[go: up one dir, main page]

WO2018033199A1 - Procédé de préparation de composés aminoorganosilicium secondaires - Google Patents

Procédé de préparation de composés aminoorganosilicium secondaires Download PDF

Info

Publication number
WO2018033199A1
WO2018033199A1 PCT/EP2016/069436 EP2016069436W WO2018033199A1 WO 2018033199 A1 WO2018033199 A1 WO 2018033199A1 EP 2016069436 W EP2016069436 W EP 2016069436W WO 2018033199 A1 WO2018033199 A1 WO 2018033199A1
Authority
WO
WIPO (PCT)
Prior art keywords
general formula
base
radical
amine
halide
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.)
Ceased
Application number
PCT/EP2016/069436
Other languages
German (de)
English (en)
Inventor
Alfred Popp
Katja HÜTTL
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
Priority to PCT/EP2016/069436 priority Critical patent/WO2018033199A1/fr
Publication of WO2018033199A1 publication Critical patent/WO2018033199A1/fr
Anticipated expiration legal-status Critical
Ceased 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 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

Definitions

  • the invention relates to a process for the preparation of secondary aminoorganosilicon compounds by reacting primary amine with (haloorganyl) silicon compounds.
  • Amino-functional silicone oils represent an important class of substances. They are used, for example, for the formulation of auto-care agents (improved polishability with simultaneously improved and longer-lasting water-repellent effect) but are also found in hair (amodimethicones) and textile care products (optimum distribution of the silicones on the Fiber surface for maximum soft grip). Another
  • QB 686,068 A notes a process for the reaction of corresponding (chloromethyl) - or (bromomethyl) triorganosilanes with ammonia, a primary or secondary amine at temperatures of at least 50 ° C for the preparation of said (aminoorganyl) (N-Organylaminoorganyl) - and (N , N-Diorganylaminoorganyl) triorganylsilanes.
  • the (chloromethyl) - or (bromomethyl) triorganosilanes are initially charged in a flask or autoclave, depending on the boiling points of the amine compounds used, and heated to temperatures above 100 ° C., preferably 110-130 ° C.
  • higher-boiling amines eg cyclohexylamine
  • (aminomethyl) silane derivatives are prepared by reacting a (chloroethyl) - or (bromomethyl) silane derivatives 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 Pat. No. 6452033 A describes the preparation of aminoethylaminoorganyltriorganosilanes by reacting the corresponding chlorofunctional organosilanes with ethylenediamine, the above-mentioned phase separation being used in various ways to separate the hydrochlorides.
  • a disadvantage of this process is the fact that it is limited to silanes which have an ethylenediamine unit.
  • WO 2009/019161 describes a process for preparing primary and secondary aminoorganyltriorganylsilanes of the general formula by reacting
  • the invention relates to a process for the preparation of secondary aminoorganyltriorganylsilicon compounds of the general formula (1) by reaction of acyclic amines of the general formula (2), with (haloorganyl) silicon compounds of the general formula (3) in which
  • R is an acyloxy radical, an alkoxy radical having 1-10 C
  • R 1 , R 4 independently of one another a Kohlenwasserstofoffreet with 1-10 C atoms
  • R 2 , R 5 are independently a divalent
  • R 3 is a hydrocarbon radical having 1-20 C atoms, this by non-adjacent heteroatoms such as N, O, S, P
  • n is a number equal to 0, 1, 2 or 3 and
  • X, Y independently of one another are chlorine, bromine or iodine, the reaction comprising the following steps:
  • the general formula (2) is released and the halide of the base (B) is formed, at a temperature at which the halide of the base (B) is present as a separate liquid phase and
  • the amine of the general formula (2) is preferably in excess, ie in molar ratios based on the proportion of the reactive groups Z and Y of 1.1 to 1 to 100 to 1, preferably from 1.5 to 1 to 50 to 1, more preferably from 2 to 1 to 20 to 1, in particular from 3 to 1 to 10 to 1
  • the base (B) is preferably in molar
  • Ratios based on the proportion of the reactive groups Z and Y of 0.5 to 1 to 10 to 1, preferably from 0.7 to 1 to 5 to 1, particularly preferably from 0.8 to 1 to 2 to 1, in particular from 0 , 9 to 1 to 1.0 to 1 used.
  • the hydrocarbon radicals can be saturated
  • the hydrocarbon radicals R 1 , 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 reagents such as the n-dodecyl radical
  • Octadecyl radicals such as the n-octadecyl radical
  • Cycloalkyl radicals such as the cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals
  • Alkenyl radicals such as the vinyl, 1-propenyl and the 2-propenyl radical
  • Aryl radicals such as the aryl radicals, such as
  • Aminoalkyl radicals such as the aminoethyl or aminopropyl radical
  • Alkylaminoalkylrest such as dimethylaminoethyl
  • R 1 and R 4 are a methyl, ethyl, iso and n-propyl, iso and n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Phenyl, benzyl or allyl radical.
  • R 3 preferably has the general formula (4) or (5)
  • a is a number equal to 1, 2, 3, 4, 5 or 6,
  • b is a number equal to 1, 2 or 3,
  • c is a number equal to 1, 2, 3, 4 or 5
  • d is a number equal to 0 or 1
  • e is a number equal to 1, 2, 3, 4, 5 or 6,
  • ff is a number equal to 1, 2 or 3,
  • g is a number equal to 1, 2, 3 or 4,
  • h is a number equal to 0 or 1
  • R 6 is a hydrocarbon radical having 1-6 C atoms, in particular ethyl or methyl and
  • R 7 is a hydrocarbon radical having 1-6 C atoms, in particular ethyl or methyl.
  • the radical R 3 is preferably selected from alkoxyalkyl radicals or alkylaminoalkyl radicals. In a particularly preferred embodiment, the radical R 3 is an alkoxyalkyl radical.
  • the radical R "preferably has the meaning of OR 1 or
  • R ' is a methoxy, ethoxy, iso and n-propoxy, butoxy, phenoxy, benzyloxy or allyloxy.
  • radicals R 2 , R 5 independently of each other, preferentially bonds to a divalent hydrocarbon radical having 1-6 C atoms, in particular to a methylene, ethylene and ethylene radical
  • Propylene oruppe more preferably around the propylene group.
  • radicals Z and Y are preferably chlorine or bromine
  • n preferably has the value 1, 2 or 3.
  • steps a) and b) can be carried out successively or simultaneously. Equally conceivable is a
  • 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 the base (B) is preferably carried out after the reaction in step a).
  • bases (B) which, in process step b), form salts which, even at temperatures ⁇ 150 ° C., are particularly preferably ⁇ 100 ° C. or ⁇ 90 ° C.
  • Step a) of the process according to the invention is preferably carried out at temperatures of 50 to 250 ° C.
  • Steps b) and c) of the inventive method are at a temperature at which the halide of the base (B) as a separate liquid phase is preferably carried out at temperatures of 0-250 e C, preferably at temperatures of 20 to 150 ° C and more preferably carried out at temperatures of 50 to 100 ° C.
  • reaction steps are preferably carried out under inert gas, e.g. Nitrogen and argon carried out.
  • inert gas e.g. Nitrogen and argon carried out.
  • the pressure in reaction steps a), b) and c) is preferably 0.05 to 2 MPa (abs.), More preferably 0.08 to 1.5 MPa (abs.), In particular 0.09 to 1 MPa (abs .).
  • the processes according to the invention can also have one or more of the following additional process steps:
  • step b) if the amine of the general formula (2) in step a) was used in excess, this excess can be completely or partially separated before the addition of the base (B) in step b).
  • the separation is preferably carried out by distillation. This measure preferably serves to reduce the solubility of the respective salts in the organic phase,
  • nonpolar solvents (L) Adding one or more nonpolar solvents (L) to the product-containing phase.
  • the additional solvent (L) can be added before, during or after the process steps a), al) b) and c). This measure serves to reduce the solubility of the respective salts in the organic phase.
  • the precipitated salts in this step are separated in an additional separation step, for example, a filtration.
  • the amounts of salt to be separated are extremely low compared with the original amount of salt in step c), the separation is correspondingly simple. If the addition of the non-polar solvent before or during step c), the respective salts are forced from the product phase into the liquid phase, which consists essentially of the halide of Baee (B), and separated together with this.
  • the amine of the general formulas (2) is preferably obtained directly in sufficiently high purity, so that it without further work-up in the next
  • halides of Baee (B) remain in the organic phase in the phase separation in step c), these are likewise preferably removed by distillation.
  • solvent (L) additionally optionally added in step d).
  • alkali metal alcoholates preferably sodium or potassium alcoholates
  • This measure may be particularly suitable for reducing the halide content in the final product.
  • polymeric polyamines to the product-containing phase after phase separation in step c).
  • This measure can be used to bind any residues of ionic halides, so that they remain in a final distillation of the product of the general formulas (1) or (4) (see step e) largely in the distillation bottoms and a corresponding low-halide product is obtained.
  • step b) amine of the general formula (2). If the amine of the general formula (2) is wholly or at least partially unsubstituted by a simple distillation - cf. Step e) - can be obtained in sufficient cleanliness, the interfering products, by-products or residues of the added in step b) base (B) be separated by one or more further purification steps.
  • Alkaline earth hydroxides carbonates, bicarbonates, etc.
  • the respective bases can be used in bulk or else in aqueous or nonaqueous solution or suspension. If aqueous solutions are used and / or water is liberated in the reaction, this is preferably removed by distillation from the base (B). If ethylenediamine was used as the base (B), this distillative separation is preferably carried out at such a high pressure that ethylene diamine and water no longer form an azeotrope. If the base (B) is a compound, e.g.
  • an amine which is itself reactive with the silane of the general formula (3) the amine of the general formulas (2) is preferably purified to such an extent by the said process steps that the content of the base (B) in the amines of the general Formulas (2) is less than 3%, preferably less than 1% and especially less than 0.5%.
  • the amine of the general formula (2) is used in excess, the excess amine being removed by a step al) by distillation substantially or at least in parts. Subsequently, if appropriate, a solvent (L) (step d)) and the base (B) is added (step b)) and the salt phase is separated off
  • Step c) the solvent (L) and the amine of the general formulas (2) liberated in step b) are removed by distillation (step e)).
  • Distillates of the amine of the general formulas (2) are preferably obtained with such high purity that they are used directly without further purification.
  • a solvent (L) whose boiling point is below that of the amine of the general formula (2) but above the boiling point of the base (B) is used in step d), so that any residues of the base (B) in the organic phase together with the solvent (L) are removed and then an amine of the general formula (2) can be obtained by distillation
  • Step e that contains over the preferred low content of the base (B).
  • the process can be carried out either batchwise, for example in stirred kettles, or continuously.
  • the latter z. B. by 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.
  • step c are suitable methods, for. B. using resting or settling vessels, Oekantem, etc., known and widely described in the literature.
  • the water content of the amines of the general formulas (2) to be used is preferably from 0 to 20 000 ppm, preferably from 0 to 5000 ppm, particularly preferably from 0 to 1000 ppm.
  • oligoamines (0) containing ethylene or propylenediamine units As base (B) it is preferred to use oligoamines (0) containing ethylene or propylenediamine units.
  • the oligoamines preferably contain (0) 1 to 20, in particular 1 to 10, ethylene or propylenediamine units.
  • Preferred oligoamines (O) are ethylenediamine, diethylenetriamine, diazabicyclooctane,
  • Pentamethyldiethylenetriamine, propylenediamine, N4-amine (BASF AG). Particular preference is given to using ethylenediamine as the base (B).
  • aminoorganyltriorganylsilicon compounds of the general formula (1) can be obtained in good to very good yields in a simple manner. The methods can be implemented on an industrial scale simply and safely.
  • the purity of the inventively prepared Aminoorganyl- triorganylsiliciumharmen the general formula (1) is preferably at least 85%, more preferably at least 95%. This purity can be determined by means of an optional downstream distillation step e) of
  • the process according to the invention offers the advantage over the prior art that the majority of the by-produced ammonium salts of the amines of the general formulas (2) no longer have to be separated off as solids, which is poor on an industrial scale
  • crystallizing ammonium salts is usually expensive and expensive.
  • many so-called multi-purpose systems do not have sufficiently powerful equipment elements (e.g., centrifuges) for separating such large quantities of solids. Due to the salting, two liquid phases can now be separated from each other. In addition, washing steps of the filter cake with additional solvent to be used unnecessary. At the same time, through the use of optimized
  • Formulas is the silicon atom tetravalent.
  • the phases separated completely within 10 min. Subsequently, the lower salt phase (ethylenediamine hydrochloride) was separated at 90 ° C in a separatory funnel. The remaining upper phase was passed through a 10 cm Vigreux column at a pressure of 10 mbar

Landscapes

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

Abstract

L'invention concerne un procédé de préparation des composés aminoorganosilicium décrits dans les revendications, par réaction d'amines cycliques ou acycliques avec un (halogénorganyl)silane, la réaction comprenant les étapes consistant à : a) faire réagir le composé (halogénorganyl)silicium représenté par la formule générale (3) et l'amine représentée par la formule générale (2) à une température de 0 à 250 °C, l'halogénure d'ammonium de l'amine représentée par la formule générale (2) se formant en plus du composé silicium représenté par la formule générale (1) en tant que produit secondaire, b) ajouter une base (B), ce qui entraîne un échange d'anion complet ou partiel, lors duquel l'amine représentée par la formule générale (2) est à nouveau libérée et l'halogénure de la base (B) se forme, à une température à laquelle l'halogénure de la base (B) est présente sous forme de phase liquide séparée, et c) séparer l'halogénure de la base (B) liquide formé.
PCT/EP2016/069436 2016-08-16 2016-08-16 Procédé de préparation de composés aminoorganosilicium secondaires Ceased WO2018033199A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2016/069436 WO2018033199A1 (fr) 2016-08-16 2016-08-16 Procédé de préparation de composés aminoorganosilicium secondaires

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2016/069436 WO2018033199A1 (fr) 2016-08-16 2016-08-16 Procédé de préparation de composés aminoorganosilicium secondaires

Publications (1)

Publication Number Publication Date
WO2018033199A1 true WO2018033199A1 (fr) 2018-02-22

Family

ID=56686828

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2016/069436 Ceased WO2018033199A1 (fr) 2016-08-16 2016-08-16 Procédé de préparation de composés aminoorganosilicium secondaires

Country Status (1)

Country Link
WO (1) WO2018033199A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3115789A1 (fr) 2020-11-03 2022-05-06 Bostik Sa polymère HYDROCARBONE à blocs POLYETHER ET POLYOLEFINE COMPRENANT AU MOINS UN groupement terminal alcoxysilane

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB686068A (en) 1950-06-30 1953-01-14 Dow Corning Ltd Improvements in or relating to organosilylamines
DE1812564A1 (de) 1968-12-04 1970-06-18 Bayer Ag Silylsubstituierte Carbamidsaeurederivate
EP0692567A1 (fr) * 1994-07-14 1996-01-17 Wacker-Chemie GmbH Organopolysiloxane aminofonctionnelle
US6452033B1 (en) 2002-02-11 2002-09-17 Dow Corning Corporation Method of making N-[2-aminoethyl] aminoalkylalkoxysilanes with ethyenediamine salt recycle
DE102004060627A1 (de) 2004-12-16 2006-07-06 Wacker Chemie Ag Verfahren zur kontinuierlichen Herstellung von Amino-Gruppen tragenden Silicium-Verbindungen
WO2009019161A1 (fr) 2007-08-07 2009-02-12 Wacker Chemie Ag Procédé de fabrication d'aminoorganosilanes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB686068A (en) 1950-06-30 1953-01-14 Dow Corning Ltd Improvements in or relating to organosilylamines
DE1812564A1 (de) 1968-12-04 1970-06-18 Bayer Ag Silylsubstituierte Carbamidsaeurederivate
EP0692567A1 (fr) * 1994-07-14 1996-01-17 Wacker-Chemie GmbH Organopolysiloxane aminofonctionnelle
US6452033B1 (en) 2002-02-11 2002-09-17 Dow Corning Corporation Method of making N-[2-aminoethyl] aminoalkylalkoxysilanes with ethyenediamine salt recycle
DE102004060627A1 (de) 2004-12-16 2006-07-06 Wacker Chemie Ag Verfahren zur kontinuierlichen Herstellung von Amino-Gruppen tragenden Silicium-Verbindungen
WO2009019161A1 (fr) 2007-08-07 2009-02-12 Wacker Chemie Ag Procédé de fabrication d'aminoorganosilanes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DEMEL, JAN; CEJKA, JIRI; STEPNICKA, PETR: "Palladium catalysts deposited on silica materials: Comparison of catalysts based on mesoporous and amorphous supports in Heck reaction", JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, vol. 329, no. 1-2, 15 June 2010 (2010-06-15), pages 13 - 20, XP002764575, ISSN: 1381-1169 *
O'BRIEN ET AL., ENERGY FUELS, vol. 28, 2014, pages 3326 - 3331

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3115789A1 (fr) 2020-11-03 2022-05-06 Bostik Sa polymère HYDROCARBONE à blocs POLYETHER ET POLYOLEFINE COMPRENANT AU MOINS UN groupement terminal alcoxysilane
WO2022096808A1 (fr) 2020-11-03 2022-05-12 Bostik Sa Polymere hydrocarbone a blocs polyether et polyolefine comprenant au moins un groupement terminal alcoxysilane

Similar Documents

Publication Publication Date Title
EP2384330A1 (fr) Procédé de production de bis et tris(silyl-organo)amines
DE102010001531A1 (de) Neuartige organomodifizierte Siloxane mit primären Aminofunktionen, neuartige organomodifizierte Siloxane mit quaternären Ammoniumfunktionen und das Verfahren zu deren Herstellung
EP2176273B1 (fr) Procédé de fabrication d'aminoorganosilanes
DE2849092A1 (de) Silylphosphate und verfahren zu deren herstellung
EP3164407B1 (fr) Procédé de production de siloxanes à partir de sels alcalins de silanols
DE10353063B4 (de) Verfahren zur Herstellung von (N-Organylaminoorganyl)- und (N,N-Diorganylaminoorganyl)triorganylsilanen sowie (N-Cyclohexylaminomethyl)trimethoxysilan und [N,N-Bis-(N',N'-dimethylaminopropyl)aminomethyl]triorganylsilan erhältliche mittels dieses Verfahrens
DE1493601C3 (de) Verfahren zur Herstellung von pentacoordinativen cyclischen Organosiliciumkomplexverbindungen
EP1831233B1 (fr) Procede pour produire en continu des composes de silicium portant des groupes amino
EP2438074A1 (fr) Procédé de préparation d'amino-organo-silanes
EP3728407A1 (fr) Procédé de production de siloxanes présentant des groupes oxamidoester
DE1156410B (de) Verfahren zur Herstellung von ª‰-Cyanalkylsilanen
EP2944642A1 (fr) Procédé de fabrication de silanes contenant de l'urée
EP0115772B1 (fr) Procédé de scission d'organosiloxanes et leurs produits et application
WO2018033199A1 (fr) Procédé de préparation de composés aminoorganosilicium secondaires
DE10303693A1 (de) Aminomethylenfunktionelle Siloxane
WO2018065070A1 (fr) Aminosiloxanes secondaires et son procédé de production
EP2445919B1 (fr) Procédé de fabrication d'organoalcoxyhydrogénosilanes
DE102012212050A1 (de) Verfahren zur Herstellung von Allylsilanen
DE102009046432A1 (de) Verfahren zur Herstellung von Organosiliciumverbindungen mit Grignardverbindungen
DE102009001758A1 (de) Verfahren zur Synthese von 1,3-Bis(aminoalkyl)disiloxanen
EP1652872A1 (fr) Méthode de la production de polysilanes ramifiés ou réticulés
WO2023057049A1 (fr) Initiateurs de radicaux silylbenzopinacol
WO2015197473A1 (fr) Composés d'organosilicium présentant des groupes amino et procédé pour leur production
DE1545059B2 (de) Verfahren zur herstellung von organopolysiloxanen mit einer oder mehreren gamma-aminoisobutylsiloxangruppen

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16751605

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16751605

Country of ref document: EP

Kind code of ref document: A1