Depolymerization of silicones to give organochlorosilanes.

Abstract

The present application relates to a method for producing organochlorosilanes CS by reacting at least one silicone S with a metal chloride or metalloid MC in the presence of at least one metal salt catalyst MS, wherein the metal chloride or metalloid MC is different from the metal salt MS.

Description

[Technical field]

[0001] The present invention generally relates to the recycling of silicone polymers. More specifically, the process of the present invention relates to the depolymerization of silicone polymers to obtain organochlorosilanes. Advantageously, the process allows the recycling of used or unused silicone polymers for the production of organochlorosilanes that can then be used in polymerization reactions. [Background technology]

[0002] Recycling of industrial products and used silicone products is a current issue. Silicone recycling involves the reduction of gases emitted from the silicone industry (CO, CO 2 ) by 75% and silicone waste by 65%.

[0003] The depolymerization of organopolysiloxanes to fluorosilanes has already been known and described. The reaction is thermodynamically favorable because the Si-F bond is very strong (about 135 kcal / mol) compared to the Si-O bond of organopolysiloxanes (about 110 kcal / mol). However, these methods have certain drawbacks, in particular the emission of volatile products and the cost of the fluorine source.

[0004] On the other hand, since the Si-Cl bond is weak (especially 90 kcal / mol), depolymerization of organopolysiloxanes to organochlorosilanes is not favored.

[0005] Enthaler et al. (J. Appl. Polym. Sci. 2015) describe the depolymerization of polydimethylsiloxanes to produce chlorosilanes. The catalyst used is an iron salt. However, this process requires a large amount of catalyst (7.5% by weight of catalyst based on the weight of organopolysiloxane), a corrosive chlorine source of the acyl chloride type, and high temperatures of about 170-190 °C.

[0006] It would therefore be advantageous to provide an alternative process for the depolymerization of silicones to organochlorosilanes. It would be of particular interest to provide a catalyst system that allows this depolymerization to be carried out at lower temperatures, limits the amount of catalyst used, and allows the use of other chloride sources. [Prior art documents] [Non-patent literature]

[0007] [Non-Patent Document 1] Enthaler et al., J.Appl.Polym.Sci.2015 Summary of the Invention [Problem to be solved by the invention]

[0008] Therefore, one objective of the present patent application is to propose a method for depolymerizing silicones in an efficient manner to obtain organochlorosilanes in good yields.

[0009] Another object of the present patent application is to provide a catalyst system for carrying out this process.

[0010] Another objective of the present patent application is to propose a simple and non-hazardous catalytic system suitable for the industrialization of this process.

[0011] Other objects will become apparent from the following description of the invention. [Means for solving the problem]

[0012] These objects are achieved by the present patent application, which relates to a process for preparing organochlorosilanes CS by reacting at least one silicone S with a metal or metalloid chloride MC in the presence of at least one metal salt catalyst MS, the metal or metalloid chloride MC being different from the metal salt MS. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Silicones, known as organopolysiloxanes, are polymeric materials that contain silicon and oxygen atoms alternating with a variety of silicon-bonded organic groups.

[0014] In the present invention, the term "silicone" or "silicone product" or "silicone polymer" or "organopolysiloxane" refers to a polymer containing a siloxane (Si-O-Si) backbone that contains silicon and oxygen atoms alternating with various silicon-bonded organic groups. These silicone polymers can be liquid or solid, depending on the molecular weight and the degree of crosslinking.

[0015] The silicones S of the invention may be of any type, for example linear organopolysiloxanes O, such as oils or gums, or branched organopolysiloxanes O, such as resins.

[0016] The organopolysiloxane O may in particular be an oil or a gum and preferably has a dynamic viscosity of 50 to 600000 mPa·s at 25° C. or a consistency of 200 to 2000, expressed in tenths of a millimeter at 25° C. All viscosities mentioned in this specification correspond to dynamic viscosity values ​​at 25° C. known as “Newtons”, i.e. dynamic viscosities measured in a manner known per se using a Brookfield viscometer at a shear rate gradient sufficiently low so that the measured viscosity is independent of the rate gradient.

[0017] The term "gum" is conventionally used for organopolysiloxane compounds having a viscosity greater than about 600,000 mPa.s (which corresponds to a molecular weight greater than 260,000 g / mol).

[0018] These organopolysiloxanes O may contain one or more functional groups such as: ·OH; ·H; alkenyl, in particular alkenyl containing 2 to 6 carbon atoms, preferably vinyl; ·O-Alk (where Alk represents an alkyl group containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably methyl); (O-Alk) x (wherein Alk represents an alkyl group containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably methyl, and x represents an integer from 2 to 200); A linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, substituted with at least one fluorine atom, for example 1 to 10 fluorine atoms, such as (C1-C5)alkyl-CF 3 (wherein alkyl is linear or branched); Amine groups, especially (Alk)-NH 2 or (Alk)-NH-(Alk)-NH 2 (wherein Alk represents an alkyl group containing 1 to 5 carbon atoms): Cyclic amines, e.g. -(CH 2 ) z -O-piperidine, where z is an integer from 1 to 5, preferably 3, which piperidine may be substituted with one or more alkyl groups, in particular having 1 to 3 carbon atoms, preferably methyl, preferably the substituted piperidine is the group: [ka] ).

[0019] Preferably, the functional units are selected from: ·OH; ·H; alkenyl, in particular alkenyl containing 2 to 6 carbon atoms, preferably vinyl; A linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, substituted with at least one fluorine atom, for example 1 to 10 fluorine atoms, such as (C1-C5)alkyl-CF 3(wherein alkyl is linear or branched).

[0020] Preferably, the organopolysiloxane O, as defined above, may contain one or more functional groups such as H, OH, alkenyl (preferably vinyl), aryl or cyclic amine.

[0021] The organopolysiloxane O of the present invention may be partially crosslinked.

[0022] The organopolysiloxanes O of the invention may in particular be used organopolysiloxanes, for example used as heat transfer fluids, which it is desired to recycle, and the process of the invention makes it possible to produce organochlorosilanes which can be used directly in industrial processes. When using used organopolysiloxanes O, they may therefore contain other elements such as additives, pigments, etc. The inventors have shown that the presence of these other elements does not prevent the depolymerization reaction and the formation of organochlorosilanes CS.

[0023] According to one embodiment of the present invention, the organopolysiloxane O of the present invention comprises: at least 5, preferably at least 10, of formula R c SiO (4-C) / 2 Siloxyl units of the formula: R may be the same or different, an alkyl group containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably methyl; an aryl group containing 6 to 10 carbon atoms, preferably phenyl; and c=0, 1, 2 or 3); and Optionally, the formula R 1 d R e SiO (4-d-e) / 2 One or more units of (In the formula, R is as defined above, R 1 may be the same or different, · alkenyl groups containing 2 to 6 carbon atoms, preferably vinyl; · Hydroxyl group (OH); The group (O-Alk), where Alk is an alkyl group containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably OCH 3 Or O.C. 2 H 5 represents); ·Group (O-Alk) x (wherein Alk represents an alkyl group containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably methyl, and x represents an integer from 2 to 200); A linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and substituted with at least one fluorine atom, for example 1 to 10 fluorine atoms, such as (C1-C5)alkyl-CF 3 (alkyl is straight or branched); (Alk)-NH 2 and (Alk)-NH-(Alk)-NH 2 an amine group selected from the group consisting of: Cyclic amines, e.g. -(CH 2 ) z -O-piperidine, where z represents an integer from 1 to 5, preferably 3, which piperidine may be substituted, in particular by one or more alkyl groups containing from 1 to 3 carbon atoms, preferably methyl; preferably the substituted piperidine is selected from the group [ka] (And) ·hydrogen represents; d=1, 2 or 3, preferably d=1 or 2, more preferably d=1; e=0, 1 or 2; and the total d+e=1, 2 or 3).

[0024] In the above formula, when there are multiple R or multiple R 1 It is understood that when present, they may be the same or different from one another.

[0025] Preferably, in the above formula, R 1 may be the same or different and represent: · alkenyl groups containing 2 to 6 carbon atoms, preferably vinyl; · Hydroxyl group (OH); A linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and substituted with at least one fluorine atom, for example 1 to 10 fluorine atoms, such as (C1-C5)alkyl-CF 3 (alkyl is straight or branched); ·hydrogen.

[0026] In the present invention "M" siloxyl units have the formula Y 3 SiO 1 / 2 represents a siloxyl unit, "D" siloxyl units have the formula Y 2 SiO 2 / 2 represents a siloxyl unit, "T" siloxyl units have the formula YSiO 3 / 2 represents a siloxyl unit, "Q" siloxyl units have the formula SiO 4 / 2 represents a siloxyl unit, and the symbol Y is R or R 1 It is.

[0027] The organopolysiloxane O may optionally contain T and Q units.

[0028] According to a preferential embodiment, the organopolysiloxanes O of the invention are preferably chosen from compounds of formula (I): R 1 a R (3-a) SiO-(SiR 2 O) n -(SiR 1 RO)m -SiR 1 a R (3-a) (I) (In the formula, R may be the same or different, an alkyl group containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, even more preferably 1 to 5 carbon atoms, more preferably methyl; an aryl group containing 6 to 10 carbon atoms, preferably phenyl; R 1 may be the same or different; · alkenyl groups containing 2 to 6 carbon atoms, preferably vinyl; · Hydroxyl group (OH); The group (O-Alk), where Alk is an alkyl group containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably OCH 3 Or O.C. 2 H 5 represents); ·Group (O-Alk) x (wherein Alk represents an alkyl group containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably methyl, and x represents an integer from 2 to 200); A linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and substituted with at least one fluorine atom, for example 1 to 10 fluorine atoms, such as (C1-C5)alkyl-CF 3 (alkyl is straight or branched); (Alk)-NH 2 and (Alk)-NH-(Alk)-NH 2 an amine group selected from the group consisting of: Cyclic amines, e.g. -(CH 2 ) z-O-piperidine, where z represents an integer from 1 to 5, preferably 3, which piperidine may be substituted, in particular by one or more alkyl groups containing from 1 to 3 carbon atoms, preferably methyl; preferably the substituted piperidine is selected from the group [ka] (And) ·hydrogen represents; a is an integer and represents 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1; n represents an integer of 10 to 10,000, preferably 10 to 5,000, more preferably 50 to 5,000, further preferably 60 to 5,000, for example, an integer of 70 to 1,000; m represents an integer of 0 to 100, preferably 0 to 50, more preferably 0 to 30, and is preferably m=0.

[0029] Particularly preferably, the organopolysiloxanes O of the invention are compounds of formula (I) in which R 1 may be the same or different, · alkenyl groups containing 2 to 6 carbon atoms, preferably vinyl; · Hydroxyl group (OH); A linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and substituted with at least one fluorine atom, for example 1 to 10 fluorine atoms, such as (C1-C5)alkyl-CF 3 (alkyl is straight or branched); Represents hydrogen.

[0030] Particularly preferably, the organopolysiloxanes O of the invention are compounds of formula (I) in which R 1 may be the same or different, CH 3 , Vinyl, H, (C1-C5) alkyl-CF 3 or OH.

[0031] Particularly preferably, the organopolysiloxanes O of the invention are compounds of formula (I) in which R may be the same or different, CH 3 or phenyl, preferably CH 3 represents; R 1 may be the same or different, · alkenyl groups containing 2 to 6 carbon atoms, preferably vinyl; · Hydroxyl group (OH); A linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and substituted with at least one fluorine atom, for example 1 to 10 fluorine atoms, such as (C1-C5)alkyl-CF 3 (alkyl is straight or branched); Represents hydrogen.

[0032] Particularly preferably, the organopolysiloxanes O of the invention are compounds of formula (I) in which R may be the same or different, CH 3 or phenyl, preferably CH 3 represents; R 1 may be the same or different, CH 3 , Vinyl, H, (C1-C5) alkyl-CF 3 or OH.

[0033] The silicones S of the present invention may also be crosslinked silicone materials, such as gels or elastomers, which can be obtained by polycondensation, radical polymerization, polyaddition by heat or UV irradiation, etc.

[0034] Silicone products have many applications, for example in food applications (molds, etc.), medical applications and the pharmaceutical sector, e.g. baby bottle nipples, catheters, implants, medical tubing, etc. In technical industrial applications silicones are often used as seals and membranes, in the automotive sector they are used as hoses, cable jackets, insulation and damping materials.

[0035] Silicone elastomers are crosslinked silicone materials that contain fillers, such as silica, to obtain good mechanical properties.

[0036] By varying the silicone oil, fillers, additives, and even crosslinking methods, silicone elastomers can exhibit a wide variety of properties and colors.

[0037] Silicone elastomers can be divided into three main groups well known to those skilled in the art: High temperature vulcanization (HTV) or heat cured rubber (HCR) elastomers are silicone elastomers obtained from very viscous silicone compositions containing silicone gums and fillers. They are generally vulcanized at high temperatures, between 140°C and 200°C. Crosslinking is obtained by radical-mediated, peroxide-catalyzed or platinum compound-catalyzed addition reactions.

[0038] Liquid silicone rubber (LSR) is a silicone elastomer derived from a composition containing silicone oil and fillers. Crosslinking occurs by addition reaction at temperatures similar to EVC, but crosslinking generally occurs more rapidly by crosslinking the two components mixed just before the start of crosslinking.

[0039] The third group are silicones obtained by crosslinking silicone compositions at room temperature from silicone oils and fillers crosslinked by polycondensation or polyaddition reactions. These elastomers are known under the name "room temperature vulcanizing" (RTV) silicone elastomers. These compositions are available in one-part and two-part systems.

[0040] In the present method, the term "silicone S" also refers to silicone-based materials, for example materials containing at least 0.1% by weight of silicone based on the total weight of the silicone-based material. Silicone-based materials may contain up to 100% by weight of silicone, preferably up to 99.9% by weight of silicone based on the total weight of the silicone-based material. These silicone-based materials may also contain additives and fillers, such as dyes, silica, calcium carbonate, calcium oxide, celite, quartz, titanium oxide, cerium hydroxide, magnesium oxide, mica, etc.

[0041] In the process of the invention, the metal or metalloid chlorides MC include in particular metalloid chlorides, transition metal chlorides and alkaline earth metal chlorides, either alone or in mixtures.

[0042] Preferably, the metal or metalloid chloride MC has the formula M'Cl z The metal chlorides are selected from: In the formula, M' represents B, Al, Ti, Zr, Mg, Zn, Ca, Sb, Ge, Si, or Cu, preferably B, Al, Ti, Zr, Mg, Ca, Zn, preferably B, Al, Mg, Zn, Ca, preferably B, Al; z represents an integer according to the valence of the metal M′; for example, z represents 3, 4, or 5.

[0043] The metal or metalloid chloride MC is preferably selected from the group consisting of BCl, ... 3 , AlCl 3 , TiCl 4 , ZrCl 4 , MgCl 2 , ZnCl 2 , CuCl 2 , CaCl 2 , SiCl 4 , GeCl 4 and SbCl 5 and preferably BCl 3 , AlCl 3 , MgCl 2 , ZnCl 2 and CaCl 2, more preferably AlCl 3 and BCl 3 , preferably BCl 3 is selected from.

[0044] The metal or metalloid chloride MC may be in solution in a solvent. This is particularly advantageous in the case of solid or gaseous metal or metalloid chlorides, making these chlorides soluble in the reaction medium. The solvent is in particular an organic solvent of the alkane, haloalkane or aromatic hydrocarbon type. Preferably, the solvent is chosen from dichloromethane, n-hexane, n-heptane, toluene, xylene, mesitylene.

[0045] Preferably, the amount of metal or metalloid chloride MC used in the process of the present invention is at least 50 mol %, preferably 50-800 mol %, preferably 50-300 mol %, for example 50-200 mol %, relative to the number of moles of Si-O.

[0046] In the present invention, the term "moles of Si-O" means the moles of Si-O bonds in the silicone S.

[0047] When the starting silicone S has an unknown formula, especially when it is a compounded commercial product, it is possible to estimate the number of moles of Si-O.Specifically, when it is a compounded product, a person skilled in the art knows that the amount of filler is 20% to 40% by weight, so he estimates the amount of filler to be an average of 30% by weight, which gives a silicone of 70% by weight, and the number of moles of Si-O bond can be calculated from the average molar mass of the repeating unit.

[0048] The metal salt MS used as catalyst in the process of the invention is preferably selected from salts of elements of group 13 of the periodic table and transition metals. The metal salt MS is preferably a metal salt containing at least one halogen atom, preferably Cl, Br, I, F, such as the salts of the formula MX m are metal halides of: In the formula, M represents Ga, Ge, Al, In or Fe, preferably Ga, Al or Fe; X is Cl, Br, I, F, OTf, BF 4 or SbF 6 represents m represents an integer according to the metal M, and preferably m represents 2, 3 or 4.

[0049] Preferably, the metal salt MS is GaCl 3 , FeCl 2 , FeCl 3 , InCl 3 , AlCl 3 and GeCl 4 Preferably, FeCl 3 , FeCl 2 , AlCl 3 , GaCl 3 and InCl 3 is selected from.

[0050] Depending on the nature of the metal salt, it may also be dissolved in a solvent, in particular an organic solvent of the alkane, haloalkane or aromatic hydrocarbon type, preferably chosen from dichloromethane, n-hexane, n-heptane, toluene, xylene, mesitylene.

[0051] Preferably, the amount of metal salt MS used in the method of the invention is between 0.01% and 10% by weight, preferably between 0.1% and 5% by weight, for example between 0.1% and 2% by weight, relative to the weight of silicone S.

[0052] Preferably, the amount of metal salt MS used in the process of the present invention is 0.01 mol % to 10 mol %, preferably 0.01 mol % to 5 mol %, for example 0.1 mol % to 2 mol %, relative to the number of moles of Si-O.

[0053] Preferably, the Cl / Si—O molar ratio (the amount of chlorine is from the metal or metalloid chloride MC and the number of moles of Si—O corresponds to the number of moles of Si—O bonds in the silicone S) is between 1 and 3, preferably between 2 and 3, for example between 2 and 2.5, for example 2.

[0054] Advantageously and preferably, the reaction is carried out at a temperature between 0 and 200°C, preferably between 0 and 150°C, more preferably between 20 and 130°C and more preferentially between 30 and 110°C.

[0055] The reaction time is from a few minutes to a few hours.

[0056] A person skilled in the art will know how to adapt the reaction temperature and time depending on the reagents and reactor used.

[0057] The process of the invention advantageously results in a mass yield of organochlorosilanes CS of at least 80%, preferably at least 90%, more preferably at least 95%.

[0058] In the present invention, the term "organochlorosilane" refers to a compound of the following formula (A), (B) or (C): R 2 SiCl 2 (A) R 3 SiCl(B) RSiCl 3 (C) where R, which may be the same or different, is selected from: ·H; linear or branched alkyl containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably methyl; aryl containing 6 to 10 carbon atoms, preferably phenyl; ·OH; alkenyl, especially containing 2 to 6 carbon atoms, preferably vinyl; A linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and substituted with at least one fluorine atom, for example 1 to 10 fluorine atoms, such as (C1-C5)alkyl-CF 3 (alkyl is linear or branched); ·O-Alk (where Alk represents an alkyl group containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably methyl); (O-Alk) x (wherein Alk represents an alkyl group containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably methyl, and x represents an integer from 2 to 200); Amine groups, especially (Alk)-NH 2 or (Alk)-NH-(Alk)-NH 2 (wherein Alk represents an alkyl group containing 1 to 5 carbon atoms); Cyclic amines, e.g. -(CH 2 ) z -O-piperidine, where z represents an integer from 1 to 5, preferably 3, which piperidine may be substituted, in particular with one or more alkyl groups containing from 1 to 3 carbon atoms, preferably methyl, the substituted piperidine being the group: [ka] ), Preferably, the organochlorosilanes of the present invention contain no more than one hydrogen atom.

[0059] Preferably, in formulae (A), (B) and (C), R, which may be the same or different, is selected from: ·H; linear or branched alkyl containing 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, preferably methyl; aryl containing 6 to 10 carbon atoms, preferably phenyl; ·OH; alkenyl, especially containing 2 to 6 carbon atoms, preferably vinyl; A linear or branched alkyl group containing 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and substituted with at least one fluorine atom, for example 1 to 10 fluorine atoms, such as (C1-C5)alkyl-CF 3 (alkyl is linear or branched); Preferably, the organochlorosilanes of the present invention contain no more than one hydrogen atom.

[0060] Preferably, the preferred organochlorosilanes of the present invention are of formula (I) or (II).

[0061] Without being limited by any theory, · The organopolysiloxane of formula (I) is derived from the D units of the silicone S, and therefore the R groups of formula (I) depend on the D units of the silicone S; The organopolysiloxane of formula (II) is derived from the M units of the silicone S, and therefore the R groups of formula (II) depend on the M units of the silicone S; The organopolysiloxane of formula (III) is derived from the T units of the silicone S, and therefore the R group of formula (III) depends on the T units of the silicone S.

[0062] Of particular advantage, the organochlorosilanes obtained by the process of the present invention can be used directly in other industrial processes as a source of starting material which can then be hydrolyzed and condensed to produce novel oils, resins or gums.

[0063] The present patent application also relates to the use of the organochlorosilanes obtained via the process of the invention for the manufacture of silicones, for example for the manufacture of silicone oils, resins or gums.

[0064] The present patent application also relates to a method for the preparation of silicones, in particular oils, resins or gums, comprising the following steps: (1) Carrying out the organochlorosilane production method of the present invention; (2) Producing silicones, in particular oils, resins or gums, from the organochlorosilanes obtained in step (1).

[0065] Step (2) can in particular be carried out by condensation hydrolysis.

[0066] The present patent application will now be described with reference to examples. EXAMPLES

[0067] Silicones used in the examples : In the following, Me = methyl, Vi = vinyl. Silicone S1: [ka] n=70, viscosity 100mPa.s Silicone S2: [ka] n=180, viscosity 1000mPa.s Silicone S3: [ka] n=70, viscosity 100mPa.s Silicone S4: [ka] n=278, viscosity 1500mPa.s Silicone S5 [ka] n=476, viscosity 10000mPa.s Silicone S6: [ka] n=46, viscosity 100mPa.s Silicone S7: [ka] n=656, viscosity 14000mPa.s Silicone S8: [ka] n=40–50, m=10–15 Silicone S9: [ka] n=800~900, m=40~120, viscosity 60000mPa.s Silicone S10: [ka] Silicone S11: Silicone gum [ka] Mn0.6~100×10 6 g / mol Silicone S12: Silicone nipple pads (commercial product, ingredients unknown) Silicone S13: Silicone cake mold (commercial product, ingredients unknown) Silicone S14: Silicone sheet (commercially available, composition unknown) Silicone S15: Silicone tube (commercially available, composition unknown) Silicone S16: EVC A Silicone S17:EVC B Silicone S18: RTV1 Silicone S19:RTV2 Silicone S20: Fluorosilicone oil (Mn=14000) (CAS63148-56-1) [ka]

[0068] Example 1: General batch protocol Silicone S and metal chloride MC are placed in a round-bottom flask (10 mL). Metal salt MS or metal salt solution is added and the reaction is heated for 30 minutes (temperature 40° C.). The reaction is cooled to room temperature (about 25° C.) and mesitylene (240 mg) is introduced (mesitylene is an internal standard substance for detecting the amount of organochlorosilane in the target product). A sample is taken. 1 H NMR and 29 Analyze by Si NMR. Measure the yield in moles of the compound of formula (I) and the compound of formula (II) relative to the moles of the D unit and the M unit of the silicone S, respectively.

[0069] Example 2: Effect of catalyst on the process of the present invention The protocol of Example 1 was repeated for silicone S1 (300 mg, 4 mmol) 2 SiO units) and as metal chlorides, 1M BCl in dichloromethane 3 (3mL, 9mmol Cl - , 350 mg BCl 3 The metal salts (MS), temperatures and reaction times are shown in Table 1 below.

[0070] [Table 1] The process of the present invention can be carried out with a variety of metal salts and gives good yields.

[0071] Example 3: Effect of Chlorine Source on the Process of the Invention The protocol of Example 1 was repeated for silicone S1 (300 mg, 4 mmol SiMe 2 O units) and GaCl as metal salts 3 (4 mg, 0.5 mol % relative to the number of moles of Si-O). The metal chlorides, temperatures and reaction times are given in Table 2 below.

[0072] [Table 2]

[0073] The process of the present invention can be carried out with different chlorine sources and still give good yields.

[0074] Example 4: Effect of Silicones on the Method of the Invention The protocol of Example 1 was repeated for various silicones and metal salts, such as GaCl, as shown in Table 3 below. 3 (0.5 mol%, 4 mg), BCl as metal chloride 3 is used at a concentration of 1M in toluene or dichloromethane solvent (3 mL, except for S10: 6 ml). The method is carried out at 40° C. The silicones, temperatures and reaction times are given in Table 3 below.

[0075] [Table 3]

[0076] The results in Table 3 show that the method of the present invention is versatile and can be used with all types of silicone, including silicone mixtures and filled silicones, as well as used silicones.

Claims

1. A process for producing organochlorosilanes CS by reacting at least one silicone S with a metal or metalloid chloride MC in the presence of at least one metal salt catalyst MS, said metal or metalloid chloride MC being different from said metal salt MS.

2. 2. The method according to claim 1, wherein the metal or metalloid chloride MC is selected, alone or in admixture, from metalloid chlorides, transition metal chlorides and alkaline earth metal chlorides.

3. The metal or metalloid chloride MC has the formula M'Cl z The method according to claim 1 or 2, wherein the metal chloride is selected from the group consisting of During the ceremony, M' represents B, Al, Ti, Zr, Mg, Zn, Ca, Sb, Ge, Si, or Cu, preferably B, Al, Ti, Zr, Mg, Ca, Zn, preferably B, Al, Mg, Zn, Ca, preferably B, Al; z represents an integer according to the valence of the metal M′; for example, z represents 3, 4, or 5.

4. The metal or metalloid chloride MC is preferably BCl 3 , AlCl 3 , TiCl 4 , ZrCl 4 , MgCl 2 , ZnCl 2 , CuCl 2 , CaCl 2 , GeCl 4 , SiCl 4 and SbCl 5 are selected from, either alone or in mixture, preferably BCl 3 , AlCl 3 , MgCl 2 , ZnCl 2 and CaCl 2 and more preferentially selected from AlCl 3 and BCl 3 Preferably, BCl 3 The method according to any one of claims 1 to 3, wherein the

5. The metal salt has the formula: m The method according to any one of claims 1 to 4, wherein the compound is selected from the group consisting of: During the ceremony, M represents Ga, Ge, Al, In or Fe, preferably Ga, Al or Fe; X is Cl, Br, I, F, OTf, BF 4 or SbF 6 represents m represents an integer according to the metal M, and preferably m represents 2, 3 or 4.

6. The metal salt is GaCl 3 , FeCl 2 , FeCl 3 , InCl 3 , AlCl 3 and GeCl 4 is selected from, preferably FeCl 3 , FeCl 2 , AlCl 3 , GaCl 3 and InCl 3 The method according to any one of claims 1 to 5, wherein the compound is selected from the group consisting of

7. 7. The process according to any one of claims 1 to 6, wherein the amount of metal salt MS used in the process is between 0.01 mol % and 10 mol %, preferably between 0.01 mol % and 5 mol %, for example between 0.1 mol % and 2 mol %, relative to the number of moles of Si-O.

8. A process according to any one of claims 1 to 7, wherein the reaction is carried out at a temperature between 0 and 200°C, preferably between 0 and 150°C, preferably between 20 and 130°C, more preferentially between 30 and 110°C.

9. A process according to any one of the preceding claims, wherein the Cl / Si-O molar ratio is between 1 and 3, preferably between 2 and 3, such as between 2 and 2.5, for example 2.

10. 10. The process according to any one of claims 1 to 9, wherein the amount of metal or metalloid chloride MC used in the process is at least 50 mol %, preferably between 50 mol % and 800 mol %, preferably between 50 mol % and 300 mol %, for example between 50 mol % and 200 mol %, relative to the number of moles of Si-O.

11. 1. A process for producing silicones, in particular silicone oils, resins or gums, comprising the steps of: (1) carrying out the process for producing organochlorosilanes according to any one of claims 1 to 10; (2) Producing silicones, particularly silicone oils and silicone resins or silicone gums, from the organochlorosilanes obtained in step (1).

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