WO2015197473A1 - Composés d'organosilicium présentant des groupes amino et procédé pour leur production - Google Patents

Composés d'organosilicium présentant des groupes amino et procédé pour leur production Download PDF

Info

Publication number
WO2015197473A1
WO2015197473A1 PCT/EP2015/063757 EP2015063757W WO2015197473A1 WO 2015197473 A1 WO2015197473 A1 WO 2015197473A1 EP 2015063757 W EP2015063757 W EP 2015063757W WO 2015197473 A1 WO2015197473 A1 WO 2015197473A1
Authority
WO
WIPO (PCT)
Prior art keywords
general formula
organosilicon compounds
radicals
amine
groups
Prior art date
Application number
PCT/EP2015/063757
Other languages
German (de)
English (en)
Inventor
Elke Fritz-Langhals
Jürgen STOHRER
Richard Weidner
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 WO2015197473A1 publication Critical patent/WO2015197473A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups

Definitions

  • the invention relates to amino-containing organosilicon compounds and a process for their preparation.
  • Amine-functional organosilicon compounds play an important role in many areas of technology. For example, amino groups significantly affect the adhesiveness and hydrophilicity of a polysiloxane. For example, amine-functionalized polysiloxanes find multiple uses, for example in the textile industry or in personal care. However, the chemical reactivity of the amine functionality also makes it possible to prepare block copolymers, for example by polyaddition using isocyanates. By combining different polymer blocks, a large number of products with tailor-made property profiles are accessible.
  • the amine functionalities are usually connected via carbon atoms with the silicon atoms of the siloxane skeleton.
  • the attachment takes place via a noble metal-catalyzed hydrosilylation reaction using H-silanes or H-siloxanes and a functionalized olefin, which then leads to aminopropyl-functionalized siloxanes.
  • hydrosilylation reactions are expensive. It will be more expensive
  • Precious metal catalyst needed which must be recycled usually.
  • the reaction is also susceptible to interference, as regards impurities in the starting materials and difficult to control due to the high exothermicity.
  • H-functional silanes and siloxanes are relatively expensive starting materials.
  • Amine-functional olefins, such as allylamine can only be used after introduction of an amine protecting group, otherwise they deactivate the catalyst. After the hydrosilylation is therefore a further reaction step, the removal of the protective group, necessary. In addition, the hydrosilylation of allylamine derivatives leads to isomeric mixtures.
  • Silicon of the organosilicon compound is connected.
  • the invention relates to aminoalkyl-functional parts organosilicon compounds in which the aminoalkyl groups are connected via an oxygen atom with the silicon of the organosilicon compounds, which is adjacent to the oxygen atom
  • Hydrocarbon radicals carries, wherein the number of carbon atoms of the two other hydrocarbon radicals together is at least two. It has surprisingly been found that amine-functional organosilicon compounds in which the aminoalkyl group is connected via an oxygen atom with the silicon of the organosilicon compound, wherein the carbon atom adjacent to the oxygen atom one or two more
  • Hydrocarbon radicals carries, wherein the number of carbon atoms of one or both further radicals together is at least two, storage-stable compounds.
  • the number of carbon atoms of the one or more further hydrocarbon radicals at the carbon atom adjacent to the oxygen atom is
  • the invention relates in particular to amine-functional organosilicon compounds consisting of at least one
  • R 2 are independently hydrogen or unsubstituted or substituted with substituents selected from -CN, NR X 2 , COOH, COOR x , halo, acrylic, epoxy, -SH, -OH and -CONR x 2 Ci-C 20 - hydrocarbon radicals or C 15 -hydrocarbonoxy radicals, in each of which one or more nonadjacent methylene units by groups -0-, -CO-, -COO-, or -0C0- -0C00-, -S- , or NR X can be replaced,
  • R 4 independently of one another are hydrogen or C 1 -C 20 -hydrocarbon radicals in which in each case one or more, non-adjacent methylene units are represented by groups -O-, -CO-, -COO-, -OCO- or -OCO-, -S - or NR X can be replaced, with the proviso that the number of carbon atoms of the two radicals is at least two,
  • Ci-C20 hydrocarbon radical may be in each of which one or more nonadjacent methylene units may be replaced by groups -O-, -CO-, -COO-, -OCO- or -OCOO-, -S-, or NR X .
  • R 7 is an acid or unbranched, branched or cyclic saturated or unsaturated alkyl group having 1 to 12 C atoms or an aryl group or aralkyl group, with individual non-adjacent methylene units passing through
  • Nitrogen atoms or oxygen atoms can be replaced, the values 0, 1, 2 or 3,
  • R 1 and R 2 preferably have 1 to 12 atoms, in particular 1 to 6 atoms, preferably only carbon atoms or an alkoxy oxygen atom and otherwise only carbon atoms.
  • R 1 and R 2 are straight-chain, branched or cyclic C 1 -C 6 -alkyl or alkoxy radicals. Particularly preferred are the radicals methyl, ethyl, phenyl, vinyl, trifluoropropyl, methoxy, ethoxy and i-propoxy.
  • the radicals R 1 and R 2 may be the same or different on the same silicon atom.
  • R 3 and R 4 preferably have 1 to 12 atoms, in particular 1 to 6 atoms, preferably only carbon atoms or an alkoxy oxygen atom and otherwise only carbon atoms. If R 3 is a hydrogen atom then R 4 must be at least two
  • R 3 must have at least two carbon atoms.
  • R 3 and R 4 are straight-chain, branched or cyclic C 1 -C 6 -alkyl radicals or aryl radicals, particularly preferably the radicals methyl, ethyl and propyl.
  • the radical R 5 is preferably a C-bonded C 1 -C 3 -hydrocarbon radical in each of which one or more non-adjacent methylene units can be replaced by groups -O-, -S-, or -NR X -.
  • R 5 is a
  • alkylene radicals are particularly preferably methylene, ethylene, propylene, butylene,
  • CH 2 -NH-CH 2 -CH 2 CH 2 -NH-CH 2 -CH 2 , CH 2 -NH-CH 2 -CH 2 -CH 2 , CH 2 -CH 2 -NH-CH 2 -CH 2 -CH 2 , CH 2 -CH 2 --NH- CH 2 -CH 2 and CH 2 -CH 2 -NH-CH 2 .
  • R 6 and R 7 are preferably independently of one another hydrogen or unbranched, branched or cyclic saturated or unsaturated alkyl group having 1 to 6 C atoms or aryl groups, non-adjacent methylene units being able to be replaced by nitrogen atoms or oxygen atoms. More preferably, R 6 and R 7 are independently hydrogen or Cx - Cs alkyl group, wherein individual non-adjacent methylene groups may be replaced by nitrogen atoms, in particular the radicals methyl, ethyl and propyl.
  • R 6 and R 7 are hydrogen.
  • amino-functional organosiloxanes of units of the general formulas I and II can be linear, branched,
  • amino-functional organosiloxanes of units of the general formulas I and II preferably contain 1 to 20, in particular 2 to 10, units of the general formula I.
  • the amino-functional organosiloxanes preferably contain 1 to 500, more preferably 4 to 200, in particular 10 to 100, units of the general formula II.
  • At least 90%, in particular at least 95% of the units of the general formula II a is 2.
  • Tacke describes in Liebigs Ann. Chem. 1982, 1706-1711, the reaction of 1, 3-dichloro-1, 1, 3, 3-tetramethyldisiloxane with a tertiary amine, the N, -Dimethylaminoethanol, to the compound N, I ⁇ T - (4, 4, 6, 6-tetramethyl-3,5,5-trioxa-4,6-disilanonamethylene) bis (dimethylamine) using five times the molar amount of a tertiary amine as the base.
  • the use of bases, especially organic bases such as tertiary amines, in high excess is uneconomical for a technical process.
  • the amine hydrochloride formed in the reaction is also separated off as a solid by filtration.
  • solid filtrations are complex in technical processes and therefore make the entire process considerably more expensive. It has now surprisingly been found that the amine-functional organosilicon compounds according to the invention can be prepared in a simple manner by reacting halogen-functional
  • Organosilicon compounds and amino alcohols without the additional use of amine bases can be produced in high yields.
  • the invention therefore also provides a process for the preparation of the compounds from at least one unit of the general formula I.
  • X is halogen, preferably Cl.
  • Chloroform siloxanes are produced on an industrial scale, they are formed in the incomplete hydrolysis of chlorosilanes with water or in the reaction of hydroxy siloxanes with chlorosilanes.
  • the amino alcohols used are simple
  • Epoxides eg 1, 1-dimethylethylene oxide or n-butylene oxide in good yields available.
  • the aminoalcohol of the general formula IV is preferably used in proportions of from 0.1 to 2 equivalents, more preferably in proportions of from 0.5 to 1.5 equivalents, based on the molar amount of Si-bonded chlorine in the units of the general formula III.
  • a molar deficit of amino alcohol remain Si-Cl groups in the reaction mixture, which can then optionally be converted in the presence of water or alcohols into other alkoxysilane or Siloxangruppêt Stuttgart.
  • the reaction is preferably carried out at temperatures between 0 and 180 ° C / more preferably between 20 and 150 ° C, and pressures preferably between 100 mbar and 10 bar, more preferably between 1 and 5 bar.
  • the reaction times are preferably 1 minute to 8 hours, more preferably 10 minutes to 4 hours.
  • the reaction can be carried out in batch mode or in semi-batch mode or continuously. Preference is given to one of the two reactants, preferably the halogen-functional organosilicon compound, and then the second component, preferably the amino alcohol added.
  • Hydrochloric acid preferably alkali metal or alkaline earth metal hydroxides, oxides or carbonates, preferably of
  • Sodium, potassium, calcium or magnesium particularly preferably of sodium and potassium, preferably in amounts of 0.9 to 1.4 equivalents, particularly preferably in amounts of 0.95 to 1.1 equivalents, in each case based on the molar amount of chloride present.
  • Unreacted Si-Cl groups react to form the corresponding Si-OH or Si-O-Si groups.
  • the bases are preferably used as aqueous solutions.
  • Hydrohalic acid with the base formed salts can then be easily separated with the aqueous phase.
  • solvents may be used in amounts of at least 1% and at most 200%, preferably at least 10% and at most 100%, based on the total reaction mass.
  • solvents are aprotic
  • Solvents preferably linear or cyclic, saturated or unsaturated hydrocarbons, e.g. Pentane, cyclohexane, toluene, ethers, such as methyl tert-butyl ether, anisole,
  • Tetrahydrofuran or dioxane Tetrahydrofuran or dioxane, halogenated hydrocarbons, such as dichloromethane, 1, 2-dichloroethane or chlorobenzene, nitriles, such as acetonitrile or propionitrile, or DMSO.
  • equilibration reactions can be carried out to achieve the desired molecular weight of the amine-functional organosilicon compound.
  • the equilibration reactions may be carried out in the manner known to those skilled in the art. In general, for this purpose, linear or branched hydroxy-containing polysiloxanes or cyclic siloxanes or
  • the mixture is stirred for a further 1 h at 100 ° C, treated with 150 ml of toluene, then cooled to room temperature, mixed with 28.5 ml of 1N NaOH and shaken out the mixture.
  • the aqueous phase is separated and the organic phase washed twice with water and then evaporated on a rotary evaporator under reduced pressure.
  • the residue obtained is the amine-functionalized oil.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Silicon Polymers (AREA)

Abstract

L'objet de l'invention est constitué par des composés d'organosilicium à fonction aminoalkyle, dans lesquels les groupes aminoalkyle sont liés par le biais d'un atome d'oxygène avec le silicium des composés d'organosilicium, l'atome de carbone du groupe aminoalkyle, adjacent de l'atome d'oxygène, portant un ou deux autres radicaux hydrocarbure, le nombre d'atomes de carbone des deux autres radicaux hydrocarbure étant conjointement au moins de deux. L'invention concerne également un procédé pour leur production.
PCT/EP2015/063757 2014-06-25 2015-06-18 Composés d'organosilicium présentant des groupes amino et procédé pour leur production WO2015197473A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014212170.1 2014-06-25
DE102014212170.1A DE102014212170A1 (de) 2014-06-25 2014-06-25 Aminogruppen aufweisende Organosiliciumverbindungen und Verfahren zu ihrer Herstellung

Publications (1)

Publication Number Publication Date
WO2015197473A1 true WO2015197473A1 (fr) 2015-12-30

Family

ID=53510839

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2015/063757 WO2015197473A1 (fr) 2014-06-25 2015-06-18 Composés d'organosilicium présentant des groupes amino et procédé pour leur production

Country Status (2)

Country Link
DE (1) DE102014212170A1 (fr)
WO (1) WO2015197473A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3338859A (en) 1966-06-30 1967-08-29 Dow Corning Silicone polyimides
DE4344082C1 (de) * 1993-12-23 1994-12-22 Goldschmidt Ag Th Verfahren zur Herstellung von Organopolysiloxanen mit über Kohlenstoff an Silicium gebundenen sekundären Aminoalkylgruppen
EP0887366A2 (fr) * 1997-06-25 1998-12-30 Dow Corning Limited Méthode pour la préparation des aminoalkoxysiloxanes
WO2002060972A2 (fr) 2001-01-29 2002-08-08 Ndsu Research Foundation Polyalkoxyalkylsiloxanes anti-neoplasiques et procedes d'utilisation
US6482912B2 (en) 2001-01-29 2002-11-19 Ndsu Research Foundation Method of preparing aminofunctional alkoxy polysiloxanes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3338859A (en) 1966-06-30 1967-08-29 Dow Corning Silicone polyimides
DE4344082C1 (de) * 1993-12-23 1994-12-22 Goldschmidt Ag Th Verfahren zur Herstellung von Organopolysiloxanen mit über Kohlenstoff an Silicium gebundenen sekundären Aminoalkylgruppen
EP0887366A2 (fr) * 1997-06-25 1998-12-30 Dow Corning Limited Méthode pour la préparation des aminoalkoxysiloxanes
WO2002060972A2 (fr) 2001-01-29 2002-08-08 Ndsu Research Foundation Polyalkoxyalkylsiloxanes anti-neoplasiques et procedes d'utilisation
US6482912B2 (en) 2001-01-29 2002-11-19 Ndsu Research Foundation Method of preparing aminofunctional alkoxy polysiloxanes

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ATHENS CONFERENCE ON COATINGS, 2001, pages 411 - 418
LIEBIGS ANN. CHEM., 1982, pages 1706 - 1711
MACROMOL. RAPID COMMUN., vol. 22, 2001, pages 655

Also Published As

Publication number Publication date
DE102014212170A1 (de) 2015-12-31

Similar Documents

Publication Publication Date Title
EP0348693B1 (fr) Procédé de préparation de diorganodialcoxysilanes
EP2531547A1 (fr) Nouveau siloxane organomodifié possédant des fonctions amine primaires, nouveau siloxane organomodifié possédant des fonctions ammonium quaternaires et leur procédé de production
DE102005009790A1 (de) Verfahren zur Herstellung von Alkoxysilylmethylisocyanuraten
WO2010086254A1 (fr) Procédé de production de bis et tris(silyl-organo)amines
EP2176273B1 (fr) Procédé de fabrication d'aminoorganosilanes
DE69906716T2 (de) Siloxane mit amino-organischer funktioneller gruppe
DE602004001641T2 (de) Herstellung verzweigter Siloxane
EP1682558A1 (fr) Procede pour produire des composes silicium portant des groupes amino
DE60127202T2 (de) Organosiliziumverbindungen
WO2013139604A1 (fr) Procédé de production d'aminoalkylalcoxysilanes
EP0401684B1 (fr) Procédé de préparation d'organosiloxanes
WO2015197473A1 (fr) Composés d'organosilicium présentant des groupes amino et procédé pour leur production
WO2010139674A1 (fr) Procédé de préparation d'amino-organo-silanes
DE60201037T2 (de) Herstellung verzweigter Siloxane
EP2452943B1 (fr) Méthode pour produire 1,2-Bis-Silyl-Ethanes alcoxy-substitué
DE69930733T2 (de) Herstellung von substituierten (amino)alkoxysilanen
EP3577123B1 (fr) Procédé pour la préparation d'aminopropylalcoxysilanes
EP2411400B1 (fr) Procédé de synthèse de 1,3-bis(aminoalkyl)disiloxanes
EP3344634B1 (fr) Composés organosiliciés présentant des groupements (méth)acrylate et procédé de production desdits composés
DE102010028170B4 (de) Verfahren zur Herstellung metallierter Hydridosilanverbindungen
DE102015205341A1 (de) ß-Aminoalkylgruppen aufweisende Organopolysiloxane und deren Herstellung
WO2018033199A1 (fr) Procédé de préparation de composés aminoorganosilicium secondaires
EP1161435B1 (fr) Procede de preparation d'un formoxysilane
DE69823341T2 (de) Verfahren zur Herstellung von Siloxanen
DE2430950C3 (de) Verfahren zur Herstellung von Kohlenwasserstoffsilanen aus Polysilanen

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: 15734086

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: 15734086

Country of ref document: EP

Kind code of ref document: A1