EP2438074A1 - Procédé de préparation d'amino-organo-silanes - Google Patents

Procédé de préparation d'amino-organo-silanes

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Publication number
EP2438074A1
EP2438074A1 EP10721166A EP10721166A EP2438074A1 EP 2438074 A1 EP2438074 A1 EP 2438074A1 EP 10721166 A EP10721166 A EP 10721166A EP 10721166 A EP10721166 A EP 10721166A EP 2438074 A1 EP2438074 A1 EP 2438074A1
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EP
European Patent Office
Prior art keywords
general formula
base
atoms
amine
groups
Prior art date
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Application number
EP10721166A
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German (de)
English (en)
Inventor
Michael Stepp
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Wacker Chemie AG
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Wacker Chemie AG
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Publication of EP2438074A1 publication Critical patent/EP2438074A1/fr
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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
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
    • 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
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • 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
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • 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
    • C07F7/20—Purification, separation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the invention relates to a process for the preparation of aminoorganosilanes, by reacting amines with (haloorganyl) silanes and liberating the by-produced ammonium halide of the amine with a base.
  • the procedure is generally such that at least 2 moles of amine or ammonia are used per mole of chloro-functional organosilane, so that in addition to the formation of amino-functional organosilane enough aminic component for the conversion of the substituted chlorine in the corresponding amine hydrochloride or ammonium chloride available ,
  • GB 686,068 A describes a process for the reaction of corresponding (chloromethyl) - or (bromomethyl) triorganosilanes with ammonia, a primary or secondary amine at temperatures of at least 5O 0 C for the preparation of said (aminoorganyl) -, (N-Organylaminoorganyl) - and (N, N-Diorganylaminoorganyl) triorganylsilanes.
  • These are usually the (chloromethyl) - or
  • (aminomethyl) silane derivatives are prepared by reacting a (chloromethyl) or ⁇ bromomethyl) silane derivative with ammonia or a primary amine.
  • the reaction is carried out at temperatures of 80 or 100 ° C in a period of 3 or 2 hours, wherein the amine in a molar excess of 1: 3.2 to 6 was already completely submitted at the beginning of the reaction.
  • US 6452033 A describes the preparation of Aminoethylaminoorganyl-triorganylsilanes by the reaction of the corresponding chlorofunctional organosilanes with ethylenediamine, the o.g. Phase separation is used for the separation of the hydrochlorides in various ways.
  • Phase separation is used for the separation of the hydrochlorides in various ways.
  • a disadvantage of this process is the fact that it is limited to silanes which have an ethylenediamine unit.
  • Salt phase which is why a costly workup of the salt phase is necessary for the quantitative recovery of the amines.
  • the distillative removal of the excess amine before the addition of the base for a largely lossless recovery of the amine is required.
  • the invention relates to a process (I) for the preparation of aminoorganyltriorganylsilanes of the general formula (1)
  • R is an acyloxy radical or an alkoxy radical having in each case 1-10 C atoms
  • R 1 is a hydrocarbon radical having 1-10 carbon atoms
  • R2 is a divalent Kohlenwasseretextt having 1-10 C atoms
  • R 3 are independently hydrogen or a
  • Cyclus may also contain further heteroatoms, NH groups or NR 2a groups,
  • R 2a is a divalent hydrocarbon radical having 1-10 C atoms, n is a number equal to 0, 1, 2 or 3 and "X is chlorine, bromine or iodine, wherein the reaction comprises the successive steps: a) conversion of 1,1 to 100 mol of the amine of the general formula (2) per mole of (haloorganyl) silane of the general formula (3) at a temperature of 0 to 25O 0 C, wherein in addition to the silane of the general formula (1) as a byproduct, the ammonium halide of the amine is formed general formula (2 ⁇ , b) adding a base (B) to the reaction mixture, wherein the base (B) contains at least 2 moles of basic functional groups per mole, resulting in a Utnsalzung in which the amine of the general formula (2) is liberated and base (B ) is added in an amount such that at least 1.6 moles of the basic functional groups of the base (B) are present as hydrogen halide adduct, c) distilling off
  • the hydrocarbon radicals R 1 , R 2 , R 2a , R 3 , R 4 may be saturated or unsaturated, branched or unbranched, substituted or unsubstituted.
  • the hydrocarbon radicals R 1 , R 3 , R 4 may be alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl , tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert.
  • Hexyl radicals such as the n-hexyl radical
  • Heptyl radicals such as the n-heptyl radical
  • Octyl radicals such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical
  • Nonyl radicals such as the n-nonyl radical
  • Decyl radicals such as the n-decyl radical
  • Dodecyl radicals such as the n-dodecyl radical
  • Octadecyl radicals such as the n-octadeeyl radical
  • Cycloalkyl radicals such as cyclopentyl, cyclohexyl,
  • Cycloheptyl radical and methylcyclohexyl radicals alkenyl radicals, such as the vinyl, 1-propenyl and the 2-propenyl radical; Aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radicals; Alkaryl radicals, such as o-, m-, p-tolyl radicals; Xylyl radicals and ethylphenyl radicals; and aralkyl radicals, such as the benzyl radical, the alpha- and the beta-phenylethyl radical; and combinations thereof linked by heteroatoms such as N, O, S, P.
  • Aryl radicals such as the phenyl, naphthyl, anthryl and phenanthryl radicals
  • Alkaryl radicals such as o-, m-, p-tolyl radicals
  • Xylyl radicals and ethylphenyl radicals and aralkyl radical
  • Hydrocarbon radicals R 1 , R 3 , R 4 preferably have 1-6, in particular 1-3 C atoms.
  • R 1 is the methyl, ethyl, iso and n-propyl, iso and n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, benzyl or allyl residue.
  • radicals R 3 and R 4 are preferably from the preferred
  • R 3 or R 4 is hydrogen.
  • the radical R 3 is a phenyl or cyclohexyl radical and the radical R 4 is hydrogen.
  • radicals R 3 and R 4 may be directly or by
  • the cyclic structures -NR 3 R 4 preferably have 5 to 10 ring atoms, in particular 5, 6 or 8 ring atoms. Examples of these are the morpholino, piperidino or pyrrolidino radical, which are also preferred.
  • the radical -NR 3 R 4 is preferably the N, N-bis (N 1 , N 1 -dimethylaminopropyl) radical.
  • the radical R preferably has the meaning of OR 1.
  • R * is a methoxy, ethoxy, iso and n-propoxy, butoxy, phenoxy, benzyloxy or allyloxy radical.
  • the radicals R 2 and R 2a is preferably a divalent hydrocarbon radical with 1-6 C atoms # especially a methylene, Bthylen- and propylene group, more preferably the methylene group.
  • the radical X is preferably chlorine or bromine, in particular chlorine.
  • n preferably has the value 1, 2 or 3.
  • the amine of general formula (2) is preferably in excess, i. in molar ratios of preferably at least 1.5 au 1, more preferably at least 2 to 1, particularly preferably at least from 3 to 1 and preferably at most 50 to 1, more preferably at most 20 to 1, particularly preferably at most 10 to 1 ,
  • a further subject of the invention is a process ⁇ II ⁇ for the preparation of cyclic arainosilanes of the general formula (4)
  • R 5 is a bivalent hydrocarbon radical having 1-10 C atoms, in which the hydrocarbon chain by carbonyl groups,
  • Carboxyl groups oxygen atoms, NH or NR 8 groups may be interrupted,
  • R 6 is hydrogen or a hydrocarbon radical having 1-10 C atoms, which may be substituted by halogen atoms, OH groups, and groups -NH 2 -, -NHR 8 , NR 8 2 ,
  • R 7 is hydrogen or a hydrocarbon radical having 1-10 C-atoms, with halogen atoms, OH groups, and groups
  • -NH 2 , -NHR 8 , NR 8 2 may be substituted
  • R is a hydrocarbon radical, an alkoxy radical having in each case 1-10 C atoms,
  • R 8 is a hydrocarbon radical having 1-10 C atoms
  • Y 1 and Y 2 are chlorine, bromine or iodine
  • the reaction comprising the successive steps: a) reacting 1.1 to 1000 mol of the amine of the general formula (5) per mole of the (haloorganyl) silane of the general formula ( 6) at a temperature of 0 to 300 0 C, wherein in addition to the silane of the general formula (4) as a by-product, the ammonium halide of the amine of the general formula (5) is formed, b) adding a base (B) to the reaction mixture, wherein the base (B) contains at least 2 moles of basic functional groups per mole, resulting in a salification, wherein the amine of the general formula (5) is liberated and base (B ) is added in an amount such that at least 1.6 moles of the basic functional groups of the base (B) are present as Halogenwasserst ⁇ ff adduct, c) distilling off the amine of the general formula (5) from the reaction mixture, d) addition of base
  • R 5 , R 6 and R 7 may be saturated or unsaturated, branched or unbranched, substituted or unsubstituted.
  • R 1 is a propylene or butylene group.
  • R 6 is preferably hydrogen or an eyelike or linear alkyl radical having 1-6 carbon atoms or a 3-
  • R 7 is preferably hydrogen or a cyclic or linear alkyl radical having 1-6 carbon atoms.
  • R 'and R 1 are also examples and preferred radicals for R.
  • the examples and preferred radicals given for R 1 are also examples and preferred radicals for R 8 .
  • the radicals Y 1 and Y 2 are preferably chlorine or bromine, especially chlorine.
  • the aminosilane of the general formula (5) is N- ((3-aminopropyl) -dimethylsilyl) -2,2-dimethyl-1-aza-2-silacyclopentane.
  • the product in step a) is preferably formed from 2 molecules of chlorosilane with R s equal to propylene, R equal to methyl and Y 1 and Y 2 equal to chlorine and 2 ammonia molecules, resulting in 4 molecules of ammonium chloride.
  • the amine of the general formula (5) is preferably in excess, that is to say in excess thereof. in molar ratios of preferably at least 1.2 to 1, particularly preferably at least 1.6 to 1, in particular at least 2 to 1 and particularly preferably at least 3 to 1 and preferably at most 500 to 1, particularly preferably at most 100 to 1, in particular at most 10 to 1, in particular preferably used at most 6 to 1.
  • the invention further provides a process (III) for the preparation of silylorganoamines of the general formula (7)
  • R 01 , R 02 is an alkoxy radical each having 1-10 C atoms
  • R 11 , R 15 is a hydrocarbon radical having 1-10 C atoms
  • R 12 is a bivalent hydrocarbon radical having 1-10 C atoms, in which the hydrocarbon chain may be interrupted by carbonyl groups, carboxyl groups, oxygen atoms or sulfur atoms,
  • R 14 is a bivalent hydrocarbon radical having 1-10 C atoms, in which the hydrocarbon chain may be interrupted by carbonyl groups, carboxyl groups, oxygen atoms, sulfur atoms, NH or NR 18 groups, wherein R 18 , the same
  • R 13 is hydrogen, a hydrocarbon radical having 1-10 carbon atoms, or a radical of the general formula R 03 R 16 0 3-0 Si-R 17 - wherein R 16 belongs to the same meaning as R 11 and R 15,
  • R 17 has the same meaning as R 12 and R 14 , and
  • R 03 has the same meaning as R 01 and R 02 and s, t, o are independently a number equal to 0, 1, 2 or 3 and Z is chlorine, bromine or iodine, the reaction comprising the successive steps: a) reacting I 1 I to 100 moles of the amine of the general formula (8) per mole of the (haloorganyl) silane of the general formula (9) at one temperature from 0 to 250 0 C, whereby in addition to the silylorganoamine the general formula (7) as a byproduct of the ammonium halide of the amines of the general formula (8) is formed, b) adding a base (B) to the reaction mixture, wherein the base (B) at least Containing 2 moles of basic functional groups per mole, resulting in a salification, in which the amine of the general formula (8) is liberated and base (B) is added in an amount such that at least 1.6 moles of the basic functional groups of C) distilling off the amine of the general formula (8) from the
  • the hydrocarbon radicals R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 may be saturated or unsaturated, branched or unbranched, substituted or unsubstituted.
  • the hydrocarbon radicals R 11 , R 13 , R 15 , R 16 may be alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso Butyl, tert. Butyl, n-pentyl, iso- Pentyl, neo-pentyl, tert.
  • Hexyl radicals such as the n-hexyl radical
  • Heptyl radicals such as the n-heptyl radical
  • Octyl radicals such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical
  • Nonyl radicals such as the n-nonyl radical
  • Decyl radicals such as the n-decyl radical
  • Dodecyl radicals such as the n-dodecyl radical
  • Octadecyl radicals such as the n-octade ⁇ yl radical
  • Cycloalkyl radicals such as the cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals
  • Alkenyl radicals such as the vinyl, 1-propenyl, 2-propenyl and the l ⁇ -undecenyl radical
  • the hydrocarbon radicals R 11 , R 13 , R 15 , R 16 preferably have 1-6, in particular 1-3 C atoms.
  • R ll # R 15, R 16 is a methyl, ethyl, iso and n-propyl, iso and n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl , Benzyl or allyl radical.
  • the radical R 13 is preferably selected from the preferred radicals of RlI 1 R 15 f R 16 and furthermore selected from hydrogen, cyclohexyl or phenyl radicals or the radical of the general formula R 03 3 or R 16 o Si-R 17 . More preferably, the radical R 13 is hydrogen.
  • radicals R 01 , R 02 , R 03 preferably have the meaning of
  • R 01 , R 02 , R 03 are preferably independently of one another methoxy, ethoxy, iso and n-propoxy, butoxy, phenoxy, benzyloxy or allyloxy. Particularly preferred are the Radicals R 01 , R 02 , R 03 are the same.
  • the radicals R 12 , R 14 , R 17 is preferably a divalent hydrocarbon radical having 1-6 C atoms, in particular a methylene, ethylene and propylene group, particularly preferably the methylene and the propylene groups. Group.
  • the radical Z is preferably chlorine or bromine, in particular chlorine.
  • B, t, o independently of one another preferably have the value 0, 1 or 2, particularly preferably 0 or 1.
  • the amine of the general formula (8) is preferably in excess, i. in molar ratios of preferably at least 1.5 to 1, more preferably of at least 2 to 1, in particular of at least 3 to 1 and preferably at most 50 to 1, particularly preferably at most 20 to 1, in particular at most 10 to 1 used.
  • the Silylorganoamine tend especially at elevated temperatures and under vacuum, ie conditions such as those occurring during distillation, to an inter- or intramolecular displacement of an alkoxy group by the NH group to form oligomers and cycles with Si-N linkage.
  • the silylorganoamine of general formula (7) formed azasilacycles of the general formulas (10a) and (10b)
  • per mole azasilacycles of the general formulas (10a) and (10b) at least l, 0 mole and not more than 1 mole l, in particular at most 1.05 mol of alcohol selected from R 01 -H, R ° 2 is -H or
  • the ring-opening reactions of the azasilacycles with alcohol formed from the target product of the general formula (7) usually proceed under mild conditions in a temperature range of at least 10 ° C., in particular at least 15 ° C and preferably at most 100 0 C, in particular at most 50 0 C, the optimum reaction conditions are easily determined in individual cases by preliminary experiments.
  • Residual R ⁇ consists of a freely mobile chain with at least 3 atoms, this tends in particular at elevated temperatures and under vacuum, so conditions such as. occur during distillation, to an inter- or intramolecular displacement of an alkoxy group by the NH group to form oligomers and cycles with Si-N linkage.
  • the cyclic structure can be reopened to the (aminoorganyl) silane of the general formula (8).
  • the addition of one with respect to the azasilacycle suffices of the general formula (11) stoichiometric amount of alcohol, so that contamination of the (aminoorganyl) silane can be avoided by an excess of alcohol.
  • per mole of azasilacycles of the general formula (11) at least 1.0 mol and at most 1.1 mol, in particular at most 1.05 mol of alcohol Given R02-H.
  • azasilacyclene-free or poor (aminoorganyl) silane of the general formula ⁇ 8 ⁇ it is also possible to add an excess of alcohol to the distilled starting material and to measure the excess after the reaction has ended under gentler conditions than the distillation conditions of azasilacycles of the general formula ( 11), so that recycling is largely avoided.
  • the ring-opening reactions of the azasilacycles the general formula (11) with alcohol extend generally under mild conditions in the temperature range of at least 1O 0 C, isbesondere at least 15 0 C and preferably at most 100 0 C, particularly at most 5O 0 C, the optimal reaction conditions are carried in the individual case Preliminary tests easy to determine.
  • the hydrohalide of base (B) can be separated in process (I), (II) or (III) simply and largely without loss as a liquid from the reaction mixture.
  • step a) The ammonium halide of the amine of the general formulas (2), (5) or (8) typically precipitates as insoluble solid in step a).
  • step c) with increasing depletion of the mixture of amine of the general formulas (2), (5) or (8) increasingly the hydrohalide of the base (B) is formed, wherein after most removal by distillation of the liberated amine due to the selected stoichiometry
  • Hydrogen halide adduct is that it is among the Distillation conditions of the amine of the general formulas ⁇ 2 ⁇ , (5) or (8) not decomposed and remains in the distillation residue.
  • step b) If more than one mole of basic functional groups in base (B) have been added per mole of silane of the general formulas (3), (6) or ⁇ 9 ⁇ in step b) and thus not all basic functional groups of the base (B) as Hydrogen halide adduct present and the base (B) under the distillation conditions of the amine of the general formulas (2), (5) and (8) is volatile, can occur during step c) disproportionation:
  • the free basic functional groups present in the base (B) are increasingly converted into their hydrogen halide adducts, and the base (B) is distilled off until all the basic functional groups have been converted into their hydrohalides.
  • some of the functional basic groups present in the added base (B) can already be used as
  • Hydrogen halide adduct present. It is only essential that sufficient free basic functional groups for the salification of the hydrohalide of amine of the general formulas (2), (5) or (8) are available.
  • step d) By adding further base (B) in step d) after the complete distillation of the amine of the general formulas (2), (5) or (8), the ratio of hydrogen halide to base (B) decreases and the melting point or the viscosity of the resulting hydrohalide of the base (B) decreases continuously with increasing metering amount of base (B).
  • the hydrogen halide exchange usually takes place very rapidly, so that during the metering of the base (B) the effect of lowering the melting point or reducing the viscosity can already be traced.
  • the amount of base (B) added in step d) is preferably at least 20%, in particular at least 50% and preferably at most 200%, in particular at most 150% of the amount of base (B) used in step b).
  • the optimum conditions for the respective requirements, the expert can determine by simple preliminary tests.
  • the phase separated in step e) contains at least 95% by weight, in particular at least 98% by weight, of the hydrohalide of the base (B) in step d).
  • a particular advantage of the process according to the invention is the complete recovery of the amine of the general formulas (2), (5) or (8).
  • step c) the amine can be separated from the other reactants such as base (B) and target product of the general formulas (1), (4) or (7) and other minor constituents in a purity, the reuse as Trustmateria.1 allowed for a follow-up approach.
  • steps a) and b) can be carried out successively or simultaneously. Also conceivable is a time-shifted implementation, in which step b), ie, the addition of the base (B), although after the start but before the end of step a) is started.
  • step b) ie the addition of this oligoamine, is preferably carried out after the reaction in step a) ) used in process step b) form salts which form at ⁇ 150 ° C. particularly preferably ⁇ 100 0 G or ⁇ 90 0 C form pesticides are particularly preferably used bases (B) which form salts in process step d), the form at temperatures ⁇ 150 0 C more preferably ⁇ 100 0 C and ⁇ 90 0 C liquids.
  • An essential property of the bases (B) is to form (poly) hydrohalides, which (under the distillation conditions of the amine of general formula 2), (5) or (8) in process step c) or of the silane of the general formulas (1), (4) or (7) do not decompose and remain in the distillation residue.
  • Step a) of the process according to the invention is preferably carried out at temperatures of at least 50 ° C.
  • temperatures of at least 8O 0 C and preferably at most 220 0 C, more preferably at most 15O 0 C have proven to be particularly advantageous.
  • step a) is usually exothermic, it is preferably carried out with cooling.
  • the steps b), c) and d) of the inventive methods are, independently of one another, preferably at temperatures of at least 0 ° C, more preferably of at least 20 0 C, especially from 5O 0 C and preferably at most 250 0 C, particularly preferably at most 150 0 C, in particular at most 100 0 C performed.
  • step b) preferably remains constant within a temperature range of preferably 30 ° C., particularly preferably 20 ° C. Since step b) is usually exothermic, it is preferably carried out with cooling. While the steps a), b), and e) are preferably carried out under the pressure of the surrounding atmosphere, the distillation of the amine of the general formulas (2), (5) or (8) is preferably carried out under reduced pressure to the thermal To keep the burden as low as possible and, where appropriate, to increase the space-time yield by shortening the heating phase.
  • step d) is carried out at atmospheric pressure or a pressure of 100 to 900 mbar, more preferably it is carried out at a pressure at which the reaction mixture boils at reflux.
  • the process according to the invention can also have one or more of the following additional process steps: a1) If the amine of the general formulas (2), (5) or (8) has been used in excess in step a), this can The residue of the general formula (2), (5) or (S) can be obtained by fractional distillation of other secondary constituents, such as Base (B) are further purified. d) Adding one or more nonpolar solvents (L) to the product-containing phase.
  • the additional solvent (L) can be carried out before or after process steps a), al) b) and d).
  • step a) and b) preferably to reduce the viscosity of the mixture in order to ensure a good mixing or flowability and in step d) preferably to the solubility of the respective salts or in the organic phase to reduce.
  • the salts precipitated in this step are preferably separated in an additional separation step, eg filtration.
  • the amounts of salt to be separated off are small and the separation is correspondingly simple. If the addition of the nonpolar solvent is carried out before or during step d), the respective salts from the product phase are forced into the liquid phase, which consists essentially of the hydrohalide of the base (B), and are separated together therewith.
  • Suitable nonpolar solvents are linear and cyclic hydrocarbons, such as (cyclo) aliphatics, aromatics, and alkylaromatics, such as paraffins, pentane, hexane, heptane, octane, decane, 10-undecene, isooctane, cyclohexene, decalin, cyclohexane, methylcyclohexane, benzene, toluene , o-xylene, m-xylene, p-xylene or mixtures thereof.
  • linear and cyclic hydrocarbons such as (cyclo) aliphatics, aromatics, and alkylaromatics, such as paraffins, pentane, hexane, heptane, octane, decane, 10-undecene, isooctane, cyclohexene, decalin, cyclohexane,
  • step e) By fractional distillation or crystallization of in step e) by phase separation isolated Proäuktphase Silane of the general formulas (1), (4) or (7) can be further purified. This is preferably used for the removal of residual amounts of amine of the general formulas (2), (5) or (8), base (B) and / or optionally added nonpolar solvent (L), provided that in the application of the products of the general Disturb formulas (1), (4) or (7).
  • step c) • further purification steps of the distillative after the first distillation (step c)) not yet sufficiently clean amine fractions; Additional addition of aliphatic ketones or aldehydes to the product-containing phase after step e) or else to the amine fractions distilled under step c).
  • the base (B) added in step b) is a compound containing primary amino groups, this measure can serve to convert residues of the base (B) still present in these phases into the corresponding imines. The latter are often easier to distillate from the products and especially from the excess used and / or at step b) again liberated amines of the general formulas (2), (5) or (8) as the base (B) itself.
  • step b) recovery of the base used in step b) (B), preferably by salting the resulting hydrohalide of this base with strong Bases, such as alkali metal or alkaline earth metal hydroxides, carbonates, bicarbonates, alcoholates, etc.
  • Bases such as alkali metal or alkaline earth metal hydroxides, carbonates, bicarbonates, alcoholates, etc.
  • the respective bases can be used in bulk or in aqueous or non-aqueous solution or suspension. If aqueous solutions are used and / or water is liberated during the reaction, this is preferably separated by distillation from the base (B). If ethylene diamine was used as the base (B), this separation by distillation is preferably carried out at such a high pressure that ethylenediamine and water no longer form an azeotrope.
  • the base (B) is a compound, e.g. to an amine which is itself reactive with the silane of the general formulas (3), (6) or (9), then the amine of the general formulas (2), (5) or (8) by the Process steps are preferably purified to such an extent that the content of base (B) in the amines of the general formulas (2), (5) or (S) is below 3%, preferably below 1% and especially below 0.5%.
  • the amine of the general formulas (2), (5) or (8) is present in excess with respect to the (haloorganyl) silane of the general formulas (3), (6) or ( 9) used.
  • step b) solid ethylenediamine bishydrohalide and the amine of general formula ⁇ 2 ⁇ , (5) and (8), respectively, are completely liberated.
  • step d) After distilling off the amine in step c), in which the amine is preferably obtained in a purity so that it can be used directly again, in step d) the distillation residue with as much ethylenediamine as base (B) with respect to (haloorganyl) silane (3) , (S) or (9) added to a second liquid phase forms on Ethylendiaminhydrohalogenid whose halide is established silane according to the ratio ethylenediamine / (haloorganyl ⁇ . preferably, at least 0 r 5 equivalents and at most 2, more preferably at most 1 , 5, in particular at most 0.8 equivalents of ethylenediamine with respect to (haloorganyl) silane (3), (6) or (9)) used.
  • the salt phase is separated off (step e)) and the product phase is optionally purified by distillation.
  • the process may be both batchwise, e.g. in stirred kettles, as well as being carried out continuously.
  • the latter for example, by the steps a), b) and optionally further steps (see above) in a tubular reactor or a Rhackgefäßkaskade done.
  • the individual substances are here together or else - preferably - metered and mixed in succession.
  • suitable methods e.g. using sedatives or settling vessels, decanters, etc., known and widely described in the literature,
  • the water content of the amines of the general formulas (2), (5) or (8) to be used is preferably from 0 to 20 000 ppm, preferably from 0 to 5000 ppm, particularly preferably from 0 to 1000 ppm.
  • the pK b value of the amines of the general formulas (2), (5) or (8) to be used is preferably greater than that of the base (B), preferably at least 1 pK b unit greater, particularly preferably 2 pK b units greater.
  • the base (B) chosen are compounds whose boiling point is determined both by the product (1), (4) or (7) and by the amine of the general formulas (2), (5) or (8) by at least 40 0 C, preferably at least 60 0 C and more preferably at least 90 0 C different, so that residues of the base (B), which remain in the phase separation in step e) in the organic phase, distillation sufficiently well both from the product of the general formulas (1), (4) or (7) as well as from the amine of the general formulas (2), (5) or (8).
  • oligoamines (O) containing ethylene or propylenediamine units or mixtures thereof.
  • Oligoamines (O) 1 to 20, in particular 1 to 10 ethylene or Propylendiaminein fraud.
  • Preferred oligoamines (O) are ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diazabicyclooctane, pentamethyldiethylenetriamine, 1,2-propylenediamine, 2,2-dimethylpropan-1,3-diamine, 1,2-dimethylimidazole, N-methylimidazole, N4-amine ( from BASF SE, Germany).
  • Ethylenediamine is particularly preferably used as base (B).
  • ethylenediamine exhibits the following surprising combination of properties: The addition of ethylenediamine leads in step b) to a substantially complete salification, if only the particularly preferred amount of ethylenediamine of 0.5-0.8 equivalents, based on the amount of (haloorganyl) silane of the general formulas (3), (6) or (9) is added.
  • step b) In the course of the formation of the ethylenediamine bishydrohalide in step b), especially in the case of aniline derivatives, the thermal stability increases markedly, which represents a great advantage with regard to thermal reaction safety. Obviously, the formation of thermally unstable anilinium salts (ammonium compounds of the silanes of the general formula (1), (4) or (7)) shifts to higher temperatures.
  • Hydrohalide can be easily liquefied by further addition of ethylenediamine (the salt phase obtained in step d) has a melting point of about 80 0 C).
  • the liquid salt phase separates completely after a few minutes from the organic phase and can thus be separated without a large and therefore costly time required for a phase separation.
  • Aminoorganylsilane of the general formula (7) can be obtained in good to very good yields.
  • the methods can be implemented on an industrial scale simply and safely.
  • the purity of the inventively prepared Aminoorganyl- triorganylsilane of the general formula (1), the cyclic Aminosilanes of the general formula (4) and the Aminoorganylsilane of the general formula (7) is preferably at least 85%, more preferably at least 90%. This purity can be increased to over 90% by means of an optional downstream distillation step e) of the product.
  • the process according to the invention has the advantage over the prior art that the majority of the by-produced ammonium salts of the amines of the general formulas (2), (5) or (8) no longer have to be separated off as solid, which is particularly true on an industrial scale in the case of poorly crystallizing ammonium salts (eg the ammonium salts of aniline) is usually expensive and expensive. By resalling, two liquid phases can now be separated from each other. In addition, washing steps of the filter cake with additional ein responsibledem solvent are unnecessary. At the same time, the use of optimized excesses of amine according to the general formulas (2), (5) and (8) can significantly reduce the formation of by-products.
  • poorly crystallizing ammonium salts eg the ammonium salts of aniline
  • the inventive method is suitable, the often comparatively costly amines of the formulas (2), (5) and (8), which would be consumed in step a) for the formation of the corresponding ammonium salts, by the salification with the usually relatively cheap base (B), eg Ethylene diamine, thereby making it available for recycling. If necessary, the resulting hydrohalides of the base (B) can also be recovered by known processes, so that by-products of the base (B)
  • Phenylaminomethyltrimethoxysilane whose purity was determined to be 96.6%.
  • Example 3a not according to the invention: In a comparative experiment, after the implementation of
  • Decomposition enthalpy of -1312 kJ / kg corresponds to an adiabatic temperature increase of approx. 875 ° C.
  • Prolonged exposure to heat, as is usual with distillation processes, can lead to a progressive lowering of the decomposition temperature (onset temperature). This means that without the addition of ethylenediamine at the o.g. Method, i. without the conversion of aniline hydrochloride into ethylenediamine bishydrochloride is a high security risk.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)

Abstract

L'invention a pour objet un procédé (a) de préparation d'organyl-triorganyl-amino-silanes de la formule générale (1) R´3-nR1 nSi -R2 -NR3R4 (1), un procédé (b) de préparation d'amino-silanes cycliques de la formule générale (4) et un procédé (III) de préparation de silyl-organo-amines de la formule générale (7) R01 3-tR11 tSi-R12-NR13-R14-SiR02 3-sR15 s (7), qui consistent à faire réagir des amines avec des halogène-organyl-silanes ; R´, R1, R2, R3, R4, R, R5, R6,R01, R02, R11, R12, R13, R14, R15, n et s ayant les significations indiquées dans les revendications 1 à 3. Après la réaction, les halogénures d'ammonium des amines produits sous forme de produits dérivés sont libérés par addition d'une base (B) au mélange réactionnel ; les amines sont enlevés du mélange réactionnel par distillation ; deux phases liquides sont formées par une addition supplémentaire de la base (B) au mélange réactionnel, une phase contenant au moins 90 % en poids d'hydro-halogénures de la base (B) et cette phase étant séparée.
EP10721166A 2009-06-04 2010-06-01 Procédé de préparation d'amino-organo-silanes Withdrawn EP2438074A1 (fr)

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DE102009026755A DE102009026755A1 (de) 2009-06-04 2009-06-04 Verfahren zur Herstellung von Aminoorganosilanen
PCT/EP2010/057582 WO2010139674A1 (fr) 2009-06-04 2010-06-01 Procédé de préparation d'amino-organo-silanes

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DE102009000500A1 (de) * 2009-01-30 2010-08-05 Wacker Chemie Ag Verfahren zur Herstellung von Bis- und Tris(silylorgano)aminen
US9337018B2 (en) * 2012-06-01 2016-05-10 Air Products And Chemicals, Inc. Methods for depositing films with organoaminodisilane precursors
JP7295965B2 (ja) * 2019-02-13 2023-06-21 ヌーリオン ケミカルズ インターナショナル ベスローテン フェノーツハップ エチレンアミン化合物を製造するための方法
JP7279790B2 (ja) * 2019-07-02 2023-05-23 信越化学工業株式会社 オルガノポリシロキサン化合物、該化合物を含む組成物及びそれらの製造方法

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US20120071650A1 (en) 2012-03-22
CN102459287A (zh) 2012-05-16
DE102009026755A1 (de) 2010-12-09
KR20120032513A (ko) 2012-04-05
JP2012528823A (ja) 2012-11-15
KR101368101B1 (ko) 2014-02-27
JP5519006B2 (ja) 2014-06-11
US8981138B2 (en) 2015-03-17
WO2010139674A1 (fr) 2010-12-09

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