EP2139863A2 - Procédé de production d'esters d'acide (méth)acrylique d'imidazoles n-hydroxyalkylés - Google Patents

Procédé de production d'esters d'acide (méth)acrylique d'imidazoles n-hydroxyalkylés

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Publication number
EP2139863A2
EP2139863A2 EP08716786A EP08716786A EP2139863A2 EP 2139863 A2 EP2139863 A2 EP 2139863A2 EP 08716786 A EP08716786 A EP 08716786A EP 08716786 A EP08716786 A EP 08716786A EP 2139863 A2 EP2139863 A2 EP 2139863A2
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EP
European Patent Office
Prior art keywords
sub
meth
acrylic acid
methyl
imidazoles
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EP08716786A
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German (de)
English (en)
Inventor
Hermann Bergmann
Frank HÖFER
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BASF SE
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BASF SE
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Priority to EP08716786A priority Critical patent/EP2139863A2/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/41—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having five-membered rings with two or more ring hetero atoms, at least one of which being nitrogen, e.g. tetrazole
    • A61K31/4164—1,3-Diazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/411—Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties

Definitions

  • the present invention relates to a process for the catalytic preparation of (meth) acrylic acid esters of N-hydroxyalkylated imidazoles and their use.
  • (meth) acrylic acid is understood to mean acrylic acid and / or methacrylic acid, acrylic acid esters and / or methacrylates being esters of (meth) acrylates.
  • (meth) acrylic esters are also referred to as (meth) acrylates.
  • (meth) acrylic esters is usually carried out by acid or base-catalyzed esterification of (meth) acrylic acid or transesterification of others
  • (meth) acrylic acid esters with alcohols In this case, strong acids or bases are frequently used, so that acid- or base-sensitive (meth) acrylic acid esters can not be selectively produced by esterification or transesterification in this way.
  • N-hydroxyethylimidazole methacrylate is described, for example, by Patrickos et al. in various publications (J. Polym., Sei .: Part A: Polym Chem 37, 1501-1512 (1999), Macromolecular Symposia 171, 209-224 (2001), Macromolecules 31 (25), 9075-9077 (1998 ), Polymer 43 (26), 7269-7273 (2002) and Colloids and Surfaces, A: Physicochemical and Engineering Aspects 167 (1-2), 61-72 (2000)). It discloses the synthesis of N-hydroxyethyl imidazole methacrylate by reacting methacrylic acid chloride with N-hydroxyethyl imidazole.
  • a disadvantage of the synthesis route described therein is the low purity and the high APHA color number of the product. This is u. a. attributed to the fact that the use of (meth) acryloyl chloride leads to the formation of salts in the reactions described and, because of its high reactivity, to unselective reactions, for example Michael additions.
  • a disadvantage of the processes in the prior art is that the resulting (meth) acrylic acid esters of N-hydroxyalkylated imidazoles are obtained in poor yields, in low purities and with high color numbers.
  • the work-up is carried out in an aqueous medium, which is disadvantageous, since the water must be separated from the product consuming.
  • the processes are uneconomical because the reactants used are expensive.
  • R 1 and R 2 independently of one another may be hydrogen or C 1 -C 20 -alkyl
  • R 3 , R 4 and R 5 independently of one another are hydrogen or C 1 -C 20 -alkyl, C 1 -C 20 -alkylcarbonyl, C 2 -C 2 o-alkenyl, C 2 -C 2 o-alkenylcarbonyl, C 2 -C 20 -alkl kynyl, C 2 -C 20 -
  • n and n are each integers in the range of 0 to 20, where m and n can not be 0 at the same time, and wherein the respective units encircled by the variables m and n are contained in any order,
  • C 1 -C 20 -alkyl straight-chain or branched hydrocarbon radicals having up to 20 carbon atoms, preferably C 1 -C 10 -alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 1, 1-dimethylethyl, Pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 2-methylpentyl, 3-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1
  • C 1 -C 20 -alkylcarbonyl a straight-chain or branched alkyl group having 1 to 20 carbon atoms (as mentioned above) which is bonded via a carbonyl group (-CO-), preferably C 1 -C 10 -alkylcarbonyl such as formyl, acetyl, n- or iso-propionyl, n-, iso-, sec- or tert-butanoyl, n-iso-, sec- or tert-pentanoyl, n- or iso-nonanoyl, n-dodecanoyl.
  • a carbonyl group preferably C 1 -C 10 -alkylcarbonyl such as formyl, acetyl, n- or iso-propionyl, n-, iso-, sec- or tert-butanoyl, n-iso-, sec- or tert-pentanoyl,
  • C2-C20-alkenyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 20 carbon atoms and having one double bond in any position, preferably C 2 -C 10 alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1 Methyl 2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl 1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3 -butenyl, 1, 1-dimethyl-2-propeny
  • C 2 -C 20 -alkenylcarbonyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 20 carbon atoms and a double bond in any position (as mentioned above) which are bonded via a carbonyl group (-CO-), preferably C 2 -C 10 -alkylcarbonyl, such as for example, ethenyl, propenoyl, butenoyl, pentenoyl, nonenoyl and their isomers.
  • C 2 -C 20 -alkynyl straight-chain or branched hydrocarbon groups having 2 to 20 carbon atoms and a triple bond in any position, preferably C 2 -C 10 -alkynyl, such as ethynyl 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3 Butinyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl 2-pentyn
  • C 2 -C 20 -alkynylcarbonyl-unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 20 carbon atoms and a triple bond in any position (as mentioned above) which are bonded via a carbonyl group (-CO-) to preferred are C 2 -C 10 -alkynylcarbonyl such as, for example, propinoyl, butinoyl, pentinoyl, noninoyl, decinoyl and also their isomers.
  • C3-C15-cycloalkyl monocyclic, saturated hydrocarbon groups having 3 to 15 carbon ring members, preferably Cs-Cs-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl and a saturated or unsaturated cyclic system such as.
  • C 3 -C 15 -cycloalkylcarbonyl monocyclic, saturated hydrocarbon groups having 3 to 15 carbon ring members (as mentioned above) which are attached via a carbonyl group (-CO-), preferably Cs-Cs-cycloalkylcarbonyl.
  • Aryl a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, e.g. As phenyl, naphthyl and anthracenyl, preferably a mono- to dinuclear, more preferably a mononuclear aromatic ring system.
  • Arylcarbonyl preferably a mono- to trinuclear aromatic ring system (as mentioned above), which is bonded via a carbonyl group (-CO-), such as.
  • B. benzoyl preferably a mono- to binuclear, more preferably a mononuclear aromatic ring system.
  • Heterocycles five- to twelve-membered, preferably five- to nine-membered, particularly preferably five- to six-membered oxygen, nitrogen and / or sulfur atoms optionally containing several rings ring system such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, Dioxolyl, dioxy, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
  • rings ring system such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, Dioxolyl, dioxy, benzimidazolyl,
  • the substituents listed in detail may each be interrupted at any position by one or more heteroatoms, the number of these heteroatoms being not more than 10, preferably not more than 8, very particularly preferably not more than 5 and in particular not more than 3 , and / or in any position, but not more than five times, preferably not more than four times, and more preferably not more than three times, by alkyl, alkyloxy, alkyloxycarbonyl, aryl, aryloxy, aryloxycarbonyl, hydroxycarbonyl, aminocarbonyl, heterocycles, heteroatoms or halogen atoms may be substituted, which may also be substituted at most twice, preferably at most once with said groups.
  • heteroatoms are oxygen, nitrogen, sulfur or phosphorus.
  • Alkyloxy denotes a straight-chain or branched alkyl group having 1 to 20 carbon atoms (as mentioned above) which are bonded via an oxygen atom (-O-), preferably C 1 -C 10 -alkyloxy, for example methoxy, ethoxy, propoxy.
  • Alkoxycarbonyl is an alkoxy group having 1 to 20 carbon atoms (as mentioned above) which is bonded via a carbonyl group (-CO-), preferably C1-C10-alkyloxycarbonyl.
  • Aryloxy is a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded via an oxygen atom (-O-), preferably a mono- to binuclear, particularly preferably a mononuclear aromatic ring system.
  • Aryloxycarbonyl is a mono- to trinuclear aryloxy group (as mentioned above) which is attached via a carbonyl group (--CO--), preferably a monosaccharide, particularly preferably a mononuclear aryloxycarbonyl.
  • Halogen atoms are fluorine, chlorine, bromine and iodine.
  • radicals R 3 and R 4 may also be linked to one another and thus together form a three- to eight-membered, preferably a five- to seven-membered and particularly preferably a five- to six-membered ring.
  • substituents may each be interrupted at any position by one or more heteroatoms, wherein the number of these heteroatoms is not more than 10, preferably not more than 8, more preferably not more than 5 and in particular not more than 3.
  • Heteroatoms are oxygen , Nitrogen, sulfur or phosphorus.
  • radicals R 1 and R 2 are each independently of one another hydrogen or C 1 -C 10 -alkyl, preferably hydrogen or C 1 -C 6 -alkyl, and particularly preferably hydrogen or C 1 -C 4 -alkyl. Most preferably, R 1 and R 2 are independently hydrogen or methyl.
  • the radicals R 3 , R 4 and R 5 are each independently of one another hydrogen or C 1 -C 10 -alkyl, preferably hydrogen or C 1 -C 6 -alkyl, and particularly preferably hydrogen or C 1 -C 4 -alkyl. Most preferably, R 3 , R 4 and R 5 are hydrogen, methyl or ethyl. In a particularly preferred embodiment, the radicals R 3 , R 4 and R 5 are identical and are hydrogen, methyl or ethyl.
  • n and n are each an integer from 0 to 10, more preferably 0 to 8, and most preferably 0 to 4, wherein as mentioned above, M and n can not be 0 at the same time.
  • the respective units which are encircled by the variables m and n, can be contained in any order.
  • suitable N-hydroxyalkylated imidazoles (I) are mono- alkylated imidazoles such as N-hydroxymethyl-imidazole and N-hydroxyethyl-imidazole. Further suitable imidazoles (I) are those which contain two or more alkoxy units, preferably exactly two alkoxy units. Preferred representatives of this group are imidazoles (I) which contain two ethoxy or propoxy units.
  • N-hydroxymethyl-imidazole and N-hydroxyethyl-imidazole.
  • N-hydroxyalkylated imidazoles (I) are optically active, they are preferably used racemically or as a mixture of diastereomers, but it is also possible to use them as pure enantiomers or diastereomers or as enantiomer mixtures.
  • the esterification with (meth) acrylic acid (S) or preferably the transesterification of the N-hydroxyalkylated imidazole (I) with at least one, preferably exactly one (meth) acrylic ester (D) is carried out according to the invention in the presence of at least one catalyst (K).
  • (meth) acrylic acid (S) or for transesterification (meth) acrylic ester (D) of a saturated alcohol can be used, preferably saturated C 1 -C 10 -alkyl esters or C 3 -C -cycloalkyl esters of (meth) acrylic acid, more preferably saturated C 1 -C 4 -alkyl esters of (meth) acrylic acid.
  • (meth) acrylic acid esters (D) are (meth) acrylic acid methyl, ethyl, n-butyl, iso-butyl, tert-butyl, n-octyl, 2-ethylhexyl and cyclohexyl esters , 1, 2-ethylene glycol di- and mono (meth) acrylate, 1, 4-butanediol di- and mono (meth) acrylate, 1, 6-hexanediol di- and mono (meth) acrylate, trimethylolpropane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate.
  • (meth) acrylic acid methyl, ethyl, n-butyl and 2-ethylhexyl esters very particular preference to methyl, ethyl and n-butyl (meth) acrylates, in particular (meth) acrylic acid methyl and ethyl ester and especially methyl (meth) acrylate.
  • Catalysts (K) which can be used according to the invention are both heterogeneous and homogeneous catalysts, these can be both acidic and basic.
  • Heterogeneous catalysts are within the scope of this document those which have a solubility in the reaction medium at 25 ° C. of not more than 1 g / l, preferably not more than 0.5 g / l and more preferably not more than 0.25 g / l.
  • catalysts (K) which are selected from the group of
  • acidic catalysts (K1) are basically all acids suitable, regardless of their acidity. However, preferred are those acids which have a pK s value of not more than 7.0, preferably not more than 4.0, and more preferably not more than 1.0. Preference is given to using sulfuric acid, phosphorous acid (H3PO3), diphosphoric acid (H4P2O7), sulfonic acids, more preferably methanesulfonic acid, trifluoromethanesulfonic acid, para-toluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, cyclododecanesulfonic acid, camphorsulfonic acid or acidic ion exchangers with sulfonic acid groups or mixtures thereof. Also conceivable are zeolites.
  • pKs value refers to the first hydrolysis stage.
  • Suitable Lewis acids (K2) are, for example, metal alkoxylates and metal acetylacetonates.
  • Metal alkoxylates are C 1 -C 6 alkoxylates such as, for example, methoxylates, ethoxylates, propoxylates, butoxylates, pentoxylates and hexoxylates, and their isomers of metals such as titanium, zirconium and aluminum.
  • Preferred representatives of this group are titanium tetraisopropoxylate (Ti (OiPr) 4 ), titanium tetraisobutoxylate (Ti (OiBu) 4 ) and aluminum triisopropoxylate (Al (OiPr) s).
  • Metal acetylacetonates are metal chelates with the enolate anion of 2,4-pentanedione (acetylacetone) and have the general formula M n (C 5 H 7 O 2) n or M n (acac) n .
  • Metals M are numerous metals, especially transition metals in question.
  • the metals used are preferably aluminum and alkali metal or alkaline earth metals such as lithium, sodium, potassium, magnesium and calcium, preferably sodium and potassium. Titanium, zirconium, chromium, manganese, cobalt, nickel and copper are preferably used as transition metals.
  • Preferred representatives of this group are potassium acetylacetonate (K (acac)) and titanium acetylacetonate (Ti (acac) 4 ).
  • the usable basic catalysts are those having a pKa of not more than 7.0, preferably not more than 4.0, and more preferably not more than 1.0.
  • the basic catalysts used are preferably alkali metal hydroxides and / or alkaline earth metal hydroxides (K3). These can be used both in solid form and in the form of solutions, for example as aqueous solutions.
  • Suitable alkali metal hydroxides are, for example, lithium hydroxide, sodium hydroxide and potassium hydroxide
  • suitable alkaline earth metal hydroxides are, for example, magnesium hydroxide and calcium hydroxide. Preference is given to using lithium hydroxide, sodium hydroxide and potassium hydroxide and mixtures thereof.
  • Inorganic salts (K4) which can be used according to the invention are preferably those which do not exceed the abovementioned limits of the pK.sub.30 value. At the same time, the pK ⁇ should not be less than 1, 0, preferably not less than 1.5, and more preferably not less than 1.6. Inorganic salts (K4) which can be used according to the invention are preferably heterogeneous inorganic salts.
  • the inorganic salt (K4) preferably has at least one anion selected from the group consisting of carbonate (CO3 2 "), bicarbonate (HCO3"), phosphate (PO 4 3 -), hydrogen phosphate (HPO 4 2- "), dihydrogen phosphate (H 2 PO 4 -), sulfate (SO 4 2 "), sulfite (SO 3 2” ) and carboxylate (R 6 -COO " ), wherein R 6 Ci - Ci 8 -Al kyl or optionally by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C2 - Cis-alkyl or C 6 - Ci2-aryl.
  • Phosphate is also to be understood as the condensation products, such as, for example, diphosphates, triphosphates and polyphosphates.
  • the inorganic salt (K4) preferably has at least one, more preferably exactly one cation selected from the group consisting of alkali metals, alkaline earth metals, ammonium, cerium, iron, manganese, chromium, molybdenum, cobalt, nickel or zinc.
  • alkali metals Preference is given to alkali metals and particular preference to lithium, sodium or potassium.
  • Particularly preferred inorganic salts (K4) are LisPCu, K3PO4, NarbaPCu, K2CO3 and Na2CÜ3 and their hydrates, very particularly preferably K3PO4.
  • K3PO4 can be used according to the invention in anhydrous form and as tri-, hepta- or nonahydrate.
  • Alkali metal bases are understood as meaning the alkali metal hydrides and alkali metal salts of C 1 -C 6 -alkanolates.
  • alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride. Particularly preferred is sodium hydride.
  • Alkali metal salts of C 1 -C 6 -alkanolates are, for example, the lithium, sodium or potassium salts of C 1 -C 6 -alkanolates, preferably C 1 -C 4 -alkanolates, such as methanolate, ethanolate, propanolate and butanolate, and their isomers. Particularly preferred are methanolates and ethanolates, particularly preferred are methanolates such as sodium and potassium.
  • Tertiary nitrogenous bases are tertiary amines such as trialkylamines, bicyclic amines such as 1, 4-diazabicyclo [2.2.2] octane (DABCO) and 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) and heterocyclic amines such as imidazole, pyridine, pyridazine, pyrimidine and pyrazine, preferred are DABCO, DBU and pyridine.
  • Suitable trialkylamines are, for example, triethylamine, tributylamine and tribenzylamine.
  • triethylamine is used as the tertiary nitrogen-containing base.
  • Organic tin compounds are also suitable as catalysts. Such compounds are disclosed, inter alia, in DE 2 752 109, DE 1 965 308 and DE 2 725 255. Preferred representatives of this group are dibutyltin laurate and dibutyltin oxide.
  • the acids (K1) are particularly suitable for the esterification of the N-hydroxyalkylated imidazoles (I) with (meth) acrylic acid (S).
  • the catalyzed esterification or transesterification is generally carried out at from 30 to 140 ° C., preferably from 30 to 100 ° C., more preferably from 40 to 90 ° C., and very preferably from 50 to 80 ° C.
  • the reaction can be carried out under a slight vacuum of, for example, 200 hPa to atmospheric pressure, preferably 200 to 600 hPa and particularly preferably 250 to 500 hPa, if the water released during the esterification or the low-boiling alcohol formed during the transesterification, if appropriate as an azeotrope , to be distilled off.
  • a slight vacuum of, for example, 200 hPa to atmospheric pressure, preferably 200 to 600 hPa and particularly preferably 250 to 500 hPa, if the water released during the esterification or the low-boiling alcohol formed during the transesterification, if appropriate as an azeotrope , to be distilled off.
  • the molar ratio between (meth) acrylic acid (S) or (meth) acrylic acid ester (D) and N-hydroxyalkylated imidazole (I) is usually 1-6 in the case of the esterification or transesterification catalyzed by one of the abovementioned catalysts (K) : 1 mol / mol, preferably 1-5: 1 mol / mol and particularly preferably 1-4 mol / mol.
  • the reaction time in the catalysed or transesterification catalyzed according to the invention is generally 45 minutes to 18 hours, preferably 2 hours to 12 hours and more preferably 3 to 10 hours.
  • the content of catalyst (K) in the reaction medium is generally in the range of about 0.01 to 5 mol%, preferably 0.1 to 1, 8 and particularly preferably 0.3 to 1, 5 mol% based on the Sum of the N-hydroxyalkylated imidazoles (I) used.
  • oxygen-containing gases s.u.
  • the reaction can take place in organic solvents or mixtures thereof or without the addition of solvents.
  • the batches are generally largely anhydrous, ie the water content is preferably below 10, more preferably below 5, more preferably less than 1 and most preferably less than 0.5 wt .-%.
  • the water content is between 100 and 5000 ppm, preferably between 500 and 1000 ppm.
  • Suitable organic solvents are known for this purpose, for example tertiary monools, such as Cs-C ⁇ alcohols, preferably tert-butanol, tert-amyl alcohol, pyridine, poly-Ci-C4-alkylenglykoldi-Ci-C4-alkyl ether, preferably polyethylene glycol -Ci-C4-alkyl ethers, such as. B.
  • tertiary monools such as Cs-C ⁇ alcohols, preferably tert-butanol, tert-amyl alcohol, pyridine
  • poly-Ci-C4-alkylenglykoldi-Ci-C4-alkyl ether preferably polyethylene glycol -Ci-C4-alkyl ethers, such as. B.
  • the reaction is carried out in the (meth) acrylic acid ester (D) used as starting material.
  • the product (F) is obtained after completion of the reaction as about 10 to 80% strength by weight solution in the (meth) acrylic acid ester (D) used as starting material, in particular as 20 to 50 wt .-% solution.
  • the educts are either dissolved, suspended as solids or in emulsion in the reaction medium before.
  • the reaction can be carried out continuously, for example in a tubular reactor or in a stirred reactor cascade, or discontinuously.
  • the reaction can be carried out in all reactors suitable for such a reaction. Such reactors are known to the person skilled in the art.
  • the reaction preferably takes place in a stirred tank reactor or a fixed bed reactor.
  • any method can be used. Special stirring devices are not required.
  • the mixing can be carried out, for example, by feeding in a gas, preferably an oxygen-containing gas (see below).
  • the reaction medium can be monophase or polyphase and the reactants are dissolved, suspended or emulsified therein.
  • the temperature is adjusted to the desired value during the reaction and, if desired, can be increased or decreased during the course of the reaction.
  • the fixed bed reactor is preferably equipped with immobilized catalyst (K), wherein the reaction mixture by a with the catalyst (K) filled column is pumped. It is also possible to carry out the reaction in a fluidized bed reactor, wherein the catalyst (K) is used immobilized on a support.
  • the reaction mixture can be pumped continuously through the column, with the flow rate, the residence time and thus the desired conversion is controllable. It is also possible to pump the reaction mixture through a column in the circulation, wherein the liberated alcohol can be distilled off simultaneously under vacuum.
  • the removal of water in the case of esterification or alcohols which are released in a transesterification of the (meth) acrylic acid esters (D) is carried out continuously or stepwise in a conventional manner, e.g. by vacuum, azeotropic removal, stripping, absorption, pervaporation and diffusion via membranes or extraction.
  • the stripping can be carried out, for example, by passing an oxygen-containing gas, preferably an air or air-nitrogen mixture, through the reaction mixture, optionally in addition to a distillation.
  • an oxygen-containing gas preferably an air or air-nitrogen mixture
  • molecular sieves or zeolites for absorption, molecular sieves or zeolites (pore size, for example, in the range of about 3-10 angstroms) are preferred, separation by distillation or by means of suitable semipermeable membranes.
  • reaction mixture obtained from the esterification or transesterification can be used without further purification or, if necessary, purified in a further step.
  • a separation of heterogeneous catalysts is usually carried out by filtration, electrofiltration, absorption, centrifugation or decantation.
  • the separated heterogeneous catalyst can then be used for further reactions.
  • the separation of homogeneous catalysts and the organic solvent is usually carried out by distillation, rectification or solid reaction products by filtration. In the first purification step, however, only the catalyst and the optionally used solvent are preferably removed.
  • the optionally purified reaction mixture is optionally subjected to a distillation in which the (meth) acrylic acid ester (F) of the N-hydroxyalkylated Imidazzole by distillation of unum pointeder (meth) acrylic acid (S) or unreacted (meth) acrylic acid ester (D) and optionally formed by-products is disconnected.
  • the distillation units are usually rectification columns of conventional design with circulation evaporator and condenser.
  • the feed is preferably in the bottom region, the bottom temperature is here for example 130- 160 0 C, preferably 150- 160 0 C, the head temperature preferably 140-145 0 C and the top pressure 3-20, preferably 3 to 5 mbar.
  • the skilled person can also determine other temperature and pressure ranges in which the respective (meth) acrylic acid esters (F) of the N-hydroxyalkylated imidazoles can be purified by distillation. What is essential here is a separation of the desired product of reactants and by-products under conditions in which the desired product is exposed to as possible no degradation reaction.
  • the distillation unit usually has from 5 to 50 theoretical plates.
  • the distillation units are of a known type and have the usual installations. In principle, all standard installations are suitable as column internals, for example trays, packings and / or fillings. Of the bottoms, bubble-cap trays, sieve trays, valve trays, Thormann trays and / or dual-flow trays are preferred; of the trays are those with rings, coils, calipers, Raschig, Intos or Pall rings, Barrel or Intalox saddles, Top-Pak etc. or braids preferred.
  • the desired product is distilled batchwise, initially low-boiling components are removed from the reaction mixture, usually solvent or unreacted (meth) acrylic acid (S) or (meth) acrylic acid ester (D). After separation of these low boilers, the distillation temperature is increased and / or reduced the vacuum and the desired product distilled off.
  • initially low-boiling components are removed from the reaction mixture, usually solvent or unreacted (meth) acrylic acid (S) or (meth) acrylic acid ester (D).
  • the distillation temperature is increased and / or reduced the vacuum and the desired product distilled off.
  • the remaining distillation residue is usually discarded.
  • the reaction conditions in the esterification or transesterification according to the invention are mild. Due to the low temperatures and other mild conditions, the formation of by-products in the reaction is avoided, otherwise by, for example unwanted radical polymerization of the (meth) acrylic acid ester (D) used would be obtained and which can otherwise be prevented only by adding stabilizers.
  • additional stabilizer can be added to the reaction mixture via the storage stabilizer which is present anyway in the (meth) acrylic compound (B), for example hydroquinone monomethyl ether, phenothiazine, phenols, such as 2-tert-butyl-4-methylphenol, 6-tert Butyl-2,4-dimethyl-phenol or N-oxyls, such as 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethyl piperidine-N-oxyl or Uvinul ® 4040P from BASF Aktiengesellschaft, for example, in amounts of 50 to 2000 ppm.
  • the esterification or transesterification is advantageously carried out in the presence of an oxygen-containing gas, preferably air or air-nitrogen mixtures.
  • Another object of the present invention are obtained from the N-hydroxyalkylated imidazoles (I) by catalytic esterification or transesterification obtained (meth) acrylic acid ester (F).
  • the (meth) acrylic acid esters (F) of N-hydroxyalkylated imidazoles (I) used according to the invention are used, for example, as monomers or comonomers in the preparation of dispersions, for example acrylic dispersions, as reactive diluents, such as in radiation-curable coating compositions or in paints, and in dispersions for use in the paper sector, in the cosmetics sector, in the pharmaceutical sector, in agricultural formulations, in the textile industry and in the field of oil extraction.
  • Another object of the present invention is N- (2'-acryloyl) -ethyl) -imidazole.
  • Potassium phosphate was used as a catalyst for the reaction on a larger scale.
  • the transesterification was carried out in a 750 ml mini-planar reactor with Oldershaw column and liquid distributor.
  • the reflux ratio was 25: 1 (return run: drain), the stirring speed (armature stirrer) 400 rpm and the air inlet 1, 5 L / h.
  • methyl acrylate (MA) and hydroxyethyl imidazole (HEI) were reacted in a molar ratio of 5: 1 in the presence of 50 ppm phenothiazine, 500 ppm hydroquinone monomethyl ether and 1.25 mole% of a catalyst (based on hydroxyethyl imidazole) for 5 h heated.
  • Zirconium acetylacetonate was used as a catalyst for the reaction on a larger scale.
  • the transesterification took place in a 750 ml miniplane reactor with Oldershaw column and liquid distributor.
  • the reflux ratio was 25: 1 (reflux: drain), the stirring speed (armature stirrer) 400 rpm and the air inlet line 1, 5 L / h.

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Abstract

Procédé de production d'esters d'acide (méth)acrylique (F) d'imidazoles n-hydroxyalkylés, selon lequel des imidazoles n-hydroxyalkylés (I) sont estérifiés avec de l'acide (méth)acrylique (S) ou transestérifiés avec au moins un ester d'acide (méth)acrylique (D), en présence d'au moins un catalyseur (K), R<SUP>1</SUP> et R<SUP>2</SUP> représentant indépendamment l'un de l'autre hydrogène ou alkyle C<SUB>1</SUB>-C<SUB>20</SUB>, R<SUP>3</SUP>, R<SUP>4</SUP> et R<SUP>5</SUP> représentant indépendamment l'un de l'autre hydrogène ou alkyle C<SUB>1</SUB>-C<SUB>20</SUB>, alkylcarbonyle C<SUB>1</SUB>-C<SUB>20</SUB>, alcényle C<SUB>2</SUB>-C<SUB>20</SUB>, alcénylcarbonyle C<SUB>2</SUB>-C<SUB>20</SUB>, alkinyle C<SUB>2</SUB>-C<SUB>20</SUB>, alkinylcarbonyle C<SUB>2</SUB>-C<SUB>20</SUB>-, cycloalkyle C<SUB>3</SUB>-C <SUB>15</SUB>, cycloalkylcarbonyle C<SUB>3</SUB>-C<SUB>15</SUB>, aryle, arylcarbonyle, un hétérocycle ou un atome halogène, m et n représentant chacun des nombres entiers de 0 à 20, m et n ne pouvant être ensemble égal à 0, les unités contenues par les variables m et n étant dans un ordre quelconque, et dans le cas où m = 2, les groupes R<SUP>1</SUP> et R<SUP>2</SUP> étant indépendants l'un de l'autre dans leurs unités respectives.
EP08716786A 2007-02-15 2008-02-11 Procédé de production d'esters d'acide (méth)acrylique d'imidazoles n-hydroxyalkylés Withdrawn EP2139863A2 (fr)

Priority Applications (1)

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EP08716786A EP2139863A2 (fr) 2007-02-15 2008-02-11 Procédé de production d'esters d'acide (méth)acrylique d'imidazoles n-hydroxyalkylés

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EP07102486 2007-02-15
EP07102757 2007-02-21
PCT/EP2008/051585 WO2008098886A2 (fr) 2007-02-15 2008-02-11 Procédé de production d'esters d'acide (méth)acrylique d'imidazoles n-hydroxyalkylés
EP08716786A EP2139863A2 (fr) 2007-02-15 2008-02-11 Procédé de production d'esters d'acide (méth)acrylique d'imidazoles n-hydroxyalkylés

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EP2139863A2 true EP2139863A2 (fr) 2010-01-06

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CN101622228B (zh) * 2007-02-15 2013-01-09 巴斯夫欧洲公司 制备n-羟烷基化内酰胺的(甲基)丙烯酸酯的催化法
EP2033626A3 (fr) 2007-09-05 2010-03-17 Basf Se Polymères d'imidazoliumalkyl(méth)acrylate
JP6424532B2 (ja) * 2014-09-17 2018-11-21 東洋インキＳｃホールディングス株式会社 フルフリルメタクリレートの製造方法

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US3642877A (en) 1968-12-27 1972-02-15 Du Pont Process for the preparation of dimethylaminoethyl methacrylate
JPS52153913A (en) 1976-06-18 1977-12-21 Nitto Chem Ind Co Ltd Preparation of dimethylaminoethylmethacrylate
JPS5365816A (en) 1976-11-26 1978-06-12 Nitto Chem Ind Co Ltd Preparation of dimethylaminoethyl methacrylate
JPS603294B2 (ja) * 1977-05-19 1985-01-26 三菱レイヨン株式会社 アクリル酸エステルまたはメタクリル酸エステルの製造法
JPS6023101B2 (ja) * 1980-10-20 1985-06-05 三井東圧化学株式会社 メタクリル酸ジメチルアミノエチルエステルの製造法
JPH01258642A (ja) * 1988-04-06 1989-10-16 Mitsubishi Gas Chem Co Inc （メタ）アクリル酸エステルの製造法
SG155168A1 (en) * 2004-07-29 2009-09-30 Basf Se Catalytic methods for the production of (meth)acrylates from n- hydroxyalkylated amides
DE102004036930A1 (de) 2004-07-29 2006-03-23 Basf Ag Katalysiertes Verfahren zur Herstellung von(Meth)acrylaten von N-hydroxyalkylierten Amiden
DE102005039536A1 (de) 2005-08-18 2007-02-22 Basf Ag Verfahren zur Herstellung von (Meth)acrylsäureestern
DE102005052931A1 (de) 2005-11-03 2007-05-10 Basf Ag Katalytisches Verfahren zur Herstellung von (Meth)acrylaten von N-hydroxyalkylierten Lactamen

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See references of WO2008098886A2 *

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JP2010529948A (ja) 2010-09-02
KR20090113882A (ko) 2009-11-02
US20100004462A1 (en) 2010-01-07
WO2008098886A2 (fr) 2008-08-21
WO2008098886A3 (fr) 2008-10-09
JP5558833B2 (ja) 2014-07-23
US8026374B2 (en) 2011-09-27
KR101492655B1 (ko) 2015-02-12

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