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Title:
METHOD FOR PREPARING A HALOSILANE
Document Type and Number:
WIPO Patent Application WO/2014/149215
Kind Code:
A1
Abstract:
A method for preparing a reaction product includes separate and consecutive step (1) and step (2), where: step (1) is contacting, at a temperature from 200 °C to 1400 °C, an ingredient including a silane of formula HaRbSiX(4-a-b), where subscript a is 0 to 4, subscript b is 0 or 1, a quantity (a + b) ≤ 4, each R is independently a monovalent organic group, and each X is independently a halogen atom, with the proviso that when the quantity (a + b) < 4, then the ingredient in step (1) further comprises H2; with a copper catalyst; thereby forming a reactant; and step (2) is contacting the reactant with an organohalide at a temperature from 100 °C to 600 °C; thereby forming the reaction product and a spent reactant. The reaction product is distinct from the silane used in step (1), and the reaction product includes a halosilane of formula R2S1X2, where each R is independently a monovalent organic group, and each X is independently a halogen atom.

Inventors:
COPPERNOLL AARON (US)
GAVE MATTHEW (US)
HORNER CATHARINE (US)
JANMANCHI KRISHNA (US)
KATSOULIS DIMITRIS (US)
PUSHKAREV VLADIMIR (US)
Application Number:
US2014/015182
Publication Date:
September 25, 2014
Filing Date:
February 07, 2014
Export Citation:
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Assignee:
DOW CORNING (US)
International Classes:
C07F7/12; C01B33/107; C08G77/04; C08L83/04
Domestic Patent References:
WO2011149593A12011-12-01
WO2014028417A12014-02-20
Foreign References:
US4973725A1990-11-27
Other References:
None
Attorney, Agent or Firm:
BROWN, Catherine, U. (Dow Corning Corporation2200 West Salzburg Roa, Midland MI, US)
Download PDF:
Claims:
CLAIMS:

1 . A method for preparing a reaction product comprising a halosilane, where the method comprises separate and consecutive step (1 ) and step (2), where:

step (1 ) is contacting, at a temperature from 200 °C to 1400 °C, an ingredient comprising a silane of formula HaRbSiX(4_a_b), where subscript a is 0 to 4, subscript b is 0 or 1 , a quantity (a + b) < 4, each R is independently a monovalent organic group, and each X is independently a halogen atom, with the proviso that when the quantity (a + b) < 4, then the ingredient in step (1 ) further comprises H2; with a copper catalyst, where the copper catalyst is a physical mixture of metallic copper and a diluent; thereby forming a reactant; and

step (2) is contacting the reactant with an organohalide at a temperature from 100 °C to 600 °C; thereby forming the reaction product and a spent reactant; and

where the method optionally further comprises separate and consecutive steps (3) and (4), where steps (3) and (4) are performed after step (2), and where

step (3) is repeating step (1 ) using an additional ingredient comprising an additional silane of formula HaRbSiX(4_a_b), and recycling the spent reactant to re-form the reactant, and

step (4) is repeating step (2) using the reactant re-formed in step (3) and additional organohalide; and

where the method optionally further comprises step (5), where step (5) is repeating steps (3) and (4) at least one time; and

where the method optionally further comprises step (6), where step (6) is recovering the halosilane.

2. The method of claim 1 , where the diluent is selected from the group consisting of carbon, metallic silicon, silicon carbide, a metal oxide, or a mixed metal oxide.

3. The method of claim 2, where the diluent is metallic silicon or silica.

4. The method of any one of claims 1 -3, where the metallic copper and the diluent are present in relative molar amounts metallic copper : diluent of 3:1 to 2:1 .

5. The method of any one of claims 1 -4, further comprising purging and/or treating:

purging and/or treating the copper catalyst, before contacting the copper catalyst with the ingredient comprising the silane in step (1 ) ; and/or purging and/or treating the reactant, before contacting the reactant with the organohalide in step (2); and/or

purging and/or treating, the spent reactant before contacting the spent reactant with the additional ingredient in step (3); and/or

purging and/or treating the reactant re-formed in step (3), before the contacting the reactant re-formed in step (3) with the additional organohalide in step (4); and/or

before step (5), purging and/or treating an additional spent reactant produced in step (4). 6. The method of any one of claims 1 -5, where in step (1 ), the H2 is present, and a mole ratio of the H2 to the silane ranges from 20:1 to 1 :1 .

7. The method of any one of claims 1 -6, where the silane comprises one or more of a tetrahalosilane of formula S1X4, a trihalosilane of formula HS1X3, a dihalosilane of formula H2SiX2, a monohalosilane of formula H3S1X, silane of formula S1H4, or a combination of two or more of S1X4, HS1X3, H2SiX2, H3S1X, and S1H4.

8. The method of any one of claims 1 -7, where a = 0, b = 0, and the silane is a tetrahalosilane of formula S1X4.

9. The method of any one of claims 1 -8, where the organohalide has formula RX, where R is alkyl or aryl, and X is CI.

10. The method of any one of claims 1 -9, further comprising recovering the reaction product.

11 . The method of any one of claims 1 -10, where the reaction product comprises a halosilane of formula R(4-c)SiXc, where subscript c is 0, 1 , 2, or 3. 12. The method of any one of claims 1 -1 1 , where the reaction product comprises a halosilane of formula R2S1X2.

13. A halosilane prepared by the method of any one of the preceding claims.

14. A method comprising using the halosilane of claim 13 as a reactant to make a polyorganosiloxane.

15. A polyorganosiloxane prepared by the method of claim 14.

Description:
METHOD FOR PREPARING A HALOSILANE

[0001 ] Various halosilanes find use in different industries. Diorganodihalosilanes, such as dimethyldichlorosilane, are hydrolyzed to produce a wide range of polyorganosiloxanes, such as polydiorganosiloxanes.

[0002] Methods of preparing halosilanes are known in the art. Typically, halosilanes are produced commercially by the Mueller-Rochow Direct Process, which comprises passing a halide compound over zero-valent silicon (Si 0 ) in the presence of a copper catalyst and various optional promoters. Mixtures of halosilanes are produced by the Direct Process. When an organohalide is used, a mixture of organohalosilanes is produced by the Direct Process.

[0003] The typical process for making the Si 0 used in the Direct Process consists of the carbothermic reduction of S1O2 in an electric arc furnace. Extremely high temperatures are required to reduce the S1O2, so the process is energy intensive. Consequently, production of Si 0 adds costs to the Direct Process for producing halosilanes. Therefore, there is a need for a more economical method of producing halosilanes that avoids or reduces the need of using Si 0 .

[0004] In addition to the Direct Process, diorganodihalosilanes have been produced by the alkylation of silicon tetrachloride and various methylchlorosilanes by passing the vapors of these chlorosilanes together with an alkyl halide over finely divided aluminum or zinc at elevated temperatures. However, this process results in the production of a large amount of aluminum chloride or zinc chloride, which is costly to dispose of on a commercial scale.

[0005] Therefore, there is a need for a more economical method of producing halosilanes that avoids the need for Si 0 produced by reducing S1O2 at extremely high temperatures and that does not require the costly disposal of byproducts.

BRIEF SUMMARY OF THE INVENTION

[0006] A method for preparing a reaction product comprising a halosilane, where the method comprises separate and consecutive step (1 ) and step (2), where:

step (1 ) is contacting, at a temperature from 200 °C to 1400 °C, an ingredient comprising a silane of formula H a R| 3 SiX(4 -a- | :) ), where subscript a is 0 to 4, subscript b is 0 or 1 , a quantity (a + b) < 4, each R is independently a monovalent organic group, and each X is independently a halogen atom with the proviso that when the quantity (a + b) < 4, then the ingredient in step (1 ) further comprises H2; with a copper catalyst; thereby forming a reactant; and step (2) is contacting the reactant with an organohalide at a temperature from 100 °C to 600 °C; thereby forming the reaction product and a spent reactant.

DETAILED DESCRIPTION OF THE INVENTION

[0007] The Brief Summary of the Invention and the Abstract are hereby incorporated by reference. All ratios, percentages, and other amounts are by weight, unless otherwise indicated. The articles 'a', 'an', and 'the' each refer to one or more, unless otherwise indicated by the context of the specification. Abbreviations used herein are defined in Table A, below.

Table A - Abbreviations

[0008] "AlkyI" means an acyclic, branched or unbranched, saturated monovalent hydrocarbon group. Examples of alkyl groups include Me, Et, Pr, 1 -methylethyl, Bu, 1 - methylpropyl, 2-methylpropyl, 1 ,1 -dimethylethyl, 1 -methylbutyl, 1 -ethylpropyl, pentyl, 2- methylbutyl, 3-methylbutyl, 1 ,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, 2- ethylhexyl, octyl, nonyl, and decyl; as well as other branched, saturated monovalent hydrocarbon groups with 6 or more carbon atoms. Alkyl groups have at least one carbon atom. Alternatively, alkyl groups may have 1 to 12 carbon atoms, alternatively 1 to 10 carbon atoms, alternatively 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms, and alternatively 1 carbon atom.

[0009] "Aralkyi" and "alkaryl" each refer to an alkyl group having a pendant and/or terminal aryl group or an aryl group having a pendant alkyl group. Exemplary aralkyi groups include benzyl, tolyl, xylyl, phenylethyl, phenyl propyl, and phenyl butyl. Aralkyi groups have at least 6 carbon atoms. Monocyclic aralkyi groups may have 6 to 12 carbon atoms, alternatively 6 to 9 carbon atoms, and alternatively 6 to 7 carbon atoms. Polycyclic aralkyl groups may have 7 to 17 carbon atoms, alternatively 7 to 14 carbon atoms, and alternatively 9 to 10 carbon atoms.

[0010] "Alkenyl" means an acyclic, branched, or unbranched unsaturated monovalent hydrocarbon group, where the monovalent hydrocarbon group has a double bond. Alkenyl groups include Vi, allyl, propenyl, and hexenyl. Alkenyl groups have at least 2 carbon atoms. Alternatively, alkenyl groups may have 2 to 12 carbon atoms, alternatively 2 to 10 carbon atoms, alternatively 2 to 6 carbon atoms, alternatively 2 to 4 carbon atoms, and alternatively 2 carbon atoms.

[0011] "Alkynyl" means an acyclic, branched, or unbranched unsaturated monovalent hydrocarbon group, where the monovalent hydrocarbon group has a triple bond. Alkynyl groups include ethynyl and propynyl. Alkynyl groups have at least 2 carbon atoms.

Alternatively, alkynyl groups may have 2 to 12 carbon atoms, alternatively 2 to 10 carbon atoms, alternatively 2 to 6 carbon atoms, alternatively 2 to 4 carbon atoms, and alternatively 2 carbon atoms.

[0012] "Aryl" means a cyclic, fully unsaturated, hydrocarbon group. Aryl is exemplified by, but not limited to, Ph and naphthyl. Aryl groups have at least 5 carbon atoms.

Monocyclic aryl groups may have 5 to 9 carbon atoms, alternatively 6 to 7 carbon atoms, and alternatively 6 carbon atoms. Polycyclic aryl groups may have 10 to 17 carbon atoms, alternatively 10 to 14 carbon atoms, and alternatively 12 to 14 carbon atoms.

[0013] "Carbocycle" and "carbocyclic" refer to a hydrocarbon ring. Carbocycles may be monocyclic or alternatively may be fused, bridged, or spiro polycyclic rings. Carbocycles have at least 3 carbon atoms. Monocyclic carbocycles may have 3 to 9 carbon atoms, alternatively 4 to 7 carbon atoms, and alternatively 5 to 6 carbon atoms. Polycyclic carbocycles may have 7 to 17 carbon atoms, alternatively 7 to 14 carbon atoms, and alternatively 9 to 10 carbon atoms. Carbocycles may be saturated or partially unsaturated.

[0014] "Cycloalkyl" refers to a saturated hydrocarbon group including a carbocycle. Cycloalkyl groups are exemplified by cyclobutyl, cyclopentyl, cyclohexyl, and

methylcyclohexyl. Cycloalkyl groups have at least 3 carbon atoms. Monocyclic cycloalkyl groups may have 3 to 9 carbon atoms, alternatively 4 to 7 carbon atoms, and alternatively 5 to 6 carbon atoms. Polycyclic cycloalkyl groups may have 7 to 17 carbon atoms, alternatively 7 to 14 carbon atoms, and alternatively 9 to 10 carbon atoms.

[0015] "Metallic" means that the metal has an oxidation number of zero.

[0016] "Purging" means to introduce a gas stream into a container to remove unwanted materials. [0017] "Treating" means to introduce a gas stream into a container to pre-treat a component before contacting the component with another component. Treating includes contacting the reactant to reduce or otherwise activate it before contacting it with the organohalide in step (2) of the method. Treating may further include contacting the copper catalyst to reduce or otherwise activate it before contacting it with the ingredients comprising the H2 and the silane in step (1 ) of the method.

[0018] "Residence time" means the time which a component takes to pass through a reactor system in a continuous process, or the time a component spends in the reactor in a batch process. For example, residence time in step (1 ) refers to the time during which one reactor volume of the copper catalyst makes contact with the ingredient comprising the silane as the copper catalyst passes through the reactor system in a continuous process or during which the copper catalyst is placed within the reactor in a batch process.

Alternatively, residence time may refer to the time for one reactor volume of reactive gas to pass through a reactor charged with the copper catalyst in step (1 ). (E.g., residence time includes the time for one reactor volume of the ingredient comprising the silane in step (1 ) to pass through a reactor charged with the copper catalyst or the time for one reactor volume of organohalide to pass through a reactor charged with the reactant in step (2) of the method described herein.)

[0019] "Reactant" means a solid product that is formed in step (1 ) of the method described herein and/or re-formed in step (3) of the method described herein, when step (3) is present in the method.

[0020] "Spent reactant" refers to the reactant after it has been contacted with the organohalide. For example, spent reactant may be present after step (2) (or after step (4), when step (4) is present in the method). The spent reactant after step (2) (or step (4)) contains an amount of silicon that is less than the amount of silicon in the reactant before beginning step (2) (or after step (3) and before beginning step (4)). Spent reactant may, or may not, be exhausted, i.e., spent reactant may contain some silicon that may or may not be reactive with the organohalide.

[0021 ] The method for preparing the reaction product comprises separate and consecutive step (1 ) and step (2), where:

step (1 ) is contacting, at a temperature from 200 °C to 1400 °C, an ingredient comprising a silane of formula H a R| 3 SiX(4 -a- | :) ), where subscript a is 0 to 4, subscript b is 0 or 1 , a quantity (a + b) < 4, each R is independently a monovalent organic group, and each X is independently a halogen atom, with the proviso that when the quantity (a + b) < 4, then the ingredient in step (1 ) further comprises H2; with a copper catalyst, where the copper catalyst is a physical mixture of metallic copper and a diluent; thereby forming a reactant; and

step (2) is contacting the reactant with an organohalide at a temperature from 100 °C to 600 °C; thereby forming the reaction product and a spent reactant; and

where the method optionally further comprises separate and consecutive steps (3) and (4), where steps (3) and (4) are performed after step (2), and where

step (3) is repeating step (1 ) using an additional ingredient, and recycling the spent reactant to re-form the reactant, and

step (4) is repeating step (2) using the reactant re-formed in step (3) and additional organohalide; and

where the method optionally further comprises step (5), where step (5) is repeating steps (3) and (4) at least one time; and

where the method optionally further comprises step (6), where step (6) is recovering the halosilane.

[0022] Steps (1 ) and (2) are performed separately and consecutively. "Separate" and "separately" mean that step (1 ) and step (2) do not overlap or coincide. "Consecutive" and "consecutively" mean that step (2) is performed after step (1 ) in the method; however, additional steps may be performed between step (1 ) and (2), as described below.

"Separate" and "separately" refer to either spatially or temporally or both. "Consecutive" and "consecutively" refers to temporally (and furthermore occurring in a defined order).

[0023] The silane used in step (1 ) has formula H a R| 3 SiX(4 -a- | :) ), where subscript a is 0 to

4, subscript b is 0 to 2, and a quantity (a + b) < 4. Alternatively, subscript a may be 0 or 1 , subscript b may be 0 or 1 , and 0 < (a + b) < 1 . Each R is independently a monovalent organic group, and each X is independently a halogen atom. Alternatively, in the formula H a R|3SiX(4_ a _b) , each X may be independently selected from Br, CI, and I; alternatively Br and CI; alternatively CI and I; and alternatively each X may be CI. Each R may be a hydrocarbyl group. Each R may be independently selected from alkyl, alkenyl, alkynyl, aryl, aralkyi, and carbocyclic as defined above. Alternatively, each R may be a hydrocarbyl group independently selected from alkyl, aryl, and carbocyclic. Alternatively, each R may be alkyl, such as Me, Et, Pr, or Bu; alternatively Me. The silane may comprise a tetrahalosilane (S1X4), a trihalosilane (HSiX3), a dihalosilane (H2SiX2), a monohalosilane

(H3S1X), silane (SiH4), or a combination thereof. Alternatively, the silane may comprise a tetrahalosilane, a trihalosilane, or a combination thereof. Alternatively, the silane may be a tetrahalosilane of formula S1X4, (i.e., where a = 0 and b = 0 in the formula above) where each X is as described above. Examples of the tetrahalosilane include, but are not limited to, silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, and silicon tetrafluoride. Alternatively, the silane may be a trihalosilane such as HS1X3, (where a = 1 and b = 0 in the formula H a R| 3 SiX(4 -a- | :) )) and/or RS1X3, (where a = 0 and b = 1 in the formula

Ha R bSiX(4-a-b))' where R and X are as described above. Examples of trihalosilanes include trichlorosilane (HSiCl3), tribromosilane, methyltrichlorosilane (ΟΗ βίΟΙ or

MeSiCh) methyltribromosilane, ethyltrichlorosilane, ethyltribromosilane, and a combination thereof. Alternatively, when the silane used comprises SiH4, then in step (1 ), H2 may be omitted; when the quantity (a + b) < 4, then in step (1 ) the ingredients further comprise H2.

The silane used in step (1 ) is distinct from the halosilane in the reaction product.

[0024] The copper catalyst used in step (1 ) comprises copper and a diluent. Without wishing to be bound by theory, it is thought that the diluent prevents sintering of the copper under the conditions of the method. The copper catalyst is a physical mixture, which includes metallic copper and the diluent. The diluent is a solid that when mixed with the metallic copper prevents the metallic copper from sintering when the method is performed. The diluent may be one of carbon, metallic silicon, silicon carbide, or a metal oxide such as silica, zirconia, alumina, or mixtures thereof; or a mixed metal oxide such as zeolite.

Alternatively, the diluent may be metallic silicon, silicon carbide, or a metal oxide such as silica or alumina. Alternatively, the diluent may be metallic silicon, or silica. Alternatively, the diluent may be metallic silicon. Alternatively, the diluent may be a metal oxide.

Alternatively, the diluent may be silica. The physical mixture useful as the copper catalyst in step (1 ) is distinguished from supported copper catalysts in that this copper catalyst is a physical mixture of the metallic copper and the diluent. The metallic copper is not coated on the surface of the diluent, and the metallic copper is not adsorbed into pores of a diluent, such as silica or alumina. The diluent is distinct from the metallic copper, e.g., the diluent may be in the form of discrete particles; and the copper catalyst may be a physical mixture of discrete particles of metallic copper and discrete particles of diluent. The physical mixture may be prepared by any convenient means, such as mixing metallic copper particles with particles of the diluent under ambient conditions of temperature and pressure (e.g., without high temperature and/or pressure treating).

[0025] The amount of metallic copper and diluent in the copper catalyst depends on various factors including the type of diluent and the conditions under which step (1 ) will be performed, however, the relative molar amounts of metallic copper : diluent may range from 3:1 to 2:1 .

[0026] The reactor in which step (1 ) is performed may be any reactor suitable for the combining of gases and solids. For example, the reactor configuration can be a batch vessel, packed bed, stirred bed, vibrating bed, moving bed, re-circulating beds, or a fluidized bed. When using re-circulating beds, the copper catalyst can be circulated from a bed for conducting step (1 ) to a bed for conducting step (2). To facilitate reaction, the reactor should have means to control the temperature of the reaction zone, e.g., the portion of the reactor in which the ingredient comprising the silane contacts the copper catalyst in step (1 ) and/or the portion of the reactor in which the organohalide contacts the reactant in step (2).

[0027] The temperature at which the ingredient comprising the silane is contacted with the copper catalyst in step (1 ) may be from 200 °C to 1400 °C; alternatively 500 °C to 1400°C; alternatively 600 °C to 1200°C; and alternatively 650 °C to 1 100 °C.

[0028] The pressure at which the ingredient comprising the silane is contacted with the copper catalyst in step (1 ) can be sub-atmospheric, atmospheric, or super-atmospheric.

For example, the pressure may range from 10 kilopascals absolute (kPa) to 2100 kPa; alternatively 101 kPa to 2101 kPa; alternatively 101 kPa to 1 101 kPa; and alternatively 101 kPa to 900 kPa; and alternatively 201 kPa to 901 kPa.

[0029] The mole ratio of H2 to silane contacted with the copper catalyst in step (1 ) may range from 10,000:1 to 0.01 :1 , alternatively 100:1 to 1 :1 , alternatively 20:1 to 5:1 , alternatively 20:1 to 4:1 , alternatively 20:1 to 2:1 , alternatively 20:1 to 1 :1 , and alternatively 4:1 to 1 :1 .

[0030] The residence time for the ingredient comprising the silane is sufficient for the ingredient comprising the silane to contact the copper catalyst and form the reactant in step (1 ). For example, a sufficient residence time for the ingredient comprising the silane may be at least 0.01 s, alternatively at least 0.1 s, alternatively 0.1 s to 10 min, alternatively 0.1 s to 1 min, alternatively 0.5 s to 10 s, alternatively 1 min to 3 min, and alternatively 5 s to 10 s. Alternatively, the residence time for the copper catalyst to be in contact with the ingredient comprising the silane in step (1 ) is typically at least 0.1 min; alternatively at least 0.5 minutes; alternatively 0.1 min to 120 min; alternatively 0.5 min to 9 min; alternatively 0.5 min to 6 min. The desired residence time may be achieved by adjusting the flow rate of the ingredient comprising the silane, or by adjusting the total reactor volume, or by any combination thereof. The desired residence time of the reactant may be achieved by adjusting the flow rate of the reactant, or by adjusting the total reactor volume, or a combination thereof.

[0031] In step (1 ), when H2 is present, the H2 and the silane may be fed to the reactor simultaneously; however, other methods of combining, such as by separate pulses, are also envisioned. The H2 and the silane may be mixed together before feeding to the reactor; alternatively, the H2 and the silane may be fed into the reactor as separate streams.

[0032] In step (1 ), the copper catalyst is in a sufficient amount. A sufficient amount of copper catalyst is enough copper catalyst to form the reactant, described below, when the ingredient comprising the silane is contacted with the copper catalyst. For example, a sufficient amount of copper catalyst may be at least 0.01 mg catalyst/cm 3 of reactor volume; alternatively at least 0.5 mg catalyst/cm 3 of reactor volume, and alternatively 1 mg catalyst/cm 3 of reactor volume to maximum bulk density of the copper catalyst based on the reactor volume, alternatively 1 mg to 5,000 mg catalyst/cm 3 of reactor volume, alternatively 1 mg to 1 ,000 mg catalyst/cm 3 of reactor volume, and alternatively 1 mg to

900 mg catalyst/cm 3 of reactor volume.

[0033] There is no upper limit on the time for which step (1 ) is conducted. For example, step (1 ) is usually conducted for at least 0.1 s, alternatively from 1 s to 5 hr, alternatively from 1 min to 1 hr.

[0034] The product of step (1 ) is the reactant. The reactant comprises an amount of silicon of at least 0.1 %, alternatively 0.1 % to 90%, alternatively 1 % to 50%, alternatively 1 % to 35%, and alternatively 0.1 % to 35%, based on the total weight of copper and silicon in the reactant. The percentage of silicon can be determined using standard analytical tests. For example, the percentage of Si may be determined using ICP-AES and ICP-MS.

[0035] Step (2) of the method is contacting the reactant with the organohalide at a temperature from l OO i to 600 °C; thereby forming the reaction product and the spent reactant. The organohalide may have formula RX, where R is a monovalent organic group and X is a halogen atom. The halogen atom selected for X in the organohalide may be the same as the halogen atom selected for X in the silane used in step (1 ). Alternatively, the halogen atom selected for X in the organohalide may differ from the halogen atom selected for X in the silane used in step (1 ). The group selected for R in the organohalide may be the same as the group selected for R for the silane described above in step (1 ) (when subscript b > 0 in the formula H a R| 3 SiX(4_ a _b))- Alternatively, the group selected for R in the organohalide may differ from the group selected for R in the silane described above for step (1 ). Alternatively, R may be selected from alkyl, alkenyl, alkynyl, aryl, aralkyl, and carbocyclic as defined above. Alternatively, R may be a hydrocarbyl group selected from alkyl, aryl, and carbocyclic. Alternatively, each R may be alkyl, such as Me, Et, Pr, or Bu; alternatively Me. Alkyl groups containing at least three carbon atoms can have a branched or unbranched structure. Alternatively, each X may be independently selected from Br, CI, and I ; alternatively Br and CI; alternatively CI and I; and alternatively each X may be CI. Examples of the organohalide include, but are not limited to, methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, cyclobutyl chloride, cyclobutyl bromide, cyclohexyl chloride, and cyclohexyl bromide.

[0036] The reactors suitable for use in step (2) are as described for step (1 ). The same reactor may be used for step (1 ) as used in step (2). Alternatively, separate reactors may be used for steps (1 ) and (2). When separate reactors are used, the type of reactor in each step may be the same or different. In step (2), the organohalide may be contacted with the reactant by feeding the organohalide into a reactor containing the reactant produced in step (1 ).

[0037] The residence time of the organohalide is sufficient for the organohalide to react with the reactant to form the reaction product comprising the halosilane in step (2). For example, a sufficient residence time of the organohalide may be at least 0.01 s, alternatively at least 0.1 s, alternatively 0.5 s to 10 min, alternatively 1 s to 1 min, alternatively 1 s to 10 s. The desired residence time can be achieved by adjusting the flow rate of the organohalide, or the total reactor volume, or a combination thereof.

[0038] The residence time for the reactant to be in contact with the organohalide in step

(2) is typically at least 1 minute; alternatively at least 5 minutes; alternatively 1 min to 120 min; alternatively 5 min to 90 min; alternatively 5 min to 60 min. Alternatively, there is no upper limit on the residence time for which step (2) is conducted. The desired residence time of the reactant in step (2) may be achieved by adjusting the flow rate of the reactant, or by adjusting the total reactor volume, or a combination thereof.

[0039] The temperature at which organohalide is contacted with the reactant in step (2) may be from 100°C to 600 °C, alternatively 200 °C to 500 °C, and alternatively 250 °C to 375 °C.

[0040] Step (2) is typically conducted until the amount of silicon in the reactant falls below a predetermined limit, e.g., until the reactant is spent. For example, step (2) may be conducted until the amount of silicon in the reactant is below 90%, alternatively 1 % to 90%, alternatively 1 % to 40%, of its initial weight percent. The initial weight percent of silicon in the reactant is the weight percent of silicon in the reactant before the reactant is contacted with the organohalide in step (2) (or the weight percent of silicon in the reactant after step

(3) and before step (4), when these steps are present). The amount of silicon in the reactant can be monitored by correlating production of the reaction product of step (2) with the weight percent of silicon in the reactant and then monitoring the reactor effluent or may be determined as described above.

[0041] The pressure at which the organohalide is contacted with the reactant in step (2) can be sub-atmospheric, atmospheric, or super-atmospheric. For example, the pressure may range from 10 kilopascals absolute (kPa) to 2100 kPa; alternatively 1 01 kPa to 2101 kPa; alternatively 101 kPa to 1 101 kPa; and alternatively 101 kPa to 900 kPa; and alternatively 201 kPa to 901 kPa.

[0042] The reactant is present in a sufficient amount. A sufficient amount of reactant is enough reactant to form the halosilane, described herein, when the reactant is contacted with the organohalide. For example, a sufficient amount of reactant may be the amount that is generated by at least 0.01 mg reactant/cm 3 of reactor volume; alternatively by at least 0.5 mg reactant/cm 3 of reactor volume; alternatively by 0.01 mg reactant/cm 3 of reactor volume to maximum bulk density of the reactant in the reactor volume, alternatively by 1 mg to 5,000 mg reactant/cm 3 of reactor volume, alternatively by 1 mg to 1 ,000 mg reactant/cm 3 of reactor volume, and alternatively by 1 mg to 900 mg reactant/cm 3 of reactor volume.

[0043] The resulting reaction product of the method described above comprises the halosilane. The halosilane may have general formula R(4-c)SiX c , where each X is independently a halogen atom, and each R is independently a monovalent organic group, as described above; and subscript c is 0, 1 , 2, or 3. Alternatively, the halosilane may be a diorganodihalosilane of formula R2S1X2, where each X is independently a halogen atom , and each R is independently a monovalent organic group, as described above.

Alternatively, the halosilane may be a mixture of two or more organohalosilanes, e.g., a diorganodihalosilane and an organotrihalosilane or two or more different

diorganodihalosilanes.

[0044] The method described herein may optionally further comprise purging and/or treating. Purging and/or treating may be performed before contacting the copper catalyst with the ingredient comprising the silane in step (1 ) and/or before contacting the reactant with the organohalide in step (2) and/or before contacting the spent reactant with the additional ingredient comprising the additional silane in step (3) and/or before contacting the reactant re-formed in step (3) with the (additional) organohalide in step (4), and/or before step (5). The purging step comprises introducing a gas stream into the reactor containing the copper catalyst, the reactant, and/or the spent reactant to remove unwanted materials. Unwanted materials in step (2), and when present step (4), may include, for example, H2, O2, H2O and HX, where X is a halogen atom as defined above. Purging may be accomplished with an inert gas, such as argon or nitrogen, or with a reactive gas, such as the organohalide; alternatively purging may be performed with an inert gas. The treating step may comprise introducing a gas stream into the reactor containing the copper catalyst to pre-treat the copper catalyst before contacting it with the ingredient comprising the silane. Alternatively, the treating step may comprise introducing a gas stream into the reactor containing the reactant to activate and/or reduce it before contacting the reactant with the organohalide. Treating may be accomplished with a gas, such as H2 or the organohalide; alternatively H2. Purging and/or treating may be performed at ambient or elevated temperature, e.g., at least 25 °C, alternatively at least 300 °C, alternatively 25 °C to 500 °C, and alternatively 300 °C to 500 °C.

[0045] In step (2) of the method the reactant and the organohalide may be contacted in the absence of H2, in the absence of the silane, or in the absence of both H2 and the silane.

[0046] The method may optionally further comprise steps (3) and (4) after step (2). Steps (3) and (4) may be performed separately and consecutively. The purpose of steps (3) and (4) is to recycle spent reactant by repeating steps (1 ) and (2), e.g., using spent reactant in place of the copper catalyst used in step (1 ) of the method. The spent reactant after step (2) contains an amount of silicon less than the amount of silicon in the reactant before beginning step (2). The spent reactant left after step (4) contains an amount of silicon less than the amount of silicon in the reactant re-formed in step (3). For example, the amount of reduction in the amount of silicon in the reactant as compared to spent reactant may be greater than 90%, alternatively greater than 95%, alternatively greater than 99%, and alternatively 99.9%, of its initial weight. Alternatively, the amount of the reduction may be 90% to 99.9%.

[0047] Step (3) comprises contacting the spent reactant with an additional ingredient comprising an additional silane, under conditions as described above for step (1 ), at a temperature from 200 ¾ to 1400°C to re-form the reactant comprising at least 0.1 % of Si. The additional silane used in step (3) may be more of the same silane used above in step (1 ). Alternatively, the additional silane used in step (3) may be a silane of formula

H a R bSiX(4-a-b) > where at least one instance of R, X, subscript a, or subscript b is different than that used in the silane in step (1 ). H2 may be used in step (3) as described above for step (1 ). Step (4) comprises contacting the reactant re-formed in step (3) with additional organohalide (under conditions as described for step (2), above) at a temperature from 100°C to 600 °C to form the reaction product comprising the halosilane.

[0048] Without wishing to be bound by theory, it is thought that the method described herein allows for maximizing the number of cycles for repeating steps (3) and (4). The method may optionally further comprise step (5), which is repeating steps (3) and (4) at least 1 time, alternatively from 1 to 10 5 times, alternatively from 1 to 1 ,000 times, alternatively from 1 to 100 times, and alternatively from 1 to 10 times. [0049] If the organohalide (or the silane) are liquids at or below standard temperature and pressure, the method may further comprise pre-heating and gasifying the organohalide (and/or the silane) by known methods before contacting the silane with the copper catalyst in step (1 ), and/or the spent reactant step (3), and/or before contacting the organohalide with the reactant in step (2) and/or step (4). Alternatively, the method may further comprise bubbling the H2 through liquid silane to vaporize the silane before contacting with the copper catalyst in step (1 ), and/or the spent reactant in step (3).

[0050] If the silane is a solid at or below standard temperature and pressure, the method may further comprise pre-heating above the melting point and liquefying or vaporizing the silane before bringing it in contact with the copper catalyst in step (1 ) and/or the spent reactant in step (3). If the organohalide is a solid at or below standard temperature and pressure, the method may further comprise pre-heating above the melting point and liquefying or vaporizing the organohalide before bringing it in contact with reactant in step (2) and/or step (4).

[0051 ] The method may optionally further comprise step (5). Step (5) comprises recovering the reaction product produced (i.e., product of step (2) and/or step (4)). The reaction product comprises the halosilane described above. The halosilane may be recovered from the reaction product by, for example, removing gaseous product from the reactor followed by isolation by distillation. The halosilane may have general formula R(4 -c )SiX c , where each X is independently a halogen atom, and each R is independently a monovalent organic group, as described above; and subscript c is 0, 1 , 2, or 3.

Alternatively, the halosilane may have formula R2S1X2, where each R and X are as described above. Exemplary halosilanes that may be produced by the method include organotrihalosilanes and/or diorganodihalosilanes. Organotrihalosilanes are exemplified by methyltrichlorosilane, methyltribromosilane, and ethyltrichlorosilane. Examples of diorganodihalosilanes prepared according to the present process include, but are not limited to, dimethyldichlorosilane (i.e. , (CH3)2SiCl2 or Me2SiCl2), dimethyldibromosilane, diethyldichlorosilane, and diethyldibromosilane. Examples of other organohalosilanes that may be produced in addition to the diorganodihalosilane include, but are not limited to, methyltrichlorosilane (i.e. , CH^ iCl^ or MeSiC^), and methyltribromosilane (i.e. , CH^ iBr^ or MeSiBr3).

[0052] A hydrogen halide may be present in the reaction product produced according the present method. The hydrogen halide has formula HX, where X is as defined above. The hydrogen halide may be separated from the halosilane via condensation, distillation, or other means and collected or fed to other chemical processes. [0053] The method described herein produces halosilanes, particularly

diorganodihalosilanes. Diorganodihalosilanes, such as dimethyldichlorosilane, can be used as reactants in processes for producing polydiorganosiloxanes. The

polydiorganosiloxanes thus produced find use in many industries and applications.

[0054] The method described herein may offer the advantage of not producing large amounts of metal halide byproducts requiring costly disposal. Still further, the method may have good selectivity to produce diorganodihalosilanes, as compared to other halosilanes. Finally, the reactant may be re-formed and reused in the method, and the re-forming and reuse may provide increasing diorganodihalosilane production and/or selectivity.

EXAMPLES

[0055] These examples are intended to illustrate some embodiments of the invention and should not be interpreted as limiting the scope of the invention set forth in the claims. In the tables below, 'nd' means not done or not determined.

[0056] The reaction apparatus used in these examples comprised a 4.8 mm inner diameter quartz glass tube in a flow reactor. The reactor tube was heated using a Lindberg/Blue Minimite 2.54 cm tube furnace. Brooks instrument 5850E mass flow controllers were used to control gas flow rates. A stainless steel SiCl4 bubbler was used to introduce S1CI4 into the H2 gas stream. The amount of SiCl4 in the H2 gas stream was adjusted by changing the temperature of the S1CI4 in the bubbler according to calculations using well-known thermodynamic principles. For reactions run at pressures above atmospheric pressure, a back pressure regulator (GO type Hastelloy® rated for 0- 500 psig) was introduced at the back end of the reactor.

[0057] The effluent of the reactor containing the reaction product was passed through an actuated 6-way valve (Vici) with constant 100 μΙ_ injection loop before being discarded. Samples were taken from the reaction effluent stream by actuating the injection valve and the 100 μΙ_ sample passed directly into the injection port of a 6890A Agilent GC for analysis with a split ratio at the injection port of 5:1 . The GC contained a single column suitable for analyzing chlorosilanes, which was split at the outlet. One path went to a TCD for quantization of the reaction products and the other path went to a Flame Ionization Detector.

COMPARATIVE EXAMPLE 1 - Production of Trichlorosilane Using Metallic Copper Catalyst

[0058] A metallic copper catalyst (4.15 grams) was treated with H2/SiCl4 for 30 min at 750 °C by bubbling H2 through the stainless steel SiCl4 bubbler. The total flow of H2 and S1CI4 was 150 seem and the mole ratio of H2 to SiCl4 was 4:1 . The S1CI4 flow was controlled by H 2 flow by keeping the bubbler temperature at 14.6°C. The gas and vapor leaving the bubbler was fed into the reactor containing the metallic copper catalyst at atmospheric pressure for 30 min. The reaction was periodically sampled and analyzed by GC to determine the weight percent HSiCl3, based on the total mass leaving the reactor. Use of metallic copper without a diluent caused pressure to build within the system, not allowing for adequate H2/SiCl4 flow, therefore GC results were not accurate. Comparative

Example 1 demonstrated that metallic copper catalyst without a diluent built up pressure within the reactor, and upon removal, was shown to be sintered together. The results are shown in Table 1 .

Table 1 : Production of Trichlorosilane Using Metallic Copper Catalyst at 750 °C with H 2 /SiCI 4 = 4 and no Diluent

COMPARATIVE EXAMPLE 2 AND EXAMPLE 1 - Production of methylchlorosilanes over silicon diluted metallic copper catalyst

[0059] Two grams of metallic copper (425 microns) were diluted with 1 gram of metallurgical grade silicon (300 microns) at room temperature. The resulting copper catalyst was a physical mixture of metallic copper and metallic silicon, which was loaded into the flow reactor. The reactor was purged under N 2 and pressure checked for any leaks. The reactor was heated at 500 °C for 2 hours under 100 seem of H 2 , and then the temperature was increased to 750 °C and maintained for 30 min. After 30 minutes, the reactor temperature was decreased to 300 °C, and when the reactor reached 300 °C, the reactor was purged with an argon flow of 50 seem for 30 min. After 30 min, the argon flow was ceased, and CH3CI (MeCI) was fed through the reactor to contact with the catalyst at a flow rate of 5 seem, a temperature of 300 °C, and atmospheric pressure (101 kPa) for 60 min. No methylchlorosilanes were observed in the products stream indicating that Si from the catalyst bed was not reactive with CH3CI (MeCI).

[0060] The copper catalyst was then treated (reduced) at 500 °C under 100 seem H 2 for 3-4 hours. Then, H 2 and S1CI4 were fed to the reactor for 30 min at 750 °C by bubbling H 2 through the stainless steel SiCl4 bubbler. The total flow of H 2 and S1CI4 was 150 seem with the mole ratio of H 2 to SiCl4 of 1 :1 . The S1CI4 flow was controlled by H 2 flow by keeping the bubbler temperature at 37.2 °C. The gas and vapor stream leaving the bubbler was fed into the flow reactor containing the copper catalyst to form a reactant containing 30% Si. After 30 minutes, the SiCl4 flow was ceased, and a H2 flow of 100 seem was maintained while cooling to 300 °C over 1 hour. When the reactor reached 300 °C, the reactor was purged with an argon flow of 50 seem for 30 min. After 30 min, the argon flow was ceased, and CH3CI (MeCI) was fed through the reactor at a flow rate of 5 seem, at

300 °C and atmospheric pressure for 60 min. The reactor effluent was periodically sampled and analyzed by GC to determine the weight percent of (CH3)2SiCl2 (Me2SiCl2) and other chlorosilanes based on the total mass leaving the reactor.

[0061] When the chlorosilane production ceased or was significantly reduced, the CH3CI

(MeCI) feed was ceased, and the spent reactant was treated with H2 at 500 °C for 30-60 min and contacted again with H2/SiCl4 for 30 min at 750 °C to re-form the reactant. The combined flow rate of H2 and SiCl4 was 150 seem, and the mole ratio of H2 to SiCl4 was

1 :1 . After the reactant was re-formed, the reactor was purged with argon, again, and CH3CI (MeCI) was contacted with the re-formed reactant as described above. The cycle was repeated, and the results are shown in Table 2. This example demonstrated that the mixture of methylchlorosilanes was produced by the method under these conditions with dimethyldichlorosilane being the major product.

Table 2: Production of methylchlorosilanes over metallic copper (425 urn) diluted with Si (300 urn) catalyst treated at 750°C with H 2 :SiCI 4 = 1 :1 in step (1 ) and 5 seem of CH3CI

(MeCI) at 300°C in step (2)

COMPARATIVE EXAMPLE 3 AND EXAMPLE 2 [0062] Two grams of metallic copper (20 microns) were diluted with 1 gram of metallurgical grade silicon (1 mm) and loaded into the reactor. The reactor was purged with N2 and pressure checked for any leaks. Then the reactor was heated at 500 °C under

100 seem of H2 for 2 hours. The temperature was then increased to 750 °C and maintained for 30 min. After 30 minutes, the reactor temperature was decreased to 300 °C, and when the reactor reached 300 °C, the reactor was purged with an argon flow of 50 seem for 30 min. After 30 min, the argon flow was ceased, and CH3CI (MeCI) was fed through the reactor at a flow rate of 5 seem, 300 °C and atmospheric pressure for 60 min. There were no methylchlorosilanes observed in the reactor effluent, indicating that Si from the catalyst bed was not reactive with CH3CI (MeCI).

[0063] The copper catalyst was then treated (reduced) by flowing 100 seem H2 through the reactor at 500 °C for 3-4 hours, then H2 and S1CI4 were flowed through the reactor for 30 min at 750 °C by bubbling H2 through the stainless steel SiCl4 bubbler. The total flow of H2 and S1CI4 was 150 seem with the mole ratio of H2 to SiCl4 of 1 :1 . The S1CI4 flow was controlled by H2 flow by keeping the bubbler temperature at 37.2 °C. The gas and vapor stream leaving the bubbler was fed into the reactor containing the copper catalyst to form a reactant containing 30 wt% Si. After 30 minutes, the SiCl4 flow was ceased, and a hydrogen flow of 100 seem was maintained while cooling to 300 °C over 1 hour. When the reactor reached 300 °C, the reactor was purged with an argon flow of 50 seem for 30 min. After 30 min, the argon flow was ceased, and CH3CI (MeCI) was fed through the reactor at a flow rate of 5 seem, 300 °C and atmospheric pressure for 60 min. The reactor effluent was periodically sampled and analyzed by GC to determine the weight percent of (CH3)2SiCl2 (Me2SiCl2) and other chlorosilanes based on the total mass leaving the reactor.

[0064] Next, the CH3CI (MeCI) feed was ceased, and the spent reactant was treated with H 2 at 500 °C for 30-60 min and contacted again with H 2 /SiCl4 for 30 min at 750 °C, to reform the reactant. The combined flow rate of H2 and SiCl4 was 150 seem, and the mole ratio of H2 to SiCl4 was 1 :1 . After the reactant was re-formed, the reactor was purged with argon, again, and CH3CI (MeCI) was contacted with the re-formed reactant as described above. The cycle was repeated, and the results are shown in Table 3. This example demonstrated that the method could produce a mixture of methylchlorosilanes with dimethyldichlorosilane being the major product under the conditions of this example 2. Table 3: Production of methylchlorosilanes over metallic copper (20 um) diluted with Si (1 mm) catalyst treated at 750°C with H 2 /SiCI 4 = 1 in step (1 ) and 5 seem of CH 3 CI (MeCI) at

300°C in step (2)

COMPARATIVE EXAMPLE 4 AND EXAMPLE 3

[0065] Two grams of metallic copper (425 microns) were diluted with 1 gram of metallurgical grade silicon (1 mm) and loaded into the reactor. The reactor was purged under N 2 and pressure checked for any leaks. The reactor was then heated under 100 seem of H 2 at 500 °C for 2 hours. The temperature was increased to 750 °C and maintained for 30 min. After 30 minutes, the reactor temperature was decreased to 300 °C, and when the temperature reached 300 °C, the reactor was purged with an argon flow of 50 seem for 30 min. After 30 min, the argon flow was ceased, and CH3CI (MeCI) was fed through the reactor at a flow rate of 5 seem, 300 °C and atmospheric pressure for 60 min. No methylchlorosilanes were observed in the reactor effluent, indicating that Si from the catalyst bed was not reactive with CH3CI (MeCI). [0066] The copper catalyst was then treated (reduced) under 100 seem H2 at 500 °C for

3-4 hours. Next, H2 and S1CI4 were fed to the reactor for 30 min at 750 °C by bubbling H2 through a stainless steel S1CI4 bubbler. The total flow of H2 and S1CI4 was 150 seem with the mole ratio of H2 to S1CI4 of 1 :1 . The S1CI4 flow was controlled by H2 flow by keeping the bubbler temperature at 37.2 °C. The gas and vapor leaving the bubbler was fed into the reactor containing the copper catalyst to form a reactant compromising 30% Si. After 30 minutes, the SiCl4 flow was ceased and a hydrogen flow of 100 seem was maintained while cooling to 300°C over a period of 1 hour. When the reactor reached 300°C, all H2 was purged from the reactor and catalyst with an argon flow of 50 seem for 30 min. After 30 min, the argon flow was ceased, and CH3CI (MeCI) was fed through the reactor at a flow rate of 5 seem, 300 ¾ and atmospheric pressure for 60 min. The reactor effluent was periodically sampled and analyzed by GC to determine the weight percent of (CH3)2SiCl2 (Me2SiCl2) and other chlorosilanes based on the total mass leaving the reactor.

[0067] Next, the CH3CI (MeCI) feed was ceased, and the spent reactant was treated with H2 at 500 °C for 30-60 min and contacted again with H2/SiCl4, to re-form the reactant, for 30 min at 750 °C. The combined flow rate of H2 and SiCl4 was 150 seem, and the mole ratio of H2 to SiCl4 was 1 :1 . After the reactant was re-formed, it was purged with argon, again, and CH3CI (MeCI) was contacted with the re-formed reactant as described above.

The cycle was repeated, and the results are shown in Table 3. This example

demonstrated that the method can produce a reaction product containing

dimethyldichlorosilane as the major product under the conditions of this example 3.

Table 3: Production of methylchlorosilanes over metallic copper (425 um) diluted with Si (1 mm) catalyst treated at 750°C with H 2 /SiCI 4 = 1 in step (1 ) and 5 seem of CH3CI (MeCI) at

300°C in step (2)

Example 3, 329 43 13 76 15 8

cycle 5

Example 3, 340 33 10 77 18 6

cycle 6

Example 3, 373 31 8 73 22 5

cycle 7

Example 3, 412 26 6 69 27 4

cycle 8

Example 3, 517 26 5 68 26 6

cycle 9

Example 3, nd 21 nd 60 34 6

cycle 10

Example 3, 41 1 24 6 65 32 4

cycle 1 1

Example 3, 415 22 5 62 33 6

cycle 12

EXAMPLE 4 - PRODUCTION OF METHYLCHLOROSILANES OVER SILICA GEL DILUTED METALLIC COPPER CATALYST

[0068] Two grams of metallic copper (425 microns) were diluted with 1 gram of silica gel spheres (425 microns) and loaded into the reactor. The reactor was purged under N2 and pressure checked for any leaks. The reactor was then heated under 100 seem H2 at 500 °C for 3-4 hours. Next, H2 and S1CI4 were fed to the reactor for 30 min at 750 °C by bubbling H2 through the stainless steel SiCl4 bubbler. The total flow of H2 and S1CI4 was 150 seem with the mole ratio of H2 to SiCl4 of 1 :1 . The S1CI4 flow was controlled by H2 flow by keeping the bubbler temperature at 37.2 °C. The gas and vapor leaving the bubbler was fed into the reactor containing the copper catalyst to form a reactant compromising 30 wt% Si. After 30 minutes, the S1CI4 flow was ceased, and a hydrogen flow of 100 seem was maintained while cooling to 300 °C over 1 hour. When the reactor reached 300 °C, the reactor was purged with an argon flow of 50 seem for 30 min. After 30 min, the argon flow was ceased, and CH3CI (MeCI) was fed through the reactor at a flow rate of 5 seem, 300 °C and atmospheric pressure for 60 min. The reactor effluent was periodically sampled and analyzed by GC to determine the weight percent of (CH3)2SiCl2 (Me2SiCl2) and other chlorosilanes based on the total mass leaving the reactor.

[0069] Next, the CH3CI (MeCI) feed was ceased, and the spent reactant was treated with H2 at 500 °C for 30-60 min and contacted again with H2/SiCl4, for 30 min at 750 °C, to reform the reactant. The combined flow rate of H2 and SiCl4 was 150 seem, and the mole ratio of H2 to SiCl4 was 1 :1 . After the reactant was re-formed, the reactor was purged with argon, again, and CH3CI (MeCI) was contacted with the re-formed reactant as described above. The cycle was repeated, and the results are shown in Table 4. This example demonstrated that under the conditions of this example 4, the mixture of

methylchlorosilanes was produced by the method with dimethyldichlorosilane being the major product.

Table 4: Production of methylchlorosilanes over metallic copper (425 urn) diluted with silica gel sphere (425 urn) catalyst treated at 750 °C with H2/S1CI4 = 1 in step (1 ) and 5 seem of

CH3CI (MeCI) at 300°C in step (2)

EXAMPLE 5 - PRODUCTION OF METHYLCHLOROSILANES OVER SILICA GEL DILUTED METALLIC COPPER CATALYST

[0070] Two grams of metallic copper (20 microns) were diluted with 1 gram of silica gel spheres (425 microns) and loaded into the reactor. The reactor was purged under N 2 and pressure checked for any leaks. The reactor was then heated under 100 seem H 2 at

500 °C with for 3-4 hours. Then, H 2 and SiCU were fed into the reactor for 30 min at 750 °C by bubbling H 2 through the stainless steel S1CI4 bubbler. The total flow of H 2 and S1CI4 was 150 seem with the mole ratio of H 2 to S1CI4 of 1 :1 . The S1CI4 flow was controlled by

H 2 flow by keeping the bubbler temperature at 37.2 °C. The gas and vapor leaving the bubbler was fed into the reactor containing the copper catalyst to form a reactant comprising 30 wt% Si. After 30 minutes, the S1CI4 flow was ceased and a hydrogen flow of 100 seem was maintained while cooling to 300 °C over 1 hour. When the reactor reached 300 °C, the reactor was purged with an argon flow of 50 seem for 30 min. After 30 min, the argon flow was ceased, and CH3CI (MeCI) was fed through the reactor at a flow rate of 5 seem, 300 °C and atmospheric pressure for 60 min. The reactor effluent was periodically sampled and analyzed by GC to determine the weight percent of (CH3)2SiCl2 (Me2SiCl2) and other chlorosilanes based on the total mass leaving the reactor.

[0071] Next, the CH3CI (MeCI) feed was ceased, and the spent reactant was treated with

H 2 at 500 °C for 30-60 min and contacted again with H 2 /SiCl4, for 30 min at 750 °C, to re- form the reactant. The combined flow rate of H2 and SiCl4 was 150 seem, and the mole ratio of H2 to SiCl4 was 1 :1 . After the reactant was re-formed, the reactor was purged with argon, again, and CH3CI (MeCI) was contacted with the re-formed reactant as described above. This was repeated, and the results are shown in Table 5. This example demonstrated that under the conditions of this example 5, the mixture of

methylchlorosilanes was produced by the method with dimethyldichlorosilane being the major product.

Table 5: Production of methylchlorosilanes over metallic copper (20 um) diluted with silica gel sphere (425 um) catalyst treated at 750 °C with H2/SiCl4 = 1 in step (1 ) and 5 seem of

CH3CI (MeCI) at 300°C in step (2)

[0072] Without wishing to be bound by theory, it is thought that the use of the catalyst described herein, which includes copper and a diluent may be more cost effective and/or scalable to commercial processes than process in which a supported copper catalyst is used instead of the catalyst described herein. The diluent may prevent sintering of the copper catalyst while being suitable to use in a commercial scale reactor, such as a fluidized bed reactor.

[0073] The disclosure of ranges includes the range itself and also anything subsumed therein, as well as endpoints. For example, disclosure of a range of 2.0 to 4.0 includes not only the range of 2.0 to 4.0, but also 2.1 , 2.3, 3.4, 3.5, and 4.0 individually, as well as any other number subsumed in the range. Furthermore, disclosure of a range of, for example, 2.0 to 4.0 includes the subsets of, for example, 2.1 to 3.5, 2.3 to 3.4, 2.6 to 3.7, and 3.8 to 4.0, as well as any other subset subsumed in the range.

[0074] With respect to any Markush groups relied upon herein for describing particular features or aspects of various embodiments, it is to be appreciated that different, special, and/or unexpected results may be obtained from each member of the respective Markush group independent from all other Markush members. Each member of a Markush group may be relied upon individually and or in combination with any other member or members of the group, and each member provides adequate support for specific embodiments within the scope of the appended claims. For example, disclosure of the Markush group: alkyl, aryl, and carbocyclic includes the member alkyl individually; the subgroup alkyl and aryl; and any other individual member and subgroup subsumed therein.

[0075] It is also to be understood that any ranges and subranges relied upon in describing various embodiments of the present disclosure independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein. The enumerated ranges and subranges sufficiently describe and enable various embodiments of the present disclosure, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on. As just one example, a range "of 200 to 1400" may be further delineated into a lower third, i.e., from 200 to 600, a middle third, i.e., from 600 to 1000, and an upper third, i.e., from 1000 to 1400, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims. In addition, with respect to the language which defines or modifies a range, such as "at least," "greater than," "less than," "no more than," and the like, it is to be understood that such language includes subranges and/or an upper or lower limit. As another example, a range of "at least 0.1 %" inherently includes a subrange from 0.1 % to 35%, a subrange from 10% to 25%, a subrange from 23% to 30%, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims. Finally, an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims. For example, a range of Ί to 9" includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1 , which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.

[0076] The subject matter of all combinations of independent and dependent claims, both singly and multiply dependent, is expressly contemplated but is not described in detail for the sake of brevity. The disclosure has been described in an illustrative manner, and it is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation. Many modifications and variations of the present disclosure are possible in light of the above teachings, and the disclosure may be practiced otherwise than as specifically described.