0.1 wt. isobutanol, tributylamine and 2,4,6-triterc. % of butylphenol and 0.05 wt. Bi ₂ O ₃ , the yields were in the upper range or even 1 to 3% higher.

By using instead of DMSO alone tetrabutylammonium hydroxide (VI), N, N-dimethylformamide (VII), diethylsulfoxide (VIII), Ν, dim-dimethylacetamide (IX), N-methyl-2-pyrrolidone (X) and the mentioned inhibitors and retarders yield yields. isobutyl vinyl ether (in%): 71 ± 3 (VI), 63 ± 3 (VII), 86 ± 3 (VHI), 58 ± 3 (IX), 69 ± 3 (X).

Example 7

The procedure was similar to that of Example 5 except that the experiments were carried out with isobutanol with different water admixtures. While in Example 5, the isobutanol was below 0.01 wt%, with the isobutanol having a water content of 0.08 wt%. the yield of isobutyl vinyl ether decreases to 65-78%, at 0.12 wt. % to 51 to 55% and at 0.25% wt. to 42 to 45%, mainly due to the hydrolysis of isobutyl vinyl ether to isobutanol and via unstable vinyl alcohol to acetaldehyde. However, even at 0.25 wt. The addition of 0.5% by weight of triisobutylamine increased the yield to 63-72%. With 0.1 wt. % Of 2,6-di-tert-butylphenol and 0.05 wt. antimony (III) acetate (at 2.5 wt% water), the yield reached 70-73%.

Example 8

The procedure was similar to that of Example 2, except that only vinylation was subjected to a mixture of butanol and 2-ethylhexanol, the vinylation was carried out at a temperature of 85 ± 5 ° C and a pressure of 0.06 to 0.7 MPa, with alcohol conversion reaching 97 ± 4%. for the corresponding butyl vinyl ether and 2-ethylhexyl vinyl ether was 81 ± 4%.

In addition, extraction rectification using diethylene glycol and triethylene glycol as extraction agents (solvents) was used to isolate pure alkyl vinyl ethers.

Example 9

The procedure was similar to that in Example 8, but only acetylene containing (in% by volume) 2.3 oxygen, 10.4 nitrogen, 1.8 methane, 0.7 ethane, 0.1 carbon dioxide, 0.6 was used for vinylation. Mixtures of saturated C ₃ to C ₇ hydrocarbons. The alcohol conversion was 95 ± 4% and the selectivity to alkyl vinyl ethers was 80 ± 4%. In addition, a mixture of C ₁₀ to C ₁₃ n-alkanes was used for the extraction.

Example 10

The procedure was similar to that of Example 2 in the vinylation of 2-ethylhexanol, only to increase the rate of water uptake and 2-ethylhexyl vinyl ether, 2-ethylhexanol containing 5 wt.

cyclohexane (variant A) and toluene (variant B). The conversion of 2-ethylhexanol in variant A was 1 to 3% higher and in variant B 2 to 5% higher, with a similar increase in selectivity to 2-ethylhexyl vinyl ether over the results in Example 2.

Industrial usability

The process according to the invention is particularly useful in the chemical industry for the production of alkyl and carboxylic acids. alkenyl vinyl ethers, as in their application to the production of copolymers, resins and organic intermediates.

Claims (10)

A process for the production of at least one alkyl vinyl ether and / or alkenyl vinyl ether by super-catalyzed addition of at least one saturated aliphatic alcohol having a carbon number of 1 to 8 and / or an unsaturated alcohol having a carbon number of 3 to 8 with acetylene at 60 to 140 ° C. characterized in that the addition is carried out in a liquid reaction medium at a pressure of 0.02 to 0.3 MPa, under the catalytic action of a super-basic catalyst system formed in situ in the reaction medium of vinylation and / or in particular, from at least one alkali metal compound and / or an alkali metal and at least one aprotic polar to bipolar solvent in a 5 to 50 molar excess per mole of alkali metal compound or compounds, the interaction of acetylene containing gas and at least one aliphatic alcohol or by adding to the reaction medium vinylation and / or special catalytic preparation on a catalyst system precursor system and / or a finished catalyst system, providing in a vinylation environment in the presence of acetylene and an alcohol a molar ratio of alkali metal compound or compounds to alcohol or alcohol or water / alcohol mixtures of 1: 0.01 to 2 , removing the formed vinyl ether or vinyl ether mixture as an azeotropic mixture with at least one alcohol and / or water and / or a solvent forming an azeotropic mixture with water and / or alcohol, wherein a part of the catalytic recovery system is gradually or simultaneously discharged from the vinylation environment; a fresh precursor or fresh precursors of the catalyst system and / or the finished catalyst system are introduced, wherein the azeotropic vinyl ether mixture or the vinyl ether mixture with at least one alcohol and other volatile components of the reaction mixture is distilled off and / or stripped, the converted acetylene is recirculated, the unconverted alcohol or alcohols, and / or the solvent is recycled to the vinylation and / or special catalyst preparation reaction medium. The method of claim 1, wherein the at least one alkali metal is selected from sodium, potassium and rubidium and the at least one alkali metal compound is selected from their oxides, hydroxides and alcoholates. The process according to claim 1 or 2, wherein the aprotic polar to bipolar solvent is selected from N-alkyl-2-pyrrolidone, Ν, Ν-dimethylformamide with an alkali metal, dimethylsulfoxide, diethylsulfoxide, sulfanoxide, sulfolaxide and tetraalkylammonium hydroxide. . Production method according to claims 1 to 3, characterized in that the solvent forming the azeotropic mixture with alcohol and / or water is selected from aliphatic, alicyclic and aromatic hydrocarbons boiling under normal conditions of 40 to 140 ° C. Production method according to claims 1 to 4, characterized in that the specially prepared catalyst system precursor or catalyst system of at least one alkali metal and / or a compound of at least one alkali metal with at least one aprotic polar to bipolar solvent is dewatered below its content. 0.8 wt The process according to claims 1 to 5, characterized in that the content of alcohol or alcohol mixture in the vinylation reaction medium is minimized such that the molar ratio of alkali metal compound to alcohol or alcohol mixture does not exceed 1: 1.5. Production process according to claims 1 to 6, characterized in that the components of the catalyst system and / or the precursor up to the catalyst system formed are added to the vinylation reaction medium discontinuously, semi-continuously or continuously. A process according to claims 1 to 7, characterized in that the gas-containing acetylene is acetylene alone and / or a mixture of acetylene with at least a vinylation-inert gas such as nitrogen, argon, carbon dioxide, carbon monoxide, methane and hydrocarbons on the number of carbons in the molecule 2 to 7. The production method according to claims 1 to 8, characterized in that the raw materials are anhydrous or with a water content below 0.1% by weight. Production process according to claims 1 to 9, characterized in that the actual vinylation of the alcohols and / or the isolation of the vinyl ether is carried out in the presence of side reaction inhibitors and / or retarders, such as oligomerization to polymerization of acetylene and vinyl ethers and / or cleavage of vinyl ethers.