EP4168416A1 - Verfahren zur herstellung von siloxanen - Google Patents

Verfahren zur herstellung von siloxanen

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Publication number
EP4168416A1
EP4168416A1 EP20760851.4A EP20760851A EP4168416A1 EP 4168416 A1 EP4168416 A1 EP 4168416A1 EP 20760851 A EP20760851 A EP 20760851A EP 4168416 A1 EP4168416 A1 EP 4168416A1
Authority
EP
European Patent Office
Prior art keywords
group
independently
radical
compounds
substituted
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.)
Pending
Application number
EP20760851.4A
Other languages
German (de)
English (en)
French (fr)
Inventor
Elke Fritz-Langhals
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
Publication of EP4168416A1 publication Critical patent/EP4168416A1/de
Pending legal-status Critical Current

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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
    • C07F7/0834—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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • 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
    • C07F17/00—Metallocenes
    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • 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
    • 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
    • C07F7/0896—Compounds with a Si-H linkage
    • 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
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20

Definitions

  • the invention relates to a process for preparing siloxanes from alkoxy organosilicon compounds of the general formula (I) and/or (II) in the presence of at least one cationic silicon and/or germanium compound.
  • Siloxanes are a technically important class of compounds that are used in numerous fields of technology.
  • the production of siloxanes is therefore an important process in technical organosilicon chemistry.
  • the hydrolytic condensation starting from chlorosilanes according to the following reaction equation is established on an industrial scale:
  • the object of the invention was to provide a process for the production of siloxanes which can be used on an industrial scale and in which alkoxy-containing organosilicon compounds can be linked to form siloxanes without a hydrolysis step.
  • radicals R 1 , R 2 and R 3 are hydrogen.
  • the radicals R 1 , R 2 and R 3 are preferably selected independently from the group consisting of hydrogen, an unsubstituted or substituted C 1 -C 12 hydrocarbon radical and an unsubstituted or substituted C 1 -C 12 hydrocarbon oxy radical.
  • the radicals R 1 , R 2 and R 3 are particularly preferably selected independently of one another from the group consisting of methyl, ethyl, vinyl, phenyl, methoxy and ethoxy.
  • the radical R x in the formulas (I) and (II) is preferably independently selected from the group with an unsubstituted or substituted C 1 -C 12 hydrocarbon radical, in particular an unsubstituted or substituted C 1 -C 6 hydrocarbon radical.
  • R x in the formulas (I) and (II) is particularly preferably selected independently from the group containing a C 1 -C 4 -alkyl radical, vinyl and phenyl.
  • the indices a, b, b', c, c', c'', d, d', d'', d''' are preferably selected independently from one another Number in the range from 0 to 1 . 000 , particularly preferably in the range from 0 to 100 .
  • the carbonyl compound is preferably selected from compounds of the general formula (III)
  • Aldehydes such as formaldehyde, acetaldehyde, propionaldehyde and benzaldehyde
  • Ketones such as acetone, methyl ethyl ketone, methyl i-butyl ketone, diethyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, acetophenone and pinacolone
  • Carboxylic acid esters such as methyl acetate, ethyl acetate and methyl propionate - Lactones such as caprolactone, butyrolactone and valerolactone
  • Ureas such as urea, N,N'-dimethylurea, N,N'-diethylurea and tetramethylurea
  • the carbonyl compound is selected from the group consisting of acetaldehyde, formaldehyde, acetone and methyl ethyl ketone.
  • the corresponding acetals or ketals can also be used since they are in equilibrium with the aldehydes in the presence of the cationic silicon and/or germanium compounds.
  • paraldehyde or acetaldehyde diethylacetal can be used instead of acetaldehyde and 1,3,5-trioxane can be used instead of formaldehyde.
  • the carbonyl compound can be used in a proportion by weight of 0.01 to 500%, preferably 0.1 to 100%, particularly preferably 1 to 50%, based on the weight of the compound of general formula (I) or (II) or if Mixtures of (I) and (II) are used, based on the total weight of the compounds of general formula (I) and (II).
  • R v is independently selected from the group consisting of hydrogen, unsubstituted or substituted C 1 -C 20 hydrocarbon radical, unsubstituted or substituted Ci-C 20 hydrocarbon oxygen radical and triorganosilyl radical of the formula --SiR b 3 , where R b is independent of one another is selected from the group C 1 -C 20 hydrocarbon radical C 1 -C 20 hydrocarbon radical f-oxy radical, it also being possible for two radicals R v to be connected to one another so that bicyclic or polycyclic rings are formed, for example indenyl - or fluorenyl rings.
  • Examples of monovalent anions X" that can be mentioned are: halides;
  • the anions X" are selected from the group consisting of compounds of the formulas [B(SiC13)4] ⁇ and [B(R a ) 4 ]-, in which the radicals R a are independently selected from aromatic C C 6 -C 14 -hydrocarbon radical in which all hydrogen atoms are independently substituted by a radical selected from the group consisting of fluorine and a triorganosilyl radical of the formula -SiR b 3 , in which the radicals R b are independently C1-C20 alkyl radicals are.
  • the anions X" are very particularly preferably selected from the group consisting of the compounds of the formulas [B(SiCl 3 ) 4 ]- and [B(R a ) 4 ]-, in which the radicals R a are independently of one another are selected from the group consisting of - C 6 F 5 , perfluorinated 1- and 2-naphthyl radical, -C 6 F 3 (SiR b 3 ) 2 and - C 6 F 4 (SiR b 3 ), in which the radicals R b are each independently C 1 -C 20 alkyl.
  • radicals R a examples include: m-difluorophenyl radical, 2,2,4,4-tetrafluorophenyl radical, perfluorinated 1-naphthyl radical, perfluorinated 2-naphthyl radical, perfluorobiphenyl radical, -C 6 F 5 , -C 6 H 3 (m-CF 3 ) 2 , - C 6 H 4 (p-CF 3 ) , - C 6 H 2 (2,4,6-CF 3 ) 3 , - C 6 F 3 (m-SiMe 3 ) 2 , - C 6 F 4 (p-SiMe 3 ), - C 6 F 4 (p-SiMe2t-butyl) .
  • radicals R v in the formula (IVa) which can be mentioned are: alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert . -butyl, n-pentyl, sec-pentyl, isopentyl, neo-pentyl, tert.
  • -pentyl radical hexyl radicals such as n-hexyl radical; heptyl radicals such as n-heptyl radical; octyl radicals such as n-octyl radical and iso-octyl radicals (eg 2,4,4-trimethylpentyl radical); nonyl radicals such as n-nonyl radical; decyl radicals such as n-decyl radical; dodecyl radicals such as n-dodecyl radical; hexadecyl radicals such as n-hexadecyl radical; octadecyl radicals such as n-octadecyl radical; cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl; aryl radicals such as phenyl, naphthyl, anthrac
  • the radicals R v are preferably selected independently of one another from the group with C 1 -C 3 -alkyl radical, hydrogen and triorganosilyl radical of the formula -SiR b 3 , in which the radicals R b are independently C 1 -C 20 _ mean alkyl radical.
  • the radicals R v are particularly preferably selected independently of one another from the methyl radical, hydrogen and trimethylsilyl radical.
  • the cyclopentadienyl radical from the formula (IV) can be pentamethylcyclopentadienyl, tris(trimethylsilyl)cyclopentadienyl and bis(trimethylsilyl)cyclopentadienyl.
  • Si(II) compounds are less preferred as they are generally more difficult to access.
  • the cationic silicon and/or germanium compounds can be selected from the group of cationic silicon(IV) and germanium(IV) compounds of the general formula (V), where R w is independently selected from the group with C C 1 -C 6 alkyl radical and phenyl radical; where Y is preferably a 1,8-naphthalenediyl radical, and where X" is preferably selected from the group with [B(C 6 F 5 ) 4 ] and [B(SiCla) 4 ]-.
  • the reactants of the formulas (I) and/or (II), the catalyst (formulas IV and V) and, if appropriate, the carbonyl compound (formula III) can be brought into contact with one another in any order.
  • Preferably means in contact bring about that the reactants and the catalyst are mixed, the mixing being carried out in a manner known to those skilled in the art.
  • the reaction according to the invention can be carried out without a solvent or with the addition of one or more solvents.
  • the proportion of the solvent or the solvent mixture, based on the total amount by weight of the compounds of the formula (I) and (II), is preferably at least 0.01% by weight and at most 1000 times the amount by weight, particularly preferably at least 0.1% by weight. % and at most 100 times the amount by weight, very particularly preferably at least 1% by weight and at most 10 times the amount by weight.
  • Preferred solvents are aprotic solvents, for example hydrocarbons such as pentane, hexane, heptane, cyclohexane or toluene, chlorinated hydrocarbons such as dichloromethane, chloroform, chlorobenzene or 1,2-dichloroethane, ethers such as diethyl ether, methyl tert. butyl ether, anisole, tetrahydrofuran or dioxane, or nitriles such as acetonitrile or propionitrile. Solvents or solvent mixtures with a boiling point or boiling range of up to 120° C. at 0.1 MPa are preferred.
  • the solvents are preferably chlorinated and non-chlorinated aromatic or aliphatic hydrocarbons.
  • the catalyst of the general formula (IV) and/or (V) is dissolved in the solvent or in the carbonyl compound and then with the compound of the general formula (I) and/or (II) mixed.
  • the pressure during the reaction can be freely chosen by the person skilled in the art; it can be carried out under ambient pressure or under reduced or superatmospheric pressure.
  • the pressure is preferably in a range from 0.01 bar to 100 bar, particularly preferably in a range from 0.1 bar to 10 bar, and the reaction is very particularly preferably carried out at ambient pressure.
  • the reaction time at 70°C was 2 days. This formed 95% each of hexamethyldisiloxane and diethyl ether.
  • the reaction time at 70°C was 2 days.
  • the conversion was 70%.
  • the reaction time at 70°C was 2 days. In the process, oligomers of siloxanes and diethyl ether were formed. The conversion was 45%.
  • MSE 100 is a siloxane formed by hydrolytic condensation of MeSi(OMe) 3 and containing 31% by weight of methoxy groups.
  • Example 11 Crosslinking of MSE 100 with Cp*Ge + B (C 6 F 5 ) 4- and acetaldehyde
  • Example 10 The experiment according to Example 10 is repeated without the addition of acetaldehyde.
  • the sample is still liquid after mixing and has hardened after 24 hours at 23°C.
  • Example 17 Crosslinking of MSE 100 with Cp (SiMea) aGe + B (C 6 F 5 ) 4 - and methyl ethyl ketone
  • MSE 100 and 134 mg acetaldehyde diethyl acetal (5% by weight based on MSE 100) are mixed in a speed mixer. Then 1.1 mg of Cp(SiMea)aGe + B(SiCla) 4 ⁇ (formula (IV), 0.043% by weight based on MSE 100) are added to this mixture without the addition of solvent and the mixture is again stirred for approx. Mixed in the speed mixer for 2 minutes. After approx. 4 hours at 23 °C the mixture has hardened and is colourless.
  • Example 19 Crosslinking of MSE 100 with Cp*Ge + B ( C 6 F 5 ) 4 - and paraldehyde 2536 mg MSE 100 and 129 mg paraldehyde (5% by weight based on MSE 100) are mixed in a speed mixer. Then 1.2 mg of Cp (SiMes) 3Ge + B (C 6 F 5 ) 4 - (formula (IV), 0.047% by weight based on MSE 100) are added to this mixture without the addition of solvent and left for approx.
  • Example 19 The experiment in Example 19 is repeated. After mixing, the sample is heated to 50 °C and after approx . Cured at this temperature for 1 hour.
  • Silres IC 368 is a hydrolytic co-condensate of PhSi(OMe) 3 and MeSi(OMe)3 in a ratio of 62:38, which contains 14% by weight of methoxy groups.
  • Example 23 Crosslinking of Silres IC 368 with Cp*Ge + B(C 6 F 5 ) 4 - and paraldehyde
  • the mixture has hardened after 24 hours at 23°C.
  • Example 23 is repeated with TRASIL instead of Silres IC 368. After approx. 24 hours at 23°C the mixture has hardened.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
EP20760851.4A 2020-08-21 2020-08-21 Verfahren zur herstellung von siloxanen Pending EP4168416A1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2020/073525 WO2022037793A1 (de) 2020-08-21 2020-08-21 Verfahren zur herstellung von siloxanen

Publications (1)

Publication Number Publication Date
EP4168416A1 true EP4168416A1 (de) 2023-04-26

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP20760851.4A Pending EP4168416A1 (de) 2020-08-21 2020-08-21 Verfahren zur herstellung von siloxanen

Country Status (6)

Country Link
US (1) US20230287018A1 (ja)
EP (1) EP4168416A1 (ja)
JP (1) JP2023542476A (ja)
KR (1) KR20230053668A (ja)
CN (1) CN115916793A (ja)
WO (1) WO2022037793A1 (ja)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023161534A2 (de) 2022-06-17 2023-08-31 Technische Universität München Kationische ge(ii) verbindungen, verfahren zu ihrer herstellung und verwendung als katalysatoren

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5196559A (en) * 1992-01-23 1993-03-23 Dow Corning Corporation Equilibration of cyclic siloxanes with novel catalysts
WO2018103864A1 (de) * 2016-12-09 2018-06-14 Wacker Chemie Ag Verfahren zur herstellung von hydridosilanen
CN110662790A (zh) * 2017-05-23 2020-01-07 瓦克化学股份公司 氢化硅氧烷与硅(ii)化合物的交联
JP2020518583A (ja) * 2017-10-06 2020-06-25 ワッカー ケミー アクチエンゲゼルシャフトＷａｃｋｅｒ Ｃｈｅｍｉｅ ＡＧ カチオン性ケイ素（ｉｉ）化合物の存在下におけるシロキサンの製造

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Publication number Publication date
KR20230053668A (ko) 2023-04-21
CN115916793A (zh) 2023-04-04
JP2023542476A (ja) 2023-10-10
US20230287018A1 (en) 2023-09-14
WO2022037793A1 (de) 2022-02-24

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