WO2007060089A2 - Composes d'organo-silicium a fonction alpha-(beta-cetocarbonyle et leur preparation - Google Patents

Composes d'organo-silicium a fonction alpha-(beta-cetocarbonyle et leur preparation Download PDF

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Publication number
WO2007060089A2
WO2007060089A2 PCT/EP2006/068162 EP2006068162W WO2007060089A2 WO 2007060089 A2 WO2007060089 A2 WO 2007060089A2 EP 2006068162 W EP2006068162 W EP 2006068162W WO 2007060089 A2 WO2007060089 A2 WO 2007060089A2
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WO
WIPO (PCT)
Prior art keywords
radical
ketocarbonyl
organosilicon compounds
hydrogen atom
radicals
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PCT/EP2006/068162
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German (de)
English (en)
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WO2007060089A3 (fr
Inventor
Christian Herzig
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Wacker Chemie Ag
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Publication of WO2007060089A2 publication Critical patent/WO2007060089A2/fr
Publication of WO2007060089A3 publication Critical patent/WO2007060089A3/fr

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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
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • 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

Definitions

  • the invention relates to OC- ( ⁇ -ketocarbonyl) -functional organosilicon compounds and a process for their preparation.
  • Polymeric ⁇ -ketoester siloxanes are known from US 4,808,649, as is a process for their preparation and their use as a stabilizer for polyvinyl chloride.
  • Aminopolysiloxanes used for the production of elastomeric films.
  • the object was to provide CC- ( ⁇ -ketocarbonyl) -functional organosilicon compounds which can be prepared selectively by a simple process and without obtaining any reclaimed products.
  • the object is achieved by the invention.
  • the invention provides CC- ( ⁇ -ketocarbonyl) -functional organosilicon compounds which have at least one Si-bonded radical B selected from the group of the general formulas
  • Y is an oxygen atom or a radical of the formula -NR -, preferably a radical of the formula -NR 2 -,
  • R 1 represents a hydrogen atom or an alkyl, cycloalkyl, aryl or aralkyl radical having 1 to 30 carbon atoms, preferably a hydrogen atom
  • R 2 is a radical R 1 or an organic radical containing one or more heteroatoms selected from the group of B, N, O, P, S, Si, Ti, F, Cl, Br and J, preferably N, O and Si
  • R 3 is a radical R 1 .
  • the radicals of the formulas (I) and (II) are tautomeric groups.
  • the CC- ( ⁇ -ketocarbonyl) -functional organosilicon compounds according to the invention preferably contain 1 to 20 radicals of the formulas (I) and / or (II) per molecule, where they are radicals of the formula (I) only radicals of the formula (II) or can contain both together. Since tautomeric groups are interconvertible, their respective content may change depending on external conditions. Their ratio can therefore vary within wide limits and quotients of about 1000: 1 to about 1: 1000 amount.
  • the organosilicon compounds of the invention may be silanes or oligomeric or polymeric organopolysiloxanes.
  • the organosilicon compounds according to the invention preferably contain 1 to 10 000 Si atoms, preferably 5 to 5000 Si Atoms, more preferably 60 to 3000 Si atoms.
  • the organosilicon compounds of the invention may be linear, branched, dendrimeric or cyclic. Also included in the scope of the organosilicon compounds according to the invention are network structures of arbitrary size, to which neither a specific or average number of Si atoms can be assigned, provided they contain at least one Si-bonded functional group of the formula (I) and / or (II).
  • the invention further provides a process for the preparation of CC- ( ⁇ -ketocarbonyl) -functional organosilicon compounds, wherein the diketenes (1) of the general formula
  • organosilicon compounds (2) which contain at least one Si-bonded radical A of the general formula
  • R 1 , R 3 and Y have the meaning given above, be implemented.
  • diketenes (1) are also their derivatives, such as
  • Acetoacetic acid tert. butyl ester or the diketene-acetone adduct can be used, wherein the reactive species by heating at temperatures of preferably 80 to 180 0 C, preferably 100 to 150 0 C, released.
  • the reaction can be carried out without addition of further substances, but also diluted in solvents, such as heptane, toluene, xylene, THF, Take ethyl acetate.
  • solvents such as heptane, toluene, xylene, THF, Take ethyl acetate.
  • solvents such as heptane, toluene, xylene, THF, Take ethyl acetate.
  • solvents such as heptane, toluene, xylene, THF, Take ethyl acetate.
  • solvents such as heptane, toluene, xylene, THF, Take eth
  • reaction can be carried out with the aid of one or more organic compounds (3) which delay or reversibly prevent the addition of the ⁇ -ketocarbonyl compounds to radicals A in (2), preferably amino radicals. Except in cases where too high an exotherm is to be expected due to high concentrations of the reactive groups (III) and (IV), the reaction without the addition of further substances is preferred.
  • Examples of compounds (3) which can be used in the process according to the invention are those which can form more or less solid adducts with amines, such as aldehydes or ketones.
  • Preferred examples are acetone, butanone, methyl isobutyl ketone and cyclohexanone.
  • Adducts can be thermally split again and thus rest A slowly released.
  • organosilicon compounds (2) which can be used in the process according to the invention can be silanes or oligomeric or polymeric organopolysiloxanes.
  • organosilicon compounds (2) organopolysiloxanes from units of the general formula. 5
  • 0 A is a radical of the general formula -CR 1 ⁇ -YH (IV), wherein R 1 and Y have the meaning given above, R is a monovalent, optionally substituted
  • Hydrocarbon radical having 1 to 18 carbon atoms per radical, 5 R 4 is a hydrogen atom or an alkyl radical having 1 to 8
  • organosilicon compounds (2) are organopolysiloxanes of the general formula
  • A, R and R 4 have the meaning given above, g is 0 or 1, k is 0 or an integer from 1 to 30 and
  • 1 is 0 or an integer from 1 to 1000
  • m is an integer from 1 to 30
  • n is 0 or an integer from 1 to 1000, provided that on average at least one residue A is contained per molecule.
  • the organosilicon compounds (2) used in the process according to the invention preferably have a viscosity of from 1 mPa.s to 1,000,000 mPa.s at 25 ° C., preferably 100 mPa.s to 50,000 mPa.s at 25 ° C.
  • radicals R are 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.
  • -Pentyl radical 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, and octadecyl radicals such as the n-octadecyl radical; Cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; Alkenyl radicals such as the vinyl, 5-hexenyl, cyclohexenyl, 1-propenyl, allyl,
  • radicals R 1 are, in addition to the preferred hydrogen, 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.
  • -Pentyl radical 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, and octadecyl radicals, such as the n-octadecyl radical; Cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; Aryl radicals, such as aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radicals; and aralkyl radicals, such as the benzyl radical, the CC and the ⁇ -phenylethyl radicals.
  • R 2 is an alkyl, cycloalkyl, aryl or aralkyl radical of 1 to 30 carbon atoms which may contain one or more heteroatoms selected from the group of N, O and Si, preferably an alkyl, cycloalkyl, aryl or Aralkyl radical having 1 to 30 carbon atoms.
  • R 1 are also fully applicable to Examples R 2 .
  • Preferred examples of R 2 are the methyl radical and the cyclohexyl radical.
  • R 2 may also contain heteroatoms. Further examples of R 2 are therefore
  • R 3 correspond to those for R 1 , hydrogen being preferred.
  • CC ( ⁇ -ketocarbonyl) functional organosilicon compounds of the invention are provided.
  • B, R, R 4, a, c and d have the meaning given above, with the proviso that the sum a + c + d ⁇ _ 3 and on average at least one radical B per molecule is included.
  • ⁇ -ketocarbonyl-functional organosilicon compounds are organopolysiloxanes of the general formula
  • B, R, R 4 , g, k, 1, m and n have the meaning given above, with the proviso that on average at least one radical B per molecule is contained.
  • diketene (1) in amounts of preferably 0.5 to 2.0 mol, preferably 0.9 to 1.2 mol, depending Mol radical A of the general formula (IV) used in the organosilicon compound (2).
  • the inventive method is preferably carried out at temperatures of 0 to 140 0 C, preferably 20 to 100 0 C, performed. Furthermore, the process of the invention is preferably carried out at the pressure of the surrounding atmosphere, but can also be carried out at higher and lower pressures.
  • the CC- ( ⁇ -ketocarbonyl) -functional organosilicon compounds according to the invention preferably have a viscosity of from 5 mPa.s to 1,000,000 mPa.s at 25 ° C., preferably 100 mPa.s to 100,000 mPa.s at 25 ° C.
  • ⁇ -ketocarbonyl-functional organosilicon compounds of the invention can be used:
  • the condensation method is used: For this purpose, 1350 g of an ⁇ , ⁇ -Dihydroxypolydimethylsiloxans with a viscosity of 67 mm 2 / s (25 ° C) with 74g cyclohexylaminomethyl methyldiethoxysilane mixed. The mixture is heated to 80 0 C and stirred for 2 hours and applying a vacuum until a constant viscosity is reached. The split-off ethanol is continuously removed, whereupon a 2940 mm 2 / s (25 ° C) aminopolysiloxane is obtained.
  • the colorless, clear oil has an amine value of 0.204 m.quad./g and thus contains on average one sec. Of amino group per 4902 g of polymer.
  • the 1 H NMR spectrum shows only traces of Si-bonded ethoxy groups: the condensation has gone to 98%.
  • the 29 Si NMR spectrum shows a sharp signal for the cyclohexylaminomethylmethylsiloxy group at -26.0 ppm relative to tetramethylsilane.
  • the total yield deducted from the resulting ethanol is 1390g, which corresponds to 99% of theory.
  • Ketocarbonyl and its tautomeric form formed, which are in the keto / enol ratio of 55/45.
  • the viscosity of the aminopolysiloxane used has only increased by about 10%, which practically precludes a secondary reaction by enamine linkage.

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

Abstract

La présente invention concerne de nouveaux composés d'organo-silicium à fonction a-(ß-cétocarbonyle), qui contiennent au moins un radical B à liaison Si sélectionné dans le groupe des radicaux de formules générales -CR<SUP>1</SUP>
PCT/EP2006/068162 2005-11-24 2006-11-07 Composes d'organo-silicium a fonction alpha-(beta-cetocarbonyle et leur preparation WO2007060089A2 (fr)

Applications Claiming Priority (2)

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DE102005056050.4 2005-11-24
DE102005056050A DE102005056050A1 (de) 2005-11-24 2005-11-24 Alpha-(beta-Ketocarbonyl)-funktionelle Organosiliciumverbindungen und deren Herstellung

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WO2007060089A2 true WO2007060089A2 (fr) 2007-05-31
WO2007060089A3 WO2007060089A3 (fr) 2007-08-02

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1852456A1 (fr) * 2006-05-04 2007-11-07 Wacker Chemie AG Procédé pour la préparation de composés organosiliciques ß-cetocarbonyl-fonctionnalisé
WO2007128680A1 (fr) * 2006-05-04 2007-11-15 Wacker Chemie Ag COMPOSÉS D'ORGANOSILICIUM CONTENANT DES GROUPES b-CÉTOAMIDE ET DES POLYMÈRES ORGANIQUES RELIÉS PAR DES LIAISONS ÉNAMINE ET PROCÉDÉ POUR LEUR PRÉPARATION
EP1889868A1 (fr) * 2006-08-16 2008-02-20 Wacker Chemie AG Compositions contenant des polymères
US20190309468A1 (en) * 2016-11-16 2019-10-10 Wacker Chemie Ag Dispersions of beta-ketocarbonyl-functional organosilicon compounds
CN111094526A (zh) * 2017-12-06 2020-05-01 瓦克化学股份公司 β-酮羰基官能化的有机硅化合物的乳液

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Publication number Priority date Publication date Assignee Title
SU555104A1 (ru) * 1975-07-21 1977-04-25 Способ получени -кремнийзамещенных амидов оксикислот
EP0010130A1 (fr) * 1978-08-28 1980-04-30 Bayer Ag Dérivés de 1,4-dihydropyridine, procédés pour leur préparation, compositions pharmaceutiques et procédé pour leur préparation

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
SU555104A1 (ru) * 1975-07-21 1977-04-25 Способ получени -кремнийзамещенных амидов оксикислот
EP0010130A1 (fr) * 1978-08-28 1980-04-30 Bayer Ag Dérivés de 1,4-dihydropyridine, procédés pour leur préparation, compositions pharmaceutiques et procédé pour leur préparation

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DATABASE BEILSTEIN [Online] BEILSTEIN INSTITUTE FOR ORGANIC CHEMISTRY, FRANKFURT-MAIN, DE; XP002432299 gefunden im XFIRE Database accession no. Reaction ID 1517264 -& TACKE R. ET AL.: "Sila-Analoga" ZEITSCHRIFT FÜR NATURFORSCHUNG B ANORG. CHEM., Bd. 35, Nr. 4, 1980, Seiten 494-501, XP009083303 *
DATABASE BEILSTEIN [Online] BEILSTEIN INSTITUTE FOR ORGANIC CHEMISTRY, FRANKFURT-MAIN, DE; XP002432300 gefunden im XFIRE Database accession no. BRN 2414120 & MIRONOV, V.F. ET AL.: J. GEN. CHEM. USSR, Bd. 37, 1967, Seiten 1821-1823, *
WEE A G H ET AL: "The rhodium(II)-catalyzed reaction of N-bis(trimethylsilylmethyl)diazoamides: steric, electronic and conformational effects" TETRAHEDRON LETTERS, ELSEVIER, AMSTERDAM, NL, Bd. 43, Nr. 35, 26. August 2002 (2002-08-26), Seiten 6173-6176, XP004373267 ISSN: 0040-4039 *
WEE, A. ET AL.: "The Bis(trimethylsilyl)methyl Group as an Effective N-Protecting Group and Site-Selective Control Element in Rhodium(II)-Catalyzed Reaction of Diazoamides" J. ORG. CHEM., Bd. 70, Nr. 21, 14. Oktober 2005 (2005-10-14), Seiten 8372-8380, XP002432277 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1852456A1 (fr) * 2006-05-04 2007-11-07 Wacker Chemie AG Procédé pour la préparation de composés organosiliciques ß-cetocarbonyl-fonctionnalisé
WO2007128680A1 (fr) * 2006-05-04 2007-11-15 Wacker Chemie Ag COMPOSÉS D'ORGANOSILICIUM CONTENANT DES GROUPES b-CÉTOAMIDE ET DES POLYMÈRES ORGANIQUES RELIÉS PAR DES LIAISONS ÉNAMINE ET PROCÉDÉ POUR LEUR PRÉPARATION
US7495119B2 (en) 2006-05-04 2009-02-24 Wacker Chemie Ag Process for preparing β-Ketocarbonyl-functional organosilicon compounds
KR101027182B1 (ko) * 2006-05-04 2011-04-05 와커 헤미 아게 엔아민 결합에 의하여 결합된 유기 중합체 및 β-케토아미드기를 함유하는 유기규소 화합물 및 이의 제조방법
US7939619B2 (en) 2006-05-04 2011-05-10 Wacker Chemie Ag Organosilicon compounds that contain β-ketoamide groups and organic polymers bound via enamine bonds, and method for producing them
EP1889868A1 (fr) * 2006-08-16 2008-02-20 Wacker Chemie AG Compositions contenant des polymères
US20190309468A1 (en) * 2016-11-16 2019-10-10 Wacker Chemie Ag Dispersions of beta-ketocarbonyl-functional organosilicon compounds
US10920369B2 (en) * 2016-11-16 2021-02-16 Wacker Chemie Ag Dispersions of β-ketocarbonyl-functional organosilicon compounds
CN111094526A (zh) * 2017-12-06 2020-05-01 瓦克化学股份公司 β-酮羰基官能化的有机硅化合物的乳液
CN111094526B (zh) * 2017-12-06 2021-08-06 瓦克化学股份公司 β-酮羰基官能化的有机硅化合物的乳液

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DE102005056050A1 (de) 2007-05-31
WO2007060089A3 (fr) 2007-08-02

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