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CN120303278A - Peracid promoters in the iridium-catalyzed hydrosilylation of halogenated alkylorganosilanes - Google Patents

Peracid promoters in the iridium-catalyzed hydrosilylation of halogenated alkylorganosilanes Download PDF

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CN120303278A
CN120303278A CN202380085978.XA CN202380085978A CN120303278A CN 120303278 A CN120303278 A CN 120303278A CN 202380085978 A CN202380085978 A CN 202380085978A CN 120303278 A CN120303278 A CN 120303278A
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acid
iridium
group
acids
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H·肖尔茨
E·克罗克
K·克劳沙尔
H·J·格拉泽
K·M·刘易斯
R·瓦格纳
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Momentive Performance Materials GmbH
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Abstract

The present invention relates to a process (R 1)y(R2O)3‑ySiCH2CHR3CR4R5 X) for producing a compound of formula (I) which comprises reacting (a) an olefinic halide, (b) an alkoxysilane, (c) a catalytically effective amount of an iridium-containing catalyst, and (d) a reaction-promoting effective amount of a peroxycarboxylic acid to produce a product of formula (I).

Description

Peracid accelerators in iridium-catalyzed hydrosilylation syntheses of haloalkylorganosilanes
Technical Field
The present invention relates to a process for preparing halogenated organosilicon compounds. More particularly, the present invention relates to a process for preparing halogenated organoalkoxysilanes, such as in particular chloropropyl triethoxysilane, via hydrosilylation of a halogenated olefin with an alkoxysilane, and to compositions comprising one or more halogenated organoalkoxysilanes, one or more iridium-containing compounds, and one or more peroxybenzoic acids, and to the use of such compositions.
Background
Haloalkyl organosilanes are key intermediates for the preparation of a variety of functionalized organosilanes, such as amino-, mercapto-, and methacryloxy organosilanes, which are used as silane coupling agents. For example, chloropropyl triethoxysilane is a key intermediate for preparing polysulfane-containing organoalkoxysilanes for use in the manufacture of silica-filled tires. It is known in the art that chloropropyl triethoxysilane (CPTES) can be produced by transesterification of chloropropyl trimethoxysilane or by hydrosilylation of the corresponding haloalkenyl allyl chloride with Triethoxysilane (TES).
Hydrosilylation of allyl chloride by Triethoxysilane (TES) in the presence of Pt catalyst showed a large variation in the yield ranging from 14% to 70% relative to the target product chloropropyl triethoxysilane (CPTES) (US 9556208 and embedded references US 3795656, JP 11-199588, belyakova et al, CHERNYSHEV et al). The reason for the low yield is the tendency to form propylene as an undesired by-product. Catalyst systems based on Rh and Pd have the same drawbacks (US 9556208).
The dimeric olefin Ir (I) halide complex is described as an effective catalyst for the synthesis of CPTES from TES and allyl chloride (US 4658050). Yields of up to 75% are described for the 100 ppm catalyst.
US 5616762 describes the synthesis of CPTES from TES and allyl chloride in the presence of Ir (III) chlorohydrate. Excess allyl chloride was used to obtain yields of greater than 80%.
Despite the potentially high yields of CPTES available in the above reactions, the Ir catalyzed reactions that produce CPTES lack reproducibility. In particular at low Ir concentrations, unpredictable changes in yield occur. Thus, additives are needed to stabilize and further increase the yield of allyl chloride through Ir-catalyzed hydrosilylation of TES.
In WO 2017/154846 A1, a process for producing (3-chloropropyl) dimethoxymethylsilane is disclosed, wherein allyl chloride is reacted with dimethoxymethylsilane in the presence of an iridium catalyst, and a composition obtained by the process.
Among them, WO 2017/154846 A1 appears to teach that iridium-catalyzed hydrosilylation of allylic species can be significantly accelerated when iridium complexes are produced by reacting a dinuclear iridium complex bearing silyl groups with allylic compounds in a pretreatment step. However, there is no disclosure therein of the presence of peroxycarboxylic acids in the hydrosilylation process or of peroxycarboxylic acids and/or carboxylic acids in the compositions obtained by the process.
In US 6015920A, a process for the production of (3-chloropropyl) trimethoxysilane by iridium-catalysed hydrosilylation of allyl chloride with trimethoxysilane is disclosed.
Generally, US 6015920A relates to a process for hydrosilylation reactions, wherein a portion of the reactor output is continuously recycled to the reactor, which is also exemplified for the production of (3-chloropropyl) trimethoxysilane by iridium-catalyzed hydrosilylation of allyl chloride with trimethoxysilane. However, the presence of peroxycarboxylic acids in the hydrosilylation process or the presence of peroxycarboxylic acids and/or carboxylic acids in the composition obtained by this process is not disclosed therein.
It is known that organic peroxy compounds and oxygen have an influence on the hydrosilylation reaction.
US 9556208 describes the use of hydroperoxides, dialkyl peroxides, and diacyl peroxides as promoters for the hydrosilylation of allyl chloride with alkoxysilanes in the presence of Ru catalysts. Di-tert-butyl peroxide is used for the reaction of allyl chloride with TES.
Meta-chloroperbenzoic acid is described as an accelerator for the reaction of 1-octene with triethylsilane in the presence of Rh-phosphine complex (Calhoun et al, trans. Metal chem.,8 (6), 365 (1983)).
DE 10133008 proposes peracids, including m-chloroperbenzoic acid, as promoters for the hydrosilylation of H-silanes or H-siloxanes with double-or triple-bond moieties containing hydrocarbons, silanes, or siloxanes. The catalyst is all known hydrosilylation catalysts, preferably based on Pt, ru, rh and Pd.
US 5559264 describes the silylation of allyl chlorohydride to Trimethoxysilane (TMS) in the presence of Ru-CO complex. Yields of greater than 80% can be achieved by adding oxygen as a promoter.
US 6872845 discloses aromatic compounds as promoters for hydrosilylation based on Ru catalysts, resulting in halogenated organoalkoxysilanes. Furthermore, the addition of oxygen for activating the summarized Ru-CO and Ru-phosphine catalysts is proposed. Typically, naturally occurring oxygen levels in the raw materials are sufficient. For example, further activation may be achieved by adding 3% O 2 to N 2.
On the other hand, US 5986122 teaches that the peroxide present in the alkenyl polyether inhibits the hydrosilylation reaction that produces SiH siloxanes in the presence of a Pt catalyst.
Furthermore, US 8580994 describes the beneficial effect of reducing the oxygen content during the hydrosilation of allyl chloride to dimethylethoxysilane in the presence of an Ir-diene complex catalyst.
From the foregoing disclosure, it can be concluded that peroxy compounds and oxygen are beneficial in some hydrosilylation reactions.
However, these findings represent isolated cases in nature. Given the wide variety of potential catalysts, unsaturated monomers, siH functionalized silanes, and peroxy compounds, no general rules for the beneficial use of peroxy compounds and oxygen can be derived from the prior art.
The situation is further complicated by the fact that seemingly contradictory reactions are found, wherein the peroxide or oxygen inhibits the desired hydrosilylation reaction.
Thus, while the disclosures in both the academic and patent literature teach that iridium-based catalysts are advantageous for hydrosilaneization of allyl chloride by triethoxysilane, there are drawbacks in reproducibly achieving the desired product selectivity, reaction rate, and reaction yield at cost-effective iridium concentrations.
Disclosure of Invention
These problems are solved by the present invention which enables the efficient synthesis of the product ：(R1)y(R2O)3- ySiCH2CHR3CR4R5X(I). of formula (I) by the hydrosilylation of an olefinic halide with an alkoxysilane catalyzed by Ir in the presence of a peroxycarboxylic acid promoter by the process of the present invention to reproducibly obtain the desired compound at the desired selectivity, rate and reaction stability at a cost effective iridium concentration.
In this process, the formation of by-products is reduced and the desired results are obtained for the solid catalyst as such as well as for the homogeneous catalyst solution. The catalyst system consisting of an Ir-containing catalyst and a peroxycarboxylic acid as promoter is highly tolerant to the olefinic halides used as such, thus rendering additional purification of the olefinic compounds superfluous.
The invention is described in detail below in relation to a process for producing an organoalkoxysilane product comprising reacting:
(a) An olefinic halide;
(b) An alkoxysilane;
(c) A catalytically effective amount of an iridium-containing catalyst, and
(D) Reaction-promoting effective amounts of peroxycarboxylic acids.
In particular, the invention relates to a process for the production of a compound of formula (I),
(R1)y(R2O)3-ySiCH2CHR3CR4R5X (I)
Comprising reacting to produce a product of formula (I)
(R1)y(R2O)3-ySiCH2CHR3CR4R5X (I):
(A) an olefinic halide having the formula H 2C=CR3CR4R5 X, (b) an alkoxysilane having the formula (R 1)y(R2O)3-y SiH, (c) a catalytically effective amount of an iridium-containing catalyst, and (d) a reaction-promoting effective amount of a peroxycarboxylic acid;
Wherein the method comprises the steps of
R 1 and R 2 are alkyl groups of 1 to 6 carbon atoms;
R 3 is alkyl of 1 to 6 carbon atoms or hydrogen;
r 4 is alkyl of 1 to 6 carbon atoms, hydrogen or halogen;
r 5 is hydrogen or alkyl of 1 to 6 carbon atoms;
X is halogen, and
Y is 0,1 or 2.
Detailed Description
The process according to the invention is a process for the production of a compound of formula (I),
(R1)y(R2O)3-ySiCH2CHR3CR4R5X (I)
The process comprises reacting to produce a product of formula (I)
(R1)y(R2O)3-ySiCH2CHR3CR4R5X (I):
(A) an olefinic halide having the formula H 2C=CR3CR4R5 X, (b) an alkoxysilane having the formula (R 1)y(R2O)3-y SiH), (c) a catalytically effective amount of an iridium-containing catalyst, and (d) a reaction-promoting effective amount of a peroxycarboxylic acid,
Wherein the method comprises the steps of
R 1 and R 2 are alkyl groups of 1 to 6 carbon atoms;
R 3 is alkyl of 1 to 6 carbon atoms or hydrogen;
r 4 is alkyl of 1 to 6 carbon atoms, hydrogen or halogen;
r 5 is hydrogen or alkyl of 1 to 6 carbon atoms;
X is halogen, and
Y is 0,1 or 2.
The present invention relates to a process for preparing halogenated organosilicon compounds and, more particularly, to a process for preparing a product of formula (I) via hydrosilylation of a halogenated olefin with an alkoxysilane in the presence of a peroxycarboxylic acid and an iridium-containing catalyst.
"Alkyl" is herein meant to include straight, branched and cyclic alkyl groups. Specific and non-limiting examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, and isobutyl.
"Substituted alkyl" as used herein refers to an alkyl group containing one or more substituents that are inert under the process conditions experienced by the compounds containing these groups. The substituents also do not substantially or deleteriously interfere with the process.
"Aryl" herein refers to a non-limiting group of any aromatic hydrocarbon from which one hydrogen atom has been removed. Aryl groups may have one or more aromatic rings, which may be fused, linked by a single bond or other groups. Specific and non-limiting examples of aryl groups include, but are not limited to, tolyl, xylyl, phenyl, and naphthyl.
"Substituted aryl" herein refers to a substituted aromatic group as set forth in the definition of "substituted alkyl" above. Similar to aryl groups, substituted aryl groups may have one or more aromatic rings, which may be fused, linked by a single bond or other group, however, when the substituted aryl groups have a heteroaromatic ring, the free valency in the substituted aryl groups may be a heteroatom (e.g., nitrogen) of the heteroaromatic ring instead of carbon. If not otherwise stated, it is preferred that the substituted aryl groups herein contain from 1 to about 30 carbon atoms.
"Alkenyl" as used herein refers to any straight, branched, or cyclic alkenyl group containing one or more carbon-carbon double bonds, where the point of substitution may be a carbon-carbon double bond or elsewhere in the group. Specific and non-limiting examples of alkenyl groups include, but are not limited to, ethenyl, propenyl, allyl, methallyl, and ethylene norbornane.
"Alkynyl" refers to any straight, branched, or cyclic alkynyl group containing one or more carbon-carbon triple bonds, where the point of substitution may be at a carbon-carbon triple bond or elsewhere in the group.
"Unsaturated" means one or more double or triple bonds. In a preferred embodiment, it refers to a carbon-carbon double or triple bond.
By "inert functional group" is meant herein a group other than a hydrocarbyl or substituted hydrocarbyl group that is inert under the process conditions experienced by the compound containing the group. The inert functional group also does not substantially or deleteriously interfere with any process described herein in which the compound in which the inert functional group is present may participate. Examples of inert functional groups include halogens (fluorine, chlorine, bromine and iodine), ethers such as-OR 30, wherein R 30 is hydrocarbyl OR substituted hydrocarbyl.
"Heteroatom" herein refers to any of group 13-17 elements other than carbon, and may include, for example, oxygen, nitrogen, silicon, sulfur, phosphorus, fluorine, chlorine, bromine, and iodine.
"Olefin" herein refers to 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, provided that the substituents do not substantially or deleteriously interfere with the process of the desired reaction to produce the product.
By "peroxycarboxylic acid" is meant herein any compound containing a peroxycarboxylic acid moiety, i.e., a structure of the formula-RC (O) -O-O-H,
Wherein R can be any organic group.
By "catalytically effective amount" is meant herein an amount effective to catalyze a hydrosilylation reaction.
Herein, "reaction-promoting effective amount" refers to an amount sufficient to promote a reaction, rather than an amount that would inhibit a reaction.
"Halogen" as used herein refers to any atom (fluorine, chlorine, bromine, iodine, astatine) that is a member of group VIIA of the periodic table. The prefix "halo" as used herein with respect to compounds refers to compounds containing halogen atoms.
In the process of the invention as defined above for producing the product of formula (I),
(R1)y(R2O)3-ySiCH2CHR3CR4R5X (I),
The main product of the hydrosilylation process of the present invention is a compound of formula (I)
(R1)y(R2O)3-ySiCH2CHR3CR4R5X (I)
Wherein R 1 and R 2 are alkyl of 1 to 6 carbon atoms, R 3 is alkyl of 1 to 6 carbon atoms or hydrogen, R 4 is alkyl of 1 to 6 carbon atoms, hydrogen or halogen, R 5 is hydrogen or alkyl of 1 to 6 carbon atoms, X is halogen, and y is 0, 1 or 2.
Specific examples of useful products of the methods of the invention include, but are not limited to (CH3O)3Si(CH2)3Cl、(C2H5O)3Si(CH2)3Cl、(C2H5O)3SiCH2CH(CH3)CH2Br、(CH3O)3SiCH2CH(Cl)CH3、CH3(CH3O)2Si(CH2)3Cl、 and (C 3H7O)3Si(CH2)2CH(Cl)CH3).
By-products having the general formula:
(R2O)4Si、(R1)Si(R2O)3、(R1)SiH2(R2O)、(R2O)3SiX、(R1 Not being hydrogen
(R2O)3SiCH2CHR3CR4R5H、(R1)yX(R2O)2-ySiCH2CHR3CR4R5X
CH 2=CHR3CR4R5H、XCH2CHR3CR4R5 H and HX.
For obtaining high yields of the product of formula (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,
(R1)y(R2O)3-ySiCH2CHR3CR4R5X (I)
Several factors have been found to be important.
According to an embodiment of the present invention, the most preferred product of formula (I) is chloropropyl triethoxysilane.
Olefinic halides
In the process according to the invention, the olefinic halide used as starting material has the general formula H 2C=CR3CR4R5 X,
Wherein R 3 is alkyl of 1 to 6 carbon atoms or hydrogen, R 4 is alkyl of 1 to 6 carbon atoms, hydrogen or halogen, R 5 is hydrogen or alkyl of 1 to 6 carbon atoms, and X is halogen.
X is a fluorine, chlorine, bromine or iodine substituent, preferably a bromine or chlorine substituent, most preferably a chlorine substituent.
R 3 and R 5 are independently selected from linear, branched or cyclic C1-C6 alkyl or hydrogen, in particular from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, cyclopentyl, cyclohexyl or hydrogen,
Preferably selected from methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl or hydrogen, more preferably selected from methyl, ethyl, n-propyl, isopropyl or hydrogen, even more preferably selected from methyl, ethyl or hydrogen, most preferably R 3 and R 5 are hydrogen.
R 4 is independently selected from linear, branched or cyclic C1-C6 alkyl or hydrogen, in particular from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, cyclopentyl, cyclohexyl, hydrogen or halogen,
Preferably selected from methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl or hydrogen, more preferably selected from methyl, ethyl, n-propyl, isopropyl or hydrogen, even more preferably selected from methyl, ethyl or hydrogen, most preferably R 4 is hydrogen.
In the case where R 4 is a halogen group independently selected from fluorine, chlorine, bromine and iodine substituents, preferably R 4 is a chlorine substituent.
Preferably, R 3、R4 and R 5 in the olefinic halide are hydrogen substituents, or two of the substituents R 3、R4 and R 5 are hydrogen substituents and the remaining substituents are C1-C6 alkyl substituents, more preferably, R 3、R4 and R 5 are hydrogen substituents, or two of the substituents R 3、R4 and R 5 are hydrogen substituents and the remaining substituents are alkyl substituents selected from methyl, ethyl and n-propyl, even more preferably, R 3、R4 and R 5 are hydrogen substituents, or two of the substituents R 3、R4 and R 5 are hydrogen substituents and the remaining substituents are methyl substituents, most preferably, R 3、R4 and R 5 are hydrogen substituents, or two of the substituents R 3 and R 5 are hydrogen substituents and the substituents R 4 are methyl substituents.
Olefinic halides suitable as starting materials for the present invention include, in particular, allyl chloride, methallyl chloride, 3-chloro-1-butene, 3, 4-dichloro-1-butene and the like. Among them, in one embodiment, allyl chloride, i.e., H 2C=CHCH2 Cl, is preferred.
According to an embodiment of the invention the olefinic halide can be used as such in technical grade purity with a content of the corresponding olefinic halide of ≡90 wt%, preferably ≡95 wt%, even more preferably ≡98 wt% and most preferably ≡99 wt%. While the 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 present invention, this is not required to carry out the process of the present invention. The meaning of the olefinic halide as such is that the olefinic halide is not subjected to a purification step, such as distillation or evaporation/condensation, prior to being subjected to the hydrosilylation step.
Thus, as the process of the present invention does not require high yields to be achieved with higher grade olefinic halides, the purity of technical grade purity olefinic halides can be in the range of 95.0 to 99.5 wt%, more specifically in the range of 95.5 to 99.0 wt%, and even more specifically in the range of 96.0 to 98.0 wt%.
Wherein the olefinic halide of technical grade purity may be as such or it may be an olefinic halide which has undergone a purification process prior to a process based on evaporation and condensation, for example.
Alkoxy silane
In the process according to the invention, the alkoxysilanes used as starting materials have the general formula (R 1)y(R2O)3-y SiH, where R 1 and R 2 are alkyl groups having 1 to 6 carbon atoms, and y is 0,1 or 2.
Thus, in the corresponding products of the formula (R 1)y(R2O)3-y SiH) alkoxysilane and of the formula (I),
(R1)y(R2O)3-ySiCH2CHR3CR4R5X (I)
R 1 and R 2 are independently selected from linear, branched or cyclic C1-C6 alkyl, especially from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, cyclopentyl or cyclohexyl, preferably from methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclopentyl or cyclohexyl, more preferably from methyl, ethyl, n-propyl, isopropyl, even more preferably from methyl and ethyl, most preferably R 1 and R 2 are methyl.
Preferably y is 0, i.e. preferably alkoxysilane (b) used in the process for producing the product of formula (I) is an alkoxysilane substituted with three alkoxy groups. In such an alkoxysilane having three alkoxy groups at the Si atom and the corresponding product of formula (I), preferably 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, isobutyl, tert-butyl, n-pentyl, cyclopentyl, n-hexyl and cyclohexyl, even more preferably an alkyl group selected from methyl, ethyl, n-propyl and isopropyl, most preferably the alkoxysilane and the corresponding product of formula (I) have three ethoxy groups at the Si atom, i.e. y=0 and R 2 is ethyl.
Alkoxysilanes suitable as starting materials in the process of the present invention include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, diethylethoxysilane, and the like. These alkoxysilanes in the embodiments of the present invention are preferably trimethoxysilane and triethoxysilane.
The trialkoxysilanes useful in the process of the present invention can be obtained via the alcohol esterification of trihalosilanes, as disclosed, for example, in US 3792071 and US 3985781. Trimethoxysilane and triethoxysilane are available in 89-92% by weight of distillation purity. Residual chloride levels can be as high as 100 ppm. Impurities include H 2Si(OR)2、HSi(OR)2Cl、Si(OR)4 and higher boiling condensed (condensed, concentrated) silicates.
Alternatively, the trialkoxysilanes useful in the process of the present invention may be obtained via direct reaction of an alcohol with copper-activated silicon, as disclosed, for example, in US 7652164 and US 7429672. Trimethoxysilane and triethoxysilane synthesized according to this method are chloride free and typically have a purity of 89-99 wt% prior to distillation. The purity of the distilled product was about 99.0 to 99.9 wt%. The impurities are H 2Si(OR)2、RSiH(OR)2、RSi(OR)3、Si(OR)4 and higher boiling condensed silicates.
Peroxycarboxylic acids
The peroxycarboxylic acid contains a-C (O) -O-OH moiety. They are decomposed by the influence of heat, acid and some metal compounds. Thus, since the reactants of the hydrosilylation process are subject to these influencing factors during the reaction, product recovery and recycling of unreacted starting materials and catalyst, the peroxide accelerator must be selected to maintain stable hydrosilylation activity throughout a batch or continuous process.
Preferably, the concentration of peroxycarboxylic acid used in embodiments of the methods of the present 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 alkoxysilane employed in the method. Preferred temperature and concentration ranges for the different types of peroxycarboxylic acids are set forth in the following detailed description of specific embodiments of the invention.
At the boiling point of allyl chloride (44-45 ℃) the half-life of the peroxycarboxylic acid may be as short as about 30 minutes, and may thus be even shorter in the temperature range of about 70 to about 100 ℃ where the hydrosilylation reaction is preferably carried out. Thus, the concentration of peroxycarboxylic acid will not always be sufficient to promote and drive the hydrosilylation reaction to completion. Thus, variable and inconsistent results are possible in laboratory experiments and commercial operations when peroxycarboxylic acids are not present at effective reaction promoting concentrations. The process of the present invention comprises the presence of peroxycarboxylic acid at a level sufficient to effect hydrosilylation. The peroxycarboxylic acid must be present in the hydrosilylation reaction zone along with the reactants and iridium-containing catalyst. They may be added directly to the reaction zone or, preferably, mixed with the olefin.
Generally, peroxycarboxylic acids as defined herein include all types of organic compounds containing one or more peroxycarboxylic acid moieties of the structure C (O) OOH.
Preferred types of peroxycarboxylic acids according to embodiments of the present invention are halogenated perbenzoic acids, unsubstituted peroxyalkanoic acids, and alpha-halogenated peroxyalkanoic acids, with halogenated perbenzoic acids making up the most preferred of the foregoing group of peroxycarboxylic acids.
The halogenated perbenzoic acids, including mono-, di-, tri-, tetra-and penta-halogenated perbenzoic acids, are preferably selected from the group consisting of monohalogenated perbenzoic acids and dihalo perbenzoic acids.
Further preferred are haloperoxide benzoic acids having at least one halogen substituent meta to the peroxycarboxyl group.
It is also preferred that at least one halogen substituent of perbenzoic acid is a fluorine or chlorine substituent, and even more preferably all halogen substituents are independently selected from fluorine and chlorine substituents.
Examples of preferred peroxycarboxylic acids selected from the group consisting of haloperoxides for use in the process of the present invention are 2-bromo-5-chlorobenzoic acid, 3, 5-difluoroperbenzoic acid, 3, 4-difluoroperbenzoic acid, 2,3, 6-trifluoroperbenzoic acid, 2,4, 5-trifluoroperbenzoic acid, 2,3,4,5, 6-pentafluorobenzoic acid, 3-chloroperbenzoic acid, 3-fluoropperbenzoic acid, and 3, 5-difluoroperbenzoic acid, with 3-chloroperbenzoic acid, 3-fluoropperbenzoic acid, and 3, 5-difluoroperbenzoic acid being particularly preferred.
The unsubstituted peroxyalkanoic acid (peroxyalkanonic acid) is preferably selected from the group consisting of C2-C12 peroxyalkanoic acids, with the peroxycarboxylic acid group further preferably being at a terminal position of a linear or branched alkyl group, and the alkyl residue further preferably being methyl or C2-C11 n-alkyl. Examples of preferred peroxycarboxylic acids selected from unsubstituted peroxyalkanoic acids for use in the methods of embodiments of the invention are peracetic acid, peroxypropionic acid, and peroxybutyric acid.
The alpha-haloperoxyalkanoic acid, i.e. the peroxyalkanoic acid bearing at least one halogen substituent at the alpha-position of the peroxycarboxylic acid group, is preferably selected from the group consisting of alpha-halogenated C2-C12 peroxyalkanoic acids, more preferably from the group consisting of linear alpha-halogenated C2-C12 peroxyalkanoic acids, wherein the halogen substituents are independently selected from the group consisting of chlorine and fluorine substituents. Examples of preferred alpha-haloperoxyalkanoic acids are chloroperacetic acid, fluoropperacetic acid, dichloropperacetic acid, difluoroperacetic acid, trifluoroperacetic acid and trichloroperacetic acid.
The presence of peroxycarboxylic acids allows to reduce the load of Ir catalyst required to carry out the hydrosilylation reaction with high yields and reasonable reaction rates, and also allows to carry out the reaction with technical grade olefinic halides without further purification steps prior to the hydrosilylation reaction.
Furthermore, commercially available Ir catalysts such as IrCl 3 and H 2IrCl6 can be successfully applied in hydrosilylation reactions in the presence of peroxycarboxylic acid promoters with low catalyst loading and without purification of technical grade olefinic halide starting materials.
Iridium-containing catalyst
Suitable iridium metal-containing catalysts may be selected from iridium metals or homogeneous and heterogeneous iridium metal-containing compounds and complexes, wherein iridium may be in any oxidation state from 0 to 8 (inclusive). Examples include 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 (IrX n, X being a halogen atom and n being any value between 2 and 4), such as IrCl 3 and Br 3;M2IrCl6, especially H2IrCl6、MIrCl3、M2Ir5Cl12、M4Ir4Cl12(M=H or alkali metals, zinc reduction and tin reduction reaction products of iridium halides, such as cycloolefin complexes of ZnIr 5Cl12 and SnIr5Cl12;IrO2、Ir3(CO)12、[Ir(CO)3Cl2]2; iridium, such as Ir (COD) (COT), COD-IrCl 2、[COD-IrCl2]2, wherein COD is cyclooctadiene and COT is cyclooctatriene, bis (6, 6-dimethylcyclopentadienyl) iridium, bis (. Eta.5-2, 4-dimethylpentadienyl) iridium, bis (1, 3-dimethylcyclopentadienyl) iridium, ir (AcAc) 3, wherein AcAc is an acetylacetonate ligand, (pi-arene) iridium complexes, such as (p-cymene) chloride (II) dimer and (benzene) chloride, and ammonia [ Ir ] complexes such as (NH) 3)6]X3.
Preferred iridium-containing catalysts are iridium chloride compounds, with H 2IrCl6 and H 2IrCl6 hydrates, irCl 3、IrCl3 hydrate and their zinc reduction products being most preferred. The catalyst from one batch can be recycled to the next without significant loss of activity. The catalyst usage level may be in the range of 1 to 300 ppm (parts per million parts per million) of Ir metal based on the total reactant feed, with 5 to 50 ppm being preferred.
The catalyst may be added to the hydrosilylation reaction in solid form, as a suspension or solution in an organic solvent. The Ir-containing catalyst can also be applied in immobilized form, for example attached or absorbed to the surface of the substrate material.
Hydrosilylation process
The hydrosilylation method according to the present invention is not limited to any particular scheme.
In a preferred embodiment of the hydrosilylation reaction using a solid catalyst according to the present invention, a preformed mixture of olefinic halide, alkoxysilane and peroxycarboxylic acid is added to the mixture of alkoxysilane and iridium-based hydrosilylation catalyst. Preferably, the preformed mixture is added stepwise or more preferably fed into the reactor to the mixture of alkoxysilane and iridium based hydrosilylation catalyst from the reaction vessel, mixing vessel or storage vessel. Preferably, the reactor in which the reactants are combined is equipped with a mixing device.
In another preferred embodiment of the process for hydrosilylation according to the invention using a catalyst solution, preferably for small-scale reactions, peroxycarboxylic acid, olefinic halide and alkoxysilane are mixed and then a solution or suspension of the catalyst in a solvent, preferably in an organic solvent, is added to the mixture to carry out the hydrosilylation reaction. Preferably, a mixing device is used to form and maintain a uniform reaction mixture.
Furthermore, the process advantageously proceeds by slowly adding the olefinic halide and the peroxycarboxylic acid to the alkoxysilane-containing reaction medium and hydrosilylating in a semi-batch or continuous process in the presence of an iridium metal-containing catalyst. This order of addition is effective to maintain a minimum concentration of unreacted olefinic halide relative to alkoxysilane in the reaction medium and thus effectively establish a very large molar excess of alkoxysilane relative to olefinic halide in the reaction medium. In common practice, the maximum rate of addition of the olefinic halide to the alkoxysilane will be determined by the reaction rate, which will depend in part on the reaction temperature, catalyst concentration, concentration of peroxycarboxylic acid and thermal stability, and by the heat transfer limitations of the reaction equipment and the reactor size, as will be appreciated by those skilled in the art.
As mentioned above, the process of the present invention may be carried out in any apparatus suitable for hydrosilylation reactions, including apparatus designed for continuous or alternatively discontinuous reactions. By using trimethoxysilane or triethoxysilane derived from silicon metal and the corresponding alkanol in the process of the present invention, the use of corrosive and hazardous hydrochlorosilanes (hydridochlorosilane) is avoided and the generation of substantial amounts of chlorine-containing waste byproducts inherent in the use of the product derived from the hydrochlorosilane is eliminated.
The reaction conditions include a reaction temperature ranging from about 15 ℃ to about 250 ℃, preferably from about 30 ℃ to about 180 ℃, more preferably from about 50 ℃ to about 130 ℃, still more preferably from about 60 ℃ to 80 ℃. In general, the process is carried out at atmospheric pressure or at a pressure above atmospheric pressure, with atmospheric pressure being preferred. It is recognized that the process of the present invention can provide high yields of the desired chloroalkylalkoxysilanes in a batch system, but can also be performed in a semi-batch process or a continuous process. However, batch reactions will typically be carried out at lower temperatures and thus longer reaction times.
Since the process of the present invention is almost quantitative in terms of conversion of the olefinic halide to the desired product (R1)y(R2O)3- ySiCH2CHR3CR4R5X(I) of formula (I), in particular the reaction of allyl chloride with triethoxysilane to provide chloropropyl triethoxysilane, the production of undesired by-products is significantly reduced. This reduces the amount of material that is disposed of as waste, separated as a separate stream (i.e., by distillation), or discharged from the reaction system. Because the process of the present invention is highly exothermic, continuous external heating is generally not required and the reaction time is short. Typically, the only significant amounts of impurities that need to be removed from the reaction product are unreacted alkoxysilane, tetraalkoxysilane, residual catalyst and peroxycarboxylic acid or their degradation products, respectively. The low levels of residual halide that may be present in the product may be neutralized by methods well known in the art. If the hydrosilylation product of the present invention is used as an intermediate for producing other organofunctional silicon compounds, the purity of the material as such may be sufficient. No additional purification steps are required. When applied to the preparation of, for example, chloropropyl triethoxysilane, the process of the present invention provides a higher yield of the target product (calculated on a molar basis) than any other one or two step process described in the prior art. This is accomplished by adding an effective amount of a peroxycarboxylic acid promoter in combination with an effective level of an iridium-containing catalyst. Furthermore, the process produces the target product at significantly lower iridium levels than described in the prior art. The process also provides higher yields per unit volume of equipment used because the use of inert solvents is avoided and no significant amounts of waste byproducts are produced.
Although the process of the present invention need not be operated at pressures above atmospheric, in one embodiment elevated pressures, e.g., up to two atmospheres, may be used to control the boiling point of the reaction mixture in the closed reactor. In another embodiment, if a reaction temperature below the atmospheric boiling point of the alkoxysilane is desired, a pressure below atmospheric pressure may be used. The product of formula (I), (R 1)y(R2O)3-ySiCH2CHR3CR4R5 X (I)) of the process of the invention may be purified by standard methods, i.e. by distillation, or may be used directly without intermediate purification.
In one embodiment according to the present 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 halide (a) used in the process according to this embodiment is preferably reacted with a trialkoxysilane, more preferably with a triethoxysilane. Most preferably, the chloropropyl triethoxysilane is obtained by reacting allyl chloride with triethoxysilane in the presence of an Ir catalyst and the peroxycarboxylic acid described herein, preferably with a haloperoxide benzoic acid acting as a promoter.
In another embodiment according to the present invention, the alkoxysilane (b) is selected from trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, diethylethoxysilane, and combinations thereof, preferably the alkoxysilane is triethoxysilane.
In yet another embodiment according to the present invention, the reaction-promoting effective amount of peroxycarboxylic acid (d) ranges from about 1 to about 2000 ppm, 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 more preferably from about 5 to about 50 ppm, still even more preferably from about 5 to about 25 ppm, and most preferably from about 5 to about 15 ppm, based on the total weight of starting materials olefinic halide (a) and alkoxysilane (b).
Preferably, the starting materials (a) and (b) are allyl chloride and triethoxysilane, and the amount of peroxycarboxylic acid (d) is calculated based on the total weight of allyl chloride and triethoxysilane.
The ratio of Ir-containing catalyst (c) to peroxycarboxylic acid (d) to promote 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 Ir-containing catalyst (c) to peroxycarboxylic acid (d) is based on the respective amounts of components (c) and (d) given in "ppm", wherein the amounts in ppm refer to the amounts of component (c) or (d) relative to the total mass of olefinic halide (a) and alkoxysilane (b), respectively. In the case of Ir catalyst (c), the amount of Ir metal in component (c) is correlated to the total mass of (a) and (b) to determine the amount of (c) in ppm.
In one embodiment according to the invention, the peroxycarboxylic acid (d) is selected from the group consisting of halogenated perbenzoic acid, unsubstituted peroxyalkanoic acid, and alpha-halogenated peroxyalkanoic acid.
As defined herein, the term "peroxyalkanoic acid" refers to a peroxycarboxylic acid consisting of a peroxycarboxyl group and an alkyl residue. Wherein the alkyl residue may be a primary n-alkyl, secondary alkyl or tertiary alkyl, with primary alkyl being preferred. The alkyl group may be a straight chain, branched or cyclic alkyl group, with C1-C11 n-alkyl groups being preferred. The term "unsubstituted" means that the C-atom of the alkyl group does not carry any other substituent other than a hydrogen atom.
As defined herein, the term "alpha-haloperoxyalkanoic acid" means that the alkyl group of these compounds bears one or more halogen substituents on the carbon atom of the alkyl group bonded to the carbon atom of the peroxycarboxyl group.
Halogenated perbenzoic acids are preferred and are advantageously used in the process of the present invention, in particular in Ir-catalyzed hydrosilylation reactions of allyl chloride and triethoxysilane catalyzed by an Ir catalyst, preferably IrCl 3 or H 2IrCl6.
In another embodiment according to the invention, the peroxycarboxylic acid (d) is selected from the group consisting of monohalogenated perbenzoic acid, dihalo perbenzoic acid, and trihalogenated, tetrahalogenated and pentahalogenated perbenzoic acids.
With respect to the nomenclature of the haloperoxide benzoic acid compounds used herein, note that the carbon ring atom bearing the peroxycarboxyl group is denoted as position "1" and the position of the halogen substituent or substituents on the benzene ring is numbered relative to that position. For example, 3-bromo-peroxybenzoic acid represents peroxybenzoic acid having a bromo substituent at the meta position of the peroxycarboxylic acid group.
Examples of monohalogenated perbenzoic acids according to embodiments are 2-, 3-or 4-chloroperbenzoic acid, with 3-chloroperbenzoic acid being preferred, and 2-, 3-or 4-fluoroperbenzoic acid, with 3-fluoroperbenzoic acid being preferred.
Examples of dihalobenzoic acids are dichloro-perbenzoic acid, such as 2, 3-dichloro-perbenzoic acid, 2, 4-dichloro-perbenzoic acid, 2, 6-dichloro-perbenzoic acid, 3, 4-dichloro-perbenzoic acid, 3, 5-dichloro-perbenzoic acid, wherein 3, 5-dichloro-perbenzoic acid is preferred, difluoro-perbenzoic acid, such as 2, 3-difluoro-perbenzoic acid, 2, 4-difluoro-perbenzoic acid, 2, 6-difluoro-perbenzoic acid, 3, 4-difluoro-perbenzoic acid, 3, 5-difluoro-perbenzoic acid, wherein 3, 5-difluoro-perbenzoic acid is preferred, monochloro-monofluoro-perbenzoic acid, such as 2-chloro-4-fluoro-perbenzoic acid, 2-chloro-5-fluoro-perbenzoic acid, 3-chloro-2-fluoro-perbenzoic acid, 5-chloro-2-fluoro-perbenzoic acid, wherein 3-chloro-5-fluoro-perbenzoic acid is preferred, and 3, 5-bromo-perbenzoic acid, wherein 3-chloro-5-bromo-perbenzoic 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-pentafluoro perbenzoic acid.
In another embodiment according to the invention, the peroxycarboxylic acid (d) is selected from halogenated perbenzoic acids bearing at least one halogen substituent in the meta position of the peroxycarboxyl group.
Preferred examples of halogenated perbenzoic acids having at least one halogen substituent meta to the peroxycarboxyl group are 3-chloroperbenzoic acid, 3-fluoropperbenzoic acid and 3, 5-difluoroperbenzoic acid.
In yet another embodiment according to the present invention, the peroxycarboxylic acid (d) is selected from the group of haloperoxides bearing a total of one, two or three halogen substituents, wherein preferably at least one halogen substituent, and more preferably all halogen substituents are independently selected from the group of fluorine and chlorine substituents, and most preferably all halogen substituents are chlorine substituents, or all halogen substituents are fluorine substituents.
According to this embodiment, the most preferred halogenated perbenzoic acids are 3-chloroperbenzoic acid, 3-fluoropperbenzoic acid, 3, 5-difluoroperbenzoic acid, 3, 5-dichloropperbenzoic 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, 2,3,4,5, 6-pentafluorobenzoic acid, 3-chloroperbenzoic acid, 3-fluoropperbenzoic acid, and 3, 5-difluoroperbenzoic acid.
Preferably, the peroxycarboxylic acid (d) is selected from the group consisting of 3-chloroperbenzoic acid, 3-fluoropperbenzoic acid, and 3, 5-difluoroperbenzoic acid.
Halogenated perbenzoic acids according to embodiments of the present invention are commercially available or readily available from the corresponding halogenated benzoic acid.
When these compounds are used as promoters in the process of the present invention in amounts of about 3 to about 200 ppm relative to the total mass of olefinic halide (a) and alkoxysilane (b), then the catalyst loading of the Ir-based catalyst, preferably IrCl 3 or H 2IrCl6, can be in the range of about 1 to about 25 ppm of Ir relative to the total mass of olefinic halide (a) and alkoxysilane (b).
In another embodiment according to the invention the peroxycarboxylic acid (d) is an alpha-haloperoxyalkanoic acid selected from the group consisting of C2-C12 alpha-haloperoxyalkanoic acids bearing one or more halogen substituents independently selected from the group consisting of chlorine and fluorine substituents, or wherein the peroxycarboxylic acid (d) is an unsubstituted C2-C12 peroxyalkanoic acid.
Preferably, the peroxycarboxylic acid (d) is an alpha-halogenated alkanoic acid selected from the group consisting of chloroperacetic acid, fluoropperacetic acid, dichloropperacetic acid, difluoroperacetic acid, trifluoroperacetic acid, and trichloroperacetic acid.
In another embodiment according to the present 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, cyclic olefin complexes of iridium, amine complexes of iridium, phosphine complexes of iridium, CO complexes of iridium, and combinations thereof.
As defined herein, a nanoparticle is a particle having an average particle size of1 to 500 nm, and a micron-sized particle is a particle having an average particle size of 0.5 to 50 μm, as determined by dynamic light scattering.
In yet another embodiment according to the present invention, the iridium-containing catalyst (c) is present in an amount of 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, based on the total weight of the starting materials olefinic halide (a) and alkoxysilane (b).
In another embodiment according to the invention, the iridium-containing catalyst (c) is selected from the group consisting of IrCl 3、Br3、M2IrCl6, wherein m=h or an alkali metal, cyclic olefin complexes of iridium, such as Ir 2Cl2(COE)4, the Crabtree catalyst, [ Ir (μ 2-Cl)(COD)]2 and Ir 2(OCH3)2(COD)2, wherein COE is cyclooctene and COD is 1, 5-cyclooctadiene, pentamethylcyclopentadienyl iridium dichloride dimer [ cp×ircl 2]2; (pi-arene) iridium complex, and combinations thereof.
In a preferred embodiment according to the invention, the iridium-containing catalyst (c) is selected from IrCl 3·xH2 O or H 2IrCl6.
The number of water molecules "x" in the IrCl 3 hydrate may be any fraction from 0 (i.e. anhydrous IrCl 3) to 1. Because IrCl 3 is strongly hygroscopic, the IrCl 3 hydrate can absorb additional water beyond one water molecule per iridium ion. H 2IrCl6 can also be used as anhydrous reagent or as the catalyst for hydrosilylation reactions with the corresponding hydrates. Both IrCl 3 and H 2IrCl6 can be applied to the hydrosilylation reaction as a solid or as a preformed stock solution or suspension. Such solutions or suspensions are preferably prepared with organic solvents having OH functionality, preferably alkanols having one, two or three hydroxyl groups, such as methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, or polyglycols such as polyethylene glycol or polypropylene glycol.
Preferably, the amount of iridium-containing catalyst IrCl 3 or H 2IrCl6 in the methods of embodiments of the invention is in the range of about 1 to about 50ppm, 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. Expressed in "ppm" means the content by mass of Ir in IrCl 3 or H 2IrCl6 relative to the total mass of the olefinic halide (a) and the alkoxysilane (b). Wherein the ratio of iridium-containing catalyst irel 3 or H 2IrCl6 to 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 acid (d) according to this embodiment is a halogenated perbenzoic acid, more preferably selected from 3-chloroperbenzoic acid, 3-fluoropperbenzoic acid and 3, 5-difluoroperbenzoic acid. The expression "ppm" with respect to the peroxycarboxylic acid (d) refers to the amount of peroxycarboxylic acid by mass relative to the total mass of the olefinic halide (a) and the alkoxysilane (b).
According to this embodiment, the above conditions are preferably applied in the hydrosilylation of allyl chloride with triethoxysilane to obtain chloropropyltriethoxysilane.
In another 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, preferably an OH-functional solvent, i.e. for example OH-functional alkanols, diols and triols, such as ethanol, polyethers, preferably catalyst (c) is added as a solid.
Examples of OH-functional solvents are methanol, ethanol, n-propanol, isobutanol, n-butanol, t-butanol, pentanol, hexanol, cyclohexanol, and polyglycols such as polyethylene glycol and polypropylene glycol, and mono-and di-ethers of glycols such as methyl and butyl ethers of ethylene glycol, diethylene glycol and triethylene glycol, and 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 technical grade olefinic halide, preferably technical grade allyl chloride.
As defined herein, the term "technical grade" means an olefinic halide having a purity of 90% by weight or more, preferably 95% by weight or more, even more preferably 98% by weight or more, and most preferably 99% by weight or more.
In general, commercially available olefinic halides have qualities with regard to purity characterized as "technical grade". However, in many cases higher purities are required, which is associated with further purification steps and higher costs.
The process of the present invention allows to carry out iridium-catalysed hydrosilylation reactions with high yields using olefinic halides (a) of technical quality in the presence of peroxycarboxylic acids (d). Thus, the olefinic halide according to this embodiment can have a purity in the range of about 95.0 wt% to about 99.5 wt%, more specifically in the range of about 95.5 to about 99.0 wt%, and even more specifically in the range of about 96.0 wt% to about 98.0 wt%. The olefinic halides may be used as such.
In one embodiment according to the invention, the molar ratio of olefinic halide (a) to alkoxysilane (b) is from about 10:1 to about 1:10, preferably from about 5:1 to about 1:5, more preferably from about 2:1 to about 1:2, even more preferably from about 1.7:1 to about 1:1.7, even more preferably from about 1.5:1 to about 1:1.5, and most preferably from about 1.2:1 to about 1:1.2.
In another embodiment according to the invention, the ratio of iridium-containing catalyst (c) to peroxycarboxylic acid (d) in [ ppm to ppm ] 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, each based on the total weight of starting materials olefinic halide (a) and alkoxysilane (b).
For the measurement of the ratio of iridium-containing catalyst (c) to peroxycarboxylic acid (d) in [ ppm to ppm ], the amount of peroxycarboxylic acid (d) by mass was divided by the total mass of olefinic halide (a) and alkoxysilane (b) and the result was multiplied by 1000000, and the amount of iridium-containing catalyst (c) by mass was divided by the total mass of olefinic halide (a) and alkoxysilane (b) and the result was multiplied by 1000000. Using this calculation, the amounts in ppm of iridium-containing catalyst (c) and peroxycarboxylic acid (d) according to the invention are obtained. Thus, the ratios given in this embodiment refer to the ratio of the amounts of iridium-containing catalyst and peroxycarboxylic acid in "ppm" as 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 IrCl 3 or H 2IrCl6, 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 iridium containing catalyst (c) is in an amount of from about 5 to about 20 ppm, and the peroxycarboxylic acid (d) is:
-mCPBA, present in an amount that satisfies the condition that the ratio of catalyst (c) to promoter (d) [ ppm/ppm ] is in the range of about 1:2.5 to about 1:20, or
-MFPBA, present in an amount that satisfies the conditions of a ratio of catalyst (c) to promoter (d) [ ppm/ppm ] in the range of about 1:2.5 to about 1:10, or
-DFPBA, present in an amount that satisfies the conditions of a ratio [ ppm/ppm ] of catalyst (c) to promoter (d) in the range from about 1:2 to about 1:4.
Preferably, the iridium-containing catalyst (c) is selected from the group consisting of IrCl 3 and H 2IrCl6.
The [ ppm/ppm ] ratio of iridium-containing catalyst (c) and promoter (d) was determined as described above.
The invention also relates to a composition obtainable when performing the method according to the invention as described in detail above, and to various embodiments.
The invention relates in particular to compositions comprising one or more compounds of 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 R 1 and R 2 are alkyl groups of 1 to 6 carbon atoms;
R 3 is alkyl of 1 to 6 carbon atoms or hydrogen;
r 4 is alkyl of 1 to 6 carbon atoms, hydrogen or halogen;
r 5 is hydrogen or alkyl of 1 to 6 carbon atoms;
X is halogen, and
Y is 0,1 or 2.
The iridium-containing compounds of the composition according to the invention are limited only insofar as they must contain one or more iridium atoms or iridium ions. Thus, the iridium-containing compound may be any iridium-containing catalyst or iridium compound or iridium particles derived from an iridium-containing hydrosilylation catalyst as described above in the description of the process of the invention. Preferably, the iridium-containing compound is a compound formed from the catalyst used in the process of the present invention, i.e. an intermediate of the catalytic cycle of the hydrosilylation reaction and an active catalytic species, such as iridium (0) nanoparticles or iridium (0) micron-sized particles.
As defined herein, a nanoparticle is a particle having an average particle size of 1 to 500 nm, and a micron-sized particle is a particle having an average particle size of 0.5 to 50 μm, as determined by dynamic light scattering. In addition, the iridium-containing compound may be a compound obtained by deactivating or decomposing the iridium-containing catalyst obtained by the process of the present invention.
In the same manner, the peroxycarboxylic acids of the compositions of the present invention are not limited in any particular way, except that they must contain peroxycarboxylic groups, such as peroxycarboxylic acids suitable for use in the methods of the present invention.
The carboxylic acids of the compositions of the present invention as defined herein are not limited in any particular way except that they must contain a carboxyl group.
In particular, the composition of the invention may comprise the peroxycarboxylic acid compounds mentioned in the above description of the method of the invention, and the composition of the invention preferably comprises the same compounds preferably applied in the method of the invention. The carboxylic acid of the composition of the invention is preferably a compound similar to the peroxycarboxylic acid compounds mentioned in the above description of the process of the invention, and the composition of the invention more preferably comprises a carboxylic acid similar to the peroxycarboxylic acid preferably used in the process of the invention. As defined herein with respect to peroxycarboxylic acids and carboxylic acids, the term "analog" means that the carboxylic acid corresponds to the peroxycarboxylic acid, so long as they are structurally identical except for having a carboxyl group instead of a peroxycarboxyl group.
The compound of formula (I) comprised in the composition according to the invention is preferably a product obtained by hydrosilylation of an olefinic halide selected from 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 trimethoxysilane, methyldimethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, and diethylethoxysilane, wherein trimethoxysilane and triethoxysilane are preferred.
The most preferred compounds of formula (I) that the compositions of the present invention may contain are chloropropyl trimethoxysilane and chloropropyl triethoxysilane.
In a preferred embodiment of the composition according to the invention, the compound of formula (I) is chloropropyl triethoxysilane.
In one embodiment, the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from the group consisting of halogenated perbenzoic acids, unsubstituted peroxyalkanoic acids, alpha-halogenated peroxyalkanoic acids, halobenzoic acids, unsubstituted alkanoic acids, and alpha-halogenated alkanoic acids.
The terms "peroxyalkanoic acid", "unsubstituted" and "alpha-haloperoxyalkanoic acid" have the same meaning as defined above. Accordingly, the term "unsubstituted alkanoic acid" refers to a carboxylic acid consisting of both a carboxyl group and an alkyl residue wherein the C atom of the alkyl group does not carry any other substituents other than a hydrogen atom. The alkyl group may be a primary n-alkyl group, a secondary alkyl group or a tertiary alkyl group, wherein primary alkyl groups are preferred, wherein the alkyl group may be a linear, branched or cyclic alkyl group, wherein C1-C11 n-alkyl groups are preferred. Likewise, the term "alpha-haloalkanoic acid" means 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, dihalo perbenzoic acids, trihalogenated, tetrahalogenated and pentahalogenated perbenzoic acids, monohalogenated benzoic acids, dihalobenzoic acids, and trihalogenated, tetrahalogenated and pentahalogenated benzoic acids.
In still further embodiments, the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from haloperoxides bearing at least one halogen substituent at the meta-position of the peroxycarboxyl group and halophenolic acids bearing at least one halogen substituent at the meta-position of the carboxyl group.
In an embodiment according to the invention the one or more compounds selected from i) peroxycarboxylic acid and/or ii) carboxylic acid are selected from the group consisting of perbenzoic acid, 2-bromo-5-chloroperbenzoic acid, 3, 5-difluoroperbenzoic acid, 3, 4-difluoroperbenzoic acid, 2,3, 6-trifluoroperbenzoic acid, 2,4, 5-trifluoroperbenzoic acid, 2,3,4,5, 6-pentafluorobenzoic acid, 3-chloroperbenzoic acid, 3-fluoropperbenzoic acid, and 3, 5-difluoroperbenzoic acid, preferably the perbenzoic acid is selected from the group consisting of 3-chloroperbenzoic acid, 3-fluoropperbenzoic acid and 3, 5-difluoroperbenzoic acid, and/or from the group consisting of benzoic acid, 2-bromo-5-chlorobenzoic acid, 3, 5-difluorobenzoic acid, 3, 4-difluorobenzoic acid, 2,3, 6-trifluorobenzoic acid, 2,4, 5-trifluorobenzoic acid, 3, 5-difluorobenzoic acid, 3-difluorochlorobenzoic acid and 3, 5-difluorochlorobenzoic acid.
According to this 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 are selected from the group consisting of C2-C12 alpha-haloperoxyalkanoic acids with one or more halogen substituents independently selected from the group consisting of chlorine and fluorine substituents, and unsubstituted C2-C12 peroxyalkanoic acids, and C2-C12 alpha-haloalkanoic acids with one or more halogen substituents independently selected from the group consisting of chlorine and fluorine substituents, and unsubstituted C2-C12 alkanoic acids.
In a further embodiment of the invention, the iridium-containing compound is selected from nano-sized iridium particles and micro-sized iridium particles.
The nano-sized iridium particles and micro-sized iridium particles are based on iridium (0) and are typically formed from iridium-containing catalysts used in the hydrosilylation reaction of the method of the present invention.
In another embodiment of the present invention, the composition comprises iridium-containing compounds in an amount ranging 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, based on the total weight of the haloorganosilane of formula (I).
Preferably, the composition comprises an iridium-containing compound in an amount within the aforementioned range, based on the total weight of chloropropyl triethoxysilane present in the composition as a compound of formula (I).
In a still further aspect, the present invention relates to the use of the aforementioned composition and the composition obtained by the method of the invention as described above for the preparation of an amino organosilane, a mercapto organosilane, or a methacryloxy organosilane.
As defined herein, the term "organosilane" includes organoalkoxysilanes, i.e., organosilanes having one, two, or three alkoxy groups at the silicon atom.
An amino organosilane, as defined herein, is an organosilane that includes a primary, secondary, or tertiary amino group in an organic residue.
Preferably, the aminoorganosilane has a structure represented by formula (II)
(R1)y(R2O)3-ySiCH2CHR3CR4R5Z1 (II),
Wherein R 1、R2、R3、R4、R5 and y are as defined above,
Z 1 is selected from the group consisting of-NH 2、-NHR6 and NR 6R7,
And、,
Wherein R 6 is independently selected from C1-C12 alkyl and residues
、,
Preferably R 6 is-CH 3、-CH2CH2NH2
Or (b),
R 7 is independently selected from C1-C12 alkyl, preferably R 7 is CH 3, and further preferably R 6 and R 7 represent the same residue, most preferably R 6 and R 7 represent-CH 3.
Mercaptoorganosilanes, as defined herein, are organosilanes bearing at least one residue selected from the group consisting of a thiol group, a disulfanyl group, a polysulfanyl group, a thioalkyl group, a dithioalkyl group, or a polythioalkyl group, the residue being bonded to the organosilane' S organo residue via an-S-atom.
Preferably, the mercaptoorganosilane has a structure represented by formula (III)
(R1)y(R2O)3-ySiCH2CHR3CR4R5Z2 (III), Wherein the method comprises the steps of
R 1、R2、R3、R4、R5 and y are as defined above,
Z 2 is selected from the group consisting of-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
R 8 is selected from:
-a C1-C12 alkyl group, preferably a C2-C12 acyl group, optionally containing a c=o group, i.e. derived from carboxylic acids, in particular from acetic acid, butyric acid, caproic acid, caprylic acid, capric acid, dodecanoic acid, neodecanoic acid, 2-ethyl-hexanoic acid and residue (R1)y(R2O)3- ySiCH2CHR3CR4R5-, wherein R 1、R2、R3、R4、R5 and y are as defined above.
The term "derived from carboxylic acid" when referring to an acyl group means that the acyl group R 8 is bonded to an S atom having a carbonyl C atom. Compounds having such R 8 groups can be formed by condensation of carboxylic acids with terminal SH groups of precursor compounds.
Thus, according to an embodiment, the preferred radicals R 8 are acetyl, butyryl, hexanoyl, octanoyl, decanoyl, dodecanoyl, neodecanoyl and 2-ethyl-hexanoyl.
As defined herein, a methacryloxy organosilane is an organosilane bearing a methacryloxy group that is bonded to at least one of the organoresidues of the organosilane via an-O-atom.
Preferably, the methacryloxy organosilane has a structure represented by formula (IV)
(R1)y(R2O)3-ySiCH2CHR3CR4R5Z3 (IV),
Wherein R 1、R2、R3、R4、R5 and y are as defined above, and
Z 3 is-OC (O) C (CH 2)CH3).
The compounds of formula (I) comprised by the composition according to the invention can be converted into the desired functionalized organosilane by replacing the halogen substituent with an amine reagent, sulfide, thiolate or polysulfide reagent or methacrylate reagent (e.g. methacrylate salt), respectively, in a nucleophilic reaction.
In an embodiment according to the invention, the composition is used for the preparation of polysulfane-containing organoalkoxysilanes.
As defined herein, the polysulfane-containing organoalkoxysilane is a mercaptoorganosilane having structure (R1)y(R2O)3- ySiCH2CHR3CR4R5Z2(III) wherein:
R 1、R2、R3、R4、R5 and y are as defined above, and
Z 2 is selected from the group consisting of-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, R 8 is selected from the group consisting of C1-C12 alkyl optionally containing a C=O group, preferably C2-C12 acyl, more preferably acetyl, butyryl, hexanoyl, octanoyl, decanoyl, dodecanoyl, neodecanoyl and 2-ethyl-hexanoyl, and residue (R1)y(R2O)3- ySiCH2CHR3CR4R5-, wherein R 1、R2、R3、R4、R5 and y are as defined above.
In a preferred embodiment, the composition is used to prepare polysulfane-containing organoalkoxysilanes for use in the manufacture of silica-filled tires.
In another embodiment of the invention, the composition for preparing an amino organosilane, mercapto silane or methacryloxy organosilane comprises chloropropyl triethoxy silane.
According to this embodiment, the chloropropyl triethoxysilane comprised in the composition is converted into aminopropyl triethoxysilane of formula (V)
(EtO)3SiCH2CH2CH2Z1 (V),
Wherein Z 1 is as defined above,
Conversion to mercaptoorganosilanes of formula (VI)
(EtO)3SiCH2CH2CH2Z2 (VI),
Wherein Z 2 is as defined above,
Or into methacryloyl groups oxypropyl triethoxysilane.
Summary of the preferred embodiments of the invention
Hereinafter, preferred embodiments of the present invention are summarized:
1. Process for the production of a compound of formula (I)
(R1)y(R2O)3-ySiCH2CHR3CR4R5X (I),
Comprising reacting to produce a product of formula (I):
(a) an olefinic halide having the formula H 2C=CR3CR4R5 X, (b) an alkoxysilane having the formula (R 1)y(R2O)3-y SiH), (c) a catalytically effective amount of an iridium-containing catalyst, and (d) a reaction-promoting effective amount of a peroxycarboxylic acid, wherein
R 1 and R 2 are alkyl groups of 1 to 6 carbon atoms;
R 3 is alkyl of 1 to 6 carbon atoms or hydrogen;
r 4 is alkyl of 1 to 6 carbon atoms, hydrogen or halogen;
r 5 is hydrogen or alkyl of 1 to 6 carbon atoms;
X is 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 method according to embodiment 1 or 2, wherein 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 method according to any of embodiments 1-3, wherein the reaction-promoting effective amount of peroxycarboxylic acid (d) ranges from about 1 to about 2000 ppm, 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, based on the total weight of starting materials olefinic halide (a) and alkoxysilane (b).
5. The method according to any of embodiments 1-4, wherein the peroxycarboxylic acid (d) is selected from the group consisting of halogenated perbenzoic acid, unsubstituted peroxyalkanoic acid, and alpha-halogenated peroxyalkanoic acid.
6. The method according to any of the preceding embodiments 1-5, wherein the peroxycarboxylic acid (d) is selected from the group consisting of monohalogenated perbenzoic acid, dihalo perbenzoic acid, and trihalogenated, tetrahalogenated and pentahalogenated perbenzoic acid.
7. The method according to any of the preceding embodiments 1-6, wherein the peroxycarboxylic acid (d) is selected from the group consisting of halogenated perbenzoic acids having at least one halogen substituent at the meta position of the peroxycarboxylic acid group.
8. The method according to any of the preceding embodiments 1-7, wherein the peroxycarboxylic acid (d) is selected from the group consisting of haloperoxides bearing a total of one, two, or three halogen substituents, wherein preferably at least one halogen substituent, more preferably all halogen substituents are independently selected from the group consisting of fluorine and chlorine substituents, and most preferably all halogen substituents are chlorine substituents or all halogen substituents are fluorine substituents.
9. The method according to any one of the preceding embodiments 1 to 8, wherein the peroxycarboxylic acid (d) is selected from the group 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, 2,3,4,5, 6-pentafluorobenzoic acid, 3-chloroperbenzoic acid, 3-fluoropperbenzoic acid, and 3, 5-difluoroperbenzoic acid.
10. The method according to any one of the preceding embodiments 1 to 9, wherein the peroxycarboxylic acid (d) is selected from the group consisting of 3-chloroperbenzoic acid, 3-fluorophenylic acid, and 3, 5-difluoroperbenzoic acid.
11. The method according to any of embodiments 1-5, wherein the peroxycarboxylic acid (d) is an alpha-haloperoxyalkanoic acid selected from the group consisting of C2-C12 alpha-haloperoxyalkanoic acids with one or more halogen substituents independently selected from the group consisting of chlorine and fluorine substituents, or wherein the peroxycarboxylic acid (d) is an unsubstituted C2-C12 peroxyalkanoic acid.
12. The method according to any of embodiments 1-5 or 11, wherein the peroxycarboxylic acid (d) is an alpha-halogenated alkanoic acid selected from the group consisting of chloroperacetic acid, fluoropperacetic acid, dichloropperacetic acid, difluoroperacetic acid, trifluoroperacetic acid, and trichloroperacetic acid.
13. The method of any of 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, cyclic olefin complexes of iridium, amine complexes of iridium, phosphine complexes of iridium, CO complexes of iridium, and combinations thereof.
14. The method of any of embodiments 1-13, wherein the iridium-containing catalyst (c) is in an amount of 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, based on the total weight of starting materials olefinic halide (a) and alkoxysilane (b).
15. The method according to any of embodiments 1-14, wherein the iridium-containing catalyst (c) is selected from the group consisting of IrCl 3、IrBr3、M2IrCl6, wherein M = H or an alkali metal, cyclic olefin complexes of iridium, such as Ir 2Cl2(COE)4, the Crabtree catalyst, [ Ir (μ 2-Cl)(COD)]2 and Ir 2(OCH3)2(COD)2, wherein COE is cyclooctene and COD is 1, 5-cyclooctadiene, pentamethylcyclopentadienyl iridium dichloride dimer [ Cp: irCl 2]2, (pi-arene) iridium complex, and combinations thereof.
16. The method according to any one of embodiments 1-15, wherein the iridium-containing catalyst (c) is selected from the group consisting of IrCl 3·xH2 O or H 2IrCl6.
17. The process according to any of embodiments 1-16, wherein iridium-containing catalyst (c) is added to the reaction as a solid or as a solution or suspension in an organic solvent, preferably an OH-functional solvent, i.e. e.g. OH-functional alkanols, diols and triols, i.e. e.g. ethanol and polyethers, preferably catalyst (c) is added as a solid.
18. The process of any of embodiments 1-17, wherein the olefinic halide (a) is an technical grade olefinic halide, preferably technical grade allyl chloride.
19. The method of any of embodiments 1-18, wherein the molar ratio of olefinic halide (a) to alkoxysilane (b) is from about 10:1 to about 1:10, preferably from about 5:1 to about 1:5, more preferably from about 2:1 to about 1:2, even more preferably from about 1.7:1 to about 1:1.7, even further preferably from about 1.5:1 to about 1:1.5, and most preferably from about 1.2:1 to about 1:1.2.
20. The method according to any one of embodiments 1 to 19, wherein the ratio of iridium-containing catalyst (c) to peroxycarboxylic acid (d) in [ ppm to ppm ] is in the range of from about 1:1 to about 1:40, preferably in the range of from about 1:1.5 to about 1:25, more preferably in the range of from about 1:2 to about 1:20, most preferably in the range of from about 1:2 to about 1:10, each based on the total weight of starting material olefinic halide (a) and alkoxysilane (b).
21. The method of any of embodiments 1-20, wherein the olefinic halide (a) is allyl chloride, the alkoxysilane (b) is triethoxysilane, the Ir-containing catalyst (c) is IrCl 3 or H 2IrCl6, and the peroxycarboxylic acid (d) is 3-chloroperbenzoic acid, 3-fluoropperbenzoic acid, or 3, 5-difluoroperbenzoic acid.
22. The method of any of 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:
-mCPBA, present in an amount that satisfies the condition that the ratio of catalyst (c) to promoter (d) [ ppm/ppm ] is in the range of about 1:2.5 to about 1:20, or
-MFPBA, present in an amount that satisfies the conditions of a ratio of catalyst (c) to promoter (d) [ ppm/ppm ] in the range of about 1:2.5 to about 1:10, or
-DFPBA, present in an amount that satisfies the conditions of a ratio [ ppm/ppm ] of catalyst (c) to promoter (d) in the range from about 1:2 to about 1:4.
23. The method according to the previous embodiment, wherein the iridium-containing catalyst is selected from the group consisting of IrCl 3 and H 2IrCl6.
24. A composition obtained by the method of any one of embodiments 1-23.
25. A composition comprising:
one or more compounds of 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
R 1 and R 2 are alkyl groups of 1 to 6 carbon atoms;
R 3 is alkyl of 1 to 6 carbon atoms or hydrogen;
r 4 is alkyl of 1 to 6 carbon atoms, hydrogen or halogen;
r 5 is hydrogen or alkyl of 1 to 6 carbon atoms;
X is halogen, and
Y is 0,1 or 2.
26. A composition according to embodiment 25 wherein the compound of formula (I) is chloropropyl triethoxysilane.
27. The composition according to embodiment 25 or 26, wherein the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from the group consisting of halogenated perbenzoic acids, unsubstituted peroxyalkanoic acids, alpha-halogenated peroxyalkanoic acids, halobenzoic acids, unsubstituted alkanoic acids, or alpha-halogenated alkanoic acids.
28. The composition according to embodiments 25-27, wherein the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from the group consisting of monohalogenated perbenzoic acids, dihalo perbenzoic acids, trihalogenated, tetrahalogenated and pentahalogenated perbenzoic acids, monohalogenated benzoic acids, dihalobenzoic acids, and trihalogenated, tetrahalogenated and pentahalogenated benzoic acids.
29. The composition according to any of embodiments 25-28, wherein the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from the group consisting of haloperoxidic acids bearing at least one halogen substituent at the meta-position of the peroxycarboxyl group and halophenolic acids bearing at least one halogen substituent at the meta-position of the carboxyl group.
30. The composition according to any of embodiments 25-29, wherein the one or more compounds selected from i) peroxycarboxylic acid and/or ii) carboxylic acid are selected from the group 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, 2,3,4,5, 6-pentafluorobenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3, 5-difluoroperbenzoic acid, and benzoic acid selected from the group 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, 5-pentafluorobenzoic acid, 3-difluorobenzoic acid and 3, 5-difluorobenzoic acid.
31. The composition according to any of 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-fluoropperbenzoic 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 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 alpha-haloperoxyalkanoic acids and unsubstituted C2-C12 peroxyalkanoic acids with one or more halogen substituents independently selected from the group consisting of chlorine and fluorine substituents, and from the group consisting of C2-C12 alpha-haloalkanoic acids and unsubstituted C2-C12 alkanoic acids with one or more halogen substituents independently selected from the group consisting of chlorine and fluorine substituents.
33. The composition according to any of embodiments 25-32, wherein the iridium-containing compound is selected from the group consisting of nanosized iridium particles and microsized iridium particles.
34. The composition according to any of embodiments 25-33, wherein the amount of iridium-containing compound ranges from about 1 to about 100ppm, 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, based on the total weight of the compound of formula (I).
35. Use of the compositions of embodiments 24-34 for preparing an amino organosilane, a mercapto organosilane, or a methacryloxy organosilane.
36. The use of the composition according to embodiment 35, wherein the composition is used for the preparation of polysulfane-containing organoalkoxysilanes.
37. The use of the composition according to embodiment 36, wherein the polysulfane-containing organoalkoxysilane is used for manufacturing silica-filled tires.
38. The use of a composition according to embodiments 35-37, wherein the composition comprises chloropropyl triethoxysilane.
While the exact scope of the invention is set forth in the appended claims, the following specific examples illustrate some aspects of the invention and more particularly point out aspects of the method for evaluating the same. However, the examples are set forth for illustrative purposes only and should not be construed as limiting the invention.
Examples
The invention is further illustrated by, but not limited to, the following examples.
Summary-chemical and abbreviation
IrCl 3·xH2 O abcr, 99.99% CAS 14996-61-3, iridium (III) chloride hydrate
H 2IrCl6: abcr, 99.90% CAS 110802-84-1, hexachloroiridium (IV) acid hydrate
Dried EtOH analytical grade EtOH dried further over molecular sieve (3A)
Allyl chloride Momentive grade (batch RBT 190731C), 99 wt.%
Concentrating allyl chloride by vacuum treatment of the as-received allyl chloride to obtain a concentrated allyl chloride.
The as-received allyl chloride was fed into a Schlenk flask and connected to a second (dry ice/iPr cooled) Schlenk flask via a glass bridge. The compound which did not volatilize at 20 ℃ per 0.4 mbar was retained in the first flask and separated from the over-concentrated allyl chloride. While NMR and GC-TCD measurements did not show a significant change in the purity of the concentrated allyl chloride when compared to the as-received allyl chloride, the non-volatile compounds formed a yellow liquid.
Triethoxysilane, momentive grade (TES; momentive grade synthesized from HSiCl 3), 89-92 wt%
Di-tert-butyl peroxide (DtBP): sigma-Aldrich;98%
Tert-butyl hydroperoxide (tBHP) Sigma-Aldrich, 5.5 molar in decane
Tert-butyl perbenzoate (tPB): SIGMA ALDRICH;98%
M-chloroperbenzoic acid or m-chloroperbenzoic acid (mCPBA): sigma-Aldrich;77% active CAS 937-14-4; commercially available mCPBA is a mixture of mCPBA with m-chlorobenzoic acid and water (for stabilization) and assuming an activity equal to the content of mCPBA in the mixture, 77% according to the supplier, determined by titration by Na 2S2O3.
M-fluoroperbenzoic acid (mFPBA) and 3, 5-difluoroperbenzoic acid (dFPBA) were synthesized according to the reference 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
NMR measurements were performed on a BRUKER DPX 400 with a 5mm multi-core probe or on BRUKER AVANCE III MHz.
The table below shows the resonance frequencies of the detected nuclei.
The compound to be investigated was bottled under argon. Thus, 0.2 ml compound was dissolved in 0.4 ml solvent. In all cases, deuterated chloroform was used as solvent and 1% tms was added as reference. Thus, TMS signal is given in ppm as a reference point for all chemical shifts. If desired, 100. Mu.L HMDSO was used as an internal reference for determining the mass fraction.
FT-IR
Spectra were generated on Nicolet 380 FT-IR using standard FT-IR ATR measurement procedures. The sample of peroxycarboxylic acid studied does not require further preparation prior to measurement.
Catalyst preparation and hydrosilylation
All catalyst preparation and hydrosilylation were performed under argon atmosphere using Schlenk technique.
The structure of the product was confirmed by 1H-NMR、13 C-NMR and FTIR spectra.
Synthesis example 1 Synthesis of m-fluoroperbenzoic acid (m-FPBA)
36 ML DI water, 3.6 g NaOH, 0.15 g MgSO 4·7H2 O and 45mL 1, 4-dioxane were mixed in a 250 mL glass beaker and cooled to 10-15 ℃.9 mL of 30 weight-% H 2O2 solution were added. After vigorous stirring, 4.76 g (30 mmol) m-fluorobenzoyl chloride was slowly added. The mixture was stirred at <25 ℃ for 15 minutes. After that, the mixture was transferred to a separating funnel. 90 mL ice-cold 3.7M H 2SO4 were added. After phase separation, the aqueous layer was extracted 4 times with 20mL ice-cold dichloromethane. The organic layers were combined and dried over MgSO 4. The methylene chloride was removed under reduced pressure, using a rotary evaporator. The water bath had a temperature of 30 ℃ and the pressure was stepped down from 200 mbar to 0 mbar in 25 mbar steps. The desired product was obtained as a white solid. Yield 1.81 g (39%). The purity is 100 percent. The structure of the product was confirmed by 1H-NMR、13 C-NMR and FTIR spectra.
Synthesis example 2 Synthesis of 3, 5-difluoroperbenzoic acid (dFPBA)
36 ML DI water, 3.6 g NaOH, 0.15 g MgSO 4·7H2 O and 45 mL 1, 4-dioxane were mixed in a 250 mL glass beaker and cooled to 10-15 ℃. 9mL of a 30% active H 2O2 solution was added. After vigorous stirring, 5.3 g (30 mmol) 3, 5-difluorobenzoyl chloride was slowly added. The mixture was stirred at <25 ℃ for 15 minutes. After that, the mixture was transferred to a separating funnel. 90 mL ice-cold 3.7M H 2SO4 were added. After phase separation, the aqueous layer was extracted 4 times with 20mL ice-cold dichloromethane. The organic layers obtained from the extraction of the aqueous layer were combined and dried over MgSO 4. The methylene chloride was removed under reduced pressure at room temperature, using a rotary evaporator. The water bath had a temperature of 30 ℃ and the pressure was stepped down from 200 mbar to 0 mbar in 25 mbar steps. A white solid was obtained. Yield 0.97 g (19%). The purity is 100 percent. The structure of the above product was confirmed by 1H-NMR、13 C-NMR and FTIR spectra.
Synthesis example 3 catalyst solution IrCl 3·xH2 O in dried EtOH
0.1 G IrCl 3·xH2 O was placed under argon in a Schlenk flask. 10 mL dry EtOH was added. The mixture was stirred at 1200 rpm for four days. A clear green solution was obtained which was usable as catalyst for about 2 days.
Synthesis example 4 solid catalyst IrCl 3·xH2 O
The commercially available solid IrCl 3·xH2 O was used for the hydrosilylation reaction without any further pretreatment.
Synthesis example 5 catalyst solution H in dried EtOH 2IrCl6
1G H 2IrCl6 was dissolved in 10 mL dry EtOH. A black catalyst solution was obtained which was used as a catalyst for about two months.
Hydrosilylation reaction
EXAMPLE 1 general scheme for hydrosilylation Using catalyst solution
The reaction was carried out in a 50 mL Schlenk bottle with reflux condenser. Calculated amounts of peracid (expressed in "ppm" based on the total mass of starting materials triethoxysilane and allyl chloride) were placed in Schlenk bottles. After that, 33.5 g of a stock solution consisting of 10g of purified (over-concentrated) allyl chloride and 23.5 g TES (triethoxysilane) was added. Calculated amounts of catalyst solution (catalyst content expressed in "ppm" based on total mass of starting materials triethoxysilane and allyl chloride, where ppm means the amount of Ir metal contained in the catalyst compound) were added and the mixture was heated to 80 ℃ with stirring using a magnetic stirring bar at a stirring speed of 300 rpm.
EXAMPLE 2 general scheme for hydrosilylation Using solid catalyst
The reaction was carried out in a 50mL Schlenk bottle with reflux condenser. Calculated amount of solid catalyst and 2.35 g (calculated amount of 10 mol%) TES were placed in Schlenk flask. The Schlenk flask was heated to 80 ℃ and the mixture was stirred at 300 rpm. Separately, a mixture consisting of 10g allyl chloride (as is or over-concentrated), 21.15 g (calculated amount of 90 mol%) TES and calculated amount of peracid was prepared and placed in a dropping funnel. The mixture was fed into Schlenk bottles over 30 minutes. After the end of the feed, the reaction temperature was maintained at 80 ℃ for the indicated reaction time.
TABLE 1 results of hydrosilylation experiments 3-11 variation of IrCl3.xH2O-Ir concentration in EtOH solution with allyl chloride and Triethoxysilane (TES)
The data in table 1 show that moderate to good yields can be achieved at high Ir concentrations (100 ppm) in the absence of any accelerator or in the presence of hydroperoxides or dialkyl peroxides (not comparative examples 3-6 of the present invention). The addition of halogenated perbenzoic acid significantly improved the yield (example 7).
The presence of halogenated perbenzoic acid derivatives is necessary for high yields at low Ir concentrations (10 ppm and below) (examples 4, 9). mFPBA is the halogenated perbenzoic acid derivative (examples 10, 11) that provided the best results.
The data presented in table 1 show a synergistic effect between Ir and haloparabenic acid, as Ir catalyst is required for the reaction if a small amount of haloparabenic acid is present. At high Ir catalyst concentrations of 100 ppm, other peroxy compounds such as tBHP are not as effective as mCPBA. DtBP has an adverse effect on the yield of the target product (example 5 and example 6).
TABLE 2 results of hydrosilylation experiments 12-16, 9 and 10 IrCl3.xH2O in EtOH solution at a fixed ppm concentration of 10 ppm as a variation in catalyst-promoter concentration for the reaction between allyl chloride and triethoxysilane
TABLE 3 results of hydrosilylation experiments 17-23 solid IrCl3.xH2O was used in combination with over-concentrated/as-received allyl chloride for reaction with TES
TABLE 4 results of hydrosilylation experiments 24-29H 2IrCl6 in EtOH solution as catalyst for the reaction of allyl chloride and TES with allyl chloride either over-concentrated or as received
The data in table 2 show that the presence of a 2.5 to 20-fold excess of the promoter provides a significantly increased yield of the desired compound (as compared to example 4, examples 12, 9, 13, 14, 10, 15, 16).
The data in table 3 show that for as-received allyl chloride, the addition of haloperoxide was necessary to achieve high yields at reasonably low Ir concentrations (examples 21, 22). The use of peroxide ethers results in significantly lower yields (example 23) when compared to similar reactions using peroxycarboxylic acids of the inventive process as promoters. It can be concluded that the presence of halogenated perbenzoic acid increases the tolerance of as-received solid IrCl 3xH2 O to the presence of impurities in as-received raw materials at low Ir concentrations. The possibility of using both as-received allyl chloride and as-received solid catalyst at low Ir concentrations is a prerequisite for a robust and economically attractive large-scale process.
The data in table 4 show that at high Ir concentrations (100 ppm), the H 2IrCl6 solution gave medium yields on CPTES (example 24).
At low Ir concentrations (10 ppm and lower), a combination of H 2IrCl6 solution and halogenated perbenzoic acid such as mFPBA is necessary for high yields of CPTES (comparative examples 25 and 27).
The results of example 28 show that H 2IrCl6 is also suitable for processes based on catalyst solutions which are easy to prepare, low Ir concentrations and allyl chloride as such. Comparative example 29 shows that the yield using the H 2IrCl6 solution is only moderate, even at significantly higher catalyst concentrations, when compared to the reaction performed in the presence of halogenated perbenzoic acid.

Claims (15)

1. Process for the production of a compound of formula (I)
(R1)y(R2O)3-ySiCH2CHR3CR4R5X (I),
The process comprises reacting to produce a product of formula (I):
(a) An olefinic halide having the formula H 2C=CR3CR4R5 X;
(b) An alkoxysilane having the formula (R 1)y(R2O)3-y SiH;
(c) A catalytically effective amount of an iridium-containing catalyst, and
(D) A reaction-promoting effective amount of a peroxycarboxylic acid;
Wherein the method comprises the steps of
R 1 and R 2 are alkyl groups of 1 to 6 carbon atoms;
R 3 is alkyl of 1 to 6 carbon atoms or hydrogen;
r 4 is alkyl of 1 to 6 carbon atoms, hydrogen or halogen;
r 5 is hydrogen or alkyl of 1 to 6 carbon atoms;
X is halogen, and
Y is 0,1 or 2;
Wherein preferably the amount of iridium-containing catalyst (c) 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, based on the total weight of starting materials olefinic halide (a) and alkoxysilane (b).
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. A process according to claim 1 to 3, wherein the peroxycarboxylic acid (d) is selected from the group consisting of monohalogenated perbenzoic acid, dihalo perbenzoic acid, and trihalogenated, tetrahalogenated and pentahalogenated halogenated perbenzoic acids, preferably wherein the peroxycarboxylic acid (d) is selected from the group consisting of halogenated perbenzoic acids bearing at least one halogen substituent in the meta position of the peroxycarboxylic acid group.
5. A process according to any one of the preceding claims 1 to 4, wherein the peroxycarboxylic acid (d) is selected from the group 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, 2,3,4,5, 6-pentafluorobenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3, 5-difluoroperbenzoic acid, preferably the peroxycarboxylic acid (d) is selected from the group consisting of 3-chloroperbenzoic acid, 3-fluoropperbenzoic acid, and 3, 5-difluoroperbenzoic acid.
6. The process according to any one of claims 1 to 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, cyclic olefin complexes of iridium, amine complexes of iridium, phosphine complexes of iridium, CO complexes of iridium, and combinations thereof, or from the group consisting of IrCl 3,IrBr3,M2IrCl6, wherein M = H or an alkali metal, cyclic olefin complexes of iridium, such as Ir 2Cl2(COE)4, a Crabtree catalyst, [ Ir (μ 2-Cl)(COD)]2, and Ir 2(OCH3)2(COD)2, wherein cole is cyclooctene and COD is 1, 5-cyclooctadiene, pentamethyl cyclopentadienyl iridium dichloride dimer [ Cp x IrCl 2]2; (pi-arene) iridium complexes, and combinations thereof.
7. The process according to any one of claims 1-6, wherein the ratio of iridium-containing catalyst (c) to peroxycarboxylic acid (d) in [ ppm to ppm ] is in the range of from about 1:1 to about 1:40, preferably in the range of from about 1:1.5 to about 1:25, more preferably in the range of from about 1:2 to about 1:20, most preferably in the range of from about 1:2 to about 1:10, each based on the total weight of starting material olefinic halide (a) and alkoxysilane (b).
8. The process of any of claims 1-7 wherein the olefinic halide (a) is allyl chloride, the alkoxysilane (b) is triethoxysilane, the iridium containing catalyst (c) is IrCl 3 or H 2IrCl6, and the peroxycarboxylic acid (d) is 3-chloroperbenzoic acid, 3-fluoropperbenzoic acid, or 3, 5-difluoroperbenzoic acid.
9. A composition comprising:
one or more compounds of 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 the method comprises the steps of
R 1 and R 2 are alkyl groups of 1 to 6 carbon atoms;
R 3 is alkyl of 1 to 6 carbon atoms or hydrogen;
r 4 is alkyl of 1 to 6 carbon atoms, hydrogen or halogen;
r 5 is hydrogen or alkyl of 1 to 6 carbon atoms;
X is halogen, and
Y is 0,1 or 2,
Wherein preferably the amount of iridium-containing compound 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, based on the total weight of the compound of formula (I).
10. The composition according to claim 9, wherein the compound of formula (I) is chloropropyl triethoxysilane.
11. The composition according to claim 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, dihalo perbenzoic acids, trihalogenated, tetrahalogenated and pentahalogenated halogenated perbenzoic acids, monohalogenated benzoic acids, dihalobenzoic acids, and trihalogenated, tetrahalogenated and pentahalogenated benzoic acids;
preferably, the one or more compounds selected from i) peroxycarboxylic acids and/or ii) carboxylic acids are selected from the group consisting of halogenated perbenzoic acids bearing at least one halogen substituent at the meta-position of the peroxycarboxyl group, and halogenated benzoic acids bearing at least one halogen substituent at the meta-position of the carboxyl group.
12. The composition according to any of claims 9 to 11, wherein the one or more compounds selected from i) peroxycarboxylic acid and/or ii) carboxylic acid are selected from the group 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, 2,3,4,5, 6-pentafluorobenzoic acid, 3-chloroperbenzoic acid, 3-fluoroperbenzoic acid, and 3, 5-difluoroperbenzoic acid, and from the group consisting of benzoic acid 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, 5-pentafluorobenzoic acid, 3-difluorobenzoic 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-fluoropperbenzoic acid, and 3, 5-difluoroperbenzoic acid, and from 3-chlorobenzoic acid, 3-fluorobenzoic acid, and 3, 5-difluorobenzoic acid.
13. A composition according to any one of claims 9 to 12, wherein the iridium-containing compound is selected from nano-sized iridium particles and micro-sized iridium particles.
14. Use of a composition according to any one of claims 9-13 for the preparation of an amino organosilane, a mercapto organosilane, or a methacryloxy organosilane, wherein preferably the composition comprises chloropropyl triethoxysilane.
15. The use of a composition according to claim 14, wherein the composition is used for the preparation of polysulfane-containing organoalkoxysilanes,
And wherein preferably the polysulfane-containing organoalkoxysilane is used for making silica-filled tires.
CN202380085978.XA 2022-12-15 2023-12-14 Peracid promoters in the iridium-catalyzed hydrosilylation of halogenated alkylorganosilanes Pending CN120303278A (en)

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