EP3110823A1 - Verfahren zur hydrosilylierung unter zusatz organischer salze - Google Patents

Verfahren zur hydrosilylierung unter zusatz organischer salze

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Publication number
EP3110823A1
EP3110823A1 EP15707311.5A EP15707311A EP3110823A1 EP 3110823 A1 EP3110823 A1 EP 3110823A1 EP 15707311 A EP15707311 A EP 15707311A EP 3110823 A1 EP3110823 A1 EP 3110823A1
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Prior art keywords
component
compounds
organic
carbon
independently
Prior art date
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EP15707311.5A
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German (de)
English (en)
French (fr)
Inventor
Agnes Baskakov
Christine Kaes
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Wacker Chemie AG
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Wacker Chemie AG
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Publication of EP3110823A1 publication Critical patent/EP3110823A1/de
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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
    • C07F7/12—Organo silicon halides
    • C07F7/14—Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions
    • 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
    • C07F7/12—Organo silicon halides
    • C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
    • C07F7/122—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving the formation of Si-C linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/10—Chlorides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B01J27/13—Platinum group metals
    • 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
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/0827—Syntheses with formation of a Si-C bond
    • C07F7/0829—Hydrosilylation reactions

Definitions

  • the invention relates to a process for preparing organosilicon compounds by hydrosilylation with the aid of a transition metal catalyst with the addition of organic salts containing one or more heteroatoms.
  • organosilicon compounds are carried out according to the prior art according to the Müller-Rochow synthesis.
  • the functionalized organosilanes are of great economic importance, especially substituted with halogen, since they serve as starting materials for the production of many important products, for example silicones, adhesion promoters, water repellents and building protection agents.
  • this direct synthesis is not equally well suited for all silanes.
  • the production of so-called manganese silanes is difficult in this way and only possible with poor yields and selectivities.
  • One way to prepare manganese silanes is to convert easily prepared silanes (excess silanes) to manganese silanes by a substituent exchange reaction.
  • the hydrosilylation of 1-alkenes is known to be catalyzed by platinum group metal complexes.
  • platinum complexes such as the so-called “Speier catalyst” [H 2 PtCl 6 * 6 H 2 0], and the “Karstedt” solution, a complex compound of [H 2 PtCl 6 * 6H 2 0] and vinyl-substituted disiloxanes, are known to be very active catalysts.
  • the transition metal catalyzed hydrosilylation reaction is characterized in certain cases by the inadequate Selectivity and low yield, methods described in the literature try to overcome these limitations by using alternative solvents, such as ionic liquids DE 10 2006 029 430 A, CN 101033235 A, US Pat.
  • the object of the present invention was to provide a process for the preparation of silanes by hydrosilylation, which is characterized by very high selectivity and yield with respect to the desired silanes and easy technical realization.
  • the invention relates to a process for the addition of Si-bonded hydrogen to aliphatic carbon-carbon multiple bond by reacting
  • [Y] represents an inorganic or organic anion
  • [A] + represents an organic cation containing at least one heteroatom selected from nitrogen, phosphorus, oxygen and sulfur in an amount of 0.01 to 10 mol%, preferably 0.1 to 5 mol%, especially preferably 0.1 to 2 mol%, in each case based on the deficiency component (A) or (B), with the proviso that the molar ratio of metal atom in component (C) to salt (D) 1: 1 to 1: 500 , preferably 1: 1 to 1: 200, more preferably 1: 1 to 1:25, is.
  • organic salt is also understood as meaning those salts which contain silicon atoms.
  • the compounds used as component (A) in the process according to the invention may be any desired and hitherto known organosilicon compounds which have at least one Si-bonded hydrogen atom, such as e.g. SiH-functional silanes (AI) and siloxanes (A2).
  • Component (A) is preferably hydrogensilane (AI) of the general formula
  • R may be the same or different and represents optionally substituted hydrocarbon radicals which are free of aliphatic carbon-carbon multiple bonds
  • X may be the same or different and represents chlorine atom, bromine atom, methoxy or ethoxy radical,
  • a 0, 1, 2 or 3 and
  • b is 0, 1, 2 or 3, with the proviso that the sum a + b is 1, 2 or 3, preferably 2 or 3, more preferably 3.
  • radical X is chlorine atom.
  • Radicals R are preferably linear, branched or cyclic alkyl groups or aryl groups, particularly preferably linear, branched or cyclic alkyl groups having 1 to 18 carbon atoms, in particular methyl radicals.
  • the hydrogen silanes of the formula (1) are preferably HSiCl 3 , HSiCl 2 Me, HSiClMe 2 , HSiCl 2 Et and HSiClEt 2 ,
  • HSi (OMe) 3 HSi (OEt) 3 , HSi (OMe) 2 Me, HSi (OEt) 2 Me, HSi (OMe) Me 2 and HSi (OEt) Me 2 , more preferably HSiCl 3; HSiMeCl 2 and
  • polymeric organosilicon compounds (A2) can be used as constituent (A) in the process according to the invention.
  • Examples of compounds which can be used as component (A2) in the process according to the invention are all polymeric hydrogenated silicon-containing silicon compounds which have hitherto been used in hydrosilylation reactions.
  • the organosilicon compounds (A2) are
  • R 1 may be the same or different and has a meaning given above for R,
  • c 0, 1, 2 or 3
  • d is 0, 1 or 2, preferably 0 or 1,
  • Examples of compounds which can be used as component (B) in the process according to the invention are all aliphatically unsaturated compounds which have hitherto also been used in hydrosilylation reactions.
  • the compound (B) used according to the invention may be silicon-free organic compounds having aliphatically unsaturated groups (B1) as well as organosilicon compounds having aliphatically unsaturated groups (B2), preferably being silicon-free organic compounds (B1).
  • Components (B1) are preferably compounds having aliphatic double or triple bonds, more preferably compounds of the general formula
  • R 8 , R 9 , R 10 and R 11 are each independently hydrogen, monovalent, optionally substituted with -F, -Cl, -OR 6 , -NR 7 2 / -CN or -NCO hydrocarbon radicals having 1 to 18 carbon atoms, chlorine atom , Fluorine atom or alkoxy radicals having 1 to 18 carbon atoms, where in each case 2 radicals of the radicals R 8 , R 9 , R 10 and R 11 with the meaning of optionally substituted hydrocarbon radicals together with the carbon atoms to which they are attached form a cyclic radical can.
  • radicals R 8 and R 9 are preferably hydrogen. If compounds of the formula (3) are non-cyclic compounds, R 10 and R 11 independently of one another have the meaning of preferably hydrogen atom or optionally chlorine atom-substituted hydrocarbon radicals having 1 to 18 hydrocarbon atoms or chlorine atom, be - Particularly preferably of hydrogen or chloromethyl.
  • radicals R 6 are preferably radicals having 1 to 18
  • Carbon atoms particularly preferably hydrocarbon radicals having 1 to 18 carbon atoms.
  • Radicals R 7 are preferably radicals having 1 to 18 carbon atoms, more preferably hydrocarbon radicals having 1 to 18 carbon atoms.
  • the compounds (B1) used according to the invention are preferably 3-chloroprene-1, which is also referred to as allyl chloride, or 3-chloro-2-methylpropene-1, also called methallyl chloride, propene, acetylene, ethylene, isobutylene , Cyclopentene, cyclohexene, 1-octene, 1-dodecene and 1-hexadecene, with 3-chloropropene-1, cyclopentene and cyclohexene being particularly preferred.
  • component (B1) 1-dodecene as component (B1), in particular in small amounts to take up component (C).
  • aliphatic unsaturated organosilicon compounds (B2) can be used as constituent (B) in the process according to the invention, although this is not preferred.
  • the organosilicon compounds (B2) are N-(2-aminosilicon compounds
  • R 2 may be the same or different and signifies Sic-bonded, aliphatically unsaturated hydrocarbon radical
  • R 3 may be the same or different and optionally substituted, Sic-bonded aliphatically saturated
  • e is 0, 1, 2, 3 or 4, preferably 0, 1 or 2
  • organosilicon compounds (B2) are trimethylvinylsilane, 1,2-divinyltetramethyldisiloxane and vinyl-terminated organopolysiloxanes.
  • components (A) and (B) used according to the invention are commercially available products or can be prepared by processes customary in chemistry.
  • HSiCl 3 , HSiMeCl 2 or HSiMe 2 Cl is used as compound (A) and allyl chloride as component (B), where Me is methyl.
  • constituent (B) is preferably used in an amount such that the molar ratio of aliphatically unsaturated groups of constituent (B) to SiH groups of constituent (A) is from 20: 1 to 1:20, more preferably 10: 1 to 1:10, in particular 2: 1 to 1: 2.
  • component (A) may represent the deficiency component, i. in the mixture comprising components (A) and (B), more aliphatically unsaturated groups of constituent (B) than SiH-
  • component (B) can represent the deficiency component, ie in the mixture comprising components (A) and (B) are less aliphatically unsaturated groups of component (B) present as SiH groups of component (A).
  • components (A) and (B) are used in amounts such that component (B) is the subunit component.
  • the hydrosilylation reaction can be accompanied by the transfer of the chlorine, alkoxy or amino functionalities to the hydrosilylation catalyst or the compounds (A) used, which is the achievable yield in the hydrosilylation process according to the prior art Restricting the technique such that, in particular for the implementation of such mixtures satisfactory technical solutions are missing.
  • the inventive solution to this problem has considerable economic potential.
  • component (C) which promotes the addition reaction (hydrosilylation) between the aliphatic carbon-carbon multiple bonds and Si-bonded hydrogen, in the masses according to the invention all hitherto known metal-containing hydrosilylation be used.
  • Complexes of platinum, iridium or rhodium are preferably used as component (C) in the process according to the invention, particularly preferably complex compounds of platinum, in particular platinum (IV) complexes, most preferably the complexes PtCl 4 and H 2 PtCl 6 .
  • catalyst (C) can be used in the process according to the invention.
  • solvents (E) which are preferably inert towards component (A), are linear hydrocarbons, aromatic hydrocarbons, preferably xylene or toluene, ketones, preferably acetone, methyl ethyl ketone or cyclohexanone, alcohols, preferably methanol, ethanol, n- or i-propanol, with the proviso that the aforementioned solvents have no aliphatic carbon-carbon multiple bonds, or the desired target product.
  • the optionally used solvent (E) are preferably aliphatic carbon-carbon multiple bonds free linear hydrocarbons, aliphatic carbon-carbon multiple bonds free aromatic hydrocarbons, preferably xylene or toluene, or the desired target product. If component (C) is to be used in the form of a mixture with component (B1) or solvent (E), the content of metal, preferably Pt, in the mixture is preferably 0.1 to 10 Wt .-%, particularly preferably 0.5 to 6 wt .-%, in particular 1 to 6 wt. -%.
  • catalyst (C) depends on the desired reaction rate and on economic aspects.
  • Anion [Y] " is preferably one selected from the group consisting of halides, thiocyanate ([SCN] “ ), tetrafluoroborate ([BF 4 ] “ ), hexafluorophosphate ([PF 6 ] “ ), [tetrafluoroborate kis- (3, 5-bis- (trifluoromethyl) -phenyl) borate] ([BARF]), Trispen- tafluoroethyltrifluorophosphat ([P (C 2 F 5) 3 F 3] "), hexafluoro antimonate ([SbF 6] “ ), Hexafluoroarsenate ([AsF 6 ] “ ), fluorosulfonate, [R'-COO] "” , [R'-SO 3 ] “ , [R'-0-SO 3 ] “ , [R ' 2 - P0 4 ] " and [(R '- S0 2 ) 2 N]
  • the anion [Y] "inorganic anions, particularly halides, such as [F] ⁇ , [Cl] ⁇ , [Br] 'or [I]", thiocyanate ([SCN] "), tetrafluoroborate ([BF 4 ] " ) or hexafluorophosphate ([PF 6 ] ⁇ ).
  • Cation [A] + is preferably one selected from the group consisting of
  • k independently 0, 1 or 2
  • Y independently of one another may be identical or different and denotes N, O, S, C, P,
  • Z independently of one another may be identical or different and is C, N, O, S, P or Si,
  • R 4 , R 5 , R 6 and R 7 may each independently be the same or different and represent hydrogen or an organic radical
  • each g may be the same or different independently and depending on the valency of Y 0, 1, 2, 3 or 4 and
  • each h may be the same or different and, depending on the valence of Z or Y, is 0, 1, 2 or 3,
  • organic radical should also encompass organosilicon radicals.
  • component (D) has an organosilicon radical, those which have neither Si-bonded hydrogen atoms nor aliphatic carbon-carbon multiple bonds are preferred.
  • the radicals R 4 and R 5 are each independently preferably hydrogen, hydrocarbon radicals having 1 to 20 carbon atoms or silyl groups.
  • the radicals R 6 and R 7 are each independently preferably hydrogen, aliphatic radicals, cycloaliphatic radicals, aromatic radicals, oligoether groups, organyloxy groups, silyl groups, siloxy groups or halides, preferably chlorides, or cyanide radicals, with which Provided that radicals R 6 and R 7 , which are bonded to heteroatoms selected from N, P, O and S, preferably not have the meaning of halide or cyanide.
  • the radicals R 6 and R 7 are, independently of one another, particularly preferably hydrogen, hydrocarbon radicals having 1 to 22 carbon atoms, silyl or organyloxy groups having 1 to 22 carbon atoms, in particular hydrogen atom, aliphatic hydrocarbon radicals having 1 to 22 carbon atoms or alkoxy groups with 1 to 22 carbon atoms.
  • radicals R 4 , R s , R e and R 7 are aliphatic groups, they are preferably independently of one another straight-chain or branched hydrocarbon radicals having 1 to 20 carbon atoms, heteroatoms in the chain such as, for example, oxygen, Nitrogen or sulfur atoms, may be included. Radicals R 4 , R 5 , R 6 and R 7 are preferably independently saturated, but they may also have one or more double or triple bonds which may be conjugated or isolated in the chain.
  • radicals R 4 , R 5 , R e and R 7 are identical aliphatic groups are independently hydrocarbon groups having 1 to 14 carbon atoms, such as methyl, ethyl, n-propyl, Isopropyl, n-butyl, sec-butyl, tert. Butyl, n-pentyl, n-hexyl, n-octyl or n-decyl.
  • cycloaliphatic groups R 4 , R 5 , R 6 and R 7 are independently cyclic hydrocarbon radicals having between 3 and 20 carbon atoms, which may contain ring heteroatoms, such as oxygen, nitrogen or sulfur atoms.
  • the cycloaliphatic groups may also be saturated or have one or more double or triple bonds which may be conjugated or isolated in the ring.
  • Aromatic groups, carbocyclic-aromatic groups or heterocyclic-aromatic groups R 4 , R 5 , R 6 and R 7 independently of one another preferably have between 6 and 22 carbon atoms, for example phenyl, biphenyl, naphthyl, binaphthyl or Anthracylreste.
  • Oligoether tendency R 6 to R 7 are independently of each other preferably groups of the general formula (13) - [(CH 2 ) x - 0] y - R "(13), wherein
  • x is a number of 1 and 250
  • y is a number from 2 to 250 and
  • R ' 1 is an aliphatic, cycloaliphatic, aromatic or
  • Silyl group represents.
  • Organyloxy groups R 6 and R 7 are independently of each other preferably groups of the general formula
  • Silyl or siloxy groups R e and R 7 are, independently of one another, preferably groups of the general formula
  • R v may be the same or different and represent aliphatic, cycloaliphatic or aromatic radicals or amine or alkoxy groups.
  • At least one Y preferably has the meaning of nitrogen atom, phosphorus atom or oxygen atom, and particularly preferably both Y in each formula have the meaning of nitrogen atom.
  • the radicals R 6 and R 7 are, independently of one another, preferably hydrogen atom or organic radicals, particularly preferably hydrogen atom or aliphatic branched and unbranched hydrocarbon radicals.
  • the radicals R 6 and R 7 are preferably hydrogen atom or organic radicals, particularly preferably hydrogen atom or aliphatic branched and unbranched hydrocarbon radicals such as, for example, saturated linear and branched hydrocarbon radicals having 1 to 10 carbon atoms.
  • the cations [A] + are particularly preferably those of the formulas (9), (10) or (11).
  • the cations [A] + of the formulas (9) to (11) are five-membered or six-membered rings.
  • Cation [A] + is particularly preferably imidazolium, imidazolinium, imidazolidinium, pyridinium, pyrazolium or pyrrolidinium cations, particularly preferably those in which the ring atoms at Y or Z are the same C bonds to hydrogen atoms, saturated linear and branched C 1 to C 10 hydrocarbon radicals, alkoxy and / or silyl groups, in particular to hydrogen atoms, and in which the ring atoms at Y or Z are identical to heteroatom bonds to hydrogen atoms, saturated linear and branched C 1 to C 10 hydrocarbon radicals, alkoxy and / or silyl groups, in particular to linear and branched C 1 to C 10 hydrocarbon radicals and when Y is nitrogen atom in addition to hydrogen atom.
  • Component (D) is preferably imidazolium, imidazolinium, imidazolidinium, pyridinium, pyrazolium or pyrrolidinium cations and halides as anions, in particular fluoride, chloride, bromide or iodide.
  • Component (D) used according to the invention may be solid or liquid at 20 ° C. and 1000 hPa.
  • component (D) can be used in pure form or in a mixture with component (A) or (B) or with a solvent (E).
  • component (D) is used in amounts of preferably 0.1 to 5 mol%, particularly preferably 0.1 to 2 mol%, in each case based on the deficiency component (A) or (B) used. '
  • components (C) and (D) are used in amounts such that the molar ratio of metal atom in component (C) to salt (D) is preferably 1: 1 to 1: 200, more preferably 1: 1 to 1 : 25, is.
  • Component (E) has solvent function. This is advantageous in controlling the exothermic reaction and has the advantage in working up the reaction mixture that no additional component interferes with the separation.
  • the template of the target product also provides a way to control the exothermic reaction when dosing the reactants; On the other hand, in order to optimize the space-time yield, too much target pro- be submitted.
  • the proportion of initial product introduced is preferably from 5 to 50% by weight, more preferably from 10 to 35% by weight, in particular from 15 to 35% by weight, of the total mass at the beginning of the reaction.
  • components (A) to (E) in addition to components (A) to (E), no further substances are used.
  • the components used in the process according to the invention may each be a type of such a component as well as a mixture of at least two types of a respective component.
  • the individual components can be mixed together in any manner known per se.
  • the process according to the invention can be carried out continuously or discontinuously, with the continuous process being preferred when using organosilicon compounds (AI) and the discontinuous process when using polymeric organosilicon compounds (A2).
  • the inventive method is carried out in the single-phase or multi-phase system. If it is a multiphase reaction, two- or three-phase reactions are preferred.
  • catalyst (C) is used as the liquid phase
  • the heteroatomic organic salt (D) as the liquid or solid phase
  • reaction educts (A) and (B) as the liquid or gas phase.
  • a continuous process catalyst (C) in the case of a continuous process catalyst (C) is used in the form of a mixture with solvent (E) or component (Bl), wherein preferably component (D) is suspended or dissolved, and this with the aid of preferably static mixers with Components (A) and (B) mixed.
  • a further variant of the continuous process according to the invention shows the hydrosilylation reaction in a fixed bed reactor, wherein the heteroatomic organic salt (D) is applied to a support material, such as preferably silica, alumina and / or glass, and the transition metal catalyst (C) together with Si. H compounds (AI) and with component (Bl) are reacted in a gas or liquid phase reaction.
  • a support material such as preferably silica, alumina and / or glass
  • component (D) is initially introduced in admixture with solvent (E) in the process according to the invention.
  • solvent (E) for example chloropropylmethyldichlorosilane
  • component (D) is added and the reaction vessel contents are thoroughly mixed.
  • the reaction mixture thus obtained is then preferably heated, and in parallel the metal catalyst (C), preferably as mixtures with solvent (E) or component (Bl), and a mixture of the components (A), for example methyldichlorosilane, and (B),
  • C metal catalyst
  • A for example methyldichlorosilane
  • B for example, allyl chloride
  • the boiling temperature is determined by the nature of the reaction components (educts). The onset of the hydrosilylation reaction usually results from an increase in the temperature in the reaction vessel. noticeable, because this addition is exothermic.
  • the reaction of the starting materials is generally followed by regular sampling and GC determination of the ingredients. As soon as no appreciable increase in the content of the desired reaction product in the reaction mixture can be ascertained, it is possible to start separating off the low-boiling constituents of the reaction mixture, preferably by distillation, if appropriate under reduced pressure. Subsequently, a fine distillation of the product can be carried out, it is often also worked here under reduced pressure.
  • elevated temperature preferably 30 to 110 ° C, and preferably slightly elevated pressure, more preferably 1000 to 10,000 hPa, fed.
  • a fine distillation of the product can be carried out, which can be carried out under reduced pressure.
  • the process according to the invention is carried out at a temperature in the range from preferably 10 to 200.degree. C., more preferably in the range from 20 to 150.degree. C., in particular from 30 to 110.degree. Furthermore, the inventive method at a pressure in
  • the process according to the invention is preferably carried out under a protective gas atmosphere, for example under nitrogen or argon.
  • the inventive method is preferably carried out in the absence of moisture.
  • the products are obtained directly after completion of the inventive reaction with a purity of preferably> 60 wt .-%.
  • the purity of the distilled product is preferably> 98% by weight.
  • the products produced according to the invention can be used for all purposes, such as the previously known organosilanes. They can also be further processed as desired. Thus, if the products are chlorosilanes, the Si-bonded chlorine atoms can be esterified with an alcohol in a conventional manner to give alkoxysilanes.
  • the alcohols used for the esterification according to the invention are preferably methanol, ethanol or 2-methoxyethanol.
  • the process according to the invention has the advantage that it is simple to carry out and can be prepared in an economical manner hydrolysis products, such as, for example, 3-chloropropylmethyldichlorosilane, with an excellent yield. Furthermore, the method according to the invention has the advantage that it has a high selectivity and valuable Si-H components can be used effectively.
  • the inventive method has the advantage that only small amounts of component (D) must be used, which on the one hand has economic advantages, on the other hand no disturbing influence on the product isolation.
  • the process according to the invention shows an unexpected technical solution based on the discovery that the transition metal complexes catalyzed hydrosilylation with the addition of very small amounts of one or more organic salts containing one or more heteroatoms, surprisingly in a selective manner, with a high yield Hydrosilylation of Si-H compounds catalyze in a multi-phase reaction.
  • Another advantage of the present invention is that these organic salts can be used in the form of solids and thus can be easily separated from the product mixture and recycled after the end of the reaction.
  • Example 1 The procedure described in Example 1 is repeated with the modification that in the 50 ml flask to dichloro (3-chloropropyl) methylsilane 0.34 g (1.52 mmol or 0.5 wt .-% bezo ⁇ gen on the total amount the components used) are submitted to 1,3-dimethylimidazolium iodide. Results can be found in Table 1.
  • Example 3 The procedure described in Example 1 is repeated with the modification that in the 50 ml flask to dichloro (3-chloropropyl) methylsilane 0.14 g (0.62 mmol or 0.2 wt .-% based on the total amount of the used Components) 1,3-Dimethylimidazoliumiodid be submitted. Results can be found in Table 1.
  • Example 3
  • Example 4 The procedure described in Example 1 is repeated with the modification that in the 50 ml flask to dichloro (3-chloropropyl) methylsilane 0.34 g (1.95 mmol or 0.5 wt .-% Bezo- to the total amount of the components used) 1-butyl-3-methylimidazoliumchlorid be submitted. Results can be found in Table 1.
  • Example 4
  • Example 1 The procedure described in Example 1 is repeated with the modification that in the 50 ml flask to dichloro (3-chloropropyl) methylsilane 0.34 g (1.72 mmol or 0.5 wt .-% based on the total amount of the used Components) 1-butyl-3-methylimidazoliumthiocyanat be submitted. Results can be found in Table 1.
  • Example 1 The procedure described in Example 1 is repeated with the modification that in the 50 ml flask to dichloro (3-chloropropyl) methylsilane 0.34 g (1.50 mmol or 0.5 wt .-% based on the total amount of the used Components) 1-butyl-3-methylimidazoliumtetraf luorborat be submitted. Results can be found in Table 1.
  • Example 1 The procedure described in Example 1 is repeated with the modification that in the 50 ml flask to dichloro (3-chloropropyl) methylsilane 0.34 g (1.24 mmol or 0.5 wt .-% based on the total amount the components used) 1,3-
  • Example 1 The procedure described in Example 1 is repeated with the modification that in the 50 ml flask to dichloro (3-chloropropyl) methylsilane 0.17 g (1.63 mmol or 0.25 wt .-% based on the total amount of the used Components) imida- zol hydrochloride are submitted. Results can be found in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP15707311.5A 2014-02-28 2015-02-20 Verfahren zur hydrosilylierung unter zusatz organischer salze Withdrawn EP3110823A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014203770.0A DE102014203770A1 (de) 2014-02-28 2014-02-28 Verfahren zur Hydrosilylierung unter Zusatz organischer Salze
PCT/EP2015/053621 WO2015128260A1 (de) 2014-02-28 2015-02-20 Verfahren zur hydrosilylierung unter zusatz organischer salze

Publications (1)

Publication Number Publication Date
EP3110823A1 true EP3110823A1 (de) 2017-01-04

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CN108033976B (zh) * 2017-12-04 2020-09-01 杭州师范大学 一种以茂金属为催化剂的不饱和化合物硅氢加成反应
CN108129507B (zh) * 2017-12-04 2020-05-29 杭州师范大学 一种以钛酸酯为催化剂的硅氢加成反应与应用
KR102618135B1 (ko) * 2021-09-23 2023-12-29 (주)제이아이테크 피롤 계열의 수소-규소 결합의 안정성 개선을 위한 첨가제

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KR101861727B1 (ko) 2018-06-29
US20170101424A1 (en) 2017-04-13
KR20160113229A (ko) 2016-09-28
WO2015128260A1 (de) 2015-09-03
JP2017510565A (ja) 2017-04-13
JP6224265B2 (ja) 2017-11-01
CN106029681A (zh) 2016-10-12
DE102014203770A1 (de) 2015-09-03

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