EP4004009A1 - Mélange hydrosilylable exempt de métal noble - Google Patents

Mélange hydrosilylable exempt de métal noble

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Publication number
EP4004009A1
EP4004009A1 EP20719420.0A EP20719420A EP4004009A1 EP 4004009 A1 EP4004009 A1 EP 4004009A1 EP 20719420 A EP20719420 A EP 20719420A EP 4004009 A1 EP4004009 A1 EP 4004009A1
Authority
EP
European Patent Office
Prior art keywords
radical
independently
group
radicals
another
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.)
Withdrawn
Application number
EP20719420.0A
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German (de)
English (en)
Inventor
Elke Fritz-Langhals
Sabine GOWANS
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
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Filing date
Publication date
Application filed by Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP4004009A1 publication Critical patent/EP4004009A1/fr
Withdrawn legal-status Critical Current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
    • C07F7/30—Germanium compounds
    • 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
    • C07F7/1876—Preparation; Treatments not provided for in 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/122—Metal aryl or alkyl compounds
    • 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
    • C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
    • C07F7/0878—Si-C bond
    • C07F7/0879—Hydrosilylation reactions
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0286—Complexes comprising ligands or other components characterized by their function
    • B01J2531/0297—Non-coordinating anions

Definitions

  • the invention relates to a mixture M which contains at least one cationic germanium (IV) compound as a catalyst and a process for the hydrosilylation of this mixture.
  • hydrosilicon compounds to alkenes and alkynes plays an important role in technical organosilicon chemistry.
  • This reaction known as hydrosilylation, is used, for example, to crosslink elastomers in silicones or to introduce functional groups into silanes or siloxanes.
  • the hydrosilylation only takes place in the presence of a catalyst.
  • platinum, rhodium or iridium complexes are used almost exclusively, which make the process considerably more expensive, especially when the precious metal cannot be recovered, for example in the manufacture of silicone elastomers.
  • the object of the present invention is therefore to provide a noble metal-free hydrosilylatable mixture and a method for hydrosilylating this mixture.
  • Transition metal complexes of iron, cobalt, nickel and manganese have been described as hydrosilylation catalysts.
  • the disadvantage here is that these often give rise to discoloration of the products.
  • Cationic germanium (II) compounds are known from PCT / EP2019 / 062003 which, in conjunction with oxygen, catalyze hydrosilylations.
  • Cationic germanium (IV) compounds are known from PCT / EP2020 / 054971. However, they have not yet been described as catalysts of hydrosilylation reactions. It has now surprisingly been found that germanium (IV) compounds which are present in cationic form - so-called germylium cations - catalyze hydrosilylation reactions.
  • the mixture M can therefore be hydrosilylated without a noble metal catalyst.
  • the cationic germanium (IV) compounds are highly effective as hydrosilation catalysts.
  • a great advantage of using germanium (IV) compounds as catalysts is that germanium (IV) compounds are non-toxic. Germanium (IV) compounds are also readily available as raw materials. For example, germanium tetrachloride is a waste product from zinc production.
  • the present invention relates to a mixture M containing (a) at least one compound A which is selected from (a1) a compound of the general formula (I) R 1 R 2 R 3 Si-H (I), wherein the radicals R 1 , R 2 and R 3 are independently selected from the group consisting of (i) hydrogen, (ii) halogen, (iii) unsubstituted or substituted C 1 -C 2 o _ hydrocarbon radical, and (iv ) unsubstituted or substituted C 1 -C 2 o _ hydrocarbonoxy radical, where two of the radicals R 1 , R 2 and R 3 can also form a monocyclic or polycyclic, unsubstituted or substituted C 2 -C 20 hydrocarbon radical, where substituted means in each case that the hydrocarbon or hydrocarbonoxy radical independently of one another has at least one of the following substitutions: a hydrogen atom can be replaced by halogen,
  • - C N, - OR z , - SR Z , - NR z 2 , - PR Z 2, - 0-C0-R z , - NH-CO-R z , - O- C0-0R z or - COOR z be replaced, a CH 2 group can be replaced by
  • R z is selected independently of one another from the group consisting of hydrogen, C 1 -C 6 - Alkyl radical, C 6 -C 14 aryl radical, and C 2 -C 6 alkenyl radical; and or
  • R x are selected independently from the group consisting of (i) halogen, (ii) unsubstituted or substituted C 1 -C 20 _ hydrocarbon radical, and (iii) unsubstituted or substituted C 1 -C 20 _ Hydrocarbonoxy radical, where substituted means in each case that the hydrocarbon or hydrocarbonoxy radical independently of one another has at least one of the following substitutions: a hydrogen atom can be replaced by halogen, a CH 2 - The group can be replaced by - O - or - NR Z -, in which R z is each independently selected from the group consisting of hydrogen, C 1 -C 6 -alkyl radical, C 6 -C 14 -aryl radical, and C 2 -C 6 -alkenyl radical; and in which the indices a, b, b ', c, c', c ", d, d ', d", d'"indicate the number of
  • R 4 R 5 C CR 6 R 7 (II), and / or
  • R 8 C ⁇ CR 9 (II '), in which the radicals R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are selected independently of one another from the group consisting of (i) hydrogen, (ii) -C ⁇ N, (iii) organosilicon radical with 1 - 100,000 silicon atoms, (iv) unsubstituted or substituted C 1 - C 20 _ hydrocarbon radical, and (v) unsubstituted or substituted C 1 -C 20 _ hydrocarbonoxy radical, where two of the radicals R 4 , R 5, R 6 and R 7 also together form a monocyclic or polycyclic, unsubstituted or substituted C 2 - may form C 20 _ hydrocarbon radical, wherein each substituted means that the hydrocarbon or hydrocarbons stoffoxyrest independently at least one of the fol- constricting Substitutions has: a hydrogen atom can through Halogen, - C N, - OR z , - SR Z ,
  • radicals R x are independently selected from the group consisting of (i) hydrogen, (ii) halogen, (iii) unsubstituted or substituted C 1 -C serstoffrest 20 _ hydrocar-, and (iv) unsubstituted or substituted C 1 - C 20 _ hydrocarbyloxy; and in which the radicals MB each independently of one another (i)
  • R is each independently selected from the group consisting of (i) hydrogen , (ii) halogen, (iii) unsubstituted or substituted C1-C20 hydrocarbon radical, and (iv) unsubstituted or substituted C 1 -C 20 _ hydrocarbyloxy, wherein each substituted means that the hydrocarbon or hydrocarbonoxy radical independently at least one of the following Has substitutions: a hydrogen atom can be replaced by halogen, - C ⁇ N, - OR 2 , - SR 2 , - NR Z 2 , - PR Z 2 , - 0-C0-R 2 ,
  • a CH 2 group can be replaced by - O -, - S - or - NR Z -, and a C atom can be replaced by a Si atom, in which R z is selected independently of one another from the group consisting of hydrogen, C 1 -C 6 -alkyl radical, C 6 -C 14 -aryl radical, and C 2 -C 6 -Alkenyl radical, and in which the indices a, b, b ', c, c', c ", d, d ', d", d'"indicate the number of the respective siloxane unit in the compound and, independently of one another, an integer im Range from 0 to 100,000, with the proviso that the sum of a, b, b ', c, c', c ", d, d ', d", d
  • the mixture M contains at least one compound A, which also includes mixtures of compounds of the general formula (I) and / or mixtures of compounds of the general formula (I ').
  • the radicals R 1 , R 2 and R 3 are preferably selected independently of one another from the group consisting of (i) hydrogen, (ii) chlorine, (iii) unsubstituted or substituted C 1 -C 12 Hydrocarbon radical, and (iv) unsubstituted or substituted C 1 -C 12 hydrocarbonoxy radical, where substituted has the same meaning as before; and preferably in formula (I '), the radicals R x independently of one another are exclusively selected from the group consisting of chlorine, C 1 -C 6 alkyl, C 2 - C 6 alkenyl, phenyl, and C 1 -C 6 - Alkoxy radical and the indices a, b, b ', c, c', c ", d, d ', d", d
  • the radicals R 1 , R 2 and R 3 in formula (I) and the radicals R x in formula (I ') are very particularly preferably selected independently of one another from the group consisting of hydrogen, chlorine, methyl, methoxy, ethyl, ethoxy, n-propyl, n-propoxy, and phenyl, and the indices a, b, b ', c, c', c ", d, d ', d", d "" are preferably selected independently of one another from an integer in the range 0 to 1,000.
  • a mixture of compounds of the formula (I ') is present in particular in the case of polysiloxanes.
  • the individual compounds of the mixture are not given for polysiloxanes, but an average formula (I'a) similar to formula (I ') is given:
  • the mixture M contains at least one compound B, whereby mixtures of compounds of the general formula (II) and / or mixtures of compounds of the general formula (II ') and / or mixtures of compounds of the general formula (II ").
  • Organosilicon radical in formulas (II) and (II ') denotes a compound with at least one direct Si-C bond in the molecule.
  • the radicals R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are particularly preferably selected independently of one another from the group consisting of (i) hydrogen, (ii) - C ⁇ N, (iii) organosilicon radical selected from the general formula (IIa) with 1-100,000 silicon atoms, in which the radicals R x are selected independently of one another from the group consisting of hydrogen, chlorine, C 1 -C 6 -alkyl radical, C 2 -C 6 -alkenyl radical, phenyl radical and C 1 -C 6 -alkoxy radical; (iv) unsubstituted or substituted C 1 -C 6 hydrocarbon radical, and (v) unsubstituted or substituted C 1 -C 6 hydrocarbonoxy radical, where substituted means in each case that the hydrocarbon or hydrocarbonoxy radical independently of one another has at least one of the following substitutions : a hydrogen atom can be replaced
  • Examples of compounds of the formula (II ′′) are R x 3 Si-0 [-SiR x 2 -0] m - [Si (MB) 2 -0] 1-100. ooo-SiR x 3 ,
  • Examples of compounds B are ethylene, propylene, 1-butylene, 2-butylene, isoprene, 1,5-hexadiene, cyclohexene, vinylcyclohexane,
  • the mixture M contains at least one compound C as a catalyst, which is selected from cationic germanium (IV) compounds.
  • the germanium (IV) compounds used are preferably those selected from compounds of the general formula (III), wherein the radicals R y are, independently of one another, a C 1 -C 50 hydrocarbon radical; and in which the radicals R z are, independently of one another, a C 1 -C 50 hydrocarbon radical; and wherein the radical Z is selected from silicon (IV) or germanium (IV); and in which the radical Y denotes a divalent C 2 -C 50 hydrocarbon radical; and in which the subscript a takes on the values 1, 2 or 3; and in which X a- is an a-valent anion.
  • Examples of anions X- in formula (III) are: Halides;
  • Tetrakis (pentafluorophenyl) metallate [M (C 6 F 5 ) 4] - with M Al, Ga; Tetrakis (pentachlorophenyl) borate [B (C 6 CI 5 ) 4 ] -;
  • Tris (perfluoroalkoxy) fluoroaluminate [FA1 (OR PF ) 3 ] - with R PF independently perfluorinated C 1 -C 14 hydrocarbon radical;
  • radicals R a are 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 ,
  • formula (III) Particularly preferred in formula (III) are the anions X- selected from the compounds of the formula [B (R a ) 4] -, in which the radicals R a are selected independently of one another from aromatic C 6 -C 14 hydrocarbon radicals in which all hydrogen atoms are independently replaced by a group selected from the group consisting of (i) fluoro, and (ii) triorganosilyl group of the formula -SiR b 3, in which the radicals R b are each independently C 1 -C 2 o _ alkyl radical substituted.
  • the anions X- selected from the compounds of the formula [B (R a ) 4] -, in which the radicals R a are independently selected from the group consisting of -C6F5, perfluorinated 1- and 2- naphthyl radical, - C 6 F 3 [2,4- (SiR b 3 ) 2 ], - C 6 F 3 [2,5- (SiR b 3 ) 2 ],
  • the R b radicals are each independently of one another C 1 -C 20 -alkyl radical.
  • the invention further provides a process for the hydrosilylation of the mixture M according to the invention, wherein at least one compound A is reacted with at least one compound B in the presence of compound C as a catalyst.
  • the reactants A and B and the catalyst C can be brought into contact with one another in any order. Bringing into contact preferably means that the reactants and the catalyst are mixed, the mixing being carried out in a manner known to the person skilled in the art. For example, compounds A and B can be mixed together and then catalyst C can be added. It is also possible to first mix compound A or B with catalyst C and then add the compound that is still missing.
  • the process according to the invention can be carried out in air or with exclusion of air.
  • the molar ratio of the compounds A and B, based on the Si — H groups present or the unsaturated carbon groups, is usually in the range from 1:10 to 10: 1; the molar ratio is preferably in the range from 1: 5 to 5: 1 , particularly preferably in the range 1: 2 to 2: 1.
  • the amount of cationic germanium (IV) compound can be freely selected by the person skilled in the art.
  • the molar ratio between compound C and the Si-H groups present in compound A is usually in the range from 1:10 7 to 1: 1, preferably in the range from 1:10 6 to 1:10, particularly preferably in the range from 1:10 5 to 1: 500.
  • the hydrosilylation 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 sum of the compounds A and B, is preferably in the range from 0.1% by weight to 1000 times the amount by weight, particularly preferably in the range from 10% by weight to 100% times the amount by weight, very particularly preferably in the range from 30% by weight to 10 times the amount by weight.
  • Aprotic solvents such as hydrocarbons such as pentane, hexane, heptane, cyclohexane or toluene, chlorohydrocarbons such as dichloromethane, chloroform, chlorobenzene or 1,2-dichloroethane, ethers such as diethyl ether, methyl tert-butyl ether, anisole, tetrahydrofuran or dioxane can be used as solvents , or nitriles such as acetonitrile or propionitrile can be used. 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 pressure in the hydrosilylation can be chosen freely by the person skilled in the art; it can be carried out under ambient pressure or under reduced or increased 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 hydrosilylation is very particularly preferably carried out at ambient pressure.
  • compounds are involved in the hydrosilylation, they are at the reaction temperature are present in gaseous form, a reaction preferably takes place under increased pressure, particularly preferably at the vapor pressure of the overall system.
  • the person skilled in the art can freely choose the temperature of the hydrosilylation.
  • the hydrosilylation is usually carried out at a temperature in the range from -100.degree. C. to + 250.degree. C., preferably in the range from -20.degree. C. to + 200.degree. C., particularly preferably in the range from 20.degree. C. to 150.degree.
  • the hydrosilylation is particularly preferably carried out at a temperature in a range from ⁇ 100 ° C. to + 250 ° C. and a pressure in a range from 0.01 bar to 100 bar.
  • the 1 H-NMR spectrum shows 87% conversion with formation of the hydrosilylation product after 20 minutes and 100% conversion after 20 hours.
  • EXAMPLE 4 Elastomer Crosslinking

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)

Abstract

La présente invention concerne un mélange M contenant (a) au moins un composé A, choisi parmi (a1) un composé de formule générale (I) et/ou (a2) un composé de formule générale (I') ; et (b) au moins un composé B choisi parmi (b1) un composé de formule générale (II) et/ou (b2) un composé de formule générale (II'), et/ou (b3) un composé de formule générale (II'') ; et (c) au moins un composé C en tant que catalyseur, choisi parmi les composés de germanium cationique (IV).
EP20719420.0A 2020-04-15 2020-04-15 Mélange hydrosilylable exempt de métal noble Withdrawn EP4004009A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2020/060581 WO2021209127A1 (fr) 2020-04-15 2020-04-15 Mélange hydrosilylable exempt de métal noble

Publications (1)

Publication Number Publication Date
EP4004009A1 true EP4004009A1 (fr) 2022-06-01

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP20719420.0A Withdrawn EP4004009A1 (fr) 2020-04-15 2020-04-15 Mélange hydrosilylable exempt de métal noble

Country Status (4)

Country Link
EP (1) EP4004009A1 (fr)
KR (1) KR20220093371A (fr)
CN (1) CN114364687A (fr)
WO (1) WO2021209127A1 (fr)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3028512B1 (fr) 2014-11-14 2016-12-09 Bluestar Silicones France Procede d'hydrosilylation mettant en œuvre un catalyseur organique derive de germylene
FR3051190A1 (fr) 2016-05-10 2017-11-17 Bluestar Silicones France Procede d'hydrosil mettant en oeuvre un catalyseur organique derive de germylene
EP3596090B1 (fr) * 2017-12-19 2020-07-22 Wacker Chemie AG Hydrosilylation avec un groupement silicium(iv) en tant que catalyseur

Also Published As

Publication number Publication date
WO2021209127A1 (fr) 2021-10-21
CN114364687A (zh) 2022-04-15
KR20220093371A (ko) 2022-07-05

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