WO2006015799A1 - Stabilisatoren für die nvp-synthese - Google Patents
Stabilisatoren für die nvp-synthese Download PDFInfo
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- WO2006015799A1 WO2006015799A1 PCT/EP2005/008466 EP2005008466W WO2006015799A1 WO 2006015799 A1 WO2006015799 A1 WO 2006015799A1 EP 2005008466 W EP2005008466 W EP 2005008466W WO 2006015799 A1 WO2006015799 A1 WO 2006015799A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/20—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/08—Preparation of carboxylic acid amides from amides by reaction at nitrogen atoms of carboxamide groups
Definitions
- the present invention relates to a process for the preparation of N-alkenyl compounds by reacting the corresponding NH compounds with alkynes in the liquid phase in the presence of a catalyst, and the use of stabilizers in a process for the preparation of N-alkenyl compounds.
- N-Alkenyl amides are used as monomers in the production of plastics and paints.
- Polyvinylamides are used, for example, as washing auxiliaries, as auxiliaries in cosmetic and medical products and for stabilizing and clarifying filtration of beers and fruit juices.
- Polyvinyl-lactams, in particular polyvinylpyrrolidone have a broad application and serve, for example, as dispersants for pigments, as washing auxiliaries, as auxiliaries in cosmetic and medical products and as auxiliaries in textile processing and adhesive technology.
- WO 00/39085 describes a one-step reaction for the preparation of N-vinylpyrrolidone or N-vinylcaprolactam from acetylene and the corresponding nitrogen compound.
- the process is carried out at a high concentration of acetylene in the nonaqueous reaction solution.
- the high concentration of acetylene in the reaction solution is achieved by carrying out the reaction at low temperatures and high pressures.
- EP-A 0 646 571 discloses a process for the preparation of N-vinyl compounds by reacting the corresponding amines with acetylene in the presence of compounds of the group of platinum metals as catalysts.
- DE-A 1 176 124 describes a process for the preparation of N-vinyl amides in which acetylene is reacted with N-amides in the liquid phase in the presence of a basic catalyst. The formed N-vinyl amide is removed as soon as possible from the reaction zone after its formation.
- DE-A 199 62 138 discloses a process for preparing N-alkenyl amides by reacting the corresponding NH amides with alkynes in the liquid phase in the presence of basic alkali metal compounds and diols as co-catalysts.
- the object of the present invention is to provide a process for the preparation of N-alkenyl compounds, wherein the formation of polymers is reduced, be ⁇ avoided or avoided.
- the object is based on a process for the preparation of N-alkenyl compounds by reacting the corresponding NH compounds with alkynes in the liquid phase in the presence of a catalyst.
- the erfmdungswashe method is then characterized in that the reaction is carried out in the presence of at least one stabilizer.
- the inventive method is characterized by high conversions even at low reaction temperatures, low catalyst concentration and low concentration of the alkyne used.
- the use of a co-catalyst is not required.
- the selectivity of the reaction can be improved by the use of stabilizers according to the invention.
- alkynes of the general formula I and NH compounds of the general formula II are preferably reacted in the presence of a catalyst and at least one stabilizer to give N-alkenyl compounds of the general formula III
- R 1, R 4 are independently hydrogen, C 1 -C 2O -alkyl, C 2 -C 2 -alkenyl, C 2 -C 2O - alkynyl, Q-Cio-cycloalkyl, C 7 -C 18 aralkyl, C 6 C 18 -aryl or C 5 -C 18 -heteroaryl, wherein said radicals may be optionally substituted by functional groups and / or one or more non-adjacent carbon atoms of the alkyl, alkenyl, alkynyl, or cycloalkyl radicals by heteroatoms, are preferred N, S or O, can be replaced.
- R 2 are independently hydrogen, Ci-C 2 -alkyl, C 2 -C 2 -alkenyl, C 2 -C 2O - alkynyl, C 3 -C 10 cycloalkyl, C 7 -C 18 aralkyl, C 6 -C 18 -aryl or C 5 -C 18 -heteroaryl, where the radicals mentioned may be optionally substituted by functional groups and / or one or more non-adjacent carbon atoms of
- Alkyl, alkenyl, alkynyl or cycloalkyl radicals may be replaced by heteroatoms, preferably N, S or O, and one of the radicals R 2 or R 3 must be different from hydrogen.
- the grouping R -NQR may also be part of a saturated, unsaturated or aromatic heterocyclic four to achy ring, which optionally contains up to two further heteroatoms, preferably selected from the group consisting of N, O and S, and optionally substituted by functional groups ⁇ iert and optionally additionally fused.
- the four to eight ring containing the grouping R 2 -NQR 3 can additionally or exclusively be selected from one or more radicals selected from the group consisting of C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 2 -C 2 o Alkynyl, C 1 -C 10 -cycloalkyl, C 7 -C 18 -aralkyl, C 6 -C 18 -aryl and / or C 5 -C 18 -heteroaryl, where the cited radicals may be optionally substituted by functional groups and / or one or a plurality of nonadjacent carbon atoms of the alkyl, alkenyl, alkynyl or cycloalkyl radicals may be substituted by heteroatoms, preferably N, O or S, may be substituted.
- Suitable functional groups are, for example, hydroxyl, aldehyde, keto, amino, amido, imido, imino, ether, thioether, carboxyl groups and derivatives thereof and halogens, phosphines and phosphites, preferably phosphines and phosphites.
- Alkynes in the process according to the invention are all organic compounds corresponding to general formula I, i. which contain at least one triple bond.
- the radicals R 1, R 2, R 3 and R 4 can be independently C 1 -C 2O -AUCyI, preferably C 1 - C 8 alkyl, for example methyl, ethyl, n-propyl, i-propyl, n- Butyl, i-butyl, sec-butyl, tert-butyl.
- R 1 , R 2 , R 3 and R 4 independently of one another may denote C 2 -C 20 -alkenyl, preferably C 2 -C 8 -alkenyl, for example ethenyl, propenyl or butenyl.
- R 1, R 2, R 3 and R 4 independently of one another C 2 -C 2O - alkynyl is, vorzugt C 2 -C 1O - alkynyl, for example, butynyl, pentynyl, hexynyl.
- R 1 , R 2 , R 3 and R 4 can furthermore be, independently of one another, C 1 -C 8 -cycloalkyl, preferably C 3 -C 6 -cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl.
- R 1 , R 2 , R 3 and R 4 may furthermore independently of one another denote C 7 -C 18 -aralkyl, preferably C 7 -C 12 -aralkyl, for example benzyl.
- R 1, R 2, R 3 and R 4 independently of each other C 6 -C 18 aryl, preferably C 6 - C 5 represent aryl, e.g., phenyl, naphthyl.
- R 1 , R 2 , R 3 and R 4 independently of one another may be C 1 -C 4 heteroaryl, preferably C 5 -C 8 -heteroaryl, for example pyridinyl, pyrimidinyl, imidazyl, benztriazyl, furyl, thiophenyl, pyryl , Phenyl, quinaldyl, naphthyl.
- alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, aryl and heteroaryl groups listed above may be substituted as mentioned above, or may have one or more carbon atoms of the alkyl, alkenyl, alkynyl or cycloalkyl groups as previously mentioned be replaced by heteroatoms.
- R 1 , R 2 , R 3 and R 4 independently of one another are preferably hydrogen, C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl.
- R and R together with the NQ grouping form a saturated, unsaturated or aromatic four- to eight-membered, preferably five- to seven-membered ring which optionally contains up to two further heteroatoms, preferably selected from N, O or S, optionally substituted by functional groups and optionally additionally fused, is preferably benzanellated.
- the ring may bear one or more radicals selected from Ci-C 2 -alkyl, C 2 -C 2O - alkenyl, C 2 -C 20 alkynyl, C 3 -C 10 cycloalkyl, Cy-Qg aralkyl C 6 ⁇ Ci 8 -aryl and / or C 5 -C 18 -Heteroaryl, wherein said radicals may be optionally substituted by functional groups and / or one or more non-adjacent carbon atoms of the alkyl, alkenyl, alkynyl or cycloalkyl radicals by heteroatoms , preferably N, O or S, may be replaced.
- radicals selected from Ci-C 2 -alkyl, C 2 -C 2O - alkenyl, C 2 -C 20 alkynyl, C 3 -C 10 cycloalkyl, Cy-Qg aralkyl C 6 ⁇ Ci 8 -aryl and / or C 5 -
- Q, R 1 , R 2 , R 3 and R 4 have the following meanings:
- R 1 , R 4 independently of one another are hydrogen, C 1 -Cs-Al kVl, C 2 -Cs-alkenyl,
- R 2 , R 3 are independently hydrogen, C 1 -C 8 -AlkVl, C 2 -C 8 alkenyl, or the group R 2 -NQR 3 is part of a saturated or ungesreli ⁇ th heterocyclic four to Achring, optionally as contains further heteroatom N, and which is optionally substituted by C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -
- Q, R 1 , R 2 , R 3 and R 4 have the following meanings:
- R 1 , R 4 is hydrogen
- R 2 , R 3, hydrogen or R 2 and R 3 together with the NQ grapping, when QC O, form a five-, six- or seven-membered ring, which no further Heteroatoms and no further substituents, or, if Q CH meaning tet, an unsaturated, N containing as heteroatom, unsaturated five-membered ring having no further substituents.
- Very particularly preferred compounds of the general formula II are 2-pyrrolidone, 2-piperidone, D-caprolactam, formamide and imidazole.
- N-vinyl-2-pyrrolidone N-vinyl- ⁇ -butyrolactam
- piperidone N-vinyl- ⁇ -valerolactam
- D-caprolactam D-caprolactam
- N-vinyl- ⁇ -caprolactam D-caprolactam
- acetylene with formamide to N-vinyl-formamide
- acetylene with imidazole to N-vinylimidazole.
- the process according to the invention is carried out in the presence of a catalyst, the catalyst used being a compound selected from the group consisting of alkali metal alkali metal compounds, alkaline earth metal compounds, rare earth metal compounds and platinum group metal compounds or mixtures thereof.
- alkali metal compounds or alkaline earth metal compounds are used as catalysts in the process according to the invention.
- Particular preference is given to using basic alkali metal compounds or basic alkaline earth metal compounds as catalysts.
- the hydrides, oxides, hydroxides and / or alcoholates of lithium, sodium, potassium, rubidium, cesium, calcium, barium and / or strontium and mixtures thereof can be used.
- Alcoholates used are preferably the compounds of the low molecular weight alcohols, for example methanolate, ethanolate, propoxide, 1-methyl-ethanolate, butoxide, 1-methylpropoxide, 2-methylpropoxide and 1,1-dimethyl-ethanolate.
- the hydrides, oxides, hydroxides and / or alcoholates of sodium and / or potassium are preferably used.
- the basic alkali metal compounds can be used as solids or solutions in water or alcohol.
- the use of solid, water- and alcohol-free alkali metal compounds is preferred.
- the catalyst is generally present in a molar fraction of from 0.01 to 10 mol%, based on the molar amount of the NH compound used, preferably from 0.02 to 6.0 mol%, and particularly preferably 0.05 to 4.0 mol% before.
- the process according to the invention is carried out in the presence of at least one stabilizer.
- Stabilizers are generally understood to mean compounds which suppress the spontaneous and therefore unwanted polymerization during the processing and storage of monomers.
- stabilizers differ from other reaction additives by definition. While the former prevent product losses due to unwanted side reactions.
- suitable reaction additives should influence the properties of the reaction mixture. In particular, a better process management is desired, for example, better mixing, faster reaction of the starting materials or the like.
- At least one compound selected from the group consisting of phenols, quinones, hydroquinones, N-oxyls, aromatic amines, phenylenediamines, hydroxylamines, urea derivatives, phosphorus-containing compounds, sulfur-containing compounds, metal salts, complexing agents and mixtures of two or several of these compounds is used.
- Phenols can be, for example, phenol, o-, m- or p-cresol (methylphenol), 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethyl-phenol, 2,6-diol.
- para-aminophenol nitro sophenols
- nitro sophenols such as para-nitrosophenol, p-nitroso-o-cresol, alkoxyphenols beispielswei ⁇ se 2-methoxyphenol (guaiacol, catechol monomethyl ether), 2-ethoxyphenol, 2-isopropoxyphenol, 4-methoxypheno (hydroquinone monomethyl ether), mono- or di-tert.
- Quinones or hydroquinones can be, for example, hydroquinone or hydroquinone methyl ether, 2,5-di-tert-butylhydroquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, 4-methylcatechol, tert-butylhydroquinone, 3-methylcatechol, benzoquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, 3-methylcatechol, 4-methylcatechol, tert-butylhydroquinone, 4-ethoxyphenol, 4-butoxyphenol, hydroquinone monobenzyl ether, p-phenoxy phenol, 2-methylhydroquinone, 2,5-di-tert-butylhydroquinone, tetramethyl-p-benzoquinone, diethyl 1,4-cyclohexanedione-2,5-dicarboxylate
- N-Oxyls may be, for example, 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-acetoxy- 2,2,6,6-tetramethyl-piperidine-N-oxyl, 2,2,6,6-tetramethyl-piperidine-N-oxyl, 4,4 ', 4 "-tris (2,2,6,6 tetramethyl-piperidine-N-oxyl) phosphite, 3-oxo-2,2,5,5-tetramethyl-pyrrolidine-N-oxyl, 1-oxyl-2,2,6,6-tetramethyl-4-methoxypiperidine, 1-oxyl-2,2,6,6-tetramethyl-4-trimethylsilyloxypiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-2-ethylhexanoate, 1-oxyl-2,2,6, 6-tetramethyl
- Aromatic amines or phenylenediamines may be, for example, N, N-diphenylamine, N-nitroso-diphenylamine, nitrosodiethylaniline, N, N'-dialkalophenylenediamine, wherein the alkyl radicals may be the same or different and each independently consist of 1 to 4 carbon atoms and straight-chain or branched, for example N, N'-di-iso-butyl-p-phenylenediamine, N, N'-di-iso- ⁇ ropyl-p-phenylenediamine, Irganox 5057 from Ciba Spezi Rund Chemie, N, N 'Di-iso-butyl-p-phenylenediamine, N, N'-di-isopropyl-p-phenylenediamine, p-phenylenediamine, N-phenyl-p-phenylenediamine, N, N'-diphenyl-p
- Hydroxylamines can be, for example, N, N-diethylhydroxylamine or N, N-dibenzylhydroxylamine.
- Urea derivatives may be, for example, urea or thiourea.
- Preferred stabilizers used in the process according to the invention are compounds selected from the group consisting of sulfur-containing compounds, N-oxyls, phenols, hydroquinones and derivatives of ethylenediamines, such as ethylenediamine or diethylenetriamines.
- Particularly preferred stabilizers are 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yloxy (HO-TEMPO), 4-methoxy-2,2,6,6-tetramethyl-p-pyridin-1-yloxy (MeO-TEMPO) , phenothiazine, diethylhydroxylamine (DEHA) or N, N'-di-sec-butyl-p-phenylenediamine (Kerobit ® BPD) or mixtures of two or more of these compounds used in the process according erfin ⁇ dung.
- the stabilizers are used in an amount of generally 1 to 500 ppm, based on the total reaction solution, preferably 10 to 400 ppm, particularly preferably 20 to 300 ppm.
- the process according to the invention can also be carried out in the presence of at least one co-stabilizer.
- compounds of general formula IV can be used in the process according to the invention.
- X independently selected from the group consisting of OH, NH 2 , OR 5 , NHR 5 , wherein R 5 is selected from the group consisting of Q-Qo-alkyl, C 2 -Qo alkenyl, C 2 -C 10 - alkynyl , C 3 -C 10 -cycloalkyl, C 7 -C 18 -aralkyl, C 6 -C 18 -aryl, N-alkyl and O-polyol, preferably N-alkyl or O-polyol,
- Y independently of one another atom or atom grouping selected from O and NH
- A is independently radical, selected from the group consisting of
- o, p independently mean value from 0 to 5
- q O or l.
- mean value means that n, o and p can also be of fractional value if nonuniform mixtures of compounds of the general formula V, VI or VII are present in which n, o or p in the individual molecules differs ne values.
- the mean values for n, o or p are then the means, averaged over all present compounds.
- An average value of n equal to 0.5 means, for example, that in one half of the compounds n is equal to 1 and in the other half n is equal to 0.
- o, p, q, X, Y and A have the following meanings:
- X independently of one another are selected from OH and NH 2 ,
- Y independently of one another atom or atom grouping selected from O and NH
- A is independently radical, selected from the group consisting of
- o, p independently of one another integer from 0 to 3
- q is O or l.
- Very particular preference is given to using the compounds V, VI and / or VE as co-stabilizers in the process according to the invention.
- q is 0 or 1.
- the stabilizers are used in an amount of 2 to 300 ppm, based on the total reaction solution, preferably 10 to 250 ppm, more preferably 20 to 200 ppm.
- the process according to the invention is preferably carried out in the liquid phase. It is possible according to the invention to use the NH compound to be reacted in the reaction itself as solvent. Furthermore, it is possible to use suitable other solvents. Suitable solvents are characterized in that they dissolve in them both the NH compound and the catalyst, they do not react chemically with the compounds used, ie that they have no acidic centers, in particular, which the basic groups and, after the synthesis of the N-alkenyl compounds from the system, they can be easily removed again, preferably by distillation.
- Suitable solvents for the process according to the invention are N-methylpyrrolidone, tetrahydrofuran or dialkyl ethers of glycols, di-, oligo- or poly-glycols, and also mixtures thereof.
- the method according to the invention can be carried out, for example, as follows:
- the catalyst is brought into contact with the NH compound. It is possible that the catalyst is added as a solid of the NH compound or a solution of the NH compound in a suitable solvent. It is also possible according to the invention to add a solution or dispersion of the catalyst to the NH compound.
- the catalyst may be dissolved in a suitable solvent, e.g. Water, alcohol or the corresponding NH compound, dissolved or dispersed.
- the catalyst is preferably added by dissolving the solid in the corresponding liquid NH compound or by adding a solution or dispersion of the catalyst in the NH compound. It is also possible to dilute the NH compound or the solution or dispersion of the catalyst in the NH compound by a suitable solvent.
- potassium hydride When potassium hydride is used as the catalyst, it is preferably used as a solid or dissolved or dispersed in an inert, i. anhydrous solvent which does not react with the potassium hydride added.
- the preparation of the solution or dispersion of the catalyst in the corresponding NH compound or its solutions is generally carried out by conventional methods by contacting the catalyst solid with the liquid under intensive skillsmi ⁇ research. As a result, an accelerated solution or dispersion of the solid is achieved and counteracts a local heating due to the heat of solution. Suitable rates are known to the person skilled in the art. Without limitation, stirred tanks, for example, may be mentioned.
- the liquid is initially charged and the catalyst solid is metered in continuously or in portions with thorough mixing, if appropriate over a period of time.
- hydroxides or alcoholates are used as catalysts in the process according to the invention as alkali metal compounds
- water or alcohols are formed as liquid by-products in the reaction of the NH compound with the alkali metal compounds in an equilibrium reaction.
- a shift of the equilibrium weight in the direction of the alkali metal salt of the NH compound is achieved, so that the stated salt stage can be obtained in sufficient concentration.
- the salt of the NH compound and gaseous hydrogen as a byproduct.
- the hydrogen of the reaction mixture escapes gaseous or can be removed by passing, for example, nitrogen, so that in this way also the said salt stage is formed. Suitable methods for removing the resulting hydrogen are known to the person skilled in the art.
- the addition of the alkali metal compound to the NH compound can be carried out in a separate process step before and optionally during the removal of the reaction water or alcohol.
- the advantageous removal of the optionally formed reaction water and / or alcohol contributes to the achievement of a particularly high selectivity and yield of N-alkenyl compounds.
- Particularly preferred methods for removing the water of reaction or the lower molecular weight reaction alcohols are evaporation, binding to a suitable desiccant (adsorption) and removal by a suitable membrane.
- the methods mentioned can also be used when using an aqueous or alcohol-containing catalyst solution.
- the evaporation of the water or the reaction alcohol at elevated temperature between 50 and 150 0 C and a reduced pressure of 1 mbar to atmospheric pressure.
- the evaporation can be done in many ways. It can be carried out, for example, in a thoroughly mixed container (eg stirred tank) by heating and / or applying an underpressure. Stripping out by passing an inert gas, for example nitrogen, is also possible. The evaporation can also be carried out by passing the solutions through an evaporator. Such devices are in the relevant Specialist literature described (see eg Ullmann's Encylclopedia of Industrial Chemistry, ⁇ 01 Edition, 1998 Electronic Release, Chapter "Evaporation").
- Particularly preferred evaporation method is distillation. It can be performed discontinuously, semi-continuously or continuously.
- the NH-compound and the catalyst which may be completely or even partially dissolved, are introduced into the distillation phase and the reaction water or the reaction alcohol is distilled off by increasing the temperature and / or lowering the pressure.
- semicontinuous distillation for example, a solution of the catalyst in the NH compound is fed to the column section and the reaction water or the reaction alcohol is continuously distilled off.
- the water- or alcohol-free product accumulates in the distillation bubble.
- the continuously carried out distillation differs from the semi-continuous mainly in that the water- or alcohol-free product is continuously removed from the bottom.
- the distillations are preferably carried out at a pressure of ⁇ 1 bar.
- drying agent When using a drying agent, the exothermic adsorption of small molecules on suitable high-surface solids is utilized. Particularly noteworthy here is the removal of water.
- suitable drying agent is described (see eg Ullmann's Encyclopedia of Industrial Chemistry, 6 ⁇ Edition, 1998, Electronic Release, Chapter "zeolite").
- the drying can successions by various methods. In one variant, for example, is the drying In another variant, the solution is passed through a bed of desiccant and only then added to the alkenylation reactor.
- the water of reaction and / or the alcohol of the reaction can also be carried out by crystallization, preferably at temperatures below 0 ° C.
- the removal of the water of reaction and / or the reaction alcohol is preferably carried out by the methods discussed above evaporation and / or adsorption. A combination of the two methods is also possible and may even be advantageous. Further preferably, the removal of the reaction water is carried out by crystallization.
- the addition of the stabilizer and optionally the co-stabilizer in the process according to the invention can in principle be carried out at any possible time.
- the stabilizer and optionally the co-stabilizer are preferably added after addition of the catalyst and after removal of the water of reaction or alcohol.
- the stabilizer and optionally the co-stabilizer contain water or low molecular weight monoalcohols, these have to be separated off before addition. In this case, however, preference is given to adding the stabilizer and optionally the co-stabilizer to the NH compound / catalyst solution before the process step for separating the reaction water or the reaction alcohol.
- the reaction with the alkyne is carried out by contacting the above-described solution containing the NH compound, the catalyst and the stabilizer and optionally the co-stabilizer and prepared (ie water and / or alcohol-free), with the alkyne in the liquid phase.
- the NH compound / catalyst / stabilizer solution according to the invention can nevertheless be thinned by a solvent which is free of water and monoalcohol.
- Suitable solvents are in general all those which can also be used in the solution of the NH compound and the catalysts. Examples of suitable solvents are N-methylpyrrolidone, tetrahydrofuran or dialkyl ethers of glycols, di-, oligo- or polyglycols.
- the reaction is carried out undiluted, that is without addition of another solvent.
- the reaction with the alkyne can be done in several ways. In the semicontinuous process, the entire NH compound / catalyst / stabilizer solution is used. puts and the alkyne, according to the course of the reaction, metered. The product solution is normally removed only after completion of the reaction.
- the NH compound / catalyst / stabilizer solution and the alkyne are continuously fed in and the corresponding product solution is continuously removed.
- NH compound / catalyst / stabilizer solution is understood according to the invention a solution which may optionally also contain a co-stabilizer.
- the reaction of the invention is generally conducted at a temperature of 80 to 240 0 C, preferably from 100 to 200 0 C, particularly preferably from 130 to 180 0 C Maschinenge leads.
- the reaction according to the invention is generally carried out at a pressure of the alkyne of ⁇ 50 bar, preferably of ⁇ 30 bar, most preferably of ⁇ 24 bar.
- the total pressure of the system can be significantly higher, since the supernatant gas atmosphere may, for example, still contain inert gases, such as nitrogen or noble gases, which can be introduced by targeted pressurization.
- a total pressure in the system of, for example, 200 bar readily possible.
- the autogenous pressure of the alkyne is very low and can be, for example, well below 1 bar.
- a pressure of the alkyne of> 1 bar is generally set. This achieves a more economical space / time yield.
- acetylene is used as the alkyne in the alkenylation, it is preferably carried out at an acetylene pressure of from 5 to 30 bar, particularly preferably from 8 to 24 bar and very particularly preferably from 16 to 20 bar.
- reactors for the alkenylation according to the invention it is possible in principle to use the apparatuses described in the relevant specialist literature for gas liquid reactions.
- intensive mixing between the NH compound / catalyst / stabilizer solution and the alkyne is important.
- nonlimiting examples are stirred tank, stirred tank cascade, flow tubes (preferably with internals), bubble columns and loop reactors.
- the reaction is worked up by known methods. Preference is given to a distillation into several fractions.
- the distillation is preferably carried out at a pressure ⁇ 1 bar.
- the distillation can be carried out batchwise, semicontinuously or continuously. In addition, it can be carried out in a column, optionally with side draws, as well as in a plurality of columns connected in series. Suitable methods are known to the person skilled in the art.
- N-alkenyl compounds can be obtained by the process according to the invention as described in a simple manner with a purity of> 99.8%.
- the optionally separated, unreacted NH compound can be recycled in the process according to the invention without further purification measures. For this purpose, it is not necessary to recover the feed in high purity, so that can be used on a crude distilled fraction. However, it is advantageous to separate the significantly higher boiling products.
- the basic alkali metal compound (catalyst) is added to the liquid NH, optionally diluted or dissolved with solvent, and mixed.
- the resulting solution is then distilled and fed to a stirred tank.
- the reaction water or the reaction alcohol is removed.
- the stabilizer and optionally the co-stabilizer are introduced into the solution, which is virtually free of water or alcohol.
- the Al kin is now initiated with intensive mixing.
- acetylene is preferably introduced up to a pressure of 24 bar. Used alkyne is tracked. After completion of the Auf ⁇ acceptance of the alkyne, the reaction system is depressurized.
- the reaction solution is transferred to a distillation column and the N-alkenyl compound is isolated after removal of the lower boiling components overhead in high purity.
- a nearly concentrated solution i. about 80% of the maximum solubility of the basic alkali metal compound in the NH compound. It can also be a 30 to 70 wt .-%
- the process according to the invention enables a simple preparation of N-alkenyl compounds by reacting the corresponding NH compounds with alkynes in the presence of catalysts and stabilizers in very high yield and purity.
- the present invention also relates to the use of stabilizers to increase the selectivity in a process for the preparation of N-alkenyl compounds by reacting the corresponding NH compounds with alkynes in the liquid phase in the presence of a catalyst, wherein the stabilizers, the N- Alkenyl compounds, the NH compounds, the alkynes, the catalysts and the process parameters are specified in the preceding part of the description.
- the present invention relates to the use of stabilizers in the process according to the invention.
- the experimental apparatus contains a preparation template, from which the catalyst solution is metered into a pumped circulating circuit.
- the pyrrolidone is first distilled outside the plant with KOH or KOM, ie the catalyst is generated by distilling off water or methanol in pyrrolidone.
- the tempered pumping circuit is maintained by a reaction mixing pump, which dissolves acetylene into the batch mixture.
- the acetylene is metered by a Combi-Flow device at a pre-pressure between 23 and 25 bar.
- the mass flow in the mixing circuit is large in comparison to the metered amount so that the system can be operated like a stirred autoclave.
- samples are taken. Connected downstream of the mixing circuit is a discharge vessel. The content of the samples is determined by calibrated gas chromatography.
- the experiments are carried out at a temperature of 150 ° C. and a catalyst concentration of 2% (calculated as KOH). There are metered 90 - 91 g / h of catalyst solution and 11.7 l / h of acetylene. The pressure is 18 bar. The circulating volume in the mixing circuit is 20 kg / h, the mixing circuit volume is 72 ml. The stabilizers / co-stabilizers are added to the catalyst solution after the preparation.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyrrole Compounds (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2005800338229A CN101035757B (zh) | 2004-08-05 | 2005-08-04 | 用于nvp合成的稳定剂 |
US11/659,331 US7674934B2 (en) | 2004-08-05 | 2005-08-04 | Stabilizers for use in NVP synthesis |
JP2007524284A JP4718550B2 (ja) | 2004-08-05 | 2005-08-04 | Nvp合成のための安定剤 |
DE112005001915.2T DE112005001915B4 (de) | 2004-08-05 | 2005-08-04 | Stabilisatoren für die NVP-Synthese |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004038109A DE102004038109A1 (de) | 2004-08-05 | 2004-08-05 | Stabilisatoren für die NVP-Synthese |
DE102004038109.7 | 2004-08-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006015799A1 true WO2006015799A1 (de) | 2006-02-16 |
Family
ID=35432725
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2005/008466 WO2006015799A1 (de) | 2004-08-05 | 2005-08-04 | Stabilisatoren für die nvp-synthese |
Country Status (5)
Country | Link |
---|---|
US (1) | US7674934B2 (de) |
JP (1) | JP4718550B2 (de) |
CN (1) | CN101035757B (de) |
DE (2) | DE102004038109A1 (de) |
WO (1) | WO2006015799A1 (de) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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ES2390364T3 (es) * | 2007-12-11 | 2012-11-12 | Basf Se | Procedimiento para la vinilación de amidas |
EP4269467A1 (de) * | 2020-12-25 | 2023-11-01 | Sanyo Chemical Industries, Ltd. | Verbindung, zusammensetzung, mittel zur biogewebeversprödung, verfahren zur biogewebeoberflächenabtrennung und kit zur biogewebeabtrennung |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2317804A (en) * | 1938-12-31 | 1943-04-27 | Reppe Walter | N-vinyl lactams |
GB573752A (en) * | 1940-12-20 | 1945-12-05 | Distillers Co Yeast Ltd | Improvements in or relating to the production of condensation products of acetylene |
US4410726A (en) * | 1981-06-12 | 1983-10-18 | Gaf Corporation | Vinylation reaction |
US20020002280A1 (en) * | 2000-05-22 | 2002-01-03 | Arnd Bottcher | Stabilized N-alkenyllactam |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL294261A (de) | 1962-06-23 | 1900-01-01 | ||
JP3185323B2 (ja) * | 1992-02-03 | 2001-07-09 | 株式会社スリーボンド | 含浸組成物 |
DE4333237A1 (de) | 1993-09-30 | 1995-04-06 | Basf Ag | Verfahren zur Herstellung von N-Vinylverbindungen |
US5665889A (en) * | 1996-01-22 | 1997-09-09 | Industrial Technology Research Institute | Method for the production of N-vinyl-2-pyrrolidone by vinylation |
US6462201B1 (en) | 1998-12-29 | 2002-10-08 | Isp Investments Inc. | Process for the production of N-vinyl-2-pyrrolidone by vinylation |
DE19938841A1 (de) * | 1999-08-17 | 2001-02-22 | Basf Ag | Inhibitorkomposition zur Stabilisierung von radikalisch polymerisierbaren Substanzen |
DE19962138A1 (de) | 1999-12-22 | 2001-06-28 | Basf Ag | Verfahren zur Herstellung von N-Alkenyl-amiden |
US6452040B2 (en) * | 2000-03-13 | 2002-09-17 | Nippon Shokubai Co., Ltd. | Production process for hydroxyalkyl (meth)acrylate |
DE10238142A1 (de) * | 2002-08-15 | 2004-03-11 | Basf Ag | Verfahren zur Aufarbeitung von (Meth)acrylsäure und (Meth)acrylsäureestern |
-
2004
- 2004-08-05 DE DE102004038109A patent/DE102004038109A1/de not_active Withdrawn
-
2005
- 2005-08-04 US US11/659,331 patent/US7674934B2/en not_active Expired - Fee Related
- 2005-08-04 WO PCT/EP2005/008466 patent/WO2006015799A1/de active Application Filing
- 2005-08-04 JP JP2007524284A patent/JP4718550B2/ja not_active Expired - Fee Related
- 2005-08-04 DE DE112005001915.2T patent/DE112005001915B4/de not_active Expired - Fee Related
- 2005-08-04 CN CN2005800338229A patent/CN101035757B/zh not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2317804A (en) * | 1938-12-31 | 1943-04-27 | Reppe Walter | N-vinyl lactams |
GB573752A (en) * | 1940-12-20 | 1945-12-05 | Distillers Co Yeast Ltd | Improvements in or relating to the production of condensation products of acetylene |
US4410726A (en) * | 1981-06-12 | 1983-10-18 | Gaf Corporation | Vinylation reaction |
US20020002280A1 (en) * | 2000-05-22 | 2002-01-03 | Arnd Bottcher | Stabilized N-alkenyllactam |
Also Published As
Publication number | Publication date |
---|---|
DE112005001915A5 (de) | 2007-05-31 |
CN101035757A (zh) | 2007-09-12 |
JP2008508346A (ja) | 2008-03-21 |
CN101035757B (zh) | 2011-06-01 |
DE112005001915B4 (de) | 2017-03-02 |
US7674934B2 (en) | 2010-03-09 |
US20080312432A1 (en) | 2008-12-18 |
JP4718550B2 (ja) | 2011-07-06 |
DE102004038109A1 (de) | 2006-03-16 |
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