EP4634196A1 - Peracid promoters in the iridium-catalyzed hydrosilylation synthesis of haloalkylorganosilanes - Google Patents

Peracid promoters in the iridium-catalyzed hydrosilylation synthesis of haloalkylorganosilanes

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Publication number
EP4634196A1
EP4634196A1 EP23829054.8A EP23829054A EP4634196A1 EP 4634196 A1 EP4634196 A1 EP 4634196A1 EP 23829054 A EP23829054 A EP 23829054A EP 4634196 A1 EP4634196 A1 EP 4634196A1
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EP
European Patent Office
Prior art keywords
acid
iridium
acids
group
ppm
Prior art date
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EP23829054.8A
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German (de)
French (fr)
Inventor
Henrik Scholz
Edwin Kroke
Konstantin KRAUSHAAR
Holger Jürgen Glatzer
Kenrick Martin Lewis
Roland Wagner
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Momentive Performance Materials GmbH
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Momentive Performance Materials GmbH
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Publication of EP4634196A1 publication Critical patent/EP4634196A1/en
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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/468—Iridium
    • 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
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • 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
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium

Definitions

  • the present invention relates to a process for making haloorganosilicon compounds. More particularly, the invention relates to a process for the preparation of haloorganoalkoxysilanes, in particular such as chloropropyltriethoxysilane, via the hydrosilylation of haloalkenes with alkoxysilanes, and compositions comprising one or more haloorganoalkoxysilanes, one or more iridium-containing compounds and one or more peroxybenzoic acids, as well as the use of such compositions.
  • haloorganoalkoxysilanes in particular such as chloropropyltriethoxysilane
  • compositions comprising one or more haloorganoalkoxysilanes, one or more iridium-containing compounds and one or more peroxybenzoic acids, as well as the use of such compositions.
  • Haloalkylorganosilanes are key intermediates for the preparation of a variety of functionalized organosilanes, for example amino-, mercapto- and methacryloyloxyorganosilanes, which are used as silane coupling agents.
  • functionalized organosilanes for example amino-, mercapto- and methacryloyloxyorganosilanes, which are used as silane coupling agents.
  • chloropropyltriethoxysilane is a key intermediate for the preparation of polysulfane-containing organoalkoxysilanes, which are used in the manufacture of silica-filled tires.
  • chloropropyltriethoxysilane CPTES
  • TES chloropropyltriethoxysilane
  • Dimeric olefin Ir (I) halide complexes were described as efficient catalysts for the synthesis of CPTES from TES and allyl chloride (US4658050). Yields up to 75 % were described for 100 ppm catalyst.
  • US 5616762 describes the synthesis of CPTES from TES and allyl chloride in the presence of Ir (III) chloride hydrate. An excess of allyl chloride is used to obtain yields greater than 80 %. Although potentially a high yield of CPTES can be obtained in the reactions described above, Ir catalyzed reactions yielding CPTES suffer from a lack of reproducibility. Especially at low Ir concentrations, unpredictable variations of the yield occur. Hence, there is a need for additives stabilizing and further increasing the yield of the Ir catalyzed hydrosilylation of allyl chloride by TES.
  • WO2017/154846 A1 appears to teach that the iridium-catalzed hydrosilylation of allylic species can be significantly accelerated when in a pretreatment step an iridium complex is produced by reacting binuclear Iridium complexes bearing silyl groups with an allyl compound.
  • US6015920 A is directed at a process for hydrosilylation reactions, wherein a portion of the reactor output is recycled continuously to the reactor, which is also exemplified for the production of (3-chloropropyl)trimethoxysilane by the iridium-catalyzed hydrosilylation of allyl chloride with trimethoxysilane.
  • US 9556208 describes the use of hydroperoxides, dialkylperoxides and diacylperoxides as promotors for the hydrosilylation of allyl chloride with alkoxysilanes in the presence of Ru catalysts.
  • Di-t-butylperoxide is used for the reaction of allyl chloride with TES.
  • m-Chloroperbenzoic acid was described as promotor for the reaction of 1 -octene with triethylsilane in the presence of Rh-phosphine complexes (Calhoun et al, Trans. Metal. Chem., 8(6), 365 (1983)).
  • DE 10133008 proposes peracids, among them m-chloroperbenzoic acid, as promotors for hydrosilylations of H-silanes or H-siloxanes with double bond or triple bond moieties containing hydrocarbons, silanes or siloxanes.
  • Catalysts are all known hydrosilylation catalysts, preferably based on Pt, Ru, Rh and Pd.
  • US 6872845 discloses aromatic compounds as promotors for Ru catalyst based hydrosilylations yielding haloorganoalkoxysilanes. Further, the addition of oxygen is proposed for an activation of the outlined Ru-CO and Ru-phosphine catalysts. Generally, the oxygen level naturally occurring in the raw materials is sufficient. A further activation is possible by addition of 3 % O2 in N2, for example.
  • US 8580994 describes the beneficial effect of a reduction of the oxygen content during the hydrosilylation of allyl chloride to dimethylethoxysilane in the presence of Ir-diene complex catalysts.
  • the catalyst system consisting of Ir-containing catalyst and peroxycarboxylic acids as promotors is highly tolerant towards the use of as received olefinic halides, thus making an additional purification of the olefinic compound redundant.
  • the present invention described in detail hereafter is directed at a process for producing an organoalkoxysilane product comprising reacting
  • the invention relates to a process for producing a compound of Formula (I),
  • R 1 and R 2 are alkyl groups of from 1 to 6 carbon atoms
  • R 3 is an alkyl group of from 1 to 6 carbon atoms or hydrogen
  • R 4 is an alkyl group of from 1 to 6 carbon atoms, hydrogen or halogen
  • R 5 is hydrogen or an alkyl group of from 1 to 6 carbon atoms
  • X is a halogen; and y is 0, 1 or 2.
  • the process according to the invention is a process for producing a compound of Formula (I),
  • R 1 and R 2 are alkyl groups of from 1 to 6 carbon atoms
  • R 3 is an alkyl group of from 1 to 6 carbon atoms or hydrogen
  • R 4 is an alkyl group of from 1 to 6 carbon atoms, hydrogen or halogen
  • R 5 is hydrogen or an alkyl group of from 1 to 6 carbon atoms
  • X is a halogen; and y is 0, 1 or 2.
  • This invention relates to a process for making haloorganosilicon compounds, and more particularly, to a process for the preparation of products of Formula (I), via the hydrosilylation of haloalkenes with alkoxysilanes in the presence of peroxycarboxylic acids and an iridium-containing catalyst.
  • alkyl herein is meant to include straight, branched and cyclic alkyl groups. Specific and non-limiting examples of alkyls include, but are not limited to, methyl, ethyl, propyl and isobutyl.
  • substituted alkyl herein is meant an alkyl group that contains one or more substituent groups that are inert under the process conditions to which the compound containing these groups is subjected.
  • the substituent groups also do not substantially or deleteriously interfere with the process.
  • aryl herein is meant a non-limiting group of any aromatic hydrocarbon from which one hydrogen atom has been removed.
  • An aryl may have one or more aromatic rings, which may be fused, connected by single bonds or other groups.
  • Specific and non-limiting examples of aryls include, but are not limited to, tolyl, xylyl, phenyl and naphthalenyl.
  • substituted aryl herein is meant an aromatic group substituted as set forth in the above definition of “substituted alkyl.” Similar to an aryl, a substituted aryl may have one or more aromatic rings, which may be fused, connected by single bonds or other groups; however, when the substituted aryl has a heteroaromatic ring, the free valence in the substituted aryl group can be to a heteroatom (such as nitrogen) of the heteroaromatic ring instead of a carbon. If not otherwise stated, it is preferred that substituted aryl groups herein contain 1 to about 30 carbon atoms.
  • alkenyl herein is meant any straight, branched, or cyclic alkenyl group containing one or more carbon-carbon double bonds, where the point of substitution can be either a carbon-carbon double bond or elsewhere in the group.
  • alkenyls include, but are not limited to, vinyl, propenyl, allyl, methallyl, and ethylidenyl norbornane.
  • alkynyl is meant any straight, branched, or cyclic alkynyl group containing one or more carbon-carbon triple bonds, where the point of substitution can be either at a carboncarbon triple bond or elsewhere in the group.
  • unsaturated is meant one or more double or triple bonds. In a preferred embodiment, it refers to carbon-carbon double or triple bonds.
  • inert functional group herein is meant a group other than hydrocarbyl or substituted hydrocarbyl, which is inert under the process conditions to which the compound containing the group is subjected.
  • the inert functional groups also do not substantially or deleteriously interfere with any process described herein that the compound in which they are present may take part in.
  • examples of inert functional groups include halo (fluoro, chloro, bromo, and iodo), ether such as -OR 30 , wherein R 30 is hydrocarbyl or substituted hydrocarbyl.
  • hetero atoms herein is meant any of the Group 13-17 elements except carbon, and can include for example oxygen, nitrogen, silicon, sulfur, phosphorus, fluorine, chlorine, bromine, and iodine.
  • olefin herein is meant any aliphatic or aromatic hydrocarbon containing one or more additional carbon-carbon double bonds. Such olefins may be linear, branched or cyclic and may be substituted with heteroatoms as described above, with the proviso that the substitutents do not interfere substantially or deleteriously with the course of the desired reaction to produce the product.
  • peroxycarboxylic acid herein is meant any compound containing a peroxycarboxylic acid moiety, i.e. a structure of the formula -RC(O)-O-O-H, wherein R can be any organyl group.
  • catalytically effective amount herein is meant an amount effective to catalyze the hydrosilylation reaction.
  • reaction-promoting effective amount herein is meant an amount sufficient to promote a reaction, but not an amount that will inhibit the reaction.
  • halogen herein is meant any atom that is a member of Group VI I A of the periodic table (fluorine, chlorine, bromine, iodine, astatine).
  • halo used herein with respect to a compound is meant a compound that contains a halogen atom.
  • the principal products of the hydrosilylation process of this invention are compounds of the general Formula (I) (R 1 )y(R 2 O) 3 -ySiCH 2 CHR 3 CR 4 R 5 X (I) wherein R 1 and R 2 are alkyl groups of from 1 to 6 carbon atoms; R 3 is an alkyl group of from 1 to 6 carbon atoms or hydrogen; R 4 is an alkyl group of from 1 to 6 carbon atoms, hydrogen or halogen; R 5 is hydrogen or an alkyl group of from 1 to 6 carbon atoms; X is a halogen; and y is 0, 1 or 2.
  • useful products of the process of the invention include, but are not limited to, (CH 3 O) 3 Si(CH 2 ) 3 CI, (C 2 H 5 O) 3 Si(CH 2 ) 3 CI, (C 2 H 5 O) 3 SiCH 2 CH(CH 3 )CH 2 Br, (CH 3 O) 3 SiCH 2 CH(CI)CH 3 , CH 3 (CH 3 O) 2 Si(CH 2 ) 3 CI, and (C 3 H 7 O) 3 Si(CH 2 ) 2 CH(CI)CH 3 .
  • the most preferred product of the Formula (I) according to an embodiment of the invention is chloropropyltriethoxysilane.
  • X is a fluoro, chloro, bromo or iodo substituent, preferably a bromo or chloro substituent, most preferably a chloro substituent.
  • R 3 and R 5 are independently selected from the group of linear, branched or cyclic C1-C6 alkyl groups or hydrogen, in particular from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, iso-butyl, tert-butyl, iso-pentyl, neo-pentyl, cyclopentyl, cyclohexyl or hydrogen, preferably from methyl, ethyl, n-propyl, n-butyl, iso-propyl, tert-butyl, cyclopentyl, cyclohexyl or hydrogen, more preferably from methyl, ethyl, n-propyl, iso-propyl or hydrogen, even more preferably from methyl, ethyl or hydrogen, most preferably R 3 and R 5 are hydrogen.
  • R 4 is independently selected from the group of linear, branched or cyclic C1-C6 alkyl groups or hydrogen, in particular from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, iso-propyl, iso-butyl, tert-butyl, iso-pentyl, neo-pentyl, cyclopentyl, cyclohexyl, hydrogen or halogen, preferably from methyl, ethyl, n-propyl, n-butyl, iso-propyl, tert-butyl, cyclopentyl, cyclohexyl or hydrogen, more preferably from methyl, ethyl, n-propyl, iso-propyl or hydrogen, even more preferably from methyl, ethyl or hydrogen, most preferably R 4 is hydrogen.
  • R 4 is a halogen group independently selected from fluoro, chloro, bromo and iodo substituents, it is preferred that R 4 is a chloro substituent.
  • R 3 , R 4 and R 5 in the olefinic halide are hydrogen substituents or two of the substituents R 3 , R 4 and R 5 are hydrogen substituents and the remaining substituent is a C1- C6 alkyl substituent, more preferably R 3 , R 4 and R 5 are hydrogen substituents or two of the substituents R 3 , R 4 and R 5 are hydrogen substituents and the remaining substituent is an alkyl substituent selected from methyl, ethyl and n-propyl, even more preferably R 3 , R 4 and R 5 are hydrogen substituents or two of the substituents R 3 , R 4 and R 5 are hydrogen substituents and the remaining substituent is a methyl substituent, most preferably R 3 , R 4 and R 5 are hydrogen substituents or two of the substituents R 3 and R 5 are hydrogen substituents and the R 4 substituent is a methyl substituent.
  • the olefinic halides can be used as received with industrial grade purity, which has a content of the respective olefinic halide of > 90 wt-%, preferably > 95 wt-%, even more preferably > 98 wt-%, and most preferably > 99 wt-%. While rectification of the olefinic halide starting material by evaporation and subsequent condensation may have a beneficial effect on the yield of the hydrosilylation reaction of the process of the invention, it is not required for performing the process of the invention.
  • the meaning of “as received” olefinic halide is that the olefinic halide is not submitted to a purification step such as distillation or evaporation/condensation before the hydrosilylation step is performed.
  • the purity of the olefinic halide of industrial grade purity can be in range from 95.0 wt-% to 99.5 wt-%, more specifically in the range from 95.5 to 99.0 wt-%, and even more specifically in the range from 96.0 wt-% to 98.0 wt-%.
  • the industrial grade purity olefinic halide can be as received, or it can be olefinic halide which has been submitted to a purification process before, for example to a process based on evaporation and condensation.
  • Alkoxysilanes used as starting materials in the process according to the invention have the general formula (R 1 ) y (R 2 O)3- y SiH, wherein R 1 and R 2 are alkyl groups of from 1 to 6 carbon atoms, and y is 0, 1 or 2.
  • R 1 and R 2 in the alkoxysilanes of the general formula (R 1 ) y (R 2 O)s- y SiH and the corresponding product of Formula (I), (R 1 ) y (R 2 O)3- y SiCH2CHR 3 CR 4 R 5 X (I) are independently selected from the group of linear, branched or cyclic C1-C6 alkyl groups, in particular from methyl, ethyl, n-propyl, n-butyl, n- pentyl, n-hexyl, iso-propyl, iso-butyl, tert-butyl, iso-pentyl, neo-pentyl, cyclopentyl or cyclohexyl, preferably from methyl, ethyl, n-propyl, n-butyl, iso-propyl, tert-butyl, cyclopentyl or cyclohex
  • the alkoxysilane (b) applied in the process for producing a product of Formula (I) is an alkoxysilane substituted with three alkoxy groups.
  • all groups R 2 represent the same type of C1-C6 alkyl group, more preferably an alkyl group selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl and cyclohexyl, even more preferably selected from methyl, ethyl, n-propyl and isopropyl, most preferably the alkoxysilane and the corresponding products of Formula (I), bears three ethoxy groups at the Si atom,
  • Alkoxysilanes that are suitable as starting materials in the process of the present invention include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, diethylethoxysilane, and the like. Of these alkoxysilanes, in an embodiment of the invention trimethoxysilane and triethoxysilane are preferred.
  • Trialkoxysilanes useful in the instant process can be obtained via alcohol esterification of trihalosilanes as disclosed, for example, in US 3792071 and US 3985781. Trimethoxysilane and triethoxysilane can be obtained in 89 - 92 weight percent distilled purity. Residual chloride levels can be as high as 100 ppm. Impurities include H2Si(OR)2 , HSi(OR)2CI, Si(OR)4 and higher boiling condensed silicates.
  • trialkoxysilanes useful in the instant process can be obtained via the Direct Reaction of alcohols with copper-activated silicon as disclosed, for example, in US 7652164 and US 7429672.
  • Trimethoxysilane and triethoxysilane synthesized according to this process are chloride-free and typically about 89 - 99 weight percent pure prior to distillation. Distilled products are about 99.0 - 99.9 weight percent pure.
  • Impurities are H2Si(OR)2, RSiH(OR)2, RSi(OR)s , Si(OR)4 and higher boiling condensed silicates.
  • Peroxycarboxylic acids contain a -C(O)-O-OH moiety. They are decomposed by the impact of heat, acids and some metal compounds. Accordingly, since the reactants of hydrosilylation processes are subjected to these impact factors during reaction, product recovery and recycling of unreacted starting materials and catalysts, peroxide promoters must be selected to maintain a stable hydrosilylation activity throughout a batch or continuous process.
  • the concentration of peroxycarboxylic acids used in an embodiment of the process of the invention ranges from about 1 to about 2000 ppm, more preferably from about 2 to about 500 ppm, more preferably from about 3 to about 200 ppm, even more preferably from about 4 to about 100 ppm, even further preferably from about 5 to about 50 ppm, still further preferably from about 5 to about 25 ppm, and most preferably from about 5 to about 15 ppm, all based on the total weight of olefinic halide and the alkoxysilane applied in the process.
  • Preferred temperature and concentration ranges for different types of peroxycarboxylic acids are set forth below in the detailed description of specific embodiments of the invention.
  • the half-life time of peroxycarboxylic acids can be as short as about 30 minutes at the boiling point of allyl chloride (44-45°C), and may thus be even shorter in the temperature range from about 70 to about 100°C, in which the hydrosilylation reactions are preferably carried out. Consequently, the concentrations of peroxycarboxylic acids will not always be adequate to promote and drive the hydrosilylation reaction to completion. So variable and inconsistent results are possible in laboratory experiments and commercial operations when the peroxycarboxylic acids are not present in effective reaction-promoting concentrations.
  • the process of the present invention encompasses the presence of peroxycarboxylic acids at levels sufficient to carry out effective hydrosilylations.
  • the peroxycarboxylic acids must be present in the hydrosilylation reaction zone along with the reactants and the iridium-containing catalyst. They can be added directly to the reaction zone, or preferably admixed with the olefin. Generally, the peroxycarboxylic acids as defined herein comprise all types of organic compounds containing one or more peroxycarboxylic acid moieties of the structure -C(O)-O-OH.
  • Preferred types of peroxycarboxylic acids according to an embodiment of the present invention are halogenated perbenzoic acids, unsubstituted peroxyalkanoic acids and a-halogenated peroxyalkanoic acids, wherein halogenated perbenzoic acids constitute the most preferred of the aforementioned groups of peroxycarboxylic acids.
  • halogenated peroxybenzoic acids which comprise mono-, bi-, tri-, tetra- and pentahalogenated perbenzoic acids are preferably selected from monohalogenated perbenzoic acids and dihalogenated perbenzoic acids.
  • halogenated peroxybenzoic acids bear at least one halogen substituent in meta-position to the peroxycarboxylic group.
  • At least one of the halogen substituents of the perbenzoic acids is a fluoro or a chloro substituent, and even more preferably all halogen substituents are independently selected from fluoro and chloro substituents.
  • peroxycarboxylic acids for the process of the invention selected from halogenated perbenzoic acids are 2-bromo-5-chlorobenzoic acid, 3,5-difluoroperbenzoic acid,
  • halogenated perbenzoic acids are 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5- difluoroperbenzoic acid.
  • Unsubstituted peroxyalkanonic acids are preferably selected from C2-C12 peroxyalkanoic acids, wherein it is further preferred that the peroxycarboxylic acid group is in a terminal position of a linear or branched alkyl group, and it is further preferred that the alkyl residue is a either a methyl group or a C2-C11 n-alkyl group.
  • Examples of preferred peroxycarboxylic acids for the process of the embodiment of the invention selected from unsubstituted peroxyalkanonic acids are peracetic acid, peroxypropionic acid and peroxybutyric acid.
  • a-Halogenated peroxyalkanoic acids i.e.
  • peroxyalkanoic acids bearing at least one halogen substituent in a-position to the peroxycarboxylic acid group are preferably selected from a- halogenated C2-C12 peroxyalkanoic acids, more preferably from linear a-halogenated C2-C12 peroxyalkanoic acids wherein the halogen substituents are independently selected from chloro and fluoro substituents.
  • a-halogenated peroxyalkanoic acids are chloroperacetic acid, fluoroperacetic acid, dichloroperacetic acid, difluoroperacetic acid, trifluoroperacetic acid and trichloroperacetic acid.
  • peroxycarboxylic acids allows to lower the loading of the Ir catalyst required to perform carry out the hydrosilylation reaction with a high yield and reasonable reaction rate and also allows to perform the reaction with industrial grade olefinic halides without additional purification steps prior to the hydrosilylation reaction.
  • Ir catalysts such as IrCh and FhlrCh can be successfully applied in the hydrosilylation reaction in the presence of peroxycarboxylic acid promoters with low catalyst loadings and without purification of the industrial grade olefinic halide starting material.
  • Suitable iridium-metal containing catalysts can be selected from iridium metal or homogeneous and heterogeneous iridium metal-containing compounds and complexes in which iridium can be in any of the oxidation states from 0 to 8 inclusive.
  • the preferred iridium-containing catalysts are the iridium chloride compounds, with H2I rCh and FhlrCh hydrate, IrCh, IrCh hydrate and its zinc-reduced product being the most preferred. Catalysts from one batch can be recycled to the next batch without significant loss of activity.
  • the catalyst use level may be in the range of 1 to 300 parts per million Ir metal based on the total reactant charge, with 5 to 50 parts per million being preferred.
  • the catalysts can be added to the hydrosilylation reactions in the form of a solid, as a suspension or a solution in an organic solvent.
  • the Ir-containing catalyst may also be applied in an immobilized form, for example linked or absorbed to the surface of a substrate material.
  • the hydrosilylation process according to the invention is not restricted to any particular protocol.
  • a preformed mixture of the olefinic halide, the alkoxysilane and the peroxycarboxylic acid is added to a mixture of alkoxysilane and the iridium-based hydrosilylation catalyst.
  • the preformed mixture is added stepwise or more preferably it is fed into the reactor to the mixture of the alkoxysilane and the iridium-based hydrosilylation catalyst from a reacting, mixing or storage vessel.
  • the reactor in which the reactants are combined is equipped with a mixing device.
  • the peroxycarboxylic acid, the olefinic halide and the alkoxysilane are mixed, and then a solution or suspension of the catalyst in a solvent, preferably a solution in an organic solvent, is added to the mixture in order to perform the hydrosilylation reaction.
  • a mixing device is used in order to form and maintain a homogeneous reaction mixture.
  • the process is advantageously carried out by slowly adding the olefinic halide and a peroxycarboxylic acid to a reaction medium containing the alkoxysilane and conducting the hydrosilylation in the presence of an iridium metal-containing catalyst in either a semi-batch or continuous process.
  • This order of addition effectively maintains a minimum concentration of unreacted olefinic halide in the reaction medium relative to the alkoxysilane, and thus effectively establishes a very large molar excess of the alkoxysilane relative to the olefinic halide in the reaction medium.
  • the maximum rate of addition of the olefinic halide to the alkoxysilane will be determined by the reaction rate, which is dependent in part on the reaction temperature, the catalyst concentration, the concentration and thermal stability of the peroxycarboxylic acid and by the heat transfer limitations of the reaction equipment and the reactor size, as will be understood by one skilled in the art.
  • the process of the invention can be carried out in any equipment suitable for hydrosilylation reactions, including equipment designed for continuous or alternatively discontinuous reactions.
  • trimethoxysilane or triethoxysilane derived from silicon metal and the corresponding alkanol By using in the present process trimethoxysilane or triethoxysilane derived from silicon metal and the corresponding alkanol, one can avoid the use of corrosive and hazardous hydridochlorosilanes and eliminate the generation of large amounts of chlorine- containing waste byproducts, which are inherent to the use of products derived from hydridochlorosilanes.
  • Reaction conditions include reaction temperatures ranging from about 15 °C to about 250 °C, preferably about 30 °C to about 180 °C, more preferably from about 50°C to about 130°C with from about 60°C to 80°C being further preferred.
  • the process is performed at a pressure at or above atmospheric pressure with atmospheric pressure being preferred. It is recognized that the process of the present invention may provide a high yield of the desired chloroalkylalkoxysilane in a batch system, but may as well be performed in a semi-batch process or a continuous process. However, a batch reaction will typically be conducted at a lower temperature with consequently longer reaction times.
  • the only impurities in significant quantities which need to be removed from the reaction product are unreacted alkoxysilanes, tetraalkoxysilane, residual catalyst and peroxycarboxylic acids or their degradation products, respectively.
  • the low level of residual halide that may be present in the product can be neutralized by methods well known in the art. If the hydrosilylation product of the present invention is used as an intermediate for the production of other organofunctional silicon compounds, the purity of the as received material can be sufficient. Additional purification steps are not needed.
  • the process of the present invention provides a higher yield of the target product, calculated on a molar basis, than any other one-step or two-step process described in the prior art. This is accomplished through the addition of an effective amount of a peroxycarboxylic acid promoter in combination with effective levels of an iridium-containing catalyst. Further, the process yields the target product at iridium levels significantly lower than the ones described in the prior art. The process also provides a higher yield per unit volume of equipment used, since the use of inert solvents is obviated and significant quantities of waste by-products are not generated.
  • an elevated pressure may be used, for example up to two atmospheres pressure, in order to control the boiling point of the reaction mixture in a closed reactor.
  • a pressure below atmospheric pressure may be used if a reaction temperature below the atmospheric pressure boiling point of the alkoxysilane is desired.
  • the products of Formula (I), (R 1 ) y (R 2 O)3- y SiCH2CHR 3 CR 4 R 5 X (I) of the process of the present invention may be purified by standard processes, i.e. by distillation, or may be used directly without intermediate purification.
  • the olefinic halide (a) is selected from the group consisting of allyl chloride, methallyl chloride, 3-chloro-1 -butene and 3, 4-dichloro-1 -butene and combinations thereof, preferably the olefinic halide (a) is allyl chloride.
  • the olefinic halides (a) used in the process according to this embodiment are preferably reacted with trialkoxysilanes, more preferably with triethoxysilane.
  • chloropropyltriethoxysilane is obtained by reacting allyl chloride with triethoxysilane in the presence of an Ir catalyst and a peroxycarboxyilic acid as specified herein, preferably with a halogenated perbenzoic acid acting as promoter.
  • the alkoxysilane (b) is selected from the group consisting of trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, diethylethoxysilane, and combinations thereof, preferably the alkoxysilane is triethoxysilane.
  • the reaction-promoting effective amount of the peroxycarboxylic acid (d) ranges from about 1 to about 2000 ppm, based on the total weight of the starting materials olefinic halide (a) and alkoxysilane (b) , preferably from about 2 to about 500 ppm, more preferably from about 3 to about 200 ppm, even more preferably from about 4 to about 100 ppm, even further preferably from about 5 to about 50 ppm, still further preferably from about 5 to about 25 ppm, and most preferably from about 5 to about 15 ppm.
  • the starting materials (a) and (b) are allyl chloride and triethoxysilane, and the amount of the peroxycarboxylic acid (d) is calculated based on the total weight of allyl chloride and triethoxysilane.
  • the ratio of the Ir-containing catalyst (c) and the peroxycarboxylic acid (d) promoting the hydrosilylation reaction is in the range of about 1 : 1 to about 1 : 40, preferably in the range of about 1 : 1 .5 to about 1 : 25, more preferably in the range of about 1 : 2 to about 1 : 20 , most preferably in the range of about 1 : 2 to about 1 : 10.
  • the ratio of the Ir-containing catalyst (c) to the peroxycarboxylic acid (d) is based on the amount of each of the components (c) and (d) given in “ppm”, wherein the amount in ppm refers to the amount of component (c) or (d), respectively, relative to the total mass of the olefinic halide (a) and the alkoxysilane (b).
  • the amount of the Ir metal in component (c) is related to the total mass of (a) and (b) in order to determine the amount of (c) in ppm.
  • the peroxycarboxylic acid (d) is selected from the group of halogenated perbenzoic acids, the group of unsubstituted peroxyalkanoic acids and from the group of a-halogenated peroxyalkanoic acids.
  • peroxyalkanoic acid refers to peroxycarboxylic acids consisting of a peroxycarboxy group and an alkyl residue.
  • the alkyl residue may be a primary n- alkyl group, a secondary alkyl group or a tertiary alkyl group, wherein primary alkyl groups are preferred.
  • the alkyl groups may be linear, branched or cyclic alkyl groups, wherein C1-C11 n- alkyl groups are preferred.
  • unsubstituted indicates that the C-atoms of the alkyl group do not bear any other substituents than hydrogen atoms.
  • a-halogenated peroxyalkanoic acids indicates that the alkyl groups of these compounds bear one or more halogen substituents on the carbon atom of the alkyl group bonded to the carbon atom of the peroxycarboxyl group.
  • the group of halogenated perbenzoic acids is preferred, and is beneficially applied in the process of the invention, in particular in the Ir-catalysed hydrosilylation reaction of allyl chloride and triethoxysilane catalyzed by an I r catalyst, preferably by I rCh or H2I rCh.
  • the peroxycarboxylic acid (d) is selected from the group of monohalogenated perbenzoic acids, from the group of dihalogenated perbenzoic acids, and the group of tri-, tetra- and pentahalogenated perbenzoic acids.
  • halogenated perbenzoic acid compounds as used herein it is noted that the carbon ring atom bearing the peroxycarboxylic group is denoted as the position “1”, and the positions of the one or more halogen substituents on the phenyl ring are numbered relative to this position.
  • 3-bromo-peroxybenzoic acid denotes peroxybenzoic acid bearing a bromo substituent in the meta-position to the peroxycarboxylic acid group.
  • Examples of monohalogenated perbenzoic acids according to the embodiment are 2-, 3- or 4- chloroperbenzoic acid, wherein 3-chloroperbenzoic acid is preferred, and 2-, 3-, or 4- fluoroperbenzoic acid, wherein 3-fluoroperbenzoic acid is preferred.
  • dihalogenated perbenzoic acids examples include dichloroperbenzoic acids such as 2,3- dichloroperbenzoic acid, 2,4-dichloroperbenzoic acid, 2,6-dichloroperbenzoic acid, 3,4- dichloroperbenzoic acid, 3,5-dichloroperbenzoic acid, wherein 3,5-dichloroperbenzoic acid is preferred, difluoroperbenzoic acids such as 2,3-difluoroperbenzoic acid, 2,4- difluoroperbenzoic acid, 2,6-difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 3,5- difluoroperbenzoic acid, wherein 3,5-difluoroperbenzoic acid is preferred, monochloromonofluoroperbenzoic acids such as 2-chloro-4-fluoroperbenzoic acid, 2-chloro-5- fluoroperbenzoic acid, 3-chloro-2-fluoroperbenzoic acid
  • Preferred examples of tri-, tetra- and pentahalogenated perbenzoic acids are 2,3,6- trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, and 2,3,4,5,6-pentafluoroperbenzoic acid.
  • the peroxycarboxylic acid (d) is selected from the group of halogenated perbenzoic acids bearing at least one halogen substituent in a meta-position to the peroxycarboxyl group.
  • halogenated perbenzoic acids having at least one halogen substituent in a meta-position to the peroxycarboxyl group are 3-chloroperbenzoic acid, 3- fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid.
  • the peroxycarboxylic acid (d) is selected from halogenated perbenzoic acids bearing one, two or three halogen substituents in total, wherein preferably at least one of the halogen substituents, and more preferably all of the halogen substituents are independently selected from fluoro and chloro substituents, and most preferably either all halogen substituents are chloro substituents or all halogen substituents are fluoro substituents.
  • halogenated perbenzoic acids are 3- chloroperbenzoic acid, 3-fluoroperbenzoic acid, 3,5-difluoroperbenzoic acid, 3,5- dichloroperbenzoic acid, and 2,3,6-trifluoroperbenzoic acid.
  • the peroxycarboxylic acid (d) is selected from the group of perbenzoic acids consisting of 2-bromo-5-chloroperbenzoic acid, 3,5- difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 2,3,6-trifluoroperbenzoic acid, 2,4,5- trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, 2,3,4,5,6-pentafluoroperbenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid and 3,5-difluoroperbenzoic acid.
  • perbenzoic acids consisting of 2-bromo-5-chloroperbenzoic acid, 3,5- difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 2,3,6-trifluoroperbenzoic acid, 2,4,5- trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, 2,3,4,5,
  • the peroxycarboxylic acid (d) is selected from 3-chloroperbenzoic acid, 3- fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid.
  • the halogenated perbenzoic acids according to this embodiment of the invention are either commercially available or readily available from the corresponding halogenated benzoic acids.
  • the catalyst loading of the Ir-based catalyst preferably of IrCh or F ⁇ IrCle, can be in the range of about 1 to about 25 ppm of Ir relative to the total mass of the olefinic halide (a) and the alkoxysilane (b).
  • the peroxycarboxylic acid (d) is an a- halogenated peroxyalkanoic acid selected from the group of C2-C12 a-halogenated peroxyalkanoic acids bearing one or more halogen substituents, which are independently selected from chloro and fluoro substituents, or wherein the peroxycarboxylic acid (d) is an unsubstituted C2-C12 peroxyalkanoic acid.
  • the peroxycarboxylic acid (d) is an a-halogenated alkanoic acid selected from chloroperacetic acid, fluoroperacetic acid, dichloroperacetic acid, difluoroperacetic acid, trifluoroperacetic acid and trichloroperacetic acid.
  • the iridium-containing catalyst (c) is selected from the group consisting of nano- and micron-sized iridium particles, iridium halides, zinc-reduced or tin reduced reaction products of iridium halides, cycloolefin complexes of iridium, amine complexes of iridium, phosphine complexes of iridium, CO-complexes of iridium, and combinations thereof.
  • nanoparticles are particles having an average particle size of 1 to 500 nm
  • micron-sized particles are particles having an average particle size of 0.5 to 50 .m as determined by Dynamic Light Scattering.
  • the amount of the iridium-containing catalyst (c) based on the total weight of the starting materials olefinic halide (a) and alkoxysilane (b) ranges from about 1 to about 100 ppm, preferably from about 1 to about 50 ppm, more preferably from about 1 to about 25 ppm, even more preferably from about 2 to about 25 ppm, and most preferably from about 3 to about 15 ppm.
  • the iridium-containing catalyst (c) is selected from IrCh xfW or ⁇ IrCle.
  • the number of water molecules in the IrCh hydrate “x” can be any fraction number from 0, i.e. anhydrous IrCh, to 1. As IrCh is strongly hygroscopic, IrCh hydrate may absorb additional water beyond the one water molecule per iridium ion. H2I rCh may also be applied as catalyst of the hydrosilylation reaction as anhydrous reagent or as the corresponding hydrate. Both IrC and H2lrCh can be applied as a solid or as a preformed stock solution or suspension to the hydrosilylation reaction.
  • Such solution or suspension is preferably prepared with an organic solvent having OH functional groups, preferably alkanols with one, two or three hydroxyl groups, such as methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, or polyglycols such as polyethylene glycols or polypropylene glycols.
  • organic solvent having OH functional groups preferably alkanols with one, two or three hydroxyl groups, such as methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, or polyglycols such as polyethylene glycols or polypropylene glycols.
  • the amount of the iridium-containing catalyst IrCh or H2lrCh in the process of the embodiment of the present invention is in the range of about 1 to about 50 ppm, more preferably in the range of about 2 to about 25 ppm and even more preferably in the range of about 3 to about 15 ppm.
  • the indication in “ppm” refers to the content of Ir in IrCh or H2lrCh by mass in relation to the total mass of the olefinic halide (a) and the alkoxysilane (b).
  • the ratio of the iridium-containing catalyst IrCh or H2lrCh to the peroxycarboxylic acid promoter (d) in [ppm to ppm] is preferably in the range of about 1 : 1.5 to about 1 : 25, more preferably in the range of about 1 : 2 to about 1 : 20, most preferably in the range of about 1 : 2 to about 1 : 10, and the preferred peroxycarboxylic acids (d) according to this embodiment are halogenated perbenzoic acids, more preferably selected from 3- chloroperbenzoic acid, 3-fluoroperbenzoic acid and 3,5-difluorperbenzoic acid.
  • ppm refers to the amount of the peroxycarboxylic acid by mass in relation to the total mass of the olefinic halide (a) and the alkoxysilane (b).
  • the iridium-containing catalyst (c) is added to the reaction as a solid, or as a solution or suspension in an organic solvent, preferred OH functionalized solvents, i.e. such as OH functional alkanols, diols and triols, for example ethanol, polyethers, preferably the catalyst (c) is added as a solid.
  • preferred OH functionalized solvents i.e. such as OH functional alkanols, diols and triols, for example ethanol, polyethers, preferably the catalyst (c) is added as a solid.
  • OH-functionalized solvents are methanol, ethanol, n-propanol, iso-butanol, n- butanol, tert-butanol, pentanol, hexanol, cyclohexanol, and polyglycols such as polyethylene glycols and polypropylene glycols, mono ethers of glycols and polyglycols, such as the methyl and butyl ethers of ethylene glycol, diethylene glycol and trietyhlene glycol and the methyl and butyl ethers of propylene glycol, dipropylene glycol and tripropylene glycol.
  • polyglycols such as polyethylene glycols and polypropylene glycols, mono ethers of glycols and polyglycols, such as the methyl and butyl ethers of ethylene glycol, diethylene glycol and trietyhlene glycol and the methyl and butyl ethers of propylene
  • the olefinic halide (a) is an industrial grade olefinic halide, preferably industrial grade allyl chloride.
  • the term “industrial grade” denotes an olefinic halide having a purity of > 90 wt-%, preferably > 95 wt-%, even more preferably > 98 wt-%, and most preferably > 99 wt-%.
  • commercially available olefinic halides have a quality with regard to purity characterized as “industrial grade”. In many cases, however, a higher degree of purity is needed which is associated with further purification steps and higher costs.
  • the process of the invention allows to carry out the iridi um-catalyzed hydrosilylation reaction in the presence of percarboxylic acids (d) with high yields using olefinic halides (a) having an industrial grade quality.
  • the olefinic halides according to the embodiment may thus have a purity in range from about 95.0 wt-% to about 99.5 wt-%, more specifically in the range from about 95.5 to about 99.0 wt-%, and even more specifically in the range from about 96.0 wt-% to about 98.0 wt-%.
  • the olefinic halides can be used as received.
  • the molar ratio of the olefinic halide (a) to the alkoxysilane (b) is in the range of about 10 : 1 to about 1 : 10, preferably about 5 : 1 to about 1 : 5, more preferably about 2 : 1 to about 1 : 2, even more preferably about 1 .7 : 1 to about 1 : 1.7, even further preferably about 1.5 : 1 to about 1 : 1.5, and most preferably about 1.2 : 1 to about 1 : 1.2.
  • the ratio of the iridium-containing catalyst (c) to the peroxycarboxylic acid (d) in [ppm to ppm], each based on the total weight of the starting materials olefinic halide (a) and alkoxysilane (b), is in the range of about 1 : 1 to about 1 : 40, preferably in the range of about 1 : 1.5 to about 1 : 25, more preferably in the range of about 1 : 2 to about 1 : 20 , most preferably in the range of about 1 : 2 to about 1 : 10.
  • the amount of the peroxycarboxylic acid (d) by mass is divided by the total mass of the olefinic halide (a) and alkoxysilane (b) and the result is multiplied with 1000000; the amount of iridium contained in the iridium-containing catalyst (c) by mass is divided by the total mass of the olefinic halide (a) and the alkoxysilane (b) and the result is multiplied with 1000000.
  • the amounts of the iridium-containing catalyst (c) and of the peroxycarboxylic acid (d) according to the invention in ppm are obtained.
  • the ratios given in this embodiment thus refer to the ratio of the amounts of the iridium-containing catalyst and the peroxycarboxylic acid in “ppm” determined as described above.
  • the olefinic halide (a) is allyl chloride
  • the alkoxysilane (b) is triethoxysilane
  • the Ir-containing catalyst (c) is IrCh or FklrCle
  • the peroxycarboxylic acid (d) is 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid or 3,5- difluoroperbenzoic acid.
  • the olefinic halide (a) is allyl chloride
  • the alkoxysilane (b) is triethoxysilane
  • the amount of iridium-containing catalyst (c) is in the range of about 5 to about 20 ppm
  • the peroxycarboxylic acid (d) is either
  • the iridium-containing catalyst (c) is selected from IrCh and FklrCle.
  • the [ppm/ppm] ratio of the iridium-containing catalyst (c) and the promoter (d) is determined as described before.
  • the invention also relates to compositions which can be obtained when performing the process according to the invention as described above in detail and with regard to various embodiments.
  • the invention specifically relates to a composition
  • a composition comprising one or more compounds of the Formula (I), (R 1 ) y (R 2 O)3- y SiCH2CHR3CR4R5X (I), one or more iridium-containing compounds, and one or more compounds selected from i) peroxycarboxylic acids, and/or ii) carboxylic acids, wherein R 1 and R 2 are alkyl groups of from 1 to 6 carbon atoms; R 3 is an alkyl group of from 1 to 6 carbon atoms or hydrogen;
  • R 4 is an alkyl group of from 1 to 6 carbon atoms, hydrogen or halogen
  • R 5 is hydrogen or an alkyl group of from 1 to 6 carbon atoms
  • X is a halogen; and y is 0, 1 or 2.
  • the iridium-containing compounds of the compositions according to the invention are only restricted insofar as they necessarily contain one or more iridium atoms or iridium ions. Accordingly, the iridium-containing compounds can be any iridium-containing catalyst or an iridium-compound or iridium particles derived from such iridium-contain hydrosilylation catalysts as described above in the description of the process of the invention.
  • the iridium-containing compounds are compounds formed from the catalysts used in the process of the invention, i.e. intermediates and active catalytic species of the catalytic cycle of the hydrosilylation reation, for example iridium(O) nanoparticles or iridium(O) micron-sized particles.
  • nanoparticles are particles having an average particle size of 1 to 500 nm
  • micron-sized particles are particles having an average particle size of 0.5 to 50 .m as determined by Dynamic Light Scattering.
  • the iridium-containing compounds can be compounds derived from the iridium-containing catalysts of the process of the invention by deactivation or decomposition.
  • the peroxycarboxylic acids of the composition of the invention are not restricted in any particular manner except that they necessarily comprise a peroxycarboxyl group, as applies for the peroxycarboxylic acids of the process of the invention.
  • carboxylic acids of the composition of the invention as defined herein are not restricted in any particular manner except that they necessarily comprise a carboxyl group.
  • the peroxycarboxylic acid compound mentioned in the above description of the process of the invention may be comprised by the compositions of the invention, and the same compounds which are preferably applied in the process of the invention are preferably comprised by the compositions of the invention.
  • the carboxylic acids of the compositions of the invention are preferably the analogous compounds to the peroxycarboxylic acid compound mentioned in the above description of the process of the invention, and the carboxylic acids analogous to the peroxycarboxylic acids preferably applied in the process of the invention are more preferably comprised by the compositions of the invention.
  • analogous as defined herein with regard to peroxycarboxlic acids and carboxylic acids means that the carboxylic acids correspond to the peroxycarboxylic acids insofar as they are structurally identical except for having a carboxyl group instead of a peroxycarboxyl group.
  • the compounds of the formula (I) comprised by the compositions according to the invention are preferably the products obtained by the hydrosilylation of an olefinic halide selected from the group of allyl chloride, methallyl chloride, 3-chloro-1 -butene and 3, 4-dichloro-1 -butene and combinations thereof, wherein allyl chloride is preferred, with an alkoxysilane selected from the group of trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane and diethylethoxysilane, wherein trimethoxysilane and triethoxysilane are preferred.
  • an olefinic halide selected from the group of allyl chloride, methallyl chloride, 3-chloro-1 -butene and 3, 4-dichloro-1 -buten
  • the most preferred compounds of the formula (I) which may be comprised by the composition of the invention are chloropropyltrimethoxysilane and chloropropyltriethoxysilane.
  • the compound of the formula (I) is chloropropyltriethoxysilane.
  • the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from halogenated perbenzoic acids, unsubstituted peroxyalkanoic acids, a-halogenated peroxyalkanoic acids, from halogenated benzoic acids, unsubstituted alkanoic acids and from of a-halogenated alkanoic acids.
  • peroxyalkanoic acid refers to carboxylic acids consisting of a carboxy group and an alkyl residue, wherein the C-atoms of the alkyl group do not bear any other substituents than hydrogen atoms.
  • the alkyl group may be a primary n-alkyl group, a secondary alkyl group or a tertiary alkyl group, with primary alkyl groups being preferred, wherein thhe alkyl groups may be linear, branched or cyclic alkyl groups, with C1-C11 n-alkyl groups being preferred.
  • a- halogenated alkanoic acids indicates that the alkyl groups of these compounds bear one or more halogen substituents on the carbon atom of the alkyl group bonded to the carbon atom of the carboxyl group.
  • the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from monohalogenated perbenzoic acids, from dihalogenated perbenzoic acids, tri-, tetra- and pentahalogenated perbenzoic acids, from monohalogenated benzoic acids, from dihalogenated benzoic acids, and tri-, tetra- and pentahalogenated benzoic acids.
  • the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from halogenated perbenzoic acids bearing at least one halogen substituent in a meta-position to the peroxycarboxyl group, and from halogenated benzoic acids bearing at least one halogen substituent in a meta-position to the carboxyl group.
  • the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from the group of perbenzoic acids consisting of 2-bromo-5-chloroperbenzoic acid, 3,5-difluoroperbenzoic acid, 3,4- difluoroperbenzoic acid, 2,3,6-trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid, 2,3,4- trifluoroperbenzoic acid, 2,3,4,5,6-pentafluoroperbenzoic acid, 3-chloroperbenzoic acid, 3- fluoroperbenzoic acid and 3,5-difluoroperbenzoic acid, preferably the perbenzoic acid is selected from 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid, and/or from the group of benzoic acids consisting of 2-bromo-5-chloroperbenzoic acid, 3,5-diflu
  • the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid, and from 3-chlorobenzoic acid, 3- fluorobenzoic acid, and 3,5-difluorobenzoic acid.
  • the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids is selected from the group consisting of C2-C12 a-halogenated peroxyalkanoic acids bearing one or more halogen substituents, which are independently selected from chloro and fluoro substituents and unsubstituted C2-C12 peroxyalkanoic acids, and from the group consisting of C2-C12 a-halogenated alkanoic acids bearing one or more halogen substituents, which are independently selected from chloro and fluoro substituents, and unsubstituted C2-C12 alkanoic acids.
  • the iridium-containing compound is selected from nano- and micron-sized iridium particles.
  • the nano- and micron-sized iridium particles are based on iridium(O) and are usually formed from iridium-containing catalysts used in the hydrosilylation reaction of the process of the invention.
  • the amount of the iridium-containing compound comprised by the composition based on the total weight of the haloorganosilane of the formula (I) ranges from about 1 to about 100 ppm, preferably from about 1 to about 50 ppm, more preferably from about 1 to about 25 ppm, even more preferably from about 2 to about 25 ppm, and most preferably from about 3 to about 15 ppm.
  • the amount of the iridium-containing compound comprised by the composition is in the range cited before based on the total weight of chloropropyltriethoxysilane present in the composition as compound of the formula (I).
  • the invention relates to the use of the compositions described before and the compositions obtained from the process of the invention as described before for the preparation of aminoorganosilanes, mercaptoorganosilanes or methacryloyloxyorganosilanes.
  • organosilanes includes organoalkoxysilanes, i.e. organosilanes bearing one, two or three alkoxygroups at the silicon atom.
  • Aminoorganosilanes as defined herein are organosilanes including a primary, secondary or tertiary amino group in the organyl residue.
  • the aminoorganosilanes have a structure represented by the Formula (II) (R 1 ) y (R 2 O)3-ySiCH 2 CHR 3 CR 4 R 5 Z 1 (II), wherein R 1 , R 2 , R 3 , R 4 , R 5 and y are as defined above,
  • Z 1 is selected from -NH 2 , -NHR 6 and NR 6 R 7 , wherein R 6 is independently selected from the group consisting of C1-C12 alkyl groups and the residues or
  • R 7 is independently selected from the group consisting of C1-C12 alkyl groups, preferably R 7 is CH3, and further preferably R 6 and R 7 represent the same residue, most preferably R 6 and R 7 represent -CH3.
  • mercaptoorganosilanes are organosilanes bearing at least one residue selected from a thiol group, a disulfanyl group, a polysulfanyl group, a thioalkyl group, a dithioalkyl group or a polythioalkyl group bonded to the organyl residue of the organosilane via an - S- atom.
  • the mercaptoorganosilanes have a structure represented by the Formula (III) (R 1 )y(R 2 O) 3 -ySiCH 2 CHR 3 CR 4 R 5 Z 2 (III), wherein
  • R 1 , R 2 , R 3 , R 4 , R 5 and y are as defined above,
  • Z 2 is selected from -SH, -S-SH, -S( U )-SH, -SR 8 , -S-SR 8 , -S( U )-SR 8 , wherein u is an integer from 2 to 8, preferably u is 2, 3 or 4, and
  • R 8 is selected from the group consisting of
  • C1-C12 alkyl groups optionally C2 to C12 acyl groups, i.e. derived from carboxylic acids, specifically derived from acetic acid, butanoic acid, hexanoic acid, octanoic acid, decanoic acid, dodecanoic acid, neodecanoic acid, 2-ethyl-hexanoic acid and the residue(R 1 ) y (R 2 O) 3.y SiCH 2 CHR 3 CR 4 R 5 -, wherein R 1 , R 2 , R 3 , R 4 , R 5 and y are as defined above.
  • derived from carboxylic acids means that an acyl group R 8 is bonded to the S-atom with the carbonyl C-atom.
  • the compounds having such R 8 group can be formed by condensation of carboxylic acids with terminal SH groups of a precursor compound.
  • preferred groups R 8 are acetyl, butanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, neodecanoyl and 2-ethyl-hexanoyl groups.
  • methacryloyloxyorganosilanes are organosilanes bearing at least one methacryloyloxy group bonded to the organyl residue of the organosilane via the -O- atom.
  • the methacryloyloxyorganosilanes have a structure represented by the Formula (IV) (R 1 )y(R 2 O) 3 -ySiCH 2 CHR 3 CR 4 R 5 Z 3 (IV), wherein R 1 , R 2 , R 3 , R 4 , R 5 and y are as defined above, and
  • Z 3 is -OC(O)C(CH 2 )CH 3 .
  • the compounds of the Formula (I) comprised by the compositions according to the invention can be transformed to the desired functionalized organosilanes by the replacement of the halide substituent in a nucleophilic reaction with an amine reagent, a sulfide, thiolate or polysulfide reagent or a methacrylate reagent, e.g. a methacrylate salt, respectively.
  • the composition is used for the preparation of polysulfane-containing organoalkoxysilanes.
  • polysulfane-containing organoalkoxysilanes are mercaptoorganosilanes of the structure (R 1 ) y (R 2 O) 3 .ySiCH 2 CHR 3 CR 4 R 5 Z 2 (III), wherein
  • R 1 , R 2 , R 3 , R 4 , R 5 and y are as defined above, and
  • the composition is used for the preparation of polysulfane- containing organoalkoxysilanes used in the manufacture of silica-filled tires.
  • the composition used for the preparation of aminoorganosilanes, mercaptosilanes or methacryloyloxyorganosilanes comprises chloropropyltriethoxysilane.
  • the chloropropyltriethoxysilane comprised by the composition is transformed to an aminopropyltriethoxysilane of the formula (V) (EtO)3SiCH 2 CH 2 CH 2 Z 1 (V), wherein Z 1 is as defined above, to a mercaptoorganosilane of the formula (VI) (EtO) 3 SiCH 2 CH 2 CH 2 Z 2 (VI), wherein Z 2 is as defined above, or to methacryloyloxypropyltriethoxysilane.
  • R 1 and R 2 are alkyl groups of from 1 to 6 carbon atoms
  • R 3 is an alkyl group of from 1 to 6 carbon atoms or hydrogen
  • R 4 is an alkyl group of from 1 to 6 carbon atoms, hydrogen or halogen
  • R 5 is hydrogen or an alkyl group of from 1 to 6 carbon atoms
  • X is a halogen; and y is 0, 1 or 2.
  • olefinic halide (a) is selected from the group consisting of allyl chloride, methallyl chloride, 3-chloro-1 -butene and 3,4-dichloro-1- butene and combinations thereof, preferably the olefinic halide (a) is allyl chloride.
  • alkoxysilane (b) is selected from the group consisting of trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, diethylethoxysilane, and combinations thereof, preferably the alkoxysilane is triethoxysilane.
  • reaction-promoting effective amount of the peroxycarboxylic acid (d) ranges from about 1 to about 2000 ppm, based on the total weight of the starting materials olefinic halide (a) and alkoxysilane (b), preferably from about 2 to about 500 ppm, more preferably from about 3 to about 200 ppm, even more preferably from about 4 to about 100 ppm, even further preferably from about 5 to about 50 ppm, still further preferably from about 5 to about 25 ppm, and most preferably from 5 to 15 ppm.
  • peroxycarboxylic acid (d) is selected from the group of halogenated perbenzoic acids, the group of unsubstituted peroxyalkanoic acids or from the group of a-halogenated peroxyal kanoic acids.
  • peroxycarboxylic acid (d) is selected from the group of monohalogenated perbenzoic acids, from the group of dihalogenated perbenzoic acids, and the group of tri-, tetra- and pentahalogenated perbenzoic acids.
  • peroxycarboxylic acid (d) is selected from the group of halogenated perbenzoic acids bearing at least one halogen substituent in a meta-position to the peroxycarboxylic group.
  • the peroxycarboxylic acid (d) is selected from halogenated perbenzoic acids bearing one, two or three halogen substituents in total, wherein preferably at least one of the halogen substituents, and more preferably all of the halogen substituents are independently selected from fluoro and chloro substituents, and most preferably either all halogen substituents are chloro substituents or all halogen substituents are fluoro substituents.
  • peroxycarboxylic acid (d) is selected from the group of perbenzoic acids consisting of 2-bromo- 5-chlorobenzoic acid, 3,5-difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 2,3,6- trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, 2,3,4,5,6-pentafluorobenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5- difluoroperbenzoic acid.
  • perbenzoic acids consisting of 2-bromo- 5-chlorobenzoic acid, 3,5-difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 2,3,6- trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, 2,3,4,5,6-p
  • peroxycarboxylic acid (d) is selected from 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid.
  • peroxycarboxylic acid (d) is an a-halogenated peroxyalkanoic acid selected from the group of C2-C12 a-halogenated peroxyalkanoic acids bearing one or more halogen substituents, which are independently selected from chloro and fluoro substituents, or wherein the peroxycarboxylic acid (d) is an unsubstituted C2-C12 peroxyalkanoic acid.
  • peroxycarboxylic acid (d) is an a-halogenated alkanoic acid selected from chloroperacetic acid, fluoroperacetic acid, dichloroperacetic acid, difluoroperacetic acid, trifluoroperacetic acid and trichloroperacetic acid.
  • the iridium-containing catalyst (c) is selected from the group consisting of nano- and micron sized iridium, iridium halides, zinc-reduced or tin reduced reaction products of iridium halides, cycloolefin complexes of iridium, amine complexes of iridium, phosphine complexes of iridium, CO-complexes of iridium, and combinations thereof.
  • the amount of the iridium- containing catalyst (c) based on the total weight of the starting materials olefinic halide (a) and alkoxysilane (b) ranges from about 1 to about 100 ppm, preferably from about 1 to 50 ppm, more preferably from about 1 to about 25 ppm, even more preferably from about 2 to about 25 ppm, and most preferably from about 3 to about 15 ppm.
  • olefinic halide (a) is an industrial grade olefinic halide, preferably industrial grade allyl chloride.
  • olefinic halide (a) is allyl chloride
  • alkoxysilane (b) is triethoxysilane
  • the Ir-containing catalyst (c) is IrCh or H2lrCh
  • the peroxycarboxylic acid (d) is 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid or 3,5- difluoroperbenzoic acid.
  • a composition comprising one or more compound of the Formula (I), (R 1 ) y (R 2 O)3-ySiCH2CHR3CR4R5X (I), one or more iridium-containing compounds, and one or more compounds selected from i) peroxycarboxylic acids, and/or ii) carboxylic acids, wherein R 1 and R 2 are alkyl groups of from 1 to 6 carbon atoms; R 3 is an alkyl group of from 1 to 6 carbon atoms or hydrogen;
  • R 4 is an alkyl group of from 1 to 6 carbon atoms, hydrogen or halogen
  • R 5 is hydrogen or an alkyl group of from 1 to 6 carbon atoms
  • X is a halogen; and y is 0, 1 or 2.
  • composition according to embodiments 25 or 26, wherein the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from halogenated perbenzoic acids, unsubstituted peroxyalkanoic acids, a-halogenated peroxyalkanoic acids, from halogenated benzoic acids, unsubstituted alkanoic acids or from of a-halogenated alkanoic acids.
  • composition according to the embodiments 25-27, wherein the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from monohalogenated perbenzoic acids, from dihalogenated perbenzoic acids, tri-, tetra- and pentahalogenated perbenzoic acids, from monohalogenated benzoic acids, from dihalogenated benzoic acids, and tri-, tetra- and pentahalogenated benzoic acids.
  • composition according to any of the embodiments 25-28, wherein the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from halogenated perbenzoic acids bearing at least one halogen substituent in a meta-position to the peroxycarboxyl group, and from halogenated benzoic acids bearing at least one halogen substituent in a meta-position to the carboxyl group.
  • composition according to any of the embodiments 25-29, wherein the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from the group of perbenzoic acids consisting of 2-bromo-5-chloroperbenzoic acid, 3,5- difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 2,3,6-trifluoroperbenzoic acid, 2,4,5- trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, 2,3,4,5,6-pentafluoroperbenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid, and from the group of benzoic acids consisting of 2-bromo-5-chlorobenzoic acid, 3,5-difluorobenzoic acid, 3,4-difluorobenzoic acid, 2,3,6-trifluorobenzoic acid, 2,
  • composition according to any of the embodiments 25-30, wherein the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid, and from 3-chlorobenzoic acid, 3-fluorobenzoic acid, and 3,5-difluorobenzoic acid.
  • composition according to any of the embodiments 25-31 wherein the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from the group consisting of C2-C12 a-halogenated peroxyalkanoic acids bearing one or more halogen substituents, which are independently selected from chloro and fluoro substituents and unsubstituted C2-C12 peroxyalkanoic acids, and from the group consisting of C2-C12 a- halogenated alkanoic acids bearing one or more halogen substituents, which are independently selected from chloro and fluoro substituents, and unsubstituted C2-C12 alkanoic acids.
  • compositions of embodiments 24-34 for the preparation of aminoorganosilanes, mercaptoorganosilanes or methacryloyloxyorganosilanes.
  • 36 Use of the compositions according to embodiment 35, wherein the composition is used for the preparation of polysulfane-containing organoalkoxysilanes.
  • compositions according to embodiment 36, wherein the polysulfane-containing organoalkoxysilanes are used in the manufacture of silica-filled tires.
  • compositions according to embodiments 35-37, wherein the composition comprises chloropropyltriethoxysilane.
  • IrCh xfW abcr; 99.99 % CAS 14996-61-3; Iridium(lll) chloride hydrate bUrCh: abcr; 99.90 % CAS 110802-84-1; Hexachloroiridic(IV) acid hydrate dry EtOH: analytical grade ETCH further dried over molecular sieve (3A) allyl chloride: Momentive grade (batch RBT190731 C), > 99 wt-% overcondensed allyl chloride: The overcondensed allyl chloride was obtained by treating as received allyl chloride with vacuum.
  • the as received allyl chloride was submitted in a Schlenk flask, connected to a second (dry ice/iPr-cooled) Schlenk flask by a glass bridge.
  • the compounds not volatile at 20 °C/0.4 mbar remained in the first flask and were thereby separated from the overcondensed allyl chloride. While NMR and GC-TCD measurements did not show a noticeable change of purity for the overcondensed ally chloride when compared to the allyl chloride as received, the non-volatile compounds formed a yellow liquid.
  • Triethoxysilane Momentive grade (TES; Momentive grade synthesized from HSiC ), 89-
  • DtBP di-tertiary-butyl peroxide
  • tBHP tertiary-butyl hydroperoxide
  • tBPB 5.5 molar in decane tertiary-butyl perbenzoate
  • mCPBA meta-Chloroper(oxy)benzoic acid
  • m-fluoroperbenzoic acid mFPBA
  • dFPBA 3,5-difluoroperbenzoic acid
  • NMR NMR The NMR measurements were either performed on a BRLIKER DPX 400 with a 5mm multinuclear probe head or on a BRLIKER AVANCE III 500 MHz.
  • the following table shows the resonance frequencies of the examined nuclei.
  • the compounds to be investigated were bottled under argon. Therefore 0.2 ml compound was dissolved in 0.4 ml solvent. In all cases deuterated chloroform was used as the solvent and 1% TMS was added as reference. Thus, the TMS signal is the reference point for all chemical shifts, given in ppm. 100 pl HMDSO were used as an internal reference for determining the substance amount fractions, if necessary.
  • the spectra were generated on a Nicolet 380 FT-IR, using standard FT-IR ATR-measurement procedures.
  • the investigated samples of the peroxycarboxylic acids did not need further preparation before measuring.
  • the aqueous layer was extracted 4 times with 20 ml ice-cold dichloromethane.
  • the organic layers were combined and dried over MgSC .
  • the dichloromethane was removed under reduced pressure, wherein a rotary evaporator was used.
  • the water bath had 30 °C and the pressure was lowered stepwise from 200 mbar to 0 mbar in 25 mbar steps.
  • the desired product was obtained as a white solid. Yield: 1.81g (39%). Purity: 100 %.
  • the structure of the product was confirmed by means of 1 H-NMR, 13 C-NMR and FTIR spectroscopy.
  • aqueous layer was extracted 4 times with 20 ml ice-cold dichloromethane.
  • the organic layers obtained from extraction of the aqueous layer were unified and dried over MgSC .
  • the dichloromethane was removed at room temperature under reduced pressure, wherein a rotary evaporator was used.
  • the water bath had 30 °C and the pressure was lowered stepwise from 200 mbar to 0 mbar in 25 mbar steps. A white solid was obtained. Yield 0.97g (19%). Purity: 100 %.
  • the structure of the product as indicated above was confirmed by means of 1 H-N MR, 13 C-NMR and FTIR spectroscopy.
  • Example 1 General protocol for hydrosilylations using a catalyst solution
  • the calculated amount of catalyst solution (the catalyst content indicated in “ppm” is based on the total mass of the starting materials triethoxysilane and allyl chloride, wherein the ppm indication refers to the amount of Ir metal contained in the catalyst compounds) was added and the mixture was heated to 80 °C under stirring using a magnetic stirring bar with a stirring speed of 300 rpm. byproducts and unreacted
  • Example 2 General protocol for hydrosilylations using a solid catalyst
  • the letter “C” denotes comparative examples, which are not according to the invention
  • a The catalyst content indicated in “ppm” is based on the total mass of the starting materials triethoxysilane and allyl chloride, wherein the ppm indication refers to the amount of Ir metal contained in the catalyst compounds.
  • b The amount of peracids indicated in “ppm” is based on the total mass of the starting materials triethoxysilane and allyl chloride; where applicable, the acitivity of the promoters as outlined in the Materials section was taken into account.
  • c The amounts in “mol-%” refer to the sum of all integrals/mol amounts of silicon species in the 29 Si-NMR spectra. The mol-% amounts were determined from the integral area in reference to the internal standard HMDSO
  • the letter “C” denotes comparative examples, which are not according to the invention ndices in Tables 2 to 4: a: The catalyst content indicated in “ppm” is based on the total mass of the starting materials triethoxysilane and allyl chloride, wherein the ppm indication refers to the amount of Ir metal contained in the catalyst compounds. b: The amount of peracids indicated in “ppm” is based on the total mass of the starting materials triethoxysilane and allyl chloride; where applicable, the acitivity of the promoters as outlined in the Materials section was taken into account. c: The mol-% refer to the sum of all integrals/mol amounts of silicon species in the 29 Si-NMR spectra. The mol-% amounts were determined from the integral area in reference to the internal standard HMDSO
  • example 28 indicates that F ⁇ IrCle is also applicable in a process based on an easy to prepare catalyst solution, low Ir concentrations and as received allyl chloride.
  • Comparative example 29 displays that even at a substantially higher catalyst concentration, the yield using an H2I rCh solution is only moderate when compared to the reactions performed in the presence of a halogenated perbenzoic acid.

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Abstract

The present invention is directed at a process for producing a compound of Formula (I): (R1)y(R2O)3-ySiCH2CHR3CR4R5X comprising reacting (a) an olefinic halide; (b) an alkoxysilane; (c) a catalytically effective amount of iridium-containing catalyst; and (d) a reaction-promoting effective amount of a peroxycarboxylic acid to produce the product of Formula (I).

Description

PERACID PROMOTERS IN THE IRIDIUM-CATALYZED HYDROSILYLATION SYNTHESIS OF HALOALKYLORGANOSILANES
TECHNICAL FIELD
The present invention relates to a process for making haloorganosilicon compounds. More particularly, the invention relates to a process for the preparation of haloorganoalkoxysilanes, in particular such as chloropropyltriethoxysilane, via the hydrosilylation of haloalkenes with alkoxysilanes, and compositions comprising one or more haloorganoalkoxysilanes, one or more iridium-containing compounds and one or more peroxybenzoic acids, as well as the use of such compositions.
BACKGROUND OF THE INVENTION
Haloalkylorganosilanes are key intermediates for the preparation of a variety of functionalized organosilanes, for example amino-, mercapto- and methacryloyloxyorganosilanes, which are used as silane coupling agents. For example, chloropropyltriethoxysilane is a key intermediate for the preparation of polysulfane-containing organoalkoxysilanes, which are used in the manufacture of silica-filled tires. It is known in the art that chloropropyltriethoxysilane (CPTES) can be produced by transesterification of chloropropyltrimethoxysilane, or by the hydrosilylation of the corresponding haloalkene allyl chloride with triethoxysilane (TES).
The hydrosilylation of allyl chloride by triethoxysilane (TES) in the presence of Pt catalysts shows large variations with respect to the yield of the target product chloropropyltriethoxysilane (CPTES) ranging from 14 to 70% (US 9556208 and embedded references US 3795656, JP 11-199588, Belyakova et al., Chernyshev et al.). The reason for low yields is the tendency to form propene as undesired side product. Rh and Pd based catalyst systems have the same deficit (US9556208).
Dimeric olefin Ir (I) halide complexes were described as efficient catalysts for the synthesis of CPTES from TES and allyl chloride (US4658050). Yields up to 75 % were described for 100 ppm catalyst.
US 5616762 describes the synthesis of CPTES from TES and allyl chloride in the presence of Ir (III) chloride hydrate. An excess of allyl chloride is used to obtain yields greater than 80 %. Although potentially a high yield of CPTES can be obtained in the reactions described above, Ir catalyzed reactions yielding CPTES suffer from a lack of reproducibility. Especially at low Ir concentrations, unpredictable variations of the yield occur. Hence, there is a need for additives stabilizing and further increasing the yield of the Ir catalyzed hydrosilylation of allyl chloride by TES. In WO2017/154846 A1 , a process for producing (3-chloropropyl)dimethoxymethylsilane, wherein allyl chloride is reacted with dimethoxymethyl silane in the presence of an iridium catalyst, and a composition obtained by this process are disclosed.
Therein, WO2017/154846 A1 appears to teach that the iridium-catalzed hydrosilylation of allylic species can be significantly accelerated when in a pretreatment step an iridium complex is produced by reacting binuclear Iridium complexes bearing silyl groups with an allyl compound. The presence of peroxycarboxylic acids in the hydrosilylation process or of peroxycarboxylic acids and/or carboxylic acids in the composition obtained by the process, however, is not disclosed therein.
In US6015920 A, a process for the production of (3-chloropropyl)trimethoxysilane by the iridium-catalyzed hydrosilylation of allyl chloride with trimethoxysilane is disclosed.
In general, US6015920 A is directed at a process for hydrosilylation reactions, wherein a portion of the reactor output is recycled continuously to the reactor, which is also exemplified for the production of (3-chloropropyl)trimethoxysilane by the iridium-catalyzed hydrosilylation of allyl chloride with trimethoxysilane. The presence of peroxycarboxylic acids in the hydrosilylation process or of peroxycarboxylic acids and/or carboxylic acids in the composition obtained by the process, however, is not disclosed therein.
Organic peroxy compounds and oxygen are known to have an impact on hydrosilylation reactions.
US 9556208 describes the use of hydroperoxides, dialkylperoxides and diacylperoxides as promotors for the hydrosilylation of allyl chloride with alkoxysilanes in the presence of Ru catalysts. Di-t-butylperoxide is used for the reaction of allyl chloride with TES. m-Chloroperbenzoic acid was described as promotor for the reaction of 1 -octene with triethylsilane in the presence of Rh-phosphine complexes (Calhoun et al, Trans. Metal. Chem., 8(6), 365 (1983)).
DE 10133008 proposes peracids, among them m-chloroperbenzoic acid, as promotors for hydrosilylations of H-silanes or H-siloxanes with double bond or triple bond moieties containing hydrocarbons, silanes or siloxanes. Catalysts are all known hydrosilylation catalysts, preferably based on Pt, Ru, Rh and Pd.
US5559264 describes the hydrosilylation of allyl chloride to trimethoxysilane (TMS) in the presence of Ru-CO complexes. Yields greater than 80 % can be achieved by the addition of oxygen as pro motor.
US 6872845 discloses aromatic compounds as promotors for Ru catalyst based hydrosilylations yielding haloorganoalkoxysilanes. Further, the addition of oxygen is proposed for an activation of the outlined Ru-CO and Ru-phosphine catalysts. Generally, the oxygen level naturally occurring in the raw materials is sufficient. A further activation is possible by addition of 3 % O2 in N2, for example.
On the other hand, US 5986122 teaches that the peroxides present in alkenyl polyethers inhibit the hydrosilylation reaction to SiH siloxanes in the presence of Pt catalysts.
Further, US 8580994 describes the beneficial effect of a reduction of the oxygen content during the hydrosilylation of allyl chloride to dimethylethoxysilane in the presence of Ir-diene complex catalysts.
It can be concluded from the prior disclosures that peroxy compounds and oxygen are beneficial in some hydrosilylation reactions.
However, in its nature these findings represent isolated cases. In view of the broad variety of potential catalysts, unsaturated monomers, SiH functionalized silanes and peroxy compounds general rules for the beneficial use of peroxy compounds and oxygen cannot be derived from the prior art.
The situation is further complicated by the fact that, seemingly contradictory, reactions were found where peroxides or oxygen inhibit the desired hydrosilylation reactions.
Accordingly, although disclosures in both the scholarly and patent literature teach that iridium- based catalysts are advantageous for the hydrosilylation of allyl chloride by triethoxysilane, deficiencies still exist in obtaining reproducibly a desirable product selectivity, reaction rate and reaction yield at cost-effective concentrations of iridium
SUMMARY OF THE INVENTION
These problems are addressed by the present invention, which enables an efficient synthesis of products of Formula (I), (R1)y(R2O)3-ySiCH2CHR3CR4R5X (I) by the Ir-catalyzed hydrosilylation of olefinic halides with alkoxysilanes in the presence of peroxycarboxylic acid promoters. By the process of the invention, the desired compounds are obtained reproducibly with a desirable selectivity, rate and reaction stability at cost-effective concentrations of iridium. In the process, the formation of by-products is reduced, and desirable results are obtained for as received solid catalysts as well as for homogeneous catalyst solutions. The catalyst system consisting of Ir-containing catalyst and peroxycarboxylic acids as promotors is highly tolerant towards the use of as received olefinic halides, thus making an additional purification of the olefinic compound redundant. The present invention described in detail hereafter is directed at a process for producing an organoalkoxysilane product comprising reacting
(a) an olefinic halide;
(b) an alkoxysilane;
(c) a catalytically effective amount of iridium-containing catalyst; and
(d) a reaction-promoting effective amount of a peroxycarboxylic acid to produce the organoalkoxysilane product.
Specifically, the invention relates to a process for producing a compound of Formula (I),
(R1)y(R2O)3.ySiCH2CHR3CR4R5X (I) comprising reacting (a) an olefinic halide having the formula H2C=CR3CR4R5X; (b) an alkoxysilane having the formula (R1)y(R2O)3.ySiH; (c) a catalytically effective amount of iridium-containing catalyst; and (d) a reaction-promoting effective amount of a peroxycarboxylic acid to produce the product of Formula (I),
(R1)y(R2O)3.ySiCH2CHR3CR4R5X (I), wherein
R1 and R2are alkyl groups of from 1 to 6 carbon atoms;
R3 is an alkyl group of from 1 to 6 carbon atoms or hydrogen;
R4 is an alkyl group of from 1 to 6 carbon atoms, hydrogen or halogen;
R5 is hydrogen or an alkyl group of from 1 to 6 carbon atoms;
X is a halogen; and y is 0, 1 or 2. DETAILED DESCRIPTION OF THE EMBODIMENTS OF THE INVENTION
The process according to the invention is a process for producing a compound of Formula (I),
(R1)y(R2O)3-ySiCH2CHR3CR4R5X (I) comprising reacting (a) an olefinic halide having the formula H2C=CR3CR4R5X; (b) an alkoxysilane having the formula (R1)y(R2O)3.ySiH; (c) a catalytically effective amount of iridium- containing catalyst; and (d) a reaction-promoting effective amount of a peroxycarboxylic acid to produce the product of Formula (I), (R1)y(R2O)3.ySiCH2CHR3CR4R5X (I), wherein
R1 and R2 are alkyl groups of from 1 to 6 carbon atoms;
R3 is an alkyl group of from 1 to 6 carbon atoms or hydrogen;
R4 is an alkyl group of from 1 to 6 carbon atoms, hydrogen or halogen;
R5 is hydrogen or an alkyl group of from 1 to 6 carbon atoms;
X is a halogen; and y is 0, 1 or 2.
This invention relates to a process for making haloorganosilicon compounds, and more particularly, to a process for the preparation of products of Formula (I), via the hydrosilylation of haloalkenes with alkoxysilanes in the presence of peroxycarboxylic acids and an iridium-containing catalyst.
By “alkyl” herein is meant to include straight, branched and cyclic alkyl groups. Specific and non-limiting examples of alkyls include, but are not limited to, methyl, ethyl, propyl and isobutyl.
By “substituted alkyl” herein is meant an alkyl group that contains one or more substituent groups that are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially or deleteriously interfere with the process.
By “aryl” herein is meant a non-limiting group of any aromatic hydrocarbon from which one hydrogen atom has been removed. An aryl may have one or more aromatic rings, which may be fused, connected by single bonds or other groups. Specific and non-limiting examples of aryls include, but are not limited to, tolyl, xylyl, phenyl and naphthalenyl.
By “substituted aryl” herein is meant an aromatic group substituted as set forth in the above definition of “substituted alkyl.” Similar to an aryl, a substituted aryl may have one or more aromatic rings, which may be fused, connected by single bonds or other groups; however, when the substituted aryl has a heteroaromatic ring, the free valence in the substituted aryl group can be to a heteroatom (such as nitrogen) of the heteroaromatic ring instead of a carbon. If not otherwise stated, it is preferred that substituted aryl groups herein contain 1 to about 30 carbon atoms.
By “alkenyl” herein is meant any straight, branched, or cyclic alkenyl group containing one or more carbon-carbon double bonds, where the point of substitution can be either a carbon-carbon double bond or elsewhere in the group. Specific and non-limiting examples of alkenyls include, but are not limited to, vinyl, propenyl, allyl, methallyl, and ethylidenyl norbornane.
By “alkynyl” is meant any straight, branched, or cyclic alkynyl group containing one or more carbon-carbon triple bonds, where the point of substitution can be either at a carboncarbon triple bond or elsewhere in the group.
By “unsaturated” is meant one or more double or triple bonds. In a preferred embodiment, it refers to carbon-carbon double or triple bonds.
By “inert functional group” herein is meant a group other than hydrocarbyl or substituted hydrocarbyl, which is inert under the process conditions to which the compound containing the group is subjected. The inert functional groups also do not substantially or deleteriously interfere with any process described herein that the compound in which they are present may take part in. Examples of inert functional groups include halo (fluoro, chloro, bromo, and iodo), ether such as -OR30, wherein R30 is hydrocarbyl or substituted hydrocarbyl.
By “hetero atoms” herein is meant any of the Group 13-17 elements except carbon, and can include for example oxygen, nitrogen, silicon, sulfur, phosphorus, fluorine, chlorine, bromine, and iodine.
By “olefin” herein is meant any aliphatic or aromatic hydrocarbon containing one or more additional carbon-carbon double bonds. Such olefins may be linear, branched or cyclic and may be substituted with heteroatoms as described above, with the proviso that the substitutents do not interfere substantially or deleteriously with the course of the desired reaction to produce the product.
By “peroxycarboxylic acid” herein is meant any compound containing a peroxycarboxylic acid moiety, i.e. a structure of the formula -RC(O)-O-O-H, wherein R can be any organyl group.
By “catalytically effective amount” herein is meant an amount effective to catalyze the hydrosilylation reaction.
By “reaction-promoting effective amount” herein is meant an amount sufficient to promote a reaction, but not an amount that will inhibit the reaction. By “halogen” herein is meant any atom that is a member of Group VI I A of the periodic table (fluorine, chlorine, bromine, iodine, astatine). By the prefix “halo” used herein with respect to a compound is meant a compound that contains a halogen atom.
In the process for producing a product of Formula (I), (R1)y(R2O)3-ySiCH2CHR3CR4R5X (I), of the invention as defined above, the principal products of the hydrosilylation process of this invention are compounds of the general Formula (I) (R1)y(R2O)3-ySiCH2CHR3CR4R5X (I) wherein R1 and R2 are alkyl groups of from 1 to 6 carbon atoms; R3 is an alkyl group of from 1 to 6 carbon atoms or hydrogen; R4 is an alkyl group of from 1 to 6 carbon atoms, hydrogen or halogen; R5 is hydrogen or an alkyl group of from 1 to 6 carbon atoms; X is a halogen; and y is 0, 1 or 2.
Specific examples of useful products of the process of the invention include, but are not limited to, (CH3O)3Si(CH2)3CI, (C2H5O)3Si(CH2)3CI, (C2H5O)3SiCH2CH(CH3)CH2Br, (CH3O)3SiCH2CH(CI)CH3, CH3(CH3O)2Si(CH2)3CI, and (C3H7O)3Si(CH2)2CH(CI)CH3.
Byproducts having the following general formulae are formed during the hydrosilylation reaction
(R2O)4Si, (R1)Si(R2O)3, (R1)SiH2(R2O), (R2O)3SiX, (R1 is not hydrogen) (R2O)3SiCH2CHR3CR4R5H, (R1)yX(R2O)2.ySiCH2CHR3CR4R5X CH2=CHR3CR4R5H, XCH2CHR3CR4R5H, and HX.
It has been found that several factors are important for obtaining high yields of product of the Formula (I),
(R1)y(R2O)3.ySiCH2CHR3CR4R5X (I) from a one-step hydrosilylation reaction between an olefinic halide and an alkoxysilane in the presence of an iridium-containing catalyst and a peroxycarboxylic acid.
The most preferred product of the Formula (I) according to an embodiment of the invention is chloropropyltriethoxysilane.
Olefinic halides
Olefinic halides used as starting materials in the process according to the invention have the general formula H2C=CR3CR4R5X, wherein R3 is an alkyl group of from 1 to 6 carbon atoms or hydrogen; R4 is an alkyl group of from 1 to 6 carbon atoms, hydrogen or halogen; R5 is hydrogen or an alkyl group of from 1 to 6 carbon atoms; X is a halogen.
X is a fluoro, chloro, bromo or iodo substituent, preferably a bromo or chloro substituent, most preferably a chloro substituent.
R3 and R5 are independently selected from the group of linear, branched or cyclic C1-C6 alkyl groups or hydrogen, in particular from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, iso-butyl, tert-butyl, iso-pentyl, neo-pentyl, cyclopentyl, cyclohexyl or hydrogen, preferably from methyl, ethyl, n-propyl, n-butyl, iso-propyl, tert-butyl, cyclopentyl, cyclohexyl or hydrogen, more preferably from methyl, ethyl, n-propyl, iso-propyl or hydrogen, even more preferably from methyl, ethyl or hydrogen, most preferably R3 and R5 are hydrogen.
R4 is independently selected from the group of linear, branched or cyclic C1-C6 alkyl groups or hydrogen, in particular from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, iso-propyl, iso-butyl, tert-butyl, iso-pentyl, neo-pentyl, cyclopentyl, cyclohexyl, hydrogen or halogen, preferably from methyl, ethyl, n-propyl, n-butyl, iso-propyl, tert-butyl, cyclopentyl, cyclohexyl or hydrogen, more preferably from methyl, ethyl, n-propyl, iso-propyl or hydrogen, even more preferably from methyl, ethyl or hydrogen, most preferably R4 is hydrogen.
In case R4 is a halogen group independently selected from fluoro, chloro, bromo and iodo substituents, it is preferred that R4 is a chloro substituent.
Preferably, R3, R4 and R5 in the olefinic halide are hydrogen substituents or two of the substituents R3, R4 and R5 are hydrogen substituents and the remaining substituent is a C1- C6 alkyl substituent, more preferably R3, R4 and R5 are hydrogen substituents or two of the substituents R3, R4 and R5 are hydrogen substituents and the remaining substituent is an alkyl substituent selected from methyl, ethyl and n-propyl, even more preferably R3, R4 and R5 are hydrogen substituents or two of the substituents R3, R4 and R5 are hydrogen substituents and the remaining substituent is a methyl substituent, most preferably R3, R4 and R5 are hydrogen substituents or two of the substituents R3 and R5 are hydrogen substituents and the R4 substituent is a methyl substituent.
Olefinic halides, which are suitable as starting materials the present invention, in particular include allyl chloride, methallyl chloride, 3-chloro-1-butene, 3, 4-dichloro-1 -butene, and the like. Of these, in an embodiment allyl chloride, i.e. H2C=CHCH2CI, is preferred.
According to an embodiment of the invention, the olefinic halides can be used as received with industrial grade purity, which has a content of the respective olefinic halide of > 90 wt-%, preferably > 95 wt-%, even more preferably > 98 wt-%, and most preferably > 99 wt-%. While rectification of the olefinic halide starting material by evaporation and subsequent condensation may have a beneficial effect on the yield of the hydrosilylation reaction of the process of the invention, it is not required for performing the process of the invention. The meaning of “as received” olefinic halide is that the olefinic halide is not submitted to a purification step such as distillation or evaporation/condensation before the hydrosilylation step is performed.
Accordingly, as the process of the invention does not require high grade olefinic halides to be performed with high yield, the purity of the olefinic halide of industrial grade purity can be in range from 95.0 wt-% to 99.5 wt-%, more specifically in the range from 95.5 to 99.0 wt-%, and even more specifically in the range from 96.0 wt-% to 98.0 wt-%.
Therein, the industrial grade purity olefinic halide can be as received, or it can be olefinic halide which has been submitted to a purification process before, for example to a process based on evaporation and condensation.
Alkoxysilanes
Alkoxysilanes used as starting materials in the process according to the invention have the general formula (R1)y(R2O)3-ySiH, wherein R1 and R2 are alkyl groups of from 1 to 6 carbon atoms, and y is 0, 1 or 2.
Accordingly, R1 and R2 in the alkoxysilanes of the general formula (R1)y(R2O)s-ySiH and the corresponding product of Formula (I), (R1)y(R2O)3-ySiCH2CHR3CR4R5X (I) are independently selected from the group of linear, branched or cyclic C1-C6 alkyl groups, in particular from methyl, ethyl, n-propyl, n-butyl, n- pentyl, n-hexyl, iso-propyl, iso-butyl, tert-butyl, iso-pentyl, neo-pentyl, cyclopentyl or cyclohexyl, preferably from methyl, ethyl, n-propyl, n-butyl, iso-propyl, tert-butyl, cyclopentyl or cyclohexyl, more preferably from methyl, ethyl, n-propyl, iso-propyl, even more preferably from methyl and ethyl, most preferably R1 and R2 are methyl groups.
Preferably y is 0, i.e. it is preferred that the alkoxysilane (b) applied in the process for producing a product of Formula (I) is an alkoxysilane substituted with three alkoxy groups. In such alkoxysilanes bearing three alkoxy groups at the Si atom and the corresponding products of Formula (I), preferably all groups R2 represent the same type of C1-C6 alkyl group, more preferably an alkyl group selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl and cyclohexyl, even more preferably selected from methyl, ethyl, n-propyl and isopropyl, most preferably the alkoxysilane and the corresponding products of Formula (I), bears three ethoxy groups at the Si atom, i.e. y = 0 and R2 is ethyl.
Alkoxysilanes that are suitable as starting materials in the process of the present invention include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, diethylethoxysilane, and the like. Of these alkoxysilanes, in an embodiment of the invention trimethoxysilane and triethoxysilane are preferred.
Trialkoxysilanes useful in the instant process can be obtained via alcohol esterification of trihalosilanes as disclosed, for example, in US 3792071 and US 3985781. Trimethoxysilane and triethoxysilane can be obtained in 89 - 92 weight percent distilled purity. Residual chloride levels can be as high as 100 ppm. Impurities include H2Si(OR)2 , HSi(OR)2CI, Si(OR)4 and higher boiling condensed silicates.
Alternatively, trialkoxysilanes useful in the instant process can be obtained via the Direct Reaction of alcohols with copper-activated silicon as disclosed, for example, in US 7652164 and US 7429672. Trimethoxysilane and triethoxysilane synthesized according to this process are chloride-free and typically about 89 - 99 weight percent pure prior to distillation. Distilled products are about 99.0 - 99.9 weight percent pure. Impurities are H2Si(OR)2, RSiH(OR)2, RSi(OR)s , Si(OR)4 and higher boiling condensed silicates.
Peroxycarboxylic acids
Peroxycarboxylic acids contain a -C(O)-O-OH moiety. They are decomposed by the impact of heat, acids and some metal compounds. Accordingly, since the reactants of hydrosilylation processes are subjected to these impact factors during reaction, product recovery and recycling of unreacted starting materials and catalysts, peroxide promoters must be selected to maintain a stable hydrosilylation activity throughout a batch or continuous process.
Preferably, the concentration of peroxycarboxylic acids used in an embodiment of the process of the invention ranges from about 1 to about 2000 ppm, more preferably from about 2 to about 500 ppm, more preferably from about 3 to about 200 ppm, even more preferably from about 4 to about 100 ppm, even further preferably from about 5 to about 50 ppm, still further preferably from about 5 to about 25 ppm, and most preferably from about 5 to about 15 ppm, all based on the total weight of olefinic halide and the alkoxysilane applied in the process. Preferred temperature and concentration ranges for different types of peroxycarboxylic acids are set forth below in the detailed description of specific embodiments of the invention.
The half-life time of peroxycarboxylic acids can be as short as about 30 minutes at the boiling point of allyl chloride (44-45°C), and may thus be even shorter in the temperature range from about 70 to about 100°C, in which the hydrosilylation reactions are preferably carried out. Consequently, the concentrations of peroxycarboxylic acids will not always be adequate to promote and drive the hydrosilylation reaction to completion. So variable and inconsistent results are possible in laboratory experiments and commercial operations when the peroxycarboxylic acids are not present in effective reaction-promoting concentrations. The process of the present invention encompasses the presence of peroxycarboxylic acids at levels sufficient to carry out effective hydrosilylations. The peroxycarboxylic acids must be present in the hydrosilylation reaction zone along with the reactants and the iridium-containing catalyst. They can be added directly to the reaction zone, or preferably admixed with the olefin. Generally, the peroxycarboxylic acids as defined herein comprise all types of organic compounds containing one or more peroxycarboxylic acid moieties of the structure -C(O)-O-OH.
Preferred types of peroxycarboxylic acids according to an embodiment of the present invention are halogenated perbenzoic acids, unsubstituted peroxyalkanoic acids and a-halogenated peroxyalkanoic acids, wherein halogenated perbenzoic acids constitute the most preferred of the aforementioned groups of peroxycarboxylic acids.
The halogenated peroxybenzoic acids, which comprise mono-, bi-, tri-, tetra- and pentahalogenated perbenzoic acids are preferably selected from monohalogenated perbenzoic acids and dihalogenated perbenzoic acids.
It is further preferred that the halogenated peroxybenzoic acids bear at least one halogen substituent in meta-position to the peroxycarboxylic group.
It is also preferred that at least one of the halogen substituents of the perbenzoic acids is a fluoro or a chloro substituent, and even more preferably all halogen substituents are independently selected from fluoro and chloro substituents.
Examples of preferred peroxycarboxylic acids for the process of the invention selected from halogenated perbenzoic acids are 2-bromo-5-chlorobenzoic acid, 3,5-difluoroperbenzoic acid,
3.4-difluoroperbenzoic acid, 2,3,6-trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid,
2.3.4-trifluoroperbenzoic acid, 2,3,4,5,6-pentafluorobenzoic acid, 3-chloroperbenzoic acid, 3- fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid, particularly preferred halogenated perbenzoic acids are 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5- difluoroperbenzoic acid.
Unsubstituted peroxyalkanonic acids are preferably selected from C2-C12 peroxyalkanoic acids, wherein it is further preferred that the peroxycarboxylic acid group is in a terminal position of a linear or branched alkyl group, and it is further preferred that the alkyl residue is a either a methyl group or a C2-C11 n-alkyl group. Examples of preferred peroxycarboxylic acids for the process of the embodiment of the invention selected from unsubstituted peroxyalkanonic acids are peracetic acid, peroxypropionic acid and peroxybutyric acid. a-Halogenated peroxyalkanoic acids, i.e. peroxyalkanoic acids bearing at least one halogen substituent in a-position to the peroxycarboxylic acid group, are preferably selected from a- halogenated C2-C12 peroxyalkanoic acids, more preferably from linear a-halogenated C2-C12 peroxyalkanoic acids wherein the halogen substituents are independently selected from chloro and fluoro substituents. Examples of preferred a-halogenated peroxyalkanoic acids are chloroperacetic acid, fluoroperacetic acid, dichloroperacetic acid, difluoroperacetic acid, trifluoroperacetic acid and trichloroperacetic acid.
The presence of peroxycarboxylic acids allows to lower the loading of the Ir catalyst required to perform carry out the hydrosilylation reaction with a high yield and reasonable reaction rate and also allows to perform the reaction with industrial grade olefinic halides without additional purification steps prior to the hydrosilylation reaction.
Further, commercially available Ir catalysts such as IrCh and FhlrCh can be successfully applied in the hydrosilylation reaction in the presence of peroxycarboxylic acid promoters with low catalyst loadings and without purification of the industrial grade olefinic halide starting material.
Iridium-containinq catalysts
Suitable iridium-metal containing catalysts can be selected from iridium metal or homogeneous and heterogeneous iridium metal-containing compounds and complexes in which iridium can be in any of the oxidation states from 0 to 8 inclusive. Examples include the following Ir compounds: Ir clusters and particles ranging from about 1 nanometer to about 100 microns; Ir on solid supports such as Ir on Fe, Ir on alumina, Ir on carbon and Ir on silica; iridium halides (IrXn, X is halogen atom and n is any value between 2 - 4), for example IrCh and IrBrs ; IVhlrCh, in particular FhlrCh, MlrCh, /klrsCI^, M4lr4Cli2, (M = H, or alkali metal); zinc-reduced and tin- reduced reaction products of iridium halides, for example, ZnlrsCli2 and SnlrsCli2 ; lrC>2, lrs(CO)i2, [lr(CO)3Cl2]2; cycloolefin complexes of iridium such as lr(COD)(COT), COD-IrCh, [COD-IrChk, in which COD is cyclooctadiene and COT is cyclooctatriene; bis(6,6- dimethylcyclopentadienyl)iridium, bis(r|5-2,4-dimethylpentadienyl)iridium, bis(1 ,3- dimethylcyclopentadienyl)iridium, lr(AcAc)s in which AcAc is the acetylacetonate ligand; (TT- arene) iridium complexes such as (p-cymene) iridium (II) chloride dimer and (benzene) iridium (II) chloride dimer; ammine complexes of iridium such as [lr(NHs)6]X2 and [lr(NH3)e]X3.
The preferred iridium-containing catalysts are the iridium chloride compounds, with H2I rCh and FhlrCh hydrate, IrCh, IrCh hydrate and its zinc-reduced product being the most preferred. Catalysts from one batch can be recycled to the next batch without significant loss of activity. The catalyst use level may be in the range of 1 to 300 parts per million Ir metal based on the total reactant charge, with 5 to 50 parts per million being preferred.
The catalysts can be added to the hydrosilylation reactions in the form of a solid, as a suspension or a solution in an organic solvent. The Ir-containing catalyst may also be applied in an immobilized form, for example linked or absorbed to the surface of a substrate material.
Hydrosilylation process
The hydrosilylation process according to the invention is not restricted to any particular protocol.
In a preferred protocol for a hydrosilylation reaction according to the invention using a solid catalyst, a preformed mixture of the olefinic halide, the alkoxysilane and the peroxycarboxylic acid is added to a mixture of alkoxysilane and the iridium-based hydrosilylation catalyst. Preferably, the preformed mixture is added stepwise or more preferably it is fed into the reactor to the mixture of the alkoxysilane and the iridium-based hydrosilylation catalyst from a reacting, mixing or storage vessel. Preferably, the reactor in which the reactants are combined is equipped with a mixing device.
In another preferred protocol for a hydrosilylation reaction according to the invention using a catalyst solution, preferably for small scale reactions, the peroxycarboxylic acid, the olefinic halide and the alkoxysilane are mixed, and then a solution or suspension of the catalyst in a solvent, preferably a solution in an organic solvent, is added to the mixture in order to perform the hydrosilylation reaction. Preferably, a mixing device is used in order to form and maintain a homogeneous reaction mixture.
Further, the process is advantageously carried out by slowly adding the olefinic halide and a peroxycarboxylic acid to a reaction medium containing the alkoxysilane and conducting the hydrosilylation in the presence of an iridium metal-containing catalyst in either a semi-batch or continuous process. This order of addition effectively maintains a minimum concentration of unreacted olefinic halide in the reaction medium relative to the alkoxysilane, and thus effectively establishes a very large molar excess of the alkoxysilane relative to the olefinic halide in the reaction medium. In general practice, the maximum rate of addition of the olefinic halide to the alkoxysilane will be determined by the reaction rate, which is dependent in part on the reaction temperature, the catalyst concentration, the concentration and thermal stability of the peroxycarboxylic acid and by the heat transfer limitations of the reaction equipment and the reactor size, as will be understood by one skilled in the art.
As mentioned above, the process of the invention can be carried out in any equipment suitable for hydrosilylation reactions, including equipment designed for continuous or alternatively discontinuous reactions. By using in the present process trimethoxysilane or triethoxysilane derived from silicon metal and the corresponding alkanol, one can avoid the use of corrosive and hazardous hydridochlorosilanes and eliminate the generation of large amounts of chlorine- containing waste byproducts, which are inherent to the use of products derived from hydridochlorosilanes.
Reaction conditions include reaction temperatures ranging from about 15 °C to about 250 °C, preferably about 30 °C to about 180 °C, more preferably from about 50°C to about 130°C with from about 60°C to 80°C being further preferred. Generally, the process is performed at a pressure at or above atmospheric pressure with atmospheric pressure being preferred. It is recognized that the process of the present invention may provide a high yield of the desired chloroalkylalkoxysilane in a batch system, but may as well be performed in a semi-batch process or a continuous process. However, a batch reaction will typically be conducted at a lower temperature with consequently longer reaction times.
Since the process of the present invention is nearly quantitative with respect to the conversion of the olefinic halide to the desired products of Formula (I), (R1)y(R2O)3-ySiCH2CHR3CR4R5X (I), particularly the reaction of allyl chloride with triethoxysilane to provide chloropropyltriethoxysilane, the generation of undesired byproducts is significantly lowered. This reduces the amounts of materials to be disposed as waste, to be isolated as separate streams, i.e. by distillation, or to be vented from the reaction system. Since the process of the present invention is highly exothermic, typically continuous external heating is not necessary and reaction times are short. Generally, the only impurities in significant quantities which need to be removed from the reaction product are unreacted alkoxysilanes, tetraalkoxysilane, residual catalyst and peroxycarboxylic acids or their degradation products, respectively. The low level of residual halide that may be present in the product can be neutralized by methods well known in the art. If the hydrosilylation product of the present invention is used as an intermediate for the production of other organofunctional silicon compounds, the purity of the as received material can be sufficient. Additional purification steps are not needed. When applied, e.g., to the preparation of chloropropyltriethoxysilane, the process of the present invention provides a higher yield of the target product, calculated on a molar basis, than any other one-step or two-step process described in the prior art. This is accomplished through the addition of an effective amount of a peroxycarboxylic acid promoter in combination with effective levels of an iridium-containing catalyst. Further, the process yields the target product at iridium levels significantly lower than the ones described in the prior art. The process also provides a higher yield per unit volume of equipment used, since the use of inert solvents is obviated and significant quantities of waste by-products are not generated. While the process of the present invention does not require operations at a pressure above atmospheric pressure, in an embodiment an elevated pressure may be used, for example up to two atmospheres pressure, in order to control the boiling point of the reaction mixture in a closed reactor. In another embodiment, a pressure below atmospheric pressure may be used if a reaction temperature below the atmospheric pressure boiling point of the alkoxysilane is desired. The products of Formula (I), (R1)y(R2O)3-ySiCH2CHR3CR4R5X (I) of the process of the present invention may be purified by standard processes, i.e. by distillation, or may be used directly without intermediate purification.
In an embodiment according to the invention, the olefinic halide (a) is selected from the group consisting of allyl chloride, methallyl chloride, 3-chloro-1 -butene and 3, 4-dichloro-1 -butene and combinations thereof, preferably the olefinic halide (a) is allyl chloride.
The olefinic halides (a) used in the process according to this embodiment are preferably reacted with trialkoxysilanes, more preferably with triethoxysilane. Most preferably, chloropropyltriethoxysilane is obtained by reacting allyl chloride with triethoxysilane in the presence of an Ir catalyst and a peroxycarboxyilic acid as specified herein, preferably with a halogenated perbenzoic acid acting as promoter.
In another embodiment according to the invention, the alkoxysilane (b) is selected from the group consisting of trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, diethylethoxysilane, and combinations thereof, preferably the alkoxysilane is triethoxysilane.
In still another embodiment according to the invention, the reaction-promoting effective amount of the peroxycarboxylic acid (d) ranges from about 1 to about 2000 ppm, based on the total weight of the starting materials olefinic halide (a) and alkoxysilane (b) , preferably from about 2 to about 500 ppm, more preferably from about 3 to about 200 ppm, even more preferably from about 4 to about 100 ppm, even further preferably from about 5 to about 50 ppm, still further preferably from about 5 to about 25 ppm, and most preferably from about 5 to about 15 ppm.
Preferably, the starting materials (a) and (b) are allyl chloride and triethoxysilane, and the amount of the peroxycarboxylic acid (d) is calculated based on the total weight of allyl chloride and triethoxysilane.
The ratio of the Ir-containing catalyst (c) and the peroxycarboxylic acid (d) promoting the hydrosilylation reaction is in the range of about 1 : 1 to about 1 : 40, preferably in the range of about 1 : 1 .5 to about 1 : 25, more preferably in the range of about 1 : 2 to about 1 : 20 , most preferably in the range of about 1 : 2 to about 1 : 10. The ratio of the Ir-containing catalyst (c) to the peroxycarboxylic acid (d) is based on the amount of each of the components (c) and (d) given in “ppm”, wherein the amount in ppm refers to the amount of component (c) or (d), respectively, relative to the total mass of the olefinic halide (a) and the alkoxysilane (b). In the case of the Ir catalyst (c), the amount of the Ir metal in component (c) is related to the total mass of (a) and (b) in order to determine the amount of (c) in ppm.
In an embodiment according to the invention, the peroxycarboxylic acid (d) is selected from the group of halogenated perbenzoic acids, the group of unsubstituted peroxyalkanoic acids and from the group of a-halogenated peroxyalkanoic acids.
As defined herein, the term “peroxyalkanoic acid” refers to peroxycarboxylic acids consisting of a peroxycarboxy group and an alkyl residue. Therein the alkyl residue may be a primary n- alkyl group, a secondary alkyl group or a tertiary alkyl group, wherein primary alkyl groups are preferred. The alkyl groups may be linear, branched or cyclic alkyl groups, wherein C1-C11 n- alkyl groups are preferred. The term “unsubstituted” indicates that the C-atoms of the alkyl group do not bear any other substituents than hydrogen atoms.
As defined herein, the term “a-halogenated peroxyalkanoic acids” indicates that the alkyl groups of these compounds bear one or more halogen substituents on the carbon atom of the alkyl group bonded to the carbon atom of the peroxycarboxyl group.
The group of halogenated perbenzoic acids is preferred, and is beneficially applied in the process of the invention, in particular in the Ir-catalysed hydrosilylation reaction of allyl chloride and triethoxysilane catalyzed by an I r catalyst, preferably by I rCh or H2I rCh.
In another embodiment according to the invention, the peroxycarboxylic acid (d) is selected from the group of monohalogenated perbenzoic acids, from the group of dihalogenated perbenzoic acids, and the group of tri-, tetra- and pentahalogenated perbenzoic acids.
Regarding the nomenclature of the halogenated perbenzoic acid compounds as used herein it is noted that the carbon ring atom bearing the peroxycarboxylic group is denoted as the position “1”, and the positions of the one or more halogen substituents on the phenyl ring are numbered relative to this position. For example, 3-bromo-peroxybenzoic acid denotes peroxybenzoic acid bearing a bromo substituent in the meta-position to the peroxycarboxylic acid group.
Examples of monohalogenated perbenzoic acids according to the embodiment are 2-, 3- or 4- chloroperbenzoic acid, wherein 3-chloroperbenzoic acid is preferred, and 2-, 3-, or 4- fluoroperbenzoic acid, wherein 3-fluoroperbenzoic acid is preferred.
Examples of dihalogenated perbenzoic acids are dichloroperbenzoic acids such as 2,3- dichloroperbenzoic acid, 2,4-dichloroperbenzoic acid, 2,6-dichloroperbenzoic acid, 3,4- dichloroperbenzoic acid, 3,5-dichloroperbenzoic acid, wherein 3,5-dichloroperbenzoic acid is preferred, difluoroperbenzoic acids such as 2,3-difluoroperbenzoic acid, 2,4- difluoroperbenzoic acid, 2,6-difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 3,5- difluoroperbenzoic acid, wherein 3,5-difluoroperbenzoic acid is preferred, monochloromonofluoroperbenzoic acids such as 2-chloro-4-fluoroperbenzoic acid, 2-chloro-5- fluoroperbenzoic acid, 3-chloro-2-fluoroperbenzoic acid, 3-chloro-5-fluoroperbenzoic acid, 4- chloro-2-fluoroperbenzoic acid, 5-chloro-2-fluoroperbenzoic acid, wherein 3-chloro-5-fluoro perbenzoic acid is preferred, and monobromo-monochloroperbenzoic acids, such as 2-bromo- 5-chloroperbenzoic acid and 3-bromo-5-chloroperbenzoic acid, wherein 3-bromo-5- chloroperbenzoic acid is preferred.
Preferred examples of tri-, tetra- and pentahalogenated perbenzoic acids are 2,3,6- trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, and 2,3,4,5,6-pentafluoroperbenzoic acid.
In another embodiment according to the invention, the peroxycarboxylic acid (d) is selected from the group of halogenated perbenzoic acids bearing at least one halogen substituent in a meta-position to the peroxycarboxyl group.
Preferred examples of halogenated perbenzoic acids having at least one halogen substituent in a meta-position to the peroxycarboxyl group are 3-chloroperbenzoic acid, 3- fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid.
In still another embodiment according to the invention, the peroxycarboxylic acid (d) is selected from halogenated perbenzoic acids bearing one, two or three halogen substituents in total, wherein preferably at least one of the halogen substituents, and more preferably all of the halogen substituents are independently selected from fluoro and chloro substituents, and most preferably either all halogen substituents are chloro substituents or all halogen substituents are fluoro substituents.
The most preferred halogenated perbenzoic acids according to this embodiment are 3- chloroperbenzoic acid, 3-fluoroperbenzoic acid, 3,5-difluoroperbenzoic acid, 3,5- dichloroperbenzoic acid, and 2,3,6-trifluoroperbenzoic acid.
In a preferred embodiment according to the invention, the peroxycarboxylic acid (d) is selected from the group of perbenzoic acids consisting of 2-bromo-5-chloroperbenzoic acid, 3,5- difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 2,3,6-trifluoroperbenzoic acid, 2,4,5- trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, 2,3,4,5,6-pentafluoroperbenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid and 3,5-difluoroperbenzoic acid.
Preferably, the peroxycarboxylic acid (d) is selected from 3-chloroperbenzoic acid, 3- fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid. The halogenated perbenzoic acids according to this embodiment of the invention are either commercially available or readily available from the corresponding halogenated benzoic acids. When these compounds are applied as promoters in the process of the invention in an amount of about 3 to about 200 ppm relative to the total mass of the olefinic halide (a) and the alkoxysilane (b), then the catalyst loading of the Ir-based catalyst, preferably of IrCh or F^IrCle, can be in the range of about 1 to about 25 ppm of Ir relative to the total mass of the olefinic halide (a) and the alkoxysilane (b).
In another embodiment according to the invention, the peroxycarboxylic acid (d) is an a- halogenated peroxyalkanoic acid selected from the group of C2-C12 a-halogenated peroxyalkanoic acids bearing one or more halogen substituents, which are independently selected from chloro and fluoro substituents, or wherein the peroxycarboxylic acid (d) is an unsubstituted C2-C12 peroxyalkanoic acid.
Preferably, the peroxycarboxylic acid (d) is an a-halogenated alkanoic acid selected from chloroperacetic acid, fluoroperacetic acid, dichloroperacetic acid, difluoroperacetic acid, trifluoroperacetic acid and trichloroperacetic acid.
In another embodiment according to the invention, the iridium-containing catalyst (c) is selected from the group consisting of nano- and micron-sized iridium particles, iridium halides, zinc-reduced or tin reduced reaction products of iridium halides, cycloolefin complexes of iridium, amine complexes of iridium, phosphine complexes of iridium, CO-complexes of iridium, and combinations thereof.
As defined herein, nanoparticles are particles having an average particle size of 1 to 500 nm, and micron-sized particles are particles having an average particle size of 0.5 to 50 .m as determined by Dynamic Light Scattering.
In still another embodiment according to the invention, the amount of the iridium-containing catalyst (c) based on the total weight of the starting materials olefinic halide (a) and alkoxysilane (b) ranges from about 1 to about 100 ppm, preferably from about 1 to about 50 ppm, more preferably from about 1 to about 25 ppm, even more preferably from about 2 to about 25 ppm, and most preferably from about 3 to about 15 ppm.
In another embodiment according to the invention, the iridium-containing catalyst (c) is selected from the group consisting of IrCh, IrBrs, IVklrCle, where M = H, or alkali metal; cycloolefin complexes of iridium such as lr2Cl2(COE)4, Crabtree’s catalyst, [lr(p2-CI)(COD)]2 and lr2(OCH3)2(COD)2, where COE is cyclooctene and COD is 1 ,5-cyclooctadiene; pentamethylcyclopentadienyl iridium dichloride dimer [Cp*lrCh]2; (n-arene) iridium complexes, and combinations thereof. In a preferred embodiment according to the invention, the iridium-containing catalyst (c) is selected from IrCh xfW or ^IrCle.
The number of water molecules in the IrCh hydrate “x” can be any fraction number from 0, i.e. anhydrous IrCh, to 1. As IrCh is strongly hygroscopic, IrCh hydrate may absorb additional water beyond the one water molecule per iridium ion. H2I rCh may also be applied as catalyst of the hydrosilylation reaction as anhydrous reagent or as the corresponding hydrate. Both IrC and H2lrCh can be applied as a solid or as a preformed stock solution or suspension to the hydrosilylation reaction. Such solution or suspension is preferably prepared with an organic solvent having OH functional groups, preferably alkanols with one, two or three hydroxyl groups, such as methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, or polyglycols such as polyethylene glycols or polypropylene glycols.
Preferably, the amount of the iridium-containing catalyst IrCh or H2lrCh in the process of the embodiment of the present invention is in the range of about 1 to about 50 ppm, more preferably in the range of about 2 to about 25 ppm and even more preferably in the range of about 3 to about 15 ppm. The indication in “ppm” refers to the content of Ir in IrCh or H2lrCh by mass in relation to the total mass of the olefinic halide (a) and the alkoxysilane (b). Therein, the ratio of the iridium-containing catalyst IrCh or H2lrCh to the peroxycarboxylic acid promoter (d) in [ppm to ppm] according to this embodiment is preferably in the range of about 1 : 1.5 to about 1 : 25, more preferably in the range of about 1 : 2 to about 1 : 20, most preferably in the range of about 1 : 2 to about 1 : 10, and the preferred peroxycarboxylic acids (d) according to this embodiment are halogenated perbenzoic acids, more preferably selected from 3- chloroperbenzoic acid, 3-fluoroperbenzoic acid and 3,5-difluorperbenzoic acid. The indication “ppm” with regard to the peroxycarboxylic acid (d) refers to the amount of the peroxycarboxylic acid by mass in relation to the total mass of the olefinic halide (a) and the alkoxysilane (b).
According to this embodiment, it is preferred that the conditions described above are applied in the hydrosilylation of allyl chloride with triethoxysilane in order to obtain chloropropyltriethoxysilane.
In a further embodiment according to the invention, the iridium-containing catalyst (c) is added to the reaction as a solid, or as a solution or suspension in an organic solvent, preferred OH functionalized solvents, i.e. such as OH functional alkanols, diols and triols, for example ethanol, polyethers, preferably the catalyst (c) is added as a solid.
Examples of OH-functionalized solvents are methanol, ethanol, n-propanol, iso-butanol, n- butanol, tert-butanol, pentanol, hexanol, cyclohexanol, and polyglycols such as polyethylene glycols and polypropylene glycols, mono ethers of glycols and polyglycols, such as the methyl and butyl ethers of ethylene glycol, diethylene glycol and trietyhlene glycol and the methyl and butyl ethers of propylene glycol, dipropylene glycol and tripropylene glycol.
In another embodiment according to the invention, the olefinic halide (a) is an industrial grade olefinic halide, preferably industrial grade allyl chloride.
As defined herein, the term “industrial grade” denotes an olefinic halide having a purity of > 90 wt-%, preferably > 95 wt-%, even more preferably > 98 wt-%, and most preferably > 99 wt-%. Typically, commercially available olefinic halides have a quality with regard to purity characterized as “industrial grade”. In many cases, however, a higher degree of purity is needed which is associated with further purification steps and higher costs.
The process of the invention allows to carry out the iridi um-catalyzed hydrosilylation reaction in the presence of percarboxylic acids (d) with high yields using olefinic halides (a) having an industrial grade quality. The olefinic halides according to the embodiment may thus have a purity in range from about 95.0 wt-% to about 99.5 wt-%, more specifically in the range from about 95.5 to about 99.0 wt-%, and even more specifically in the range from about 96.0 wt-% to about 98.0 wt-%. The olefinic halides can be used as received.
In an embodiment according to the invention, the molar ratio of the olefinic halide (a) to the alkoxysilane (b) is in the range of about 10 : 1 to about 1 : 10, preferably about 5 : 1 to about 1 : 5, more preferably about 2 : 1 to about 1 : 2, even more preferably about 1 .7 : 1 to about 1 : 1.7, even further preferably about 1.5 : 1 to about 1 : 1.5, and most preferably about 1.2 : 1 to about 1 : 1.2.
In another embodiment according to the invention, the ratio of the iridium-containing catalyst (c) to the peroxycarboxylic acid (d) in [ppm to ppm], each based on the total weight of the starting materials olefinic halide (a) and alkoxysilane (b), is in the range of about 1 : 1 to about 1 : 40, preferably in the range of about 1 : 1.5 to about 1 : 25, more preferably in the range of about 1 : 2 to about 1 : 20 , most preferably in the range of about 1 : 2 to about 1 : 10.
For the determination of the ratio of the iridium-containing catalyst (c) to the peroxycarboxylic acid (d) in [ppm to ppm], the amount of the peroxycarboxylic acid (d) by mass is divided by the total mass of the olefinic halide (a) and alkoxysilane (b) and the result is multiplied with 1000000; the amount of iridium contained in the iridium-containing catalyst (c) by mass is divided by the total mass of the olefinic halide (a) and the alkoxysilane (b) and the result is multiplied with 1000000. Using this calculation, the amounts of the iridium-containing catalyst (c) and of the peroxycarboxylic acid (d) according to the invention in ppm are obtained. The ratios given in this embodiment thus refer to the ratio of the amounts of the iridium-containing catalyst and the peroxycarboxylic acid in “ppm” determined as described above. In a preferred embodiment according to the invention, the olefinic halide (a) is allyl chloride, the alkoxysilane (b) is triethoxysilane, the Ir-containing catalyst (c) is IrCh or FklrCle, and the peroxycarboxylic acid (d) is 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid or 3,5- difluoroperbenzoic acid.
In a further preferred embodiment according to the invention, the olefinic halide (a) is allyl chloride, the alkoxysilane (b) is triethoxysilane, the amount of iridium-containing catalyst (c) is in the range of about 5 to about 20 ppm, and the peroxycarboxylic acid (d) is either
- mCPBA, present in an amount fulfilling the condition that the ratio of catalyst (c) to promoter (d) in [ppm/ppm] is in the range of about 1 : 2.5 to about 1 : 20, or
- mFPBA, present in an amount fulfilling the condition that the ratio of catalyst (c) to promoter (d) in [ppm/ppm] is in the range of about 1 : 2.5 to about 1 : 10, or
- dFPBA present in an amount fulfilling the condition that the ratio of catalyst (c) to promoter (d) in [ppm/ppm] is in the range of about 1 : 2 to about 1 : 4 .
Preferably, therein the iridium-containing catalyst (c) is selected from IrCh and FklrCle.
The [ppm/ppm] ratio of the iridium-containing catalyst (c) and the promoter (d) is determined as described before.
The invention also relates to compositions which can be obtained when performing the process according to the invention as described above in detail and with regard to various embodiments.
The invention specifically relates to a composition comprising one or more compounds of the Formula (I), (R1)y(R2O)3-ySiCH2CHR3CR4R5X (I), one or more iridium-containing compounds, and one or more compounds selected from i) peroxycarboxylic acids, and/or ii) carboxylic acids, wherein R1 and R2 are alkyl groups of from 1 to 6 carbon atoms; R3 is an alkyl group of from 1 to 6 carbon atoms or hydrogen;
R4 is an alkyl group of from 1 to 6 carbon atoms, hydrogen or halogen;
R5 is hydrogen or an alkyl group of from 1 to 6 carbon atoms;
X is a halogen; and y is 0, 1 or 2.
The iridium-containing compounds of the compositions according to the invention are only restricted insofar as they necessarily contain one or more iridium atoms or iridium ions. Accordingly, the iridium-containing compounds can be any iridium-containing catalyst or an iridium-compound or iridium particles derived from such iridium-contain hydrosilylation catalysts as described above in the description of the process of the invention. Preferably, the iridium-containing compounds are compounds formed from the catalysts used in the process of the invention, i.e. intermediates and active catalytic species of the catalytic cycle of the hydrosilylation reation, for example iridium(O) nanoparticles or iridium(O) micron-sized particles.
As defined herein, nanoparticles are particles having an average particle size of 1 to 500 nm, and micron-sized particles are particles having an average particle size of 0.5 to 50 .m as determined by Dynamic Light Scattering. Further, the iridium-containing compounds can be compounds derived from the iridium-containing catalysts of the process of the invention by deactivation or decomposition.
In the same manner, the peroxycarboxylic acids of the composition of the invention are not restricted in any particular manner except that they necessarily comprise a peroxycarboxyl group, as applies for the peroxycarboxylic acids of the process of the invention.
The carboxylic acids of the composition of the invention as defined herein are not restricted in any particular manner except that they necessarily comprise a carboxyl group.
In particular, the peroxycarboxylic acid compound mentioned in the above description of the process of the invention may be comprised by the compositions of the invention, and the same compounds which are preferably applied in the process of the invention are preferably comprised by the compositions of the invention. The carboxylic acids of the compositions of the invention are preferably the analogous compounds to the peroxycarboxylic acid compound mentioned in the above description of the process of the invention, and the carboxylic acids analogous to the peroxycarboxylic acids preferably applied in the process of the invention are more preferably comprised by the compositions of the invention. The term “analogous” as defined herein with regard to peroxycarboxlic acids and carboxylic acids means that the carboxylic acids correspond to the peroxycarboxylic acids insofar as they are structurally identical except for having a carboxyl group instead of a peroxycarboxyl group.
The compounds of the formula (I) comprised by the compositions according to the invention are preferably the products obtained by the hydrosilylation of an olefinic halide selected from the group of allyl chloride, methallyl chloride, 3-chloro-1 -butene and 3, 4-dichloro-1 -butene and combinations thereof, wherein allyl chloride is preferred, with an alkoxysilane selected from the group of trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane and diethylethoxysilane, wherein trimethoxysilane and triethoxysilane are preferred.
The most preferred compounds of the formula (I) which may be comprised by the composition of the invention are chloropropyltrimethoxysilane and chloropropyltriethoxysilane. In a preferred embodiment of the composition according to the invention, the compound of the formula (I) is chloropropyltriethoxysilane.
In an embodiment, the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from halogenated perbenzoic acids, unsubstituted peroxyalkanoic acids, a-halogenated peroxyalkanoic acids, from halogenated benzoic acids, unsubstituted alkanoic acids and from of a-halogenated alkanoic acids.
The terms “peroxyalkanoic acid”, “unsubstituted” and “a-halogenated peroxyalkanoic acids” have the same meaning as defined above. Correspondingly, the term “unsubstituted alkanoic acids” refers to carboxylic acids consisting of a carboxy group and an alkyl residue, wherein the C-atoms of the alkyl group do not bear any other substituents than hydrogen atoms. The alkyl group may be a primary n-alkyl group, a secondary alkyl group or a tertiary alkyl group, with primary alkyl groups being preferred, wherein thhe alkyl groups may be linear, branched or cyclic alkyl groups, with C1-C11 n-alkyl groups being preferred. Likewise, the term “a- halogenated alkanoic acids” ” indicates that the alkyl groups of these compounds bear one or more halogen substituents on the carbon atom of the alkyl group bonded to the carbon atom of the carboxyl group.
In a further embodiment, the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from monohalogenated perbenzoic acids, from dihalogenated perbenzoic acids, tri-, tetra- and pentahalogenated perbenzoic acids, from monohalogenated benzoic acids, from dihalogenated benzoic acids, and tri-, tetra- and pentahalogenated benzoic acids.
In still a further embodiment, the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from halogenated perbenzoic acids bearing at least one halogen substituent in a meta-position to the peroxycarboxyl group, and from halogenated benzoic acids bearing at least one halogen substituent in a meta-position to the carboxyl group.
In an embodiment according to the invention, the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from the group of perbenzoic acids consisting of 2-bromo-5-chloroperbenzoic acid, 3,5-difluoroperbenzoic acid, 3,4- difluoroperbenzoic acid, 2,3,6-trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid, 2,3,4- trifluoroperbenzoic acid, 2,3,4,5,6-pentafluoroperbenzoic acid, 3-chloroperbenzoic acid, 3- fluoroperbenzoic acid and 3,5-difluoroperbenzoic acid, preferably the perbenzoic acid is selected from 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid, and/or from the group of benzoic acids consisting of 2-bromo-5-chlorobenzoic acid, 3,5- difluorobenzoic acid, 3,4-difluorobenzoic acid, 2,3,6-trifluorobenzoic acid, 2,4,5- trifluorobenzoic acid, 2,3,4-trifluorobenzoic acid, 2,3,4,5,6-pentafluorobenzoic acid, 3- chlorobenzoic acid, 3-fluorobenzoic acid and 3,5-difluorobenzoic acid, preferably the benzoic acid is selected from 3-chlorobenzoic acid, 3-fluorobenzoic acid, and 3,5-difluorobenzoic acid. According to the embodiment, it is preferred that the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid, and from 3-chlorobenzoic acid, 3- fluorobenzoic acid, and 3,5-difluorobenzoic acid.
In another embodiment according to the invention, the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids is selected from the group consisting of C2-C12 a-halogenated peroxyalkanoic acids bearing one or more halogen substituents, which are independently selected from chloro and fluoro substituents and unsubstituted C2-C12 peroxyalkanoic acids, and from the group consisting of C2-C12 a-halogenated alkanoic acids bearing one or more halogen substituents, which are independently selected from chloro and fluoro substituents, and unsubstituted C2-C12 alkanoic acids.
In a further embodiment of the invention, the iridium-containing compound is selected from nano- and micron-sized iridium particles.
The nano- and micron-sized iridium particles are based on iridium(O) and are usually formed from iridium-containing catalysts used in the hydrosilylation reaction of the process of the invention.
In another embodiment of the invention, the amount of the iridium-containing compound comprised by the composition based on the total weight of the haloorganosilane of the formula (I) ranges from about 1 to about 100 ppm, preferably from about 1 to about 50 ppm, more preferably from about 1 to about 25 ppm, even more preferably from about 2 to about 25 ppm, and most preferably from about 3 to about 15 ppm.
Preferably, the amount of the iridium-containing compound comprised by the composition is in the range cited before based on the total weight of chloropropyltriethoxysilane present in the composition as compound of the formula (I).
In still a further aspect, the invention relates to the use of the compositions described before and the compositions obtained from the process of the invention as described before for the preparation of aminoorganosilanes, mercaptoorganosilanes or methacryloyloxyorganosilanes. As defined herein, the term “organosilanes” includes organoalkoxysilanes, i.e. organosilanes bearing one, two or three alkoxygroups at the silicon atom.
Aminoorganosilanes as defined herein are organosilanes including a primary, secondary or tertiary amino group in the organyl residue.
Preferably, the aminoorganosilanes have a structure represented by the Formula (II) (R1)y(R2O)3-ySiCH2CHR3CR4R5Z1 (II), wherein R1, R2, R3, R4, R5 and y are as defined above,
Z1 is selected from -NH2, -NHR6 and NR6R7, wherein R6 is independently selected from the group consisting of C1-C12 alkyl groups and the residues or
R7 is independently selected from the group consisting of C1-C12 alkyl groups, preferably R7 is CH3, and further preferably R6 and R7 represent the same residue, most preferably R6 and R7 represent -CH3. As defined herein, mercaptoorganosilanes are organosilanes bearing at least one residue selected from a thiol group, a disulfanyl group, a polysulfanyl group, a thioalkyl group, a dithioalkyl group or a polythioalkyl group bonded to the organyl residue of the organosilane via an - S- atom.
Preferably, the mercaptoorganosilanes have a structure represented by the Formula (III) (R1)y(R2O)3-ySiCH2CHR3CR4R5Z2 (III), wherein
R1, R2, R3, R4, R5 and y are as defined above,
Z2 is selected from -SH, -S-SH, -S(U)-SH, -SR8, -S-SR8, -S(U)-SR8, wherein u is an integer from 2 to 8, preferably u is 2, 3 or 4, and
R8 is selected from the group consisting of
- optionally C=O group-containing C1-C12 alkyl groups, preferably C2 to C12 acyl groups, i.e. derived from carboxylic acids, specifically derived from acetic acid, butanoic acid, hexanoic acid, octanoic acid, decanoic acid, dodecanoic acid, neodecanoic acid, 2-ethyl-hexanoic acid and the residue(R1)y(R2O)3.ySiCH2CHR3CR4R5-, wherein R1, R2, R3, R4, R5 and y are as defined above.
The term “derived from carboxylic acids” used when referring to the acyl groups means that an acyl group R8 is bonded to the S-atom with the carbonyl C-atom. The compounds having such R8 group can be formed by condensation of carboxylic acids with terminal SH groups of a precursor compound.
Accordingly, preferred groups R8 according to the embodiment are acetyl, butanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, neodecanoyl and 2-ethyl-hexanoyl groups.
As defined herein, methacryloyloxyorganosilanes are organosilanes bearing at least one methacryloyloxy group bonded to the organyl residue of the organosilane via the -O- atom. Preferably, the methacryloyloxyorganosilanes have a structure represented by the Formula (IV) (R1)y(R2O)3-ySiCH2CHR3CR4R5Z3 (IV), wherein R1, R2, R3, R4, R5 and y are as defined above, and
Z3 is -OC(O)C(CH2)CH3.
The compounds of the Formula (I) comprised by the compositions according to the invention can be transformed to the desired functionalized organosilanes by the replacement of the halide substituent in a nucleophilic reaction with an amine reagent, a sulfide, thiolate or polysulfide reagent or a methacrylate reagent, e.g. a methacrylate salt, respectively. In an embodiment according to the invention, the composition is used for the preparation of polysulfane-containing organoalkoxysilanes.
As defined herein, polysulfane-containing organoalkoxysilanes are mercaptoorganosilanes of the structure (R1)y(R2O)3.ySiCH2CHR3CR4R5Z2 (III), wherein
R1, R2, R3, R4, R5 and y are as defined above, and
Z2 is selected from -S-SH, -S(U)-SH, -S-SR8, -S(U)-SR8, wherein u is an integer from 2 to 8, preferably u is 2, 3 or 4, and R8 is selected from the group consisting of optionally C=O group- containing C1-C12 alkyl groups, preferably C2 to C12 acyl groups, , more preferably selected from acetyl, butanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, neodecanoyl and 2-ethyl- hexanoyl groups, and the residue(R1)y(R2O)3-ySiCH2CHR3CR4R5-, wherein R1, R2, R3, R4, R5 and y are as defined above.
In a preferred embodiment, the composition is used for the preparation of polysulfane- containing organoalkoxysilanes used in the manufacture of silica-filled tires.
In another embodiment of the invention, the composition used for the preparation of aminoorganosilanes, mercaptosilanes or methacryloyloxyorganosilanes comprises chloropropyltriethoxysilane.
According to the embodiment, the chloropropyltriethoxysilane comprised by the composition is transformed to an aminopropyltriethoxysilane of the formula (V) (EtO)3SiCH2CH2CH2Z1 (V), wherein Z1 is as defined above, to a mercaptoorganosilane of the formula (VI) (EtO)3SiCH2CH2CH2Z2 (VI), wherein Z2 is as defined above, or to methacryloyloxypropyltriethoxysilane.
Summary of preferred embodiments of the invention
In the following, the preferred embodiments of the invention are summarized:
1 . A process for producing a compound of Formula (I), (R1)y(R2O)3.ySiCH2CHR3CR4R5X (I) comprising reacting (a) an olefinic halide having the formula H2C=CR3CR4R5X; (b) an alkoxysilane having the formula (R1)y(R2O)3.ySiH; (c) a catalytically effective amount of iridium- containing catalyst; and (d) a reaction-promoting effective amount of a peroxycarboxylic acid to produce the product of Formula (I), wherein
R1 and R2 are alkyl groups of from 1 to 6 carbon atoms;
R3 is an alkyl group of from 1 to 6 carbon atoms or hydrogen;
R4 is an alkyl group of from 1 to 6 carbon atoms, hydrogen or halogen;
R5 is hydrogen or an alkyl group of from 1 to 6 carbon atoms;
X is a halogen; and y is 0, 1 or 2.
2. The process according to embodiment 1 , wherein the olefinic halide (a) is selected from the group consisting of allyl chloride, methallyl chloride, 3-chloro-1 -butene and 3,4-dichloro-1- butene and combinations thereof, preferably the olefinic halide (a) is allyl chloride.
3. The process according to embodiment 1 or 2, wherein the alkoxysilane (b) is selected from the group consisting of trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, diethylethoxysilane, and combinations thereof, preferably the alkoxysilane is triethoxysilane.
4. The process according to any of embodiments 1-3, wherein the reaction-promoting effective amount of the peroxycarboxylic acid (d) ranges from about 1 to about 2000 ppm, based on the total weight of the starting materials olefinic halide (a) and alkoxysilane (b), preferably from about 2 to about 500 ppm, more preferably from about 3 to about 200 ppm, even more preferably from about 4 to about 100 ppm, even further preferably from about 5 to about 50 ppm, still further preferably from about 5 to about 25 ppm, and most preferably from 5 to 15 ppm.
5. The process according to any of embodiments 1-4, wherein the peroxycarboxylic acid (d) is selected from the group of halogenated perbenzoic acids, the group of unsubstituted peroxyalkanoic acids or from the group of a-halogenated peroxyal kanoic acids.
6. The process according to any of the previous embodiments 1-5, wherein the peroxycarboxylic acid (d) is selected from the group of monohalogenated perbenzoic acids, from the group of dihalogenated perbenzoic acids, and the group of tri-, tetra- and pentahalogenated perbenzoic acids.
7. The process according to any of the previous embodiments 1-6, wherein the peroxycarboxylic acid (d) is selected from the group of halogenated perbenzoic acids bearing at least one halogen substituent in a meta-position to the peroxycarboxylic group.
8. The process according to any of the previous embodiments 1-7, wherein the peroxycarboxylic acid (d) is selected from halogenated perbenzoic acids bearing one, two or three halogen substituents in total, wherein preferably at least one of the halogen substituents, and more preferably all of the halogen substituents are independently selected from fluoro and chloro substituents, and most preferably either all halogen substituents are chloro substituents or all halogen substituents are fluoro substituents.
9. The process according to any of the previous embodiments 1-8, wherein the peroxycarboxylic acid (d) is selected from the group of perbenzoic acids consisting of 2-bromo- 5-chlorobenzoic acid, 3,5-difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 2,3,6- trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, 2,3,4,5,6-pentafluorobenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5- difluoroperbenzoic acid.
10. The process according to any of the previous embodiments 1-9, wherein the peroxycarboxylic acid (d) is selected from 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid.
11 . The process according to any of the embodiments 1-5, wherein the peroxycarboxylic acid (d) is an a-halogenated peroxyalkanoic acid selected from the group of C2-C12 a-halogenated peroxyalkanoic acids bearing one or more halogen substituents, which are independently selected from chloro and fluoro substituents, or wherein the peroxycarboxylic acid (d) is an unsubstituted C2-C12 peroxyalkanoic acid.
12. The process according to any of the embodiments 1-5 or 11 , wherein the peroxycarboxylic acid (d) is an a-halogenated alkanoic acid selected from chloroperacetic acid, fluoroperacetic acid, dichloroperacetic acid, difluoroperacetic acid, trifluoroperacetic acid and trichloroperacetic acid.
13. The process according to any of the embodiments 1-12, wherein the iridium-containing catalyst (c) is selected from the group consisting of nano- and micron sized iridium, iridium halides, zinc-reduced or tin reduced reaction products of iridium halides, cycloolefin complexes of iridium, amine complexes of iridium, phosphine complexes of iridium, CO-complexes of iridium, and combinations thereof.
14. The process according to any of embodiments 1-13, wherein the amount of the iridium- containing catalyst (c) based on the total weight of the starting materials olefinic halide (a) and alkoxysilane (b) ranges from about 1 to about 100 ppm, preferably from about 1 to 50 ppm, more preferably from about 1 to about 25 ppm, even more preferably from about 2 to about 25 ppm, and most preferably from about 3 to about 15 ppm.
15. The process according to any of the embodiments 1-14, wherein the iridium-containing catalyst (c) is selected from the group consisting of IrCh, IrBrs, IVklrCle, where M = H, or alkali metal; cycloolefin complexes of iridium such as lr2Cl2(COE)4, Crabtree’s catalyst, [lr(p2- CI)(COD)]2 and lr2(OCH3)2(COD)2, where COE is cyclooctene and COD is 1 ,5-cyclooctadiene; pentamethylcyclopentadienyl iridium dichloride dimer [Cp*lrCh]2; (n-arene) iridium complexes, and combinations thereof.
16. The process according to any of the embodiments 1-15, wherein the iridium-containing catalyst (c) is selected from IrCh xfW or H2lrCh.
17. The process according to any of the embodiments 1-16, wherein the iridium-containing catalyst (c) is added to the reaction as a solid, or as a solution or suspension in organic solvents, preferred OH functionalized solvents, i.e. such as OH functional alkanols, diols and triols, i.e. for example ethanol, and polyethers, preferably the catalyst (c) is added as a solid.
18. The process of any of the embodiments 1-17, wherein the olefinic halide (a) is an industrial grade olefinic halide, preferably industrial grade allyl chloride.
19. The process of any of the embodiments 1-18, wherein the molar ratio of the olefinic halide (a) to the alkoxysilane (b) is in the range of about 10 : 1 to about 1 : 10, preferably about 5 : 1 to about 1 : 5, more preferably about 2 : 1 to about 1 : 2, even more preferably about 1.7 : 1 to about 1 : 1.7, even further preferably about 1.5 : 1 to about 1 : 1.5, and most preferably about 1.2 : 1 to about 1 : 1.2
20. The process according to any of the embodiments 1 to 19, wherein the ratio of the iridium- containing catalyst (c) to the peroxycarboxylic acid (d) in [ppm to ppm] , each based on the total weight of the starting materials olefinic halide (a) and alkoxysilane (b), is in the range of about 1 : 1 to about 1 : 40, preferably in the range of about 1 : 1.5 to about 1 : 25, more preferably in the range of about 1 : 2 to about 1 : 20 , most preferably in the range of about 1 : 2 to about 1 : 10.
21. The process of any of the embodiments 1-20, wherein olefinic halide (a) is allyl chloride, alkoxysilane (b) is triethoxysilane, the Ir-containing catalyst (c) is IrCh or H2lrCh, and the peroxycarboxylic acid (d) is 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid or 3,5- difluoroperbenzoic acid.
22. The process according to any of the embodiments 1-21 , wherein the olefinic halide (a) is allyl chloride, the alkoxysilane (b) is triethoxysilane, the amount of iridium-containing catalyst (c) is in the range of 5 to 20 ppm, and the peroxycarboxylic acid (d) is either - mCPBA, present in an amount fulfilling the condition that the ratio of catalyst (c) to promoter (d) in [ppm/ppm] is in the range of about 1 : 2.5 to about 1 : 20, or
- mFPBA, present in an amount fulfilling the condition that the ratio of catalyst (c) to promoter (d) in [ppm/ppm] is in the range of about 1 : 2.5 to about 1 : 10, or
- dFPBA present in an amount fulfilling the condition that the ratio of catalyst (c) to promoter (d) in [ppm/ppm] is in the range of about 1 : 2 to about 1 : 4 .
23. The process according to the previous embodiment, wherein the iridium-containing catalyst is selected from IrCh and FklrCle.
24. A composition obtained by the process of any of the embodiments 1-23.
25. A composition comprising one or more compound of the Formula (I), (R1)y(R2O)3-ySiCH2CHR3CR4R5X (I), one or more iridium-containing compounds, and one or more compounds selected from i) peroxycarboxylic acids, and/or ii) carboxylic acids, wherein R1 and R2 are alkyl groups of from 1 to 6 carbon atoms; R3 is an alkyl group of from 1 to 6 carbon atoms or hydrogen;
R4 is an alkyl group of from 1 to 6 carbon atoms, hydrogen or halogen;
R5 is hydrogen or an alkyl group of from 1 to 6 carbon atoms;
X is a halogen; and y is 0, 1 or 2.
26. The composition according to embodiment 25, wherein the compound of the formula (I) is chloropropyltriethoxysilane.
27. The composition according to embodiments 25 or 26, wherein the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from halogenated perbenzoic acids, unsubstituted peroxyalkanoic acids, a-halogenated peroxyalkanoic acids, from halogenated benzoic acids, unsubstituted alkanoic acids or from of a-halogenated alkanoic acids.
28. The composition according to the embodiments 25-27, wherein the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from monohalogenated perbenzoic acids, from dihalogenated perbenzoic acids, tri-, tetra- and pentahalogenated perbenzoic acids, from monohalogenated benzoic acids, from dihalogenated benzoic acids, and tri-, tetra- and pentahalogenated benzoic acids.
29. The composition according to any of the embodiments 25-28, wherein the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from halogenated perbenzoic acids bearing at least one halogen substituent in a meta-position to the peroxycarboxyl group, and from halogenated benzoic acids bearing at least one halogen substituent in a meta-position to the carboxyl group.
30. The composition according to any of the embodiments 25-29, wherein the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from the group of perbenzoic acids consisting of 2-bromo-5-chloroperbenzoic acid, 3,5- difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 2,3,6-trifluoroperbenzoic acid, 2,4,5- trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, 2,3,4,5,6-pentafluoroperbenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid, and from the group of benzoic acids consisting of 2-bromo-5-chlorobenzoic acid, 3,5-difluorobenzoic acid, 3,4-difluorobenzoic acid, 2,3,6-trifluorobenzoic acid, 2,4,5-trifluorobenzoic acid, 2,3,4- trifluorobenzoic acid, 2,3,4,5,6-pentafluorobenzoic acid, 3-chlorobenzoic acid, 3-fluorobenzoic acid, and 3,5-difluorobenzoic acid.
31. The composition according to any of the embodiments 25-30, wherein the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid, and from 3-chlorobenzoic acid, 3-fluorobenzoic acid, and 3,5-difluorobenzoic acid.
32. The composition according to any of the embodiments 25-31 , wherein the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from the group consisting of C2-C12 a-halogenated peroxyalkanoic acids bearing one or more halogen substituents, which are independently selected from chloro and fluoro substituents and unsubstituted C2-C12 peroxyalkanoic acids, and from the group consisting of C2-C12 a- halogenated alkanoic acids bearing one or more halogen substituents, which are independently selected from chloro and fluoro substituents, and unsubstituted C2-C12 alkanoic acids.
33. The composition according to any of the embodiments 25-32, wherein the iridium- containing compound is selected from nano- and micron-sized iridium particles.
34. The composition according to any of the embodiments 25-33, wherein the amount of the iridium-containing compound based on the total weight of the compound of the formula (I) ranges from about 1 to about 100 ppm, preferably from about 1 to about 50 ppm, more preferably from about 1 to about 25 ppm, even more preferably from about 2 to about 25 ppm, and most preferably from about 3 to about 15 ppm.
35. Use of the compositions of embodiments 24-34 for the preparation of aminoorganosilanes, mercaptoorganosilanes or methacryloyloxyorganosilanes. 36. Use of the compositions according to embodiment 35, wherein the composition is used for the preparation of polysulfane-containing organoalkoxysilanes.
37. Use of the compositions according to embodiment 36, wherein the polysulfane-containing organoalkoxysilanes are used in the manufacture of silica-filled tires. 38. Use of the composition according to embodiments 35-37, wherein the composition comprises chloropropyltriethoxysilane.
Whereas the exact scope of the present invention is set forth in the appended claims, the following specific examples illustrate certain aspects of the present invention and, more particularly, point out the various aspects of the method for evaluating the same. However, the examples are set forth for illustrative purposes only and are not to be construed as limitations on the present invention.
EXAMPLES
The present invention is further illustrated by the following examples, without being limited thereto.
General - Chemicals and abbreviations
IrCh xfW: abcr; 99.99 % CAS 14996-61-3; Iridium(lll) chloride hydrate bUrCh: abcr; 99.90 % CAS 110802-84-1; Hexachloroiridic(IV) acid hydrate dry EtOH: analytical grade ETCH further dried over molecular sieve (3A) allyl chloride: Momentive grade (batch RBT190731 C), > 99 wt-% overcondensed allyl chloride: The overcondensed allyl chloride was obtained by treating as received allyl chloride with vacuum.
The as received allyl chloride was submitted in a Schlenk flask, connected to a second (dry ice/iPr-cooled) Schlenk flask by a glass bridge. The compounds not volatile at 20 °C/0.4 mbar remained in the first flask and were thereby separated from the overcondensed allyl chloride. While NMR and GC-TCD measurements did not show a noticeable change of purity for the overcondensed ally chloride when compared to the allyl chloride as received, the non-volatile compounds formed a yellow liquid.
Triethoxysilane: Momentive grade (TES; Momentive grade synthesized from HSiC ), 89-
92 wt-% di-tertiary-butyl peroxide (DtBP): Sigma-Aldrich; 98 % tertiary-butyl hydroperoxide (tBHP): Sigma-Aldrich; 5.5 molar in decane tertiary-butyl perbenzoate (tBPB): Sigma Aldrich; 98 % m-chloroperbenzoic acid or meta-Chloroper(oxy)benzoic acid (mCPBA): Sigma-Aldrich; 77 % active CAS 937-14-4; the purchased mCPBA is a mixture of mCPBA with m-chlorobenzoic acid and water (for stabilization), and it is assumed that the activity equals the content of mCPBA in the mixture, which is 77 % according to the provider as determined by titration by Na2S20s. m-fluoroperbenzoic acid (mFPBA) and 3,5-difluoroperbenzoic acid (dFPBA) were synthesized according to Reference with DOI: 10.15227/orgsyn.050.0015 (Organic Syntheses, Coll. Vol. 6, p. 276 (1988); Vol. 50, p.15 (1970), “m-Chloroperbenzoic Acid”)
Analytical details
NMR The NMR measurements were either performed on a BRLIKER DPX 400 with a 5mm multinuclear probe head or on a BRLIKER AVANCE III 500 MHz. The following table shows the resonance frequencies of the examined nuclei.
The compounds to be investigated were bottled under argon. Therefore 0.2 ml compound was dissolved in 0.4 ml solvent. In all cases deuterated chloroform was used as the solvent and 1% TMS was added as reference. Thus, the TMS signal is the reference point for all chemical shifts, given in ppm. 100 pl HMDSO were used as an internal reference for determining the substance amount fractions, if necessary.
FT-IR
The spectra were generated on a Nicolet 380 FT-IR, using standard FT-IR ATR-measurement procedures. The investigated samples of the peroxycarboxylic acids did not need further preparation before measuring.
Catalyst preparation and hydrosilylation
All catalyst preparations and hydrosilylations were carried out under an argon atmosphere using Schlenk technique.
The structure of the products was confirmed by means of 1H-NMR, 13C-NMR and FTIR spectroscopy.
Synthesis Example 1 : Synthesis m-fluoroperbenzoic acid (m-FPBA)
F
36 ml DI water, 3.6 g NaOH, 0.15 g MgSC ■ 7H2O and 45 ml 1 ,4-dioxane were mixed in a 250 ml glass beaker and cooled to 10-15 °C. 9 ml of a 30 % (weight-%) H2O2 solution were added. Upon intense stirring 4.76 g (30 mmol) m-fluorobenzoyl chloride was added slowly. The mixture was stirred at < 25 °C for 15 minutes. Afterwards, the mixture was transferred to a separatory funnel. 90 ml of ice-cold 3.7 M H2SO4 were added. After phase separation, the aqueous layer was extracted 4 times with 20 ml ice-cold dichloromethane. The organic layers were combined and dried over MgSC . The dichloromethane was removed under reduced pressure, wherein a rotary evaporator was used. The water bath had 30 °C and the pressure was lowered stepwise from 200 mbar to 0 mbar in 25 mbar steps. The desired product was obtained as a white solid. Yield: 1.81g (39%). Purity: 100 %. The structure of the product was confirmed by means of 1H-NMR, 13C-NMR and FTIR spectroscopy.
Synthesis Example 2: Synthesis 3,5-difluoroperbenzoic acid (dFPBA)
36 ml DI water, 3.6 g NaOH, 0.15 g MgSC ■ 7H2O and 45 ml 1 ,4-dioxane were mixed in a 250 ml glass beaker and cooled to 10-15 °C. 9 ml of a 30 % active H2O2 solution were added. Upon intense stirring 5.3 g (30 mmol) 3,5-difluorobenzoyl chloride were added slowly. The mixture was stirred at < 25 °C for 15 minutes. Afterwards, the mixture was transferred to a separatory funnel. 90 ml of ice-cold 3.7 M H2SO4 were added. After phase separation the aqueous layer was extracted 4 times with 20 ml ice-cold dichloromethane. The organic layers obtained from extraction of the aqueous layer were unified and dried over MgSC . The dichloromethane was removed at room temperature under reduced pressure, wherein a rotary evaporator was used. The water bath had 30 °C and the pressure was lowered stepwise from 200 mbar to 0 mbar in 25 mbar steps. A white solid was obtained. Yield 0.97g (19%). Purity: 100 %. The structure of the product as indicated above was confirmed by means of 1H-N MR, 13C-NMR and FTIR spectroscopy.
Synthesis Example 3: Catalyst solution IrCh-xHzO in dry EtOH
0.1 g IrCh xfW were placed in a Schlenk bottle under argon. 10 ml dry EtOH were added. The mixture was stirred with 1200 rpm for four days. A clear greenish solution was obtained which can be used as catalyst for approx. 2 days. Synthesis Example 4: Solid catalyst IrCh-xHzO
Commercial solid IrCh x W was used without any further pretreatment for the hydrosilylation reactions.
Synthesis Example 5: Catalyst solution HalrCk in dry EtOH
1 g H2I rCh were dissolved in 10ml dry EtOH. A black catalyst solution was obtained which can be used as catalyst for approx, two months.
Hydrosilylation Reactions
Example 1 : General protocol for hydrosilylations using a catalyst solution
The reactions were carried out in 50 ml Schlenk bottles with reflux condenser. The calculated amount of peracids (indicated in “ppm” based on the total mass of the starting materials triethoxysilane and allyl chloride) was placed in the Schlenk bottle. Afterwards, 33.5 g of a stock solution consisting of 10 g purified (overcondensed) allyl chloride and 23.5 g TES (triethoxysilane) were added. The calculated amount of catalyst solution (the catalyst content indicated in “ppm” is based on the total mass of the starting materials triethoxysilane and allyl chloride, wherein the ppm indication refers to the amount of Ir metal contained in the catalyst compounds) was added and the mixture was heated to 80 °C under stirring using a magnetic stirring bar with a stirring speed of 300 rpm. byproducts and unreacted
TES CPTES monomers
Example 2: General protocol for hydrosilylations using a solid catalyst
The reactions were carried out in 50 ml Schlenk bottles with reflux condenser. The calculated amount of solid catalyst and 2.35 g
(10 mol-% of the calculated amount) TES were placed in the Schlenk bottle. The Schlenk bottle was heated to 80 °C and the mixture was stirred at 300 rpm. Separately, a mixture consisting of 10 g allyl chloride (either as received or overcondensed), 21.15 g (90 mol-% of the calculated amount) TES and the calculated amount of peracid was prepared and placed in a dropping funnel. This mixture was fed into the Schlenk bottle over 30 minutes. After the end of the feeding, the reaction temperature was maintained at 80 °C for the reaction times as indicated. Table 1 : Results of hydrosilylation experiments 3 - 11 : lrCl3 xH2O in EtOH solution with allyl chloride and triethoxysilane (TES) - variation of Ir concentration
*: The letter “C” denotes comparative examples, which are not according to the invention a: The catalyst content indicated in “ppm” is based on the total mass of the starting materials triethoxysilane and allyl chloride, wherein the ppm indication refers to the amount of Ir metal contained in the catalyst compounds. b: The amount of peracids indicated in “ppm” is based on the total mass of the starting materials triethoxysilane and allyl chloride; where applicable, the acitivity of the promoters as outlined in the Materials section was taken into account. c: The amounts in “mol-%” refer to the sum of all integrals/mol amounts of silicon species in the 29Si-NMR spectra. The mol-% amounts were determined from the integral area in reference to the internal standard HMDSO
The data in Table 1 show that at high Ir concentrations (100ppm) in the absence of any promotor or in the presence of hydroperoxides or dialkyl peroxides (non-inventive comparative examples 3-6) moderate to good yields can be achieved. The addition of halogenated perbenzoic acids significantly increases the yield (example 7). At low Ir concentrations (10ppm and lower) the presence of the halogenated perbenzoic acid derivatives is mandatory for high yields (examples 4, 9). mFPBA is the halogenated perbenzoic acid derivative delivering the best results (examples 10,11).
The data as presented in Table 1 display a synergistic effect between Ir and halogenated perbenzoic acids, as the reaction requires I r catalyst if a low amount of halogenated perbenzoic acids is present. At high Ir catalyst concentrations of 100 ppm, other peroxy compounds such as tBHP are less effective than of mCPBA. DtBP has a detrimental effect on the yield of the target product (example 5 and example 6).
Table 2: Results of hydrosilylation experiments 12-16, 9 and 10: lrCl3 xH2O in EtOH solution at fixed ppm concentration of 10 ppm as catalyst for the reaction between allyl chloride and triethoxysilane - variation of the promotor concentration
Table 3: Results of hydrosilylation experiments 17-23: Solid lrCl3 xH2O in combination with overcondensed/as received allyl chloride for the reaction with TES
: The letter “C” denotes comparative examples, which are not according to the invention
able 4: Results of hydrosilylation experiments 24-29: H2lrCI6 in EtOH solution as catalyst for the reaction of allyl chloride and TES usingvercondensed or as received allyl chloride
*: The letter “C” denotes comparative examples, which are not according to the invention ndices in Tables 2 to 4: a: The catalyst content indicated in “ppm” is based on the total mass of the starting materials triethoxysilane and allyl chloride, wherein the ppm indication refers to the amount of Ir metal contained in the catalyst compounds. b: The amount of peracids indicated in “ppm” is based on the total mass of the starting materials triethoxysilane and allyl chloride; where applicable, the acitivity of the promoters as outlined in the Materials section was taken into account. c: The mol-% refer to the sum of all integrals/mol amounts of silicon species in the 29Si-NMR spectra. The mol-% amounts were determined from the integral area in reference to the internal standard HMDSO
The data in Table 2 show that the presence of a 2.5 to 20 fold excess of promoter provides a substantially increased yield of the desired compound (examples 12, 9, 13, 14, 10, 15, 16 compared to example 4)
The data in Table 3 show that for as received allyl chloride, the addition of halogenated perbenzoic acids is mandatory in order to achieve high yields at reasonably low Ir concentrations (examples 21 , 22). The use of a peroxide ether, when compared to the analogous reaction utilizing the peroxycarboxylic acids of the process of the invention as promoters, leads to significantly lower yields (example 23). It can be concluded that the presence of halogenated perbenzoic acids increases the tolerance of as received solid IrChx W at low Ir concentrations towards the presence of impurities in as received raw materials. Both, the possibility to use as received allyl chloride and an as received solid catalyst at low Ir concentrations are prerequisites for a robust and economically attractive large scale process.
The data in Table 4 show that at high Ir concentrations (100 ppm) F^IrCle solutions give moderate yields on CPTES (example 24).
At low Ir concentrations (10ppm and lower) the combination of F^IrCle solutions and a halogenated perbenzoic acid such as mFPBA is mandatory for high yields of CPTES (compare examples 25 and 27).
The result of example 28 indicates that F^IrCle is also applicable in a process based on an easy to prepare catalyst solution, low Ir concentrations and as received allyl chloride. Comparative example 29 displays that even at a substantially higher catalyst concentration, the yield using an H2I rCh solution is only moderate when compared to the reactions performed in the presence of a halogenated perbenzoic acid.

Claims

1 . A process for producing a compound of Formula (I) (R1)y(R2O)3.ySiCH2CHR3CR4R5X (I), comprising reacting
(a) an olefinic halide having the formula H2C=CR3CR4R5X;
(b) an alkoxysilane having the formula (R1)y(R2O)3.ySiH;
(c) a catalytically effective amount of iridium-containing catalyst; and
(d) a reaction-promoting effective amount of a peroxycarboxylic acid to produce the product of Formula (I), wherein
R1 and R2 are alkyl groups of from 1 to 6 carbon atoms;
R3 is an alkyl group of from 1 to 6 carbon atoms or hydrogen;
R4 is an alkyl group of from 1 to 6 carbon atoms, hydrogen or halogen;
R5 is hydrogen or an alkyl group of from 1 to 6 carbon atoms;
X is a halogen; and y is 0, 1 or 2, wherein preferably the amount of the iridium-containing catalyst (c) based on the total weight of the starting materials olefinic halide (a) and alkoxysilane (b) ranges from about 1 to about 100 ppm, preferably from about 1 to about 50 ppm, more preferably from about 1 to about 25 ppm, even more preferably from about 2 to about 25 ppm, and most preferably from about 3 to about 15 ppm.
2. The process according to claim 1 , wherein the olefinic halide (a) is selected from the group consisting of allyl chloride, methallyl chloride, 3-chloro-1 -butene and 3, 4-dichloro-1 -butene and combinations thereof, preferably the olefinic halide (a) is allyl chloride.
3. The process according to claim 1 or 2, wherein the alkoxysilane (b) is selected from the group consisting of trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, diethylethoxysilane, and combinations thereof, preferably the alkoxysilane is triethoxysilane.
4. The process according to any of the previous claims 1-3, wherein the peroxycarboxylic acid (d) is selected from the group of monohalogenated perbenzoic acids, from the group of dihalogenated perbenzoic acids, and the group of tri-, tetra- and pentahalogenated halogenated perbenzoic acids, preferably wherein the peroxycarboxylic acid (d) is selected from the group of halogenated perbenzoic acids bearing at least one halogen substituent in a meta-position to the peroxycarboxylic group.
5. The process according to any of the previous claims 1-4, wherein the peroxycarboxylic acid (d) is selected from the group of perbenzoic acids consisting of 2-bromo-5- chloroperbenzoic acid, 3,5-difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 2,3,6- trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, 2,3,4,5,6-pentafluoroperbenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid, preferably the peroxycarboxylic acid (d) is selected from 3- chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid.
6. The process according to any of the claims 1-5, wherein the iridium-containing catalyst (c) is selected from the group consisting of nano- and micron-sized iridium, iridium halides, zinc- reduced or tin-reduced reaction products of iridium halides, cycloolefin complexes of iridium, amine complexes of iridium, phosphine complexes of iridium, CO-complexes of iridium, and combinations thereof, or from the group consisting of I rCh, IrBrs, M2I rCle, where M = H, or alkali metal; cycloolefin complexes of iridium such as lr2Cl2(COE)4, Crabtree’s catalyst, [lr(p2- CI)(COD)]2 and lr2(OCH3)2(COD)2, where COE is cyclooctene and COD is 1 ,5-cyclooctadiene; pentamethylcyclopentadienyl iridium dichloride dimer [Cp*lrCh]2; (n-arene) iridium complexes, and combinations thereof.
7. The process according to any of the claims 1-6, wherein the ratio of the iridium-containing catalyst (c) to the peroxycarboxylic acid (d) in [ppm to ppm], each based on the total weight of the starting materials olefinic halide (a) and alkoxysilane (b), is in the range of about 1 : 1 to about 1 : 40, preferably in the range of about 1 : 1.5 to about 1 : 25, more preferably in the range of about 1 : 2 to about 1 : 20 , most preferably in the range of about 1 : 2 to about 1 : 10.
8. The process of any of the claims 1-7, wherein the olefinic halide (a) is allyl chloride, the alkoxysilane (b) is triethoxysilane, the iridium-containing catalyst (c) is I rCh or H2I rCh, and the peroxycarboxylic acid (d) is 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid or 3,5- difluoroperbenzoic acid.
9. A composition comprising one or more compounds of the Formula (I), (R1)y(R2O)3-ySiCH2CHR3CR4R5X (I), one or more iridium-containing compounds, and one or more compounds selected from i) peroxycarboxylic acids, and/or ii) carboxylic acids, wherein R1 and R2 are alkyl groups of from 1 to 6 carbon atoms; R3 is an alkyl group of from 1 to 6 carbon atoms or hydrogen;
R4 is an alkyl group of from 1 to 6 carbon atoms, hydrogen or halogen;
R5 is hydrogen or an alkyl group of from 1 to 6 carbon atoms;
X is a halogen; and y is 0, 1 or 2, wherein preferably the amount of the iridium-containing compound based on the total weight of the compound of the formula (I) ranges from about 1 to about 100 ppm, preferably from about 1 to about 50 ppm, more preferably from about 1 to about 25 ppm, even more preferably from about 2 to about 25 ppm, and most preferably from about 3 to about 15 ppm.
10. The composition according to claim 9, wherein the compound of the formula (I) is chloropropyltriethoxysilane.
11. The composition according to the claims 9 or 10, wherein the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from monohalogenated perbenzoic acids, from dihalogenated perbenzoic acids, tri-, tetra- and pentahalogenated halogenated perbenzoic acids, from monohalogenated benzoic acids, from dihalogenated benzoic acids, and tri-, tetra- and pentahalogenated benzoic acids, preferably the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from halogenated perbenzoic acids bearing at least one halogen substituent in a meta-position to the peroxycarboxyl group, and from halogenated benzoic acids bearing at least one halogen substituent in a meta-position to the carboxyl group.
12. The composition according to any of the claims 9-11 , wherein the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acidsare selected from the group of perbenzoic acids consisting of 2-bromo-5-chloroperbenzoic acid, 3,5-difluoroperbenzoic acid, 3,4-difluoroperbenzoic acid, 2,3,6-trifluoroperbenzoic acid, 2,4,5-trifluoroperbenzoic acid, 2,3,4-trifluoroperbenzoic acid, 2,3,4,5,6-pentafluoroperbenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5-difluoroperbenzoic acid, and from the group of benzoic acids consisting of 2-bromo-5-chlorobenzoic acid, 3,5-difluorobenzoic acid, 3,4-difluorobenzoic acid, 2,3,6-trifluorobenzoic acid, 2,4,5-trifluorobenzoic acid, 2,3,4-trifluorobenzoic acid, 2, 3, 4,5,6- pentafluorobenzoic acid, 3-chlorobenzoic acid, 3-fluorobenzoic acid, and 3,5-difluorobenzoic acid, preferably the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3,5- difluoroperbenzoic acid, and from 3-chlorobenzoic acid, 3-fluorobenzoic acid, and 3,5- difluorobenzoic acid.
13. The composition according to any of the claims 9-12, wherein the iridium-containing compound is selected from nano- and micron-sized iridium particles.
14. Use of the compositions according to any of claims 9-13 for the preparation of aminoorganosilanes, mercaptoorganosilanes or methacryloyloxyorganosilanes, wherein preferably the composition comprises chloropropyltriethoxysilane.
15. Use of the compositions according to claim 14, wherein the composition is used for the preparation of polysulfane-containing organoalkoxysilanes, and wherein preferably the polysulfane-containing organoalkoxysilanes are used in the manufacture of silica-filled tires.
EP23829054.8A 2022-12-15 2023-12-14 Peracid promoters in the iridium-catalyzed hydrosilylation synthesis of haloalkylorganosilanes Pending EP4634196A1 (en)

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PCT/EP2023/085840 WO2024126692A1 (en) 2022-12-15 2023-12-14 Peracid promoters in the iridium-catalyzed hydrosilylation synthesis of haloalkylorganosilanes

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US6015920A (en) * 1998-09-11 2000-01-18 Ck Witco Corporation Hydrosilation reaction process with recycle
WO2017154846A1 (en) * 2016-03-09 2017-09-14 国立研究開発法人産業技術総合研究所 Method for producing silyl compound by means of hydrosilylation of allyl compound using iridium complex or like

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