WO2012084773A1 - Procédé de production de siloxycarboxylates - Google Patents

Procédé de production de siloxycarboxylates Download PDF

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Publication number
WO2012084773A1
WO2012084773A1 PCT/EP2011/073177 EP2011073177W WO2012084773A1 WO 2012084773 A1 WO2012084773 A1 WO 2012084773A1 EP 2011073177 W EP2011073177 W EP 2011073177W WO 2012084773 A1 WO2012084773 A1 WO 2012084773A1
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acid
auxiliary base
hydrogen
salt
monocarboxylic acid
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PCT/EP2011/073177
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German (de)
English (en)
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Martin GÄRTNER
Jochen Petzoldt
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage

Definitions

  • the invention relates to a process for the preparation of silylated monocarboxylic acids by reacting monocarboxylic acids in the presence of an auxiliary base.
  • a process for the separation of acids which are formed as a by-product in the course of a reaction or added to a reaction mixture, for example for pH regulation is known from the reaction mixtures by means of an auxiliary base such as 1-methylimidazole or 2-ethylpyridine.
  • the acids form with the auxiliary base a liquid salt which is immiscible with the desired product and can therefore be separated by means of liquid-liquid phase separation.
  • silylations of alcohols or amines with halosilanes are described.
  • hydrochloric acid and acetic acid are disclosed.
  • a method for the siloxylation of monocarboxylic acids is not disclosed.
  • WO 2005/061416 A1 likewise discloses a process for the separation of acids from reaction mixtures by means of an auxiliary base, wherein the auxiliary base is an alkylimidazole which has a solubility in 30% strength by weight sodium chloride solution at 25 ° C. of 10% by weight. -% or less and its hydrochloride has a melting point below 55 ° C.
  • the auxiliary base is used for the separation of acids which are formed in the course of the reaction or added during the reaction, for example for pH regulation.
  • a method for the siloxylation of monocarboxylic acids is not disclosed.
  • WO 2010/072532 describes the silylation of monocarboxylic acids, but siloxylation is not disclosed.
  • the invention is therefore based on the object to provide a process for the siloxylation of monocarboxylic acids available, which is characterized by high yields and high selectivity and is economically attractive.
  • the object is achieved by a method for producing a Siloxycarboxylats comprising the steps of: a) reacting a C 2 -C 0 monocarboxylic acid with a halosiloxane the general formula (I),
  • Hai is fluorine, chlorine, bromine or iodine
  • R is the same or different hydrogen
  • C is Cio-alkyl or C 6 -C 4 -aryl and x is an integer from 1 to 20, in the presence of an auxiliary base and optionally a solvent
  • the auxiliary base is chosen so that it reacts with the in the reaction of monocarboxylic acid and halosilane liberated hydrogen halide forms a salt which is immiscible in the liquid phase with the siloxycarboxylate or the solution of Siloxycarboxylats in the solvent optionally present
  • the optionally used solvent is chosen such that it with the siloxycarboxylate is miscible and is immiscible with the liquid salt of auxiliary base and split hydrogen halide, and
  • the novel siloxycarboxylates are easily and economically produced by the hydrogen halide liberated during the reaction forms a salt with the auxiliary base, which is liquid under the reaction conditions and is immiscible with the siloxycarboxylate.
  • the added auxiliary base surprisingly removes selectively the residual hydrogen halide and not the monocarboxylic acid from the reaction mixture.
  • the siloxycarboxylate can be separated from this salt of the auxiliary base with the hydrogen halide.
  • the siloxylation of the monocarboxylic acid proceeds rapidly and in high yields.
  • the inventive method is suitable for the conversion of C 2 -C 0 - monocarboxylic acids having halosiloxanes of the general formula (I). It is irrelevant whether it is a straight-chain or branched and / or saturated or mono- or polyunsaturated monocarboxylic acid.
  • the process according to the invention is preferably suitable for saturated C 2 -C 8 monocarboxylic acids and monoethylenically unsaturated C 3 -C 8 monocarboxylic acids.
  • Saturated C 2 -C 8 -monocarboxylic acids are, for example, acetic acid, propionic acid, butyric acid, valeric acid (pentanoic acid), caproic acid (hexanoic acid), heptanoic acid and octanoic acid (caprylic acid) and also their isomers.
  • the group of monoethylenically unsaturated monocarboxylic acids having 3 to 8 carbon atoms include, for example, acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, glutaconic acid, aconitic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid and crotonic acid.
  • Preferred monoethylenically unsaturated monocarboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid and maleic acid.
  • the C 2 -C 0 used monocarboxylic acid is used with respect to the halosiloxane either in equimolar amounts or in excess. It is preferably 1, 0 to 2.0 mol / mol, more preferably 1, 0 to 1, 5 mol / mol and in particular 1, 0 to 1, 25 mol / mol monocarboxylic acid used.
  • any mixtures of the aforementioned C 2 -C 0 monocarboxylic acids may be used in the inventive process, however, only one is preferred C 2 -C reacted with a monocarboxylic acid 0 halosiloxane.
  • the halosiloxanes are those of the general formula (I)
  • R is the same or different hydrogen
  • C is Cio-alkyl or aryl
  • x is an integer from 1 to 20.
  • Shark is preferably chlorine or bromine.
  • Preference is given to using one (1) halosiloxane, more preferably one (1) chlorine or bromosiloxane.
  • the substituents R may be identical or different and independently of one another denote hydrogen, C 1 -C 10 -alkyl or C 6 -C 4 -aryl.
  • the substituents R are the same or different and are independently C 1 -C 4 -alkyl or C 6 -C 4 -aryl, more preferably they are identical and are C 1 -C 4 -alkyl or phenyl.
  • C 1 -C 4 -alkyl in the context of the invention means straight-chain or branched hydrocarbon radicals having up to 10 carbon atoms, for example 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-methylpropyl, 1-e
  • Aryl is understood to mean mono- to trinuclear aromatic ring systems containing 6 to 14 carbon ring members, for example phenyl, naphthyl and anthryl, preferably a mononuclear aromatic ring system, more preferably phenyl.
  • x is an integer from 1 to 20, preferably an integer from 1 to 5, and particularly preferably 3 or 4.
  • halosiloxanes are, for example, CI-SiMe 2 -O-SiMe 3 , Cl- ( SiMe 2 -O) 2 -SiMe 3 , CI- (SiMe 2 -O) 3 -SiMe 3 , CI- (SiMe 2 -O) 4 -SiMe 3 , CI- (SiMe 2 -O) 5 -SiMe 3 , Br - (SiMe 2 -O) 3 -SiMe 3 , Br- (SiMe 2 -O) 4 -SiMe 3 , CI- (SiEt 2 -O) 3 -SiMe 3 , CI- (SiEt 2 -O) 4 -SiMe 3 , Cl- (SiMe 2 -
  • Suitable auxiliary bases are in particular those compounds which are mentioned in WO 03/062171 A2 and WO 05/061416 A1.
  • the compounds which can be used as auxiliary bases can contain phosphorus sulfur or nitrogen atoms, for example at least one nitrogen atom, preferably one to ten nitrogen atoms, particularly preferably one to five, very particularly preferably one to three and in particular one to two nitrogen atoms. If appropriate, further heteroatoms, such as oxygen, sulfur or phosphorus atoms, can also be present. Preference is given to those compounds which contain at least one five- to six-membered heterocycle which has at least one nitrogen atom and optionally an oxygen or sulfur atom, particularly preferably those compounds which contain at least one five- to six-membered heterocycle containing one, two or three nitrogen atoms and a sulfur or an oxygen atom, most preferably those having two nitrogen atoms.
  • Particularly preferred compounds are those which have a molecular weight below 1000 g / mol, very particularly preferably below 500 g / mol and in particular below 250 g / mol. Furthermore, preference is given to those compounds which can be used as bases and are selected from the compounds of the formulas (IIa) to (Nr)
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, C 1 - Ci 8 alkyl, optionally by one or more oxygen and / or sulfur atoms and / or a or more substituted or unsubstituted imino groups
  • C 2 - C 8 - alkyl, C 6 - C 2 aryl, C 5 - C 2 denote cycloalkyl or a five- to six-membered, oxygen-, nitrogen- and / or sulfur-containing heterocycle or two of them together form an unsaturated, saturated or aromatic ring optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, said radicals being in each case denoted by functional groups, aryl, alkyl, aryloxy , Alkyloxy, halogen, heteroatoms and / or heterocycles.
  • C 1 -C 8 -alkyl which is optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl , Pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, hetadecyl, octadecyl, 1, 1 -
  • radicals can together be 1, 3-propylene, 1, 4-butylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3-propylene, 2-oxa-1, 3 -propylene, 1-oxa-1, 3-propenylene, 1-aza-1, 3-propenylene, 1-CrC 4 -alkyl-1-aza-1, 3-propenylene, 1, 4-buta-1, 3 dienylene, 1-aza-1, 4-buta-1, 3-dienylene or 2-aza-1,4-buta-1,3-dienylene.
  • the number of oxygen and / or sulfur atoms and / or imino groups is not limited. As a rule, it is not more than 5 in the radical, preferably not more than 4, and very particularly preferably not more than 3. Furthermore, at least one carbon atom, preferably at least two, is usually present between two heteroatoms.
  • Substituted and unsubstituted imino groups can be so-propylimino, n-butylimino or te / f-butylimino example, imino, methylimino, / '.
  • functional groups are carboxy, carboxamide, hydroxy, di- (CC 4 -alkyl) -amino, CC 4 -alkyloxycarbonyl, cyano or CC 4 -alkyloxy, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroaryl roatome and / or heterocycles substituted C 6 - C 2 -aryl, for example phenyl, tolyl, xylyl, ⁇ -naphthyl, ß-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, / ' so-propylphenyl, tert-butylphenyl, dodec
  • Ethoxynaphthyl 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4- dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl, optionally roatome by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, hetero- and / or heterocycles substituted C 5 - Ci 2 cycloalkyl, for example,
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently hydrogen, methyl, ethyl, n-butyl, 2-hydroxyethyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- ( Ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, dimethylamino, diethylamino and chloro.
  • Particularly preferred pyridines (IIa) are those in which one of the radicals R 1 to R 5 is methyl, ethyl or chlorine and all others are hydrogen, or R 3 are dimethylamino and all others are hydrogen or are all hydrogen or R 2 is carboxy or carboxy - amide and all others are hydrogen or R 1 and R 2 or R 2 and R 3 are 1, 4-buta-1, 3-dienylene and all others are hydrogen.
  • Particularly preferred pyridazines (IIb) are those in which one of the radicals R 1 to R 4 is methyl or ethyl and all others are hydrogen or all hydrogen.
  • Particularly preferred pyrimidines are those in which R 2 to R 4 is hydrogen or methyl and R 1 is hydrogen, methyl or ethyl, or R 2 and R 4 are methyl, R 3 is hydrogen and R 1 is hydrogen, methyl or ethyl.
  • Particularly preferred pyrazines are those in which R 1 to R 4 are all methyl or all hydrogen.
  • Particularly preferred imidazoles (IIe) are those in which R 1 is independently selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, 2-hydroxyethyl or 2-cyanoethyl and
  • R 2 to R 4 independently of one another denote hydrogen, methyl or ethyl.
  • Particularly preferred 1 H-pyrazoles (IIf) are those in which independently of one another R 1 is hydrogen, methyl or ethyl,
  • R 2 , R 3 and R 4 are hydrogen or methyl
  • Particularly preferred 3H-pyrazoles (IIg) are those in which, independently of one another, R 1 is hydrogen, methyl or ethyl,
  • R 2 , R 3 and R 4 are hydrogen or methyl
  • Particularly preferred 4H-pyrazoles (IIh) are those in which, independently of one another, R 1 to R 4 are hydrogen or methyl,
  • Particularly preferred 1-pyrazolines (III) are those in which, independently of one another, R 1 to R 6 are hydrogen or methyl
  • Particularly preferred 2-pyrazolines (IIj) are those in which independently of one another R 1 is hydrogen, methyl, ethyl or phenyl and
  • R 2 to R 6 are hydrogen or methyl
  • Particularly preferred 3-pyrazolines (IIk) are those in which independently of one another R 1 or R 2 is hydrogen, methyl, ethyl or phenyl and
  • R 3 to R 6 are hydrogen or methyl are selected.
  • Particularly preferred imidazolines (III) are those in which, independently of one another, R 1 or R 2 is hydrogen, methyl, ethyl, n-butyl or phenyl and R 3 or R 4 are hydrogen, methyl or ethyl and R 5 or R 6 is hydrogen or methyl are selected.
  • Particularly preferred imidazolines (Ilm) are those in which, independently of one another, R 1 or R 2 are selected from hydrogen, methyl or ethyl and R 3 to R 6 are selected from hydrogen or methyl.
  • Particularly preferred imidazolines (IIn) are those in which, independently of one another, R 1 , R 2 or R 3 are selected from hydrogen, methyl or ethyl and R 4 to R 6 are selected from hydrogen or methyl.
  • Particularly preferred thiazoles (Mo) or oxazoles (Up) are those in which independently of one another
  • R 1 is hydrogen, methyl, ethyl or phenyl
  • R 2 or R 3 are selected from hydrogen or methyl.
  • Particularly preferred 1, 2,4-triazoles are those in which independently of one another R 1 or R 2 is hydrogen, methyl, ethyl or phenyl and R 3 are selected from hydrogen, methyl or phenyl.
  • Particularly preferred 1, 2,3-triazoles (Nr) are those in which independently of one another R 1 is selected from hydrogen, methyl or ethyl and R 2 or R 3 are selected from hydrogen or methyl or
  • R 2 and R 3 are 1, 4-buta-1, 3-dienylene and all others are hydrogen.
  • pyridines and imidazoles are preferred. Very particular preference is given as bases to 3-chloropyridine, 4-dimethylaminopyridine, 2-ethyl-4-aminopyridine, 2-methylpyridine ( ⁇ -picoline), 3-methylpyridine ( ⁇ -picoline), 4-methylpyridine ( ⁇ -picoline), 2 -Ethylpyridine, 2-ethyl-6-methylpyridine, quinoline, isoquinoline, 1-CrC 4 -alkylimidazole, 1-methylimidazole, 1, 2-dimethylimidazole, 1-n-butylimidazole, 1, 4,5-trimethylimidazole, 1, 4- Dimethylimidazole, imidazole, 2-methylimidazole, 1-butyl-2-methylimidazole, 4-methylimidazole, 1-n-pentylimidazole, 1-n-hexylimid
  • R a, R b and R c are each independently Ci - Ci 8 alkyl, optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, C 2 - C 8 alkyl, C 6 - Ci 2 -aryl or C 5 - Ci 2 -cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle or two of them together an unsaturated, saturated or aromatic and optionally by one or more oxygen form - and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted ring, wherein said radicals each- because they may be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles,
  • At least two of the three radicals R a , R b and R c are different and
  • R a , R b and R c together have at least 8, preferably at least 10, more preferably at least 12 and most preferably at least 13 carbon atoms.
  • R a, R b and R c are each independently Ci - Ci 8 alkyl, C 6 - C 2 -aryl or C 5 - Ci 2 cycloalkyl, and more preferably Ci - Ci 8 alkyl, where the radicals mentioned may each be may be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles.
  • R a , R b and R c are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl (n-amyl), 2-pentyl ( sec-amyl), 3-pentyl, 2,2-dimethyl-prop-1-yl (neo-pentyl), n-hexyl, n-heptyl, n-octyl, iso-octyl, 2-ethylhexyl, 1, 1 - Dimethylpropyl, 1, 1-dimethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, phenyl, tolyl, xylyl, ⁇ -naphthyl, ⁇ -naphthyl, cyclopent
  • tertiary amines of the formula (III) are diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethyl-hexylamine, diethyl-octylamine, diethyl (2-ethylhexyl) -amine, di-n propyl-butylamine, di-n-propyl-n-pentylamine, di-n-propyl-hexylamine, di-n-propyl-octylamine, di-n-propyl- (2-ethylhexyl) -amine, di-iso-propyl -ethylamine, di-isopropyl-n-propylamine, di-isopropyl-n-propylamine, di-isopropyl-n-propylamine, di-opropyl-n-propylamine, di--
  • Preferred tertiary amines (III) are di-iso-propyl-ethylamine, diethyl-tert-butylamine, di-isopropyl-butylamine, di-n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary Amines of pentyl isomers.
  • Particularly preferred tertiary amines are di-n-butyl-n-pentylamine and tertiary amines of pentyl isomers.
  • a tertiary amine which is likewise preferred and can be used according to the invention, but in contrast to the above-mentioned three identical radicals, is triallylamine.
  • Tertiary amines preferably of the formula (III), are generally preferred over heterocyclic compounds, for example of the formulas (IIa) to (Nr), if the basicity of the latter auxiliary bases is not sufficient for the reaction, for example for eliminations.
  • auxiliary bases whose salts of auxiliary bases and acids have a melting temperature at which no significant decomposition of the siloxycarboxylate occurs during the separation of the salt as the liquid phase, i. less than 10 mol% per hour, preferably less than 5 mol% / h, more preferably less than 2 mol% / h, and most preferably less than 1 mol% / h.
  • the melting points of the salts of the particularly preferred auxiliary bases are generally below 160 ° C., more preferably below 100 ° C. and most preferably below 80 ° C.
  • auxiliary bases very particular preference is given to those whose salts have an E T (30) value of> 35, preferably of> 40, particularly preferably of> 42.
  • the E T (30) value is a measure of polarity and is reviewed by C. Reichardt of Reichardt, Christian Solvent Effects in Organic Chemistry Weinheim: VCH, 1979. XI, (Monographs in Modern Chemistry; 3), ISBN 3-527-25793-4 page 241.
  • a preferred base which fulfills the task e.g. is satisfied, is 1-methylimidazole.
  • 1-Methylimidazole is also effective as a nucleophilic catalyst [Julian Chojnowski, Marek Cypryk, Witold Fortuniak, Heteroatom. Chemistry, 1991, 2, 63-70]. Chojnowski et al. have found that 1-methylimidazole accelerates the phosphorylation of f-butanol by a factor of 33 and the silylation of pentamethyldisiloxanol by a factor of 930 compared to triethylamine. Instead of 1-methylimidazole, for example, 1-butylimidazole can be used.
  • the hydrochloride of 1-butylimidazole is already liquid at room temperature, so that 1-butylimidazole can be used as the auxiliary base and catalyst for reactions which handle materials which are already decomposable at temperatures above room temperature. Also liquid at room temperature is the acetate and formate of 1-methylimidazole.
  • imidazole whose salts have an E T (30) value of> 35, preferably of> 40, more preferably of> 42, and which have a melting temperature during which the salt is separated off as the liquid phase no significant decomposition of the siloxycarboxylate occurs.
  • the polar salts of these imidazoles form two immiscible phases as noted above with less polar organic media.
  • Another exceptionally preferred base that fulfills the task is 2-ethylpyridine.
  • hydrochloride of 2-ethylpyridine has a melting point of about 55 ° C and is immiscible with the nonpolar organic siloxycarboxylates or solvents.
  • 2-ethylpyridine can at the same time serve as auxiliary base and nucleophilic catalyst and be separated off from organic media as liquid hydrochloride by a process-technically simple liquid-liquid phase separation.
  • auxiliary bases are also alkylimidazoles of the formula (IV)
  • R 'and R " can each independently be hydrogen or linear or branched C 1 -C 6 -alkyl, with the proviso that R' and R" have in total at least 1 carbon atom and in total not more than 6 carbon atoms, preferably in total 1 have up to 4 carbon atoms, more preferably have a total of 1 to 2 carbon atoms and most preferably have in total 2 carbon atoms.
  • R 'and R are hydrogen, methyl, ethyl, /' so-propyl, n-propyl, n-butyl, iso- butyl, s / (-. Butyl, te / f-butyl and n-hexyl Preferred radicals R 'and R "are hydrogen, methyl and ethyl.
  • Examples of compounds of formula (IV) are n-propylimidazole, n-butylimidazole, iso- butylimidazole, 2'-Methylbutylimidazol, / 'so-Pentylimidazo, n-Pentylimidazol, iso- Hexylimidazo, n-hexylimidazole, /' so-Octylimidazol and n-Octylimidazol.
  • auxiliary bases are those compounds which form a salt with the hydrogen halide formed during the reaction, which forms two immiscible phases at the reaction temperature with the siloxycaroxylate or the solution of the siloxycarboxylate in a suitable solvent and is separated off. Preference is given to those auxiliary bases which do not participate in the reaction as a reactant.
  • this auxiliary base can act as a nucleophilic catalyst in the reaction, so that the addition of a further base, for example the bases cited in the literature diethylamine or triethylamine, is not required.
  • the auxiliary base forms a salt with the hydrogen halide formed during the reaction.
  • hydrogen chloride (HCl) or hydrogen bromide (HBr) is preferably formed.
  • the auxiliary base is suitable for binding other acids which are added, for example, during the pH-adjusting reaction, for example nitric acid, nitrous acid, carbonic acid, sulfuric acid, phosphoric acid or sulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid.
  • acids which are added, for example, during the pH-adjusting reaction, for example nitric acid, nitrous acid, carbonic acid, sulfuric acid, phosphoric acid or sulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid.
  • the reaction mixture contains beside the used C 2 -C 0 monocarboxylic acid no further acids, as is per mol separated is hydrogen halide, at least one mole of auxiliary base used as a rule, preferably 1, 0 to 1, 5 mol / mol, particularly preferably 1, 0 to 1.3 mol / mol and especially 1.0-0.1, 25 mol / mol. If other acids are added, for example for pH regulation, the amount of auxiliary base must be adjusted accordingly.
  • the residence time of the auxiliary base in the reaction mixture is a few minutes to several hours, preferably 5 to 120 minutes, more preferably 10 to 60 minutes and most preferably 10 to 30 minutes.
  • the auxiliary base is used together with the to siloxylierenden C 2 -C 0 - submitted monocarboxylic acid, and then the halosiloxane added completely or continuously.
  • the salt of the auxiliary base with the hydrogen halide formed during the reaction forms two immiscible phases with the siloxycarboxylate or a solution of the siloxycarboxylate in a suitable solvent.
  • Immiscible means that two separate phases are formed by a phase interface.
  • a solvent may also be added to the siloxycarboxylate to achieve segregation or solubility reduction. This is useful, for example, if the solubility of the salt in the siloxycarboxylate or vice versa is 20% by weight or more, preferably 15% by weight or more, particularly preferably 10% by weight or more and very particularly preferably 5% by weight. % or more. The solubility is determined under the conditions of the respective separation.
  • the solubility is preferably determined at a temperature which is above the melting point of the salt and preferably 10 ° C., particularly preferably 20 ° C., below the lowest of the following temperatures: boiling point of the siloxycarboxylate, boiling point of the solvent and temperature of the significant decomposition of the Siloxycarboxylates.
  • the solvent is suitable if the mixture of siloxycarboxylate and solvent is able to dissolve the salt or the salt, the siloxycarboxylate or a mixture of siloxycarboxylate and solvent less than the amounts indicated above.
  • Suitable solvents are, for example, benzene, toluene, o-, m- or p-xylene, cyclohexane, cyclopentane, pentane, hexane, heptane, octane, petroleum ether, acetone, isobutyl methyl ketone, diethyl ketone, diethyl ether, tert-butyl methyl ether, tert-butyl ethyl ether .
  • the siloxycarboxylate is immiscible with the salt of auxiliary base and hydrogen halide, so that the addition of a solvent can be dispensed with.
  • the particular advantage of the method according to the invention is that the separation of the salt from auxiliary base and hydrogen halide can be carried out by a simple liquid-liquid phase separation, so that eliminates a procedurally complex handling of solids.
  • the recovery of the free auxiliary base can be carried out, for example, by reacting the salt of the auxiliary base with a strong base, for. B. NaOH, KOH, Ca (OH) 2 , lime, Na 2 C0 3 , NaHC0 3 , K 2 C0 3 or KHC0 3 , optionally in a solvent such as water, methanol, ethanol, n- or iso-propanol, n-butanol, n-pentanol, butanol or pentanol isomer mixtures or acetone releases.
  • a strong base for. B. NaOH, KOH, Ca (OH) 2 , lime, Na 2 C0 3 , NaHC0 3 , K 2 C0 3 or KHC0 3 , optionally in a solvent such as water, methanol, ethanol, n- or iso-propanol, n-butanol, n-pentanol, butanol or pentanol isomer mixtures
  • the auxiliary base thus liberated if it forms its own phase, separated or, if it is miscible with the salt of the stronger base or the solution of the salt of the stronger base, are separated by distillation from the mixture. If necessary, the liberated auxiliary base can also be separated from the salt of the stronger base or the solution of the salt of the stronger base by extraction with an extractant, such as solvents, alcohols or amines.
  • an extractant such as solvents, alcohols or amines.
  • the auxiliary base can be washed with water or aqueous NaCl or Na 2 SO 4 solution and then dried, for. B. by removal of any water contained by means of an azeotropic distillation with benzene, toluene, xylene, butanol or cyclohexane.
  • the auxiliary base can be distilled before being used again in the process according to the invention.
  • the auxiliary base 2 -C suitable on the one hand to separate the hydrogen halide formed during the reaction and on the other hand as a nucleophilic catalyst in the Siloxyl mich the C 0 monocarboxylic acid.
  • the execution of the siloxylation is not limited and can be carried out according to the invention intercepting the released hydrogen halide and the optionally added acid batchwise or continuously and in air or under a protective atmosphere.
  • the siloxylation can be carried out without pressure but also at overpressure or underpressure. Preferably, work is carried out at normal pressure.
  • the reaction temperature is selected so that the salt of the auxiliary base with the halogenated hydrogen at the respective pressure is in liquid form, so that a liquid-liquid phase separation is possible.
  • Monoethylenically unsaturated C 3 -C 8 monocarboxylic acids and their siloxylation products are polymerizable compounds. Therefore, in the case of the siloxylation of monoethylenically unsaturated C 3 -C 8 monocarboxylic acids, it is important to pay attention to a sufficient polymerization inhibition and therefore to work in the presence of conventional amounts of polymerization inhibitors known per se. An unwanted polymerization is safety-critical due to the released large amount of heat.
  • ppm based on the monoethylenically unsaturated monocarboxylic acid, from 1 to 10,000 ppm, preferably from 10 to 5,000 ppm, more preferably from 30 to 2,500 ppm and in particular from 50 to 1,500 ppm of a suitable stabilizer are used per single substance.
  • Suitable stabilizers are, for example, N-oxides (nitroxyl or N-oxyl radicals, ie compounds which have at least one> N-0 group), such as 4-hydroxy-2,6,6,6-tetramethylpiperidine-N-oxyl , 4-Oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetoxy-2, 2,6,6-tetramethylpiperidine-N-oxyl, 2,2,6,6-tetramethylpiperidine-N -oxyl, 4,4 ', 4 "-tris (2,2,6,6-tetramethyl-piperidine-N-oxyl) phosphite or 3-oxo-2,2,5,5-tetramethylpyrrolidine-N- monohydric or polyhydric phenols optionally having one or more alkyl groups, such as alkylphenols, for example o-, m- or p-cresol (methylphenol), 2-tert-butylphenol, 4-tert-butylphenol
  • N-methyl-4-toluenesulfonamide or N-tert-butyl-4-toluenesulfonamide oximes, such as Aldoxime, Ketoxime or amidoximes, such as diethyl, methylethylketoxime or salicyladoxime, phosphorus-containing compounds such as triphenylphosphine, triphenyl phosphite, triethyl phosphite, hypophosphorous acid or Alkyl ester of phosphorous acids; sulfur-containing compounds such as diphenyl sulfide or phenothiazine; Metal salts, such as copper or manganese, cerium, nickel, chromium salts, for example chlorides, sulfates, salicylates, tosylates, acrylates or acetates, such as copper acetate, copper (II) chloride, copper salicylate, cerium (III) acetate or cerium (II) ethoximes,
  • polymerization inhibitor at least one compound from the group of hydroquinone, hydroquinone monomethyl ether, phenothiazine, 4-hydroxy-2, 2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine N-oxyl, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4-methylphenol, 6-tert-butyl-2, 4-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-methyl-4-tert-butylphenol, hypophosphorous acid, copper acetate, copper (II) chloride, copper salicylate and cerium (II) acetate, used.
  • an oxygen-containing gas preferably air or a mixture of air and nitrogen (lean air) may be present.
  • the educts of the siloxylation and any other auxiliary agents such as solvents or polymerization inhibitors present may be carried out as desired.
  • the C 2 -C 0 monocarboxylic acid and the auxiliary base in each case at least partially, preferably completely in each case, charged to a suitable reactor and heated.
  • the halosilane is metered in, wherein the dosage usually takes place within a few minutes to several hours, preferably 5 to 120 minutes, more preferably 10 to 60 minutes and most preferably 10 to 30 minutes continuously or in portions.
  • siloxylated C 2 -C 0 produced by the inventive method - monocarboxylic acids may be used as comonomers in copolymers for various applications, such as for waterproofing coatings or for the production of antifouling paints.
  • the following examples are intended to illustrate the invention without, however, limiting it.
  • Nonamethyltetrasiloxymethacrylate (MAD3M) 162 g (1.88 mol, 1.13 equivalents) of methacrylic acid and 136 g (1.66 mol) of 1-methylimidazole under argon were initially introduced into a 2 l double-shell plane-milling reactor. Subsequently, 546 g (purity: 97%; 1.65 mol) of 1-chlorononamethyltetrasiloxane were added within one minute, the internal temperature rising to 70 ° C. Thereafter, the jacket temperature was raised to 90 ° C and the reaction mixture stirred for one hour.

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  • Organic Chemistry (AREA)
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Abstract

L'invention concerne un procédé de production de siloxycarboxylates qui est caractérisé par la réaction d'acides monocarboxyliques en C2-C10 avec des halogénures de siloxane de la formule générale (I), Hal-(SiR2-O)x-SiR3 dans laquelle Hal est identique ou différent du fluor, chlore, brome ou iode, R représente hydrogène, alkyle en C1-C10 ou aryle en C6-C14 et x est un nombre entier de 1 à 20, avec formation d'halogénure d'hydrogène en présence d'une base auxiliaire, la base auxiliaire formant avec l'halogénure d'hydrogène un sel qui forme avec le siloxycarboxylate ou la dissolution du siloxycarboxylate dans un solvant approprié deux phases liquides non miscibles et est séparé par une séparation liquide-liquide. Le procédé permet une production simple et économique de siloxycarboxylates.
PCT/EP2011/073177 2010-12-20 2011-12-19 Procédé de production de siloxycarboxylates WO2012084773A1 (fr)

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GB1040147A (en) 1963-11-21 1966-08-24 Ici Ltd Preparation of halogen-containing compounds
WO2003062171A2 (fr) 2002-01-24 2003-07-31 Basf Aktiengesellschaft Procede de separation d'acides a partir de melanges reactionnels au moyen de liquides ioniques
WO2004000759A1 (fr) 2002-06-20 2003-12-31 Kemira Growhow Oyj Particules d'engrais enrobees
EP1380611A1 (fr) 2002-07-10 2004-01-14 SigmaKalon Group B.V. Procédé de préparation des monomères polyorganosilylé à fonctions carboxylate et polymères correspondants
WO2004056838A1 (fr) 2002-12-20 2004-07-08 Sigma Coatings B.V. Procede de production de monomeres de silyle carboxylate
JP2005047852A (ja) 2003-07-29 2005-02-24 Dow Corning Toray Silicone Co Ltd １−オルガノキシテトラシロキサンの製造方法
WO2005061416A1 (fr) 2003-12-19 2005-07-07 Basf Aktiengesellschaft Procede de separation d'acides contenus dans des melanges reactionnels chimiques, a l'aide de 1-alkylimidazoles
DE102007047866A1 (de) 2007-11-27 2009-05-28 Wacker Chemie Ag Herstellung von organofunktionellen Siliziumverbindungen
EP2182000A1 (fr) * 2008-10-29 2010-05-05 Shin-Etsu Chemical Co., Ltd. Composé de silyl (méth)acrylate contenant un groupe de silioxy doté d'un substituant volumineux et son procédé de production
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Publication number Priority date Publication date Assignee Title
GB1040147A (en) 1963-11-21 1966-08-24 Ici Ltd Preparation of halogen-containing compounds
WO2003062171A2 (fr) 2002-01-24 2003-07-31 Basf Aktiengesellschaft Procede de separation d'acides a partir de melanges reactionnels au moyen de liquides ioniques
WO2004000759A1 (fr) 2002-06-20 2003-12-31 Kemira Growhow Oyj Particules d'engrais enrobees
EP1380611A1 (fr) 2002-07-10 2004-01-14 SigmaKalon Group B.V. Procédé de préparation des monomères polyorganosilylé à fonctions carboxylate et polymères correspondants
WO2004056838A1 (fr) 2002-12-20 2004-07-08 Sigma Coatings B.V. Procede de production de monomeres de silyle carboxylate
JP2005047852A (ja) 2003-07-29 2005-02-24 Dow Corning Toray Silicone Co Ltd １−オルガノキシテトラシロキサンの製造方法
WO2005061416A1 (fr) 2003-12-19 2005-07-07 Basf Aktiengesellschaft Procede de separation d'acides contenus dans des melanges reactionnels chimiques, a l'aide de 1-alkylimidazoles
DE102007047866A1 (de) 2007-11-27 2009-05-28 Wacker Chemie Ag Herstellung von organofunktionellen Siliziumverbindungen
EP2182000A1 (fr) * 2008-10-29 2010-05-05 Shin-Etsu Chemical Co., Ltd. Composé de silyl (méth)acrylate contenant un groupe de silioxy doté d'un substituant volumineux et son procédé de production
WO2010072532A1 (fr) 2008-12-16 2010-07-01 Basf Se Procédé de silylation d'acides monocarboxyliques

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