EP2828270A1 - Procédé de production d'aminoalkylalcoxysilanes - Google Patents

Procédé de production d'aminoalkylalcoxysilanes

Info

Publication number
EP2828270A1
EP2828270A1 EP13709393.6A EP13709393A EP2828270A1 EP 2828270 A1 EP2828270 A1 EP 2828270A1 EP 13709393 A EP13709393 A EP 13709393A EP 2828270 A1 EP2828270 A1 EP 2828270A1
Authority
EP
European Patent Office
Prior art keywords
general formula
carbon atoms
atoms
ammonia
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13709393.6A
Other languages
German (de)
English (en)
Inventor
Elke Fritz-Langhals
Sotirios KNEISSL
Jürgen STOHRER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP2828270A1 publication Critical patent/EP2828270A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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 System
    • 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
    • C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O 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 System
    • 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

Definitions

  • the invention relates to the preparation of aminoalkylalkoxysilanes from the corresponding halo (haloalkyl) silanes by reaction with ammonia or organic amines and of alcohol.
  • Aminoalkylalkoxysilanes are important intermediates in the art.
  • the amine functionality allows the linkage with other synthesis building blocks, for example, for the construction of copolymers.
  • Alkoxy groups on the silicon take over the function of attachment to Polysiloxangerüste.
  • Starting materials for the synthesis of the aminoalkylalkoxysilanes are usually the corresponding alkoxy (haloalkyl) silanes which are converted into the aminoalkylalkoxysilanes using ammonia or of organic amines.
  • Alkoxy (haloalkyl) silanes required for the amination are prepared in the art via a separate, independent alkoxylation process.
  • 2003246789 describes the use of ammonia or organic amines in the alkoxylation, but this only serves to remove hydrogen chloride in the preparation of the corresponding alkoxychloroalkylsilanes,
  • aminoalkylalkoxysilanes as also disclosed in J. Org. Chem, 1971, 36, 3120-3126 - obtained by alcoholysis of silazanes.
  • the added alcohol does not participate in the reaction but serves only as an inert additive.
  • Starting material are the corresponding alkoxysilanes, which have an independent
  • the invention relates to a process for the synthesis of Arainoalkylalkoxysilanen of the general formula I.
  • R and R ' are hydrogen or a hydrocarbon radical having 1 to 12 C atoms, where nonadjacent carbon atoms may be replaced by nitrogen atoms or oxygen atoms,
  • R 1 hydrocarbon radical having 1 to 8 carbon atoms, where not
  • adjacent carbon atoms can be replaced by oxygen
  • Carbon atoms can be replaced by oxygen
  • X is a bivalent alkyl group having 1 to 12 C atoms
  • Y and Z are halogen
  • n are the values 0, 1 or 2.
  • the process offers the advantage that the ammonium halide formed remains partially or even completely dissolved in the presence of alcohol, so that the caking of ammonium chloride or amine hydrochlorides which hinders the reaction, as described for example in EP 1295889 in aminations, is avoided.
  • R and R ' are preferably independently of one another hydrogen or unbranched, branched or cyclic saturated or unsaturated alkyl group, aryl group or aralkyl group,
  • R and R ' have 1 to 6 carbon atoms.
  • R and R ' are hydrogen or alkyl group having 1 to 6 carbon atoms with non-adjacent carbon atoms through
  • Nitrogen can be replaced.
  • Examples of compounds of general formula III are ammonia, methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, tert. Butylamine, cyclohexylamine, 1,2-diaminoethane, 1, 2-diaminopropane, 1, 3-diaminopropane, 1,4-diaminobutane.
  • X is a divalent unbranched, branched or cyclic saturated or unsaturated alkyl group having 1 to 12 carbon atoms. More preferably, X is a divalent
  • R 1 is a
  • Phenyl group very particularly preferably R ⁇ is a
  • R 2 is a linear or branched alkyl group having 1 to 8 carbon atoms, non-adjacent carbon atoms may be replaced by oxygen. Particularly preferred
  • R 2 is a linear or branched alkyl group having 1 to 5 C atoms, preferably 1 to 2 C atoms may be replaced by oxygen. Particularly preferred are alkyl groups having 1 to 5 carbon atoms, more preferably 1 C atom is replaced by oxygen.
  • radicals R 2 are methyl, ethyl, n-propyl, i-propyl, 2-methoxyethyl or 2-methoxypropyl.
  • Y is preferably Cl or Br, particularly preferably Cl.
  • Z is preferably Cl or Br, particularly preferably Cl.
  • the process according to the invention is preferably carried out at temperatures of at least 30 ° C., more preferably of at least 50 ° C. and very particularly preferably of at least 70 ° C., and more preferably not more than 230 ° C., more preferably not more than 200 ° C., very particularly preferably not exceeding 170 ° C,
  • Aminoalkylalkoxysilanes of the general formula I is preferably at least 5 minutes, more preferably at least 10 minutes, most preferably at least 20 minutes, and preferably at most 100 hours, more preferably at most 30 hours, and most preferably at most 15 hours.
  • the pressure in the preparation of the aminoalkylalkoxysilanes of the general formula I is preferably at least 1 bar and at most 200 bar, more preferably at most 120 bar, in particular at most 90 bar. All stated pressures are absolute values.
  • the process according to the invention can be carried out, for example, as a batch reaction, as a semibatch reaction or continuously.
  • the reactants can be mixed simultaneously.
  • the reactants can be mixed simultaneously.
  • Alcohol of the general formula IV and ammonia or organic amine of the general formula III are presented as a mixture and then mixed with the silane of the general formula II, this can be done at ambient temperature or at elevated temperature.
  • the addition of the silane of the general formula II takes place at elevated temperature.
  • the reaction is carried out with mixing.
  • the mixing method known to those skilled in the art can be used.
  • the mixing can be done by stirring.
  • the reaction according to the invention can also be continuous
  • ammonia or organic amine is the
  • the excess of ammonia or organic amine used of the general formula III is preferably at most 200 equivalents, particularly preferably at most 100 equivalents.
  • the alcohol of the general formula IV is preferably at most 200 equivalents, particularly preferably at most 100 equivalents.
  • the alcohol of the general formula IV is preferably used in a molar amount of the group Z in the silane used general formula II of a maximum of 30 equivalents, particularly preferably used by a maximum of 15 equivalents.
  • solvents for example solvents, in proportions by weight of at least 1% and at most 500%, preferably at least 10% and at most 100%, based on the total reaction mass.
  • these components may be added before, during or after the reaction. They are preferably inert, i. there is no reaction with the reactants,
  • Examples of preferred solvents are saturated or olefinically or aromatically unsaturated linear or
  • Alkanes or their isomers or isomer mixtures Shellsol ® or Sarasol ® from Shell, solvent of the hydro-Seal ® -., Isane ® -, Ketrul ® -, Kerdane ® -, Spirdane ® - or Solvarex ® series from the company Total, heat transfer oils. eg Marlotherm ® SH Fa.
  • AVIA ⁇ , ⁇ - bis (trimethylsilyl) terminated poly (dimethylsiloxanes), such as WACKER AK oils, methyl tert-butyl ether, hydrofuren tetra-, 1,4-dioxane, ethylene glycol dibutyl ether, dioctyl ethers, diphenyl ethers, dibenzyl ethers, the isomeric ditolyl ethers, preferably as isomer mixtures.
  • WACKER AK oils methyl tert-butyl ether
  • hydrofuren tetra-, 1,4-dioxane ethylene glycol dibutyl ether
  • dioctyl ethers diphenyl ethers
  • dibenzyl ethers dibenzyl ethers
  • the isomeric ditolyl ethers preferably as isomer mixtures.
  • the aminoalkylalkoxysilane of the general formula I is partly or completely present at the end of the reaction as ammonium alkylalkoxysilane-halide.
  • the isolation of the aminoalkylalkoxysilane of the general formula I can be carried out in a manner known to those skilled in the art. The separation of formed in the reaction
  • Ammonium halide can be made, for example, by crystallization.
  • precipitants such as organic solvents can be used.
  • Another possibility is to add suitable bases after the reaction, which convert the ammonium alkylalkoxysilane halide into the aminoalkylalkoxysilane.
  • reaction mixture after the reaction as a base alkali metal alcoholate
  • the solid alkali metal halide formed is separated, for example, by filtration or by centrifugation and the liquid phase for purification of the product of the general formula I.
  • Formulas is the silicon atom tetravalent.
  • example 1 212 g (6.63 mol) of methanol are introduced into a 1 l autoclave, 269 g (15.8 mol) of ammonia are introduced in liquid form and the mixture is heated to 133 ° C. A pressure of 54 bar is reached. 4 g (0.54 mol) of chloro- (3-chloropropyl) -dimethylsilane in 20 min and allowed to after-react for a further 70 min at 133 ° C.
  • reaction mixture is analyzed by NMR spectroscopy in d4 -methanol: relative Proportion of (3-aminopropyl) methoxydimethylsilane 88%, di-3- (dimethylmethoxysilyl) propylamine 12%, tri-3- (dimethylmethoxysilyl) propylamine about 0.5%, conversion 99.7.
  • reaction mixture is neutralized with 194 g of a 30% sodium methoxide solution in methanol, filtered from the solid and the solution fractionally distilled,
  • reaction mixture is analyzed by gas chromatography:
  • reaction mixture is analyzed by NMR spectroscopy in d4-methanol: relative proportion (3-aminopropyl) methoxydimethylsilane 76, di-3 - (dimethylmethoxysilyl) propylamine 23%, tri-3 - (dimethylmethoxysilyl) propylamine ca. 2%; Sales> 99.7%.
  • reaction mixture is made alkaline with 30% sodium methylate solution in methanol and the clear product solution is analyzed by gas chromatography: (3-aminopropyl) methoxydimethylsilane 76%, di-3- (dimethylmethoxysilyl) ropylamine 23%, tri-3- ⁇ dimethylmethoxysilyl) propylamine 2% (3-methoxypropyl) methoxydimethylsilane 0.2%.
  • reaction mixture is made alkaline with 30% sodium methylate solution and the clear product solution is analyzed by gas chromatography: (3-aminopropyl) methoxydimethylsilane 76%, di-3- (dimethylmethoxysilyl) propylamine 23%, tri-3 - (dimethylmethoxysilyl) ropylamine 1 %, (3-methoxypropyl) methoxydimethylsilane 0.3%.
  • reaction solution was analyzed by NMR spectroscopy in d4-methanol: relative proportion (3-aminopropyl) methoxydimethylsilane 80%, di-3- (dimethylmethoxysilyl) propylamine 20%, conversion> 99.9%.
  • Chloro- (3-chloropropyl) dimethylsilane in 110 min. to and leaves at 133 ° C for 90 min. afterreact.
  • the final pressure is 60 bar.
  • Evaporate ammonia at 42-48 ° C and then pumped 581 g (1.71 Mol) of a 20% sodium ethylate solution in ethanol in the autoclave and allowed at 56 to 72 ° C 45 min, to react.
  • reaction solution is analyzed by NMR spectroscopy in d-methanol: relative proportion (3-aminopropyl) ethoxydimethylsilane 69, di-3- (dimethylmethoxysilyl) ropylamine 29%, tri-3- (dimethylmethoxysilyl) propylamine 2%; Sales quantitatively.

Abstract

L'invention concerne un procédé de synthèse d'aminoalkylalcoxysilanes de formule générale I, RR'N-X-Si(R1)n(OR2)3-n, et de leurs hydrohalogénures, en faisant réagir le silane halogéné (alkylhalogéné) de formule générale II, Y-X-Si(R1)nZ3-n, avec de l'ammoniaque ou avec une amine organique de formule générale III, R-NH-R', et avec un alcool de formule générale IV, R2-OH, où R et R' sont chacun un hydrogène ou un reste hydrocarbure de 1 à 12 atomes de carbone où des atomes de carbone non contigus peuvent être remplacés par des atomes d'azote ou d'oxygène, R1 est un reste hydrocarbure de 1 à 8 atomes de carbone où des atomes de carbone non contigus peuvent être remplacés par des atomes d'oxygène, R2 est un groupe alkyle de 1 à 8 atomes de carbone où des atomes de carbone non contigus peuvent être remplacés par des atomes d'oxygène, X est un groupe alkyle divalent de 1 à 12 atomes de carbone, Y et Z sont chacun un halogène, et n vaut 0, 1 ou 2.
EP13709393.6A 2012-03-19 2013-03-06 Procédé de production d'aminoalkylalcoxysilanes Withdrawn EP2828270A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012204315A DE102012204315A1 (de) 2012-03-19 2012-03-19 Verfahren zur Herstellung von Aminoalkylalkoxysilanen
PCT/EP2013/054503 WO2013139604A1 (fr) 2012-03-19 2013-03-06 Procédé de production d'aminoalkylalcoxysilanes

Publications (1)

Publication Number Publication Date
EP2828270A1 true EP2828270A1 (fr) 2015-01-28

Family

ID=47884302

Family Applications (1)

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EP13709393.6A Withdrawn EP2828270A1 (fr) 2012-03-19 2013-03-06 Procédé de production d'aminoalkylalcoxysilanes

Country Status (7)

Country Link
US (1) US9181284B2 (fr)
EP (1) EP2828270A1 (fr)
JP (1) JP2015510902A (fr)
KR (1) KR20140129387A (fr)
CN (1) CN104203963A (fr)
DE (1) DE102012204315A1 (fr)
WO (1) WO2013139604A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019154479A1 (fr) 2018-02-06 2019-08-15 Wacker Chemie Ag Procédé pour la préparation d'aminopropylalcoxysilanes

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015207673A1 (de) * 2015-04-27 2016-10-27 Wacker Chemie Ag Verfahren zur Herstellung von Aminogruppen aufweisenden Organosiliciumverbindungen
FR3115789B1 (fr) 2020-11-03 2024-04-12 Bostik Sa polymère HYDROCARBONE à blocs POLYETHER ET POLYOLEFINE COMPRENANT AU MOINS UN groupement terminal alcoxysilane
CN114478616A (zh) * 2022-01-12 2022-05-13 湖北江瀚新材料股份有限公司 一种3-(n-咪唑)丙基三乙氧基硅烷及其合成方法

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Publication number Priority date Publication date Assignee Title
DE2521399A1 (de) * 1975-05-14 1976-11-25 Bayer Ag Verfahren zur herstellung von aminoalkylsilanen
PL145671B1 (en) * 1985-05-15 1988-10-31 Univ Adama Mickiewicza Method of obtaining n-2-aminoethyl-3-aminopropylotrimetoxysilane
PL162752B1 (pl) * 1990-06-08 1994-01-31 Univ Adama Mickiewicza Sposób otrzymywania N-2-aminoetylo-3-aminopropylotrimetoksysilanu PL
CN1182088A (zh) * 1997-10-06 1998-05-20 南京曙光化工总厂 氨基硅烷偶联剂及其生产方法
DE10146087A1 (de) 2001-09-19 2003-04-03 Degussa Verfahren zur Herstellung von Aminoalkylsilanen
JP2003246789A (ja) 2002-02-26 2003-09-02 Daiso Co Ltd アルコキシシラン化合物の製造方法
FR2841244B1 (fr) 2002-06-21 2007-10-05 Rhodia Chimie Sa Procede de preparation d'organo dialkylalcoxysilane
FR2925513A1 (fr) 2007-12-20 2009-06-26 Bluestar Silicones France Soc Composition organopolysiloxanique vulcanisable a temperature ambiante en elastomere et nouveaux catalyseurs de polycondensation d'organopolysiloxanes.
CN102596972B (zh) * 2009-10-16 2014-12-10 道康宁公司 生产氨烷基烷氧基硅烷的方法

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019154479A1 (fr) 2018-02-06 2019-08-15 Wacker Chemie Ag Procédé pour la préparation d'aminopropylalcoxysilanes
US11440926B2 (en) 2018-02-06 2022-09-13 Wacker Chemie Ag Method for preparing aminopropylsilanes

Also Published As

Publication number Publication date
WO2013139604A1 (fr) 2013-09-26
DE102012204315A1 (de) 2013-09-19
KR20140129387A (ko) 2014-11-06
US9181284B2 (en) 2015-11-10
US20150051418A1 (en) 2015-02-19
JP2015510902A (ja) 2015-04-13
CN104203963A (zh) 2014-12-10

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