[go: up one dir, main page]

WO2018036848A1 - Vinylation avec de l'acétylène en présence d'eau - Google Patents

Vinylation avec de l'acétylène en présence d'eau Download PDF

Info

Publication number
WO2018036848A1
WO2018036848A1 PCT/EP2017/070530 EP2017070530W WO2018036848A1 WO 2018036848 A1 WO2018036848 A1 WO 2018036848A1 EP 2017070530 W EP2017070530 W EP 2017070530W WO 2018036848 A1 WO2018036848 A1 WO 2018036848A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
vinylation
acetylene
starting
starting compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2017/070530
Other languages
German (de)
English (en)
Inventor
Veit WASCHOLOWSKI
Franz Niklaus Windlin
Pavel TUZINA
Pierre Fournier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2018036848A1 publication Critical patent/WO2018036848A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • C07C41/08—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only to carbon-to-carbon triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the invention relates to a process for preparing a vinyl compound by vinylating a starting compound having at least one primary or secondary amino group, at least one hydroxyl group or at least one thiol group with acetylene, which is characterized in that the vinylation in the presence of 0.2 to 5 parts by weight of water, based on 100 parts by weight of the starting compound is performed.
  • vinyl ethers which are prepared by vinylation of hydroxy compounds with acetylene or else, for example N-vinylpyrrolidone, which is prepared by vinylation of pyrrolidone with acetylene.
  • US 2003/0105354 describes such vinylations of starting compounds having at least one secondary amino group, at least one hydroxyl group or at least one thiol group.
  • the described implementation has two stages. In a first step, the starting compound is reacted with an alkali metal. The obtained salt of the starting compound acts as a catalyst. The resulting in the reaction of water and optionally used as a solvent for the alkali metal hydroxide are distilled off. Then the vinylation takes place.
  • WO 2009/074534 or DE-A 19509362 describes the vinylation of pyrrolidone with acetylene. Water is separated in the described method from the reaction with the alkali metal.
  • the starting compound contains at least one primary or secondary amino group, at least one hydroxyl group or at least one thiol group.
  • Preferred starting compounds having at least one primary or secondary amino group are cyclic or non-cyclic amides. Preferably, these starting compounds contain only one amino group.
  • Non-cyclic amides are in particular those of the formula I.
  • R 2 -C ( O) -NHR wherein R 1 is an H atom or a C 1 to C 4 alkyl group and R 2 is a C 1 to C 10 alkyl group.
  • the amino group is preferably a secondary amino group; R 1 then represents a C 1 - to C 4 -alkyl group.
  • R 2 is preferably a C 1 - to C 4 -alkyl group.
  • the starting compounds of the formula I are vinyl compounds of the formula II
  • R 1 and R 2 have the above meaning or preferred meaning.
  • a particularly preferred starting compound having a primary or secondary amino group is N-metylacetamide, the vinyl compound obtained therefrom is N-vinyl-N-methylacetamide (VIMA) of the formula III:
  • Preferred cyclic amides are caprolactam, piperidone or pyrrolidone.
  • the vinyl compounds obtained therefrom are N-vinylcaprolactam, N-vinylpiperidone and N-vinylpyrrolidone.
  • Preferred starting compounds having at least one hydroxyl group are aliphatic or cycloaliphatic compounds having one or two hydroxyl groups. Preference is given to aliphatic or cycloaliphatic compounds having 1 to 20 C atoms, in particular having 2 to 14 C atoms.
  • the aliphatic or cycloaliphatic compounds may contain further heteroatoms, in particular they may contain ether groups.
  • the starting compounds having at least one hydroxyl group are aliphatic or cycloaliphatic see compounds having one or two hydroxyl groups, which consist of a total of 2 to 14 carbon atoms, which may contain ether groups and except oxygen contain no further heteroatoms, ie consist exclusively of H, C and O.
  • alkanols in particular C 2 - to C 8 -alkanols, alkanediols, in particular C 2 - to C 8 -alkanediols, polyalkyleneglycols, in particular di-, tri- or tetraalkyleneglycols, preferably di-, tri- or tetraethylene glycols, and also cyclohexanol, cyclohexanediol, hydroxyalkylcyclohexanes, in particular hydroxymethylcyclohexane, and bis-hydroxyalkylcyclohexanes, in particular bis-hydroxymethylcyclohexanes.
  • the polyalkylene glycols preferably correspond to the formula HO- (Y-O-) n -Y-OH, where n is an integer of at least 1 and Y is an alkylene group having 1 to 10 C atoms, preferably having 2 to 4 C atoms , particularly preferably with 2 or 3 C atoms.
  • n 1 (dialkylene glycol)
  • n 2 (trialkylene glycol)
  • n 3 (tetraalkylene glycol).
  • the vinyl compounds obtained from starting compounds having at least one hydroxyl group are vinyl ethers.
  • monovinyl ethers are obtained.
  • Starting compounds having two hydroxyl groups result in monovinyl ethers, or divinyl ethers or mixtures thereof. This depends on the molar ratios of the starting materials used and / or their conversion.
  • Preferred starting compounds having at least one thiol group are aliphatic compounds having a thiol group, in particular alkanethiols having 2 to 8 C atoms or alkanethiols having 2 to 8 C atoms substituted by a hydroxyl group.
  • the vinyl compounds obtained therefrom are vinyl thioethers.
  • S-vinylmercaptoethanol S-vinylmercaptoethanol.
  • Thiol groups generally react faster with acetylene than hydroxyl groups. Therefore, in reactions of compounds having a thiol group and a hydroxyl group, S-vinyl compounds containing a hydroxyl group can be selectively obtained.
  • the starting compounds of the vinylation are cyclic amides or compounds having one or two hydroxyl groups or compounds having a mercapto group; the corresponding vinyl compounds are cyclic N-vinylamides, monovinyl ethers, divinyl ethers or monovinylthioethers, e.g. S-vinylmercaptoethanol.
  • the starting compounds of the vinylation are a compound having one or two hydroxyl groups.
  • the corresponding vinyl In the case of the starting compound having a hydroxyl group, compounds are monovinyl ether. In the case of the starting compound having two hydroxyl groups, the corresponding vinyl compounds are monovinyl ethers, divinyl ethers or mixtures thereof.
  • the starting compounds of the vinylation are a compound having two hydroxyl groups; the vinyl compounds obtained therefrom are monovinyl ethers, divinyl ethers or mixtures thereof; in particular, the products of vinylation are the corresponding divinyl ethers.
  • Pyrrolidone, caprolactam, di- or triethylene glycol and bis-hydroxyalkylcyclohexanes, in particular bishydroxy- methylcyclohexanes, may be mentioned in particular as starting compounds.
  • the vinyl compounds obtained therefrom are N-vinylpyrrolidone, N-vinylcaprolactam, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, bis-hydroxymethylcyclohexane monovinyl ether or bis-hydroxymethylcyclohexane divinyl ether.
  • Very particularly preferred vinyl compounds are diethylene glycol divinyl ether, triethylene glycol divinyl ether and bis-hydroxymethylcyclohexane divinyl ether, in particular 1,4-bis-hydroxymethylcyclohexane divinyl ether.
  • the vinylation of the starting compound is carried out with acetylene in the presence of 0.2 to 5 parts by weight of water, based on 100 parts by weight of the starting compound.
  • the content of water is preferably at least 0.3 and more preferably at least 0.5 parts by weight, in particular at least 0.7 parts by weight, based on 100 parts by weight of the starting compound.
  • the content of water is preferably not more than 3, in particular not more than 2 and particularly preferably not more than 1.5 parts by weight of water, based on 100 parts by weight of the starting compound.
  • the desired amount of water can be added, for example, to the starting materials or directly to the reaction mixture of the vinylation.
  • the water content is determined according to Karl Fischer by volumetric titration.
  • water is generally already contained in the starting material by a preliminary reaction of the starting material with an alkali metal hydroxide.
  • the alkali salt of the starting material serves as a catalyst in the vinylation. It is described in the prior art that the by-product salt formation or the water used as the solvent for the alkali hydroxide is removed by distillation prior to the vinylation. In a preferred embodiment, therefore, no water must be added. Rather, the water content must be adjusted during or after the reaction of the starting material with the alkali metal hydroxide. Generally, excess water must be removed, preferably by distillation. In a preferred embodiment of the method is therefore
  • the starting compound is reacted with an alkali hydroxide before the vinylation
  • the resulting mixture of starting compound, alkali salt of the starting compound and water (called short starting mixture) is then fed to the reactor for vinylation with acetylene.
  • alkali hydroxide e.g. to act a lithium, sodium or potassium hydroxide; particularly preferred is potassium hydroxide.
  • the alkali hydroxide may be used as a solid or in the form of an aqueous solution.
  • the content of alkali hydroxide in the aqueous solution may be e.g. 5 to 90 wt.%, Based on the solution amount; In particular, it is 30 to 60 wt.%, Particularly preferably 45 to 55 wt.%.
  • the amount of alkali hydroxide is preferably selected so that 0.25 to 25 wt.%, Preferably 1 to 10 wt.% Of the starting compound is present as an alkali metal salt.
  • the alkali salt at least one hydrogen of the primary or secondary amino group or the hydrogen of the hydroxyl group or the thio group is replaced by the alkali cation (for example, alkanol as potassium alkoxide, pyrrolidone as potassium pyrrolidate, etc.).
  • the reaction of the compound with the alkali hydroxide is preferably carried out at temperatures of 50 to 250 ° C and 1 mbar to 1 bar, in particular at 20 to 250 ° C.
  • the reaction takes place in a column, particularly preferably in a packed column or packed column, which is operated at the above temperatures and pressures.
  • the temperature at the top of the column is preferably 20 to 100, in particular 25 to 60 ° C; the temperature in the bottom of the column is preferably 100 to 250 ° C, in particular 120 to 200 ° C.
  • the reaction can be carried out batchwise, semi-continuously or continuously. In a preferred embodiment, it is operated continuously.
  • columns which contain both random packings and packings, e.g. in the lower part contain random packings and in the upper part with packing elements (for example built-in steel sheets).
  • the column preferably has at least two, more preferably at least 3 theoretical plates. It can e.g. 2 to 100, especially 3 to 20 theoretical plates have.
  • the alkali metal hydroxide and the compound are preferably added in the upper third, more preferably in the upper fourth of the column.
  • the corresponding alkali metal salt of the starting compound is formed.
  • the mixture obtained from the reaction can be withdrawn continuously in the lower part of the column or at the bottom of the column.
  • the resulting mixture contains the starting compound, the alkali salt of the starting compound and water.
  • the resulting mixture is referred to below as the starting mixture
  • the vinylation of the starting compound or the starting mixture with acetylene is then preferably carried out in a separate reaction vessel.
  • the vinylation with acetylene can be carried out batchwise, semicontinuously or continuously.
  • the reaction can be carried out in any reactors, which may be mentioned, for example, stirred tanks, stirred tank cascades, tubular reactors or loop reactors.
  • the reaction takes place in a loop reactor.
  • the reaction takes place while avoiding a contiguous gas phase of the acetylene, as described in EP-A 733,401.
  • the reaction vessel is preferably completely filled with the starting mixture and acetylene introduced into the liquid phase to the desired degree of saturation.
  • a portion of the output stream is preferably expanded into a surge tank and returned to the reactor so as to determine the composition and acetylene concentration in the reaction mixture.
  • the vinylation with acetylene is preferably carried out at temperatures of 120 to 220, more preferably from 140 to 170 ° C and preferably at pressures of 1, 0 to 25, particularly preferably from 10 to 20 bar.
  • the product mixture obtained can be worked up and purified in a customary manner.
  • the basic salts of the alkali metals can first be separated off. This can be z. B carried in a thin-film evaporator through which the entire product mixture or only a partial stream of the product mixture are passed.
  • the further work-up of the product mixture can e.g. by distillation or extraction.
  • Unreacted starting compound can be recycled in a continuous procedure either in the reaction with the alkali metal hydroxide or in the vinylation.
  • vinyl compounds are available in high yield and purity. Compared with anhydrous procedure, a high yield is achieved faster. Therefore, the yield is higher for the same residence time, or the same yield is achieved after a shorter residence time in the vinylation. Also, the viscosity is reduced by the water content, which has an advantageous effect on the process control, in particular on the operation of pumps. Examples
  • the water content was determined by volumetric titration according to Karl Fischer with the 870 KF Titrino plus instrument from Metrohm (titrant Hydranal Composite 5).
  • the vinylation was carried out at 155 ° C and a pressure of 18 bar. Acetylene was continuously repressed to maintain the pressure of 18 bars. After 4.5 hours, no more acetylene was consumed, the reaction was stopped. A total of 309 liters of acetylene were added. The ratio 1, 4-cyclohexanedimethanol / monovinyl ether / divinyl ether was measured by GC (area%):
  • the vinylation was carried out at 155 ° C and a pressure of 18 bar. Acetylene was continuously repressed to maintain the pressure of 18 bars. After 6.5 hours, no more acetylene was consumed, the reaction was stopped. A total of 303 liters of acetylene were added. The ratio 1, 4-cyclohexanedimethanol / monovinyl ether / divinyl ether was measured by GC (area%):
  • the attached figure shows the uptake of acetylene as a function of the reaction time.
  • the uptake of acetylene corresponds to the conversion of acetylene.
  • the uptake of acetylene ends after 4.5 hours, i. the total sales of acetylene is essentially already after 4.5 hours.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de préparation d'un composé vinylique par vinylation d'un composé de départ comprenant au moins un groupe amino primaire ou secondaire, au moins un groupe hydroxyle ou au moins un groupe thiol avec de l'acétylène, caractérisé en ce que la vinylation est réalisée en présence de 0,2 à 5 parties en poids d'eau, par rapport à 100 parties en poids du composé de départ.
PCT/EP2017/070530 2016-08-23 2017-08-14 Vinylation avec de l'acétylène en présence d'eau Ceased WO2018036848A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16185342.9 2016-08-23
EP16185342 2016-08-23

Publications (1)

Publication Number Publication Date
WO2018036848A1 true WO2018036848A1 (fr) 2018-03-01

Family

ID=56800188

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2017/070530 Ceased WO2018036848A1 (fr) 2016-08-23 2017-08-14 Vinylation avec de l'acétylène en présence d'eau

Country Status (1)

Country Link
WO (1) WO2018036848A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020043518A1 (fr) 2018-08-30 2020-03-05 Basf Se Procédé de production d'un éther monovinylique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19509362A1 (de) 1995-03-15 1996-09-19 Basf Ag Verfahren zur Herstellung von N-Vinyllactamen
EP0733401A2 (fr) 1995-03-24 1996-09-25 Basf Aktiengesellschaft Procédé pour la mise en oeuvre de réactions gaz-liquide en évitant une phase gazeuse continue
US20030105354A1 (en) 2001-12-05 2003-06-05 Rolf Pinkos Continuous preparation of alkenyl compounds
WO2009074534A1 (fr) 2007-12-11 2009-06-18 Basf Se Procédé de vinylation des amides
WO2013004579A2 (fr) * 2011-07-01 2013-01-10 Basf Se Éthers de bis(hydroxyméthyl)cyclohexanes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19509362A1 (de) 1995-03-15 1996-09-19 Basf Ag Verfahren zur Herstellung von N-Vinyllactamen
EP0733401A2 (fr) 1995-03-24 1996-09-25 Basf Aktiengesellschaft Procédé pour la mise en oeuvre de réactions gaz-liquide en évitant une phase gazeuse continue
US20030105354A1 (en) 2001-12-05 2003-06-05 Rolf Pinkos Continuous preparation of alkenyl compounds
WO2009074534A1 (fr) 2007-12-11 2009-06-18 Basf Se Procédé de vinylation des amides
WO2013004579A2 (fr) * 2011-07-01 2013-01-10 Basf Se Éthers de bis(hydroxyméthyl)cyclohexanes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020043518A1 (fr) 2018-08-30 2020-03-05 Basf Se Procédé de production d'un éther monovinylique
US11401227B2 (en) 2018-08-30 2022-08-02 Basf Se Process to produce a mono vinyl ether

Similar Documents

Publication Publication Date Title
EP1784375B1 (fr) Procede de production d'acide formique
EP2318384B2 (fr) Procédé de préparation d'épichlorhydrine à partir de glycérol
DE2447551C3 (de) Verfahren zur Herstellung von Methylchlorid
EP2675780B1 (fr) Procédé de production d'éthers divinyliques
DE2705538A1 (de) Verfahren zur reindarstellung von methyl-tert.-butylaether
DE19625283A1 (de) Verfahren zur Herstellung und Auftrennung eines Gemischs aus Dimethylether und Chlormethan mit Wasser als Extraktionsmittel
WO2018036848A1 (fr) Vinylation avec de l'acétylène en présence d'eau
DE3413212C1 (de) Verfahren zur Herstellung von wasserfreiem Kalium-tert.-butoxid
DE69707825T2 (de) Verfahren zur Herstellung von alicyclischen Hydrazin-derivaten.
DE2525636B2 (de) Verfahren zur Herstellung von Bis[2-(N,Ndimethylamino)äthyl] -äther
EP3010880B1 (fr) Procédé de préparation de 2-chlorodialkylbenzylamines par hydrogénation
EP0087585A1 (fr) Méthode de préparation de 3-alcoxi-acrylonitriles
EP2297126A1 (fr) Procédé de préparation d esters de glycidyle
WO2006056436A1 (fr) Procédé pour produire du chlorure de phtaloyle
EP0413264B1 (fr) Procédé pour la préparation des chlorures d'acides chlorocarboxyliques
EP2229357A1 (fr) Procédé de fabrication de n-vinylpyrrolidone à partir de pyrrolidone exempte de lactone
EP2070912B1 (fr) Procédé de vinylation d'amides
DE2519295B2 (de) Verfahren zur kontinuierlichen Herstellung von organischen Lösungen von 1 bis 4 Kohlenstoffatome enthaltenden Percarbonsäuren
DE2541526C2 (de) Verfahren zur Herstellung eines Alkylenoxids
EP0768291A2 (fr) Procédé pour la séparation d'un mélange du chlorure de benzyle, de l'alcool de benzyle, de l'éther dibenzylique et de l'acide hydrochlorique aqueux
DE2729974B2 (de) Verfahren zur Herstellung von wäßrigen Lösungen bzw. feinteiligen wäßrigen Dispersionen von Polyenyltriarylphosphoniumsalzen
DE2361988A1 (de) Verfahren zur herstellung von trialkylaluminiumverbindungen
DE69005000T2 (de) Verfahren zur Herstellung von Acrylsäurechlorid.
DE69418343T2 (de) Herstellung von difluormethan
DE650380C (de) Verfahren zur Darstellung von Morpholin bzw. 2, 6-Dimethylmorpholin

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17757495

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17757495

Country of ref document: EP

Kind code of ref document: A1