WO2005123812A1 - Procede pour produire des hydroxyalkylpolysiloxanes - Google Patents

Procede pour produire des hydroxyalkylpolysiloxanes Download PDF

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Publication number
WO2005123812A1
WO2005123812A1 PCT/EP2005/005664 EP2005005664W WO2005123812A1 WO 2005123812 A1 WO2005123812 A1 WO 2005123812A1 EP 2005005664 W EP2005005664 W EP 2005005664W WO 2005123812 A1 WO2005123812 A1 WO 2005123812A1
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WO
WIPO (PCT)
Prior art keywords
general formula
integer
groups
halogen
integer values
Prior art date
Application number
PCT/EP2005/005664
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German (de)
English (en)
Inventor
Oliver SCHÄFER
Andrea Kneissl
Original Assignee
Consortium für elektrochemische Industrie GmbH
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 Consortium für elektrochemische Industrie GmbH filed Critical Consortium für elektrochemische Industrie GmbH
Publication of WO2005123812A1 publication Critical patent/WO2005123812A1/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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0874—Reactions involving a bond of the Si-O-Si linkage

Definitions

  • the invention relates to a process for the preparation of hydroxyalkylpolysiloxanes and hydroxyalkylpolysiloxane resins.
  • Hydroxyalkyl polysiloxanes and hydroxyalkyl silicone resins are used in many areas of application, e.g. in the
  • EP-A-629648 describes a further process which starts from special cyclic silanes of the general formula I which can react with HO-Si groups (silanol groups) at the end of a silicone chain without the use of catalysts.
  • R 3 is a carbon residue with up to 20 carbon atoms
  • R 4 is hydrogen or a hydrocarbon residue with up to 20 carbon atoms.
  • reaction is carried out at temperatures between 25 ° C and 150 ° C without the use of catalysts.
  • siloxanes of the general formula IV are also generally not obtainable as defined compounds, but vary due to their polymeric nature, e.g. strong in viscosity. This behavior can e.g. complicate the technical use of such connections.
  • the object of the present invention is therefore to provide an improved method for producing
  • the invention relates to a process for the preparation of hydroxyalkylpolysiloxanes of the general formula V.
  • R x is hydrogen or a C] _- C] _Q hydrocarbon residue which is optionally substituted by -CN or halogen
  • b is an integer value of at least 1
  • s is an integer value of at least 1
  • r is an integer value of at least 1
  • n 0 or integer values s + t mean the value of r and k + m + p + q integer values of at least 2.
  • compounds of the general formula VII react easily and in a targeted manner with good yields with silanol end groups to give carbinols.
  • Compounds of the general formula VII are stable, storable, can be easily removed from simple precursors e.g. Synthesize according to DE 1593867 A and are therefore particularly well suited for use on an industrial scale.
  • the C] _- C20 ⁇ hydrocarbon radicals and C] _- C20 "" hydrocarbonoxy radicals R 1 , R 3 , R 4 can be aliphatic saturated or unsaturated, aromatic, straight-chain or branched.
  • R 1 , R 3 , 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.
  • R ⁇ -, R 3 , R 4 are preferably straight-chain or branched C - Cg alkyl radicals or phenyl radicals. The are particularly preferred
  • the compounds of the general formula V are preferably prepared in which R 3 is a methyl radical and R 4 is hydrogen.
  • B preferably has values of at most 50, in particular at most 10. In particularly preferred embodiments, b is 2 or 3.
  • the hydroxy-functional organosiloxane of the general formula VI can be linear, cyclic, branched or crosslinked.
  • the sum of k, m, p, q, s and t is preferably a number from 3 to 20,000, in particular 8 to 1,000.
  • the organosiloxane of general formula VI must contain hydroxyl groups.
  • a preferred variant for an organosiloxane of the general formula VI is a linear silicone polymer with k and m equal to 0, p greater than or equal to 1, q equal to 0 or 1 and r equal to 1 or 2, the condition q being equal to 2 minus r.
  • r is s.
  • the preferred organosiloxanes of the general formula VI can be either monomodal or multimodal, at the same time they can be in a narrow or very wide distribution.
  • organosilicone resin Another preferred variant for a branched organosiloxane of the general formula VI used is an organosilicone resin. This can consist of several units, as indicated in the general formula VI, the mole percent of the units contained being denoted by the indices k, m, p, q, r, s and t, k + m must be> 0.
  • Hydroxyalkylpolysiloxane resins are preferred. prepared in which 5% ⁇ k + m ⁇ 90%, based on the sum of k, m, p, q, s and t. Such resins are also the subject of the invention.
  • t is preferably 0.
  • a value of 0.1 to 20 mol% of units r is preferred, based on the sum of k, m, p, q and r.
  • the radical R 3 is a
  • R 1 is a methyl radical and b is 2 or 3 and
  • R 4 stands for hydrogen
  • R 3 , R 4 and b have the above meanings.
  • b is 2 and R 4 is hydrogen and R 3 is methyl or ethyl.
  • the process can be carried out uncatalyzed, preferably at temperatures from 0 ° C. to 200 ° C. However, reaction temperatures of at least 40 ° C. are preferably used. However, the process can be further improved by adding certain catalysts. These catalysts are acidic or basic compounds and mean that both reaction times and reaction temperatures can be reduced.
  • the catalyst used is an inorganic or organic Lewis acid or Lewis base, such as organic
  • Preferred acids are carboxylic acids, partially esterified carboxylic acids, especially monocarboxylic acids, preferably formic acid or acetic acid or unesterified or partially esterified mono-, oligo- or polyphosphoric acids.
  • Alkylammonium hydroxides, aluminum ammonium anolates, ammonium alkoxides, alkylammonium fluorides, amine bases or metal alcoholates or metal alkyls are preferably used as preferred bases.
  • preferred Metal alcoholates are lithium or sodium alcoholates.
  • Preferred organometallic reagents are organo-tin compounds, organo-zinc compounds or organo-titanium compounds or organolithium compounds or Gringard reagents.
  • Preferred salts are tetraalkylammonium fluorides.
  • R ⁇ is an optionally substituted linear or branched C] _- C 3 o-alkyl, C 2 -C 4 o-alkenyl or alkoxyalkyl, C 2 -C ⁇ polyether, Cs-C ⁇ cycloalkyl or - Aryl radical and v are 0, 1 or 2.
  • the catalysts used are preferably added by so-called anti-catalysts or
  • catalyst poisons are e.g. Acids and when using acid e.g. Bases, which ultimately leads to a simple neutralization reaction with corresponding neutralization products, which can be filtered off or extracted if necessary. The corresponding
  • the reaction product between the catalyst and the catalyst poison can either be removed from the product or remain in the product.
  • the amount of the compound used with units of the general formula VII depends on the amount r of the silanol groups to be functionalized in the organosiloxane of the general formula VI. If, however, complete functionalization of the OH groups is desired, the compound with units of the general formula VII must be added in at least equimolar amounts, based on n. If one uses compound with units of the general formula VII in excess, then unreacted compound in the
  • Connection either be distilled off or hydrolyzed and then, if appropriate, also distilled off.
  • R 6 is hydrogen or a — optionally substituted with —CN or halogen -CC-C] _ ⁇ " Ko hl enwasserst ° ffrest and R 7 is a C] _- C ] _ Q hydrocarbon residue which is optionally substituted by -CN or halogen.
  • the hydrocarbon radicals R 1 and R 7 preferably have 1 to 5 carbon atoms.
  • the radicals methyl, ethyl and vinyl are particularly preferred.
  • Hydrogen is preferred as R 7 .
  • the process is preferably carried out at 0 ° C. to 200 ° C., particularly preferably at 40 ° C. to 150 ° C.
  • the process can be carried out with the inclusion of solvents or without the use of solvents in suitable reactors. If necessary, work is carried out under vacuum or under positive pressure or at normal pressure (0.1 Mpa).
  • solvents such as aliphatic hydrocarbons, such as, for example, heptane or decane, and aromatic hydrocarbons, such as, for example, toluene or xylene, are preferred.
  • Ethers such as THF, diethyl ether or MTBE can also be used.
  • the amount of solvent should be sufficient to ensure sufficient homogenization of the reaction mixture to ensure '. Solvents or solvent mixtures with a boiling point or boiling range of up to 120 ° C. at 0.1 MPa are preferred.
  • the filtrate was subjected to fractional distillation at normal pressure, 26 g of pure 2,2-dimethyl-2-sila-1,4-dioxane (132.23 g / mol, 20 mol) being obtained in a yield in the fraction passing through 132 ° C. receives from 27%.
  • Example 5 280 g of a bishydroxy-terminated polydimethylvinyl siloxane with a vinyl: methyl ratio of 1: 4 and a Mn of 2800 g / mol (determined by ⁇ H NMR spectroscopy) were determined at 80 ° C. with 26.7 g (200 mmol) of 2,2-dimethyl- [1,] dioxa-2-silacyclohexane and 900 mg (300 ppm) of lithium methoxide solution (10% in methanol). ⁇ H-NMR and 29 Si-NMR showed that after 4 hours all OH groups had been converted to hydroxyethyl methyl ether units. What remained was pure bis (hydroxyethyl methyl ether) -terminated polydimethyl vinyl siloxane.

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

Abstract

La présente invention concerne un procédé pour produire des hydroxyalkylpolysiloxanes de formule générale (V) (SiO4/2)k(R1SiO3/2)m(R12SiO2/2)p(R13SiO1/2)q [O1/2SiR32-CR42-O-(CR42)b-OH]s[O1/2H]t, selon lequel des organosiloxanes contenant du silanol, de formule générale (IV) (SiO 4/2)k(R1SiO3/2)m(R12SiO2/2)p(R13SiO1/2)q[O1/2H]r, sont mis en réaction avec des composés de formule générale (VII), avec R1, R3, R4, b, k, m, n, p, q, r, s et t ayant les significations énoncées dans la revendication 1. La présente invention concerne également des résines d'hydroxyalkylpolysiloxanes.
PCT/EP2005/005664 2004-06-17 2005-05-25 Procede pour produire des hydroxyalkylpolysiloxanes WO2005123812A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004029259.0 2004-06-17
DE200410029259 DE102004029259B4 (de) 2004-06-17 2004-06-17 Verfahren zur Herstellung von Hydroxyalkylpolysiloxanen

Publications (1)

Publication Number Publication Date
WO2005123812A1 true WO2005123812A1 (fr) 2005-12-29

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WO (1) WO2005123812A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006048217A1 (de) * 2006-10-11 2008-04-17 Wacker Chemie Ag Verfahren zur Herstellung siliciumorganischer Verbindungen
DE102009046254A1 (de) 2009-10-30 2011-05-19 Wacker Chemie Ag Verfahren zur Herstellung von (Hydroxymethyl)polysiloxanen
DE102012013711A1 (de) 2012-07-11 2014-01-16 Technische Universität München Oxasilacyclen und Verfahren zu deren Herstellung
DE102012013710A1 (de) 2012-07-11 2014-01-16 Technische Universität München Vernetzbare Siloxane durch säurekatalysierte Polymerisation von Oxasilacyclen

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0629648A2 (fr) * 1993-06-14 1994-12-21 Dow Corning Corporation Procédé de préparation de silioxanes à fonctions carbinole

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1357444A (fr) * 1963-05-24 1964-04-03 Bayer Ag Procédé de préparation de composés de 2-sila-1, 4-dioxanne
GB1052009A (fr) * 1964-07-30

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0629648A2 (fr) * 1993-06-14 1994-12-21 Dow Corning Corporation Procédé de préparation de silioxanes à fonctions carbinole

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 12 May 1984 (1984-05-12), ANDRIANOV, K. A. ET AL: "Organosilicon compounds containing .beta.-oxyethoxymethyl groups", XP002347497, retrieved from STN Database accession no. 1972:449146 *

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DE102004029259A1 (de) 2006-01-05

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