WO2014143289A1

WO2014143289A1 - Preparation of organometallic compounds, hydrocarbyloxysilanes and hydrocarbyloxy-functional polyorganosiloxanes from alkali metal-impregnated silica

Info

Publication number: WO2014143289A1
Application number: PCT/US2013/076039
Authority: WO
Inventors: Aswini DASH; Charles Alan Hall; Dimitris Katsoulis; Matthew J. Mclaughlin; Jonathan Wineland
Original assignee: Dow Corning Corporation
Priority date: 2013-03-15
Filing date: 2013-12-18
Publication date: 2014-09-18

Abstract

A process for preparing a reaction product involves combining ingredients including: (A) a hydrocarbylating agent, and (B) an alkali metal/silica gel composition (M-SG). The M-SG includes (a) a silica gel, and (b) a Group 1 metal. The reaction product contains one or more of an organometallic compound, a hydrocarbyloxysilane, a hydrocarbyloxy-functional polyorganosiloxane, or a combination thereof.

Description

PREPARATION OF ORGANOMETALLIC COMPOUNDS, HYDROCARBYLOXYSI LANES AND HYDROCARBYLOXY-FUNCTIONAL POLYORGANOSILOXANES FROM ALKALI METAL- IMPREGNATED SILICA

[0001] Diorganodihalosilanes are hydrolyzed to produce a wide range of polyorganosiloxanes, which are sold into many different industries. Typically, diorganodihalosilanes are produced commercially by the Mueller-Rochow Direct Process, which comprises passing a hydrocarbyl halide, such as methyl chloride, over zero-valent silicon (SiO) in the presence of a copper catalyst and various promoters to produce a mixture of organohalosilanes. Of the organohalosilanes produced in the Direct Process, dimethyldichlorosilane is the most valuable.

[0002] A typical commercial process to make S^'fi comprises the carbothermic reduction of S1O2 in an electric arc furnace at extremely high temperatures. Generation of these extreme temperatures requires significant amounts of energy, which adds significant cost to the process of producing SiO.

Consequently, the use of Si^ adds significant costs to the production of diorganodihalosilanes.

[0003] 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.

[0004] Therefore, there is a need for a more economical method of producing

diorganodihalosilanes that avoids the need for S^'fi produced by reducing S1O2 at extremely high temperatures and that does not require the costly disposal of byproducts.

BRIEF SUMMARY OF THE INVENTION

[0005] A process for preparing a reaction product comprises combining ingredients comprising: (A) a hydrocarbylating agent, and (B) an alkali metal/silica gel composition (M-SG). The M-SG comprises (a) silica gel, and (b) a Group 1 metal. The reaction product comprises one or more of an organometallic compound, a hydrocarbyloxysilane, a hydrocarbyloxy-functional

polyorganosiloxane, or a combination thereof.

DETAILED DESCRPTION OF THE INVENTION

[0006] 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 prefix "poly" means more than one. Abbreviations used herein are defined in Table A, below. Table A - Abbreviations

[0007] "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, decyl, and other branched, saturated hydrocarbon groups of 6 to 12 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. [0008] "Aralkyl" 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 aralkyl groups include benzyl, tolyl, xylyl, phenylethyl, phenyl propyl, and phenyl butyl. Aralkyl groups have at least 4 carbon atoms. Monocyclic aralkyl groups may have 4 to 12 carbon atoms, alternatively 4 to 9 carbon atoms, and alternatively 4 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.

[0009] "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.

[0010] "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.

[0011] "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 6 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.

[0012] "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.

[0013] "Cycloalkyl" refers to a saturated hydrocarbon group including a saturated 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. [0014] The terms "Group 1 metal" and "Group 1 metals" mean those metals in the Group 1 family of the Periodic Table of the elements, which may be found at

http://oldJupac.orq/reports/periodic table/I UPAC Periodic Table-1 Jun12.pdf. The terms "Group 1 metal" and "Group 1 metals" include both alkali metals, and alloys of the alkali metals, which may be used to prepare the alkali metal/silica gel composition used in the process herein.

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

[0016] "Purging" means to introduce a gas stream to the reactor containing the alkali metal/silica gel composition to remove unwanted materials.

[0017] "Residence time" means the time which a material takes to pass through a reactor system in a continuous process, or the time a material spends in the reactor in a batch process. For example, residence time may refer to the time during which one reactor volume of the alkali metal/silica gel composition makes contact with the hydrocarbylating agent as the alkali metal/silica gel composition passes through the reactor system in a continuous process or during which the alkali metal/silica gel composition is placed within the reactor in a batch process. Alternatively, residence time may refer to the time for one reactor volume of reactant gas or liquid to pass through a reactor charged with the alkali metal/silica gel composition, e.g., the time for one reactor volume of the hydrocarbylating agent to pass through a reactor charged with the alkali metal/silica gel composition.

[0018] The hydrocarbylating agent used in the process described herein may be a hydrocarbyl halide. The hydrocarbyl halide may have the formula RX, where R is a hydrocarbyl group and X is a halogen. R may be selected from the group consisting of alkyl, aralkyl, alkenyl, alkynyl, aryl, and carbocyclic, as defined above. Alternatively, R may be an alkyl group or a cycloalkyl group. The alkyl groups for R may have 1 to 10 carbon atoms, alternatively 1 to 6 carbon atoms, and alternatively 1 to 4 carbon atoms. The cycloalkyl groups for R may have 4 to 10 carbon atoms, alternatively 6 to 8 carbon atoms. Alkyl groups containing at least three carbon atoms may have a branched or unbranched structure. Alternatively, R may be Me, Et, Pr, Bu, hexyl, or Ph.

Alternatively, R may be Me. Alternatively, X may be Br, CI or I; alternatively Br or CI; and alternatively CI. Examples of the hydrocarbyl halide 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.

[0019] Alternatively, the hydrocarbyl halide may be an aliphatic hydrocarbyl halide. The aliphatic hydrocarbyl halide may be a compound of formula H_mC_nX₀, where subscript m represents average number of hydrogen atoms present, subscript n represents average number of carbon atoms present, and subscript o represents average number of halogen atoms present. Subscript m is 0 or more, subscript n is 1 or more, and subscript o is 1 or more. When the hydrocarbyl halide is a noncyclic aliphatic hydrocarbyl halide, then a quantity (m + o) = a quantity (2n + 2). When the hydrocarbyl halide is a monocyclic cycloalkyi halide, then the quantity (m + o) = 2n. Each X is independently a halogen atom, as described above. Alternatively, subscript n may be 1 to 10, alternatively 1 to 6, alternatively 1 to 4, and alternatively 1 . Alternatively, subscript o may be 1 to 4. Alternatively, subscript o may be at least 2, alternatively 2 to 4. Examples of suitable hydrocarbyl halides include, but are not limited to, methyl chloride (H3CCI), methylene chloride (H2CCI2), chloroform (HCCI3), carbon tetrachloride (CCI4), and dichloroethane.

ely, the hydrocarbylating agent may be a carbonate of formula:

, where each R¹ and each R² are independently a hydrocarbyl group. R¹ and

R² may each be independently selected from the group consisting of alkyl, aralkyl, alkenyl, alkynyl, aryl, and carbocyclic groups, as defined above. Alternatively, R¹ and R² may each be an alkyl group or a cycloalkyi group. The alkyl groups for R¹ and R² may each have 1 to 10 carbon atoms, alternatively 1 to 6 carbon atoms, and alternatively 1 to 4 carbon atoms. The cycloalkyi groups for

R¹ and R² may each have 4 to 10 carbon atoms, alternatively 6 to 8 carbon atoms. Alkyl groups containing at least three carbon atoms may have a branched or unbranched structure.

Alternatively, and R² may each be Me, Et, Pr, hexyl, or Ph. Alternatively, and R² may each be Me.

[0021] The alkali metal/silica gel composition (M-SG) used in the process described herein may be commercially available or prepared by a method, such as that disclosed in WO2005/051839. The alkali metals used to prepare the M-SG are those metals in the Group 1 family of the Periodic Table of the elements, which may be found at

http://old.iupac.org/reports/periodic_table/IUPAC_Periodic_Table-1 Jun12.pdf. The terms "Group 1 metal" or "Group 1 metals" are used here to describe alkali metals and alloys of alkali metals which may be used to prepare the M-SG. Suitable Group 1 metals include sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs). Alternatively, the Group 1 metal may be Na or K. Alternatively, the Group 1 metal may be Na. Alternatively, the Group 1 metal may be K.

[0022] Alternatively, alkali metal alloys may be used to prepare the M-SG. The alloy may be an alloy of two or more Group 1 metals, for example, such alloys include sodium-potassium alloys, alloys containing two or more of K, Cs, and Rb with each other, and alternatively, alloys containing Na and further comprising one or more of K, Cs, and/or Rb may be used. Alternatively, the alloy may be a sodium-potassium alloy. The alkali metal alloys are within the "Group 1 metal" definition as used in the specification and claims. Alternatively, the Group 1 metal is selected from sodium, potassium, rubidium, cesium, and an alloy of one or more of sodium, potassium, rubidium, and cesium. Alternatively, the Group 1 metal is selected from sodium, potassium, and sodium- potassium alloys.

[0023] In one embodiment of the process described herein, the process further comprises forming the M-SG by a technique comprising combining the Group 1 metal and the silica gel, optionally with heating. The Group 1 metal may be mixed with the silica gel by any convenient means. The viscosity of the liquid Group 1 metal should be at least low enough to be absorbed by the silica gel. One method to accomplish this is heating the Group 1 metal to a temperature allowing it to melt under in an inert atmosphere before mixing with the silica gel. Alternatively, depending on the stage of M-SG to be prepared (as discussed below), the Group 1 metal may be mixed as a solid with the silica gel and the mixture heated to melt the alkali metal. An alternative method to introduce Group 1 metals into silica gel is from the vapor phase. In another method, a Group 1 metal can be deposited onto the silica gel from a metal-ammonia solution. The metal-ammonia solution can be used to avoid agglomeration of the metal when mixing with the silica gel and to prepare an intimate mixture of the metal with the silica gel.

[0024] As discussed below, for at least Stage 0 M-SG, the Group 1 metal may be selected to have a melting point within Ι δ 'Ό of room temperature of 25°C, i.e., a melting point from Ι Ο 'Ό to 40 'Ό. For example, Cs and Rb have melting points of 28.5 °C and 38.5 'Ό, respectively. Typically alloys of the two or more alkali metals are liquid at or near room temperature. An exemplary low- melting alloy is that between sodium and potassium (Na-K alloy) at various molar ratios of Na to K, which may be from 1 :5 to 5:1 , alternatively 1 :2 to 1 :5 (e.g., Nal<2 or NaKs). Other binary alloys of these metals, such as Cs with Rb, K, or Na; and Rb with Na or K also melt below, or only slightly above room temperature and would therefore be appropriate to use. Ternary alloys, made from three of these four metals, or an alloy of all four would also be expected to melt at low enough temperatures to form an M-SG for use in the process herein.

[0025] Silica gel is a porous form of amorphous silica. It is a free-flowing powder that may be at least 99% S1O2. Silica gel is commercially available and inexpensive. Suitable silica gel for use herein generally has a pore volume ranging from 0.6 cm^/g to 1 .2 cm^/g, and a surface area ranging from 300 m^/g to 750 m^/g. Silica gel is commonly available in the following mesh sizes: 3- 8, 6-16, 14-20, 14-42, 30-60, 28-200, and as small as mesh 325. The silica gels used in the M-SG may have pore sizes ranging from 50 A to 1000 A. Alternatively, the pore size may range from 100 A to 300 A. Suitable forms of silica gel include Davisil™ Grades 646 and 50, which are both 30 to 60 mesh obtained from chemical suppliers such as Aldrich and directly from the Davison Chemical Division of WR Grace Company, (i.e., 150 A pore size, granular, 30-60 mesh, plain white, no indicator). An alternate supplier of such silica gel is the Eagle Chemical Division of Multisorb.

[0026] Silica gel typically contains large amounts of gaseous material, such as water and air. These may be removed before mixing the silica gel with the Group 1 metal to form the M-SG. The silica gel may be degassed using methods known in the art. For example, to remove the gaseous material the silica gel may be heated, optionally under vacuum, to temperatures of up to 300 'C. It is also possible to remove the gases and to passivate active sites by heating the silica gel to 600 'C or hotter (900°C) in air (calcination). Heating the silica gel to 600 'C or higher may cause at least some of Si-OH sites in the pores or silica gel lattice to form siloxane, Si-O-Si, groups with the concomitant loss of water. Heating the silica gel at a lower temperature would also produce a usable starting silica gel, but a portion of the Group 1 metal might be rendered inert by reaction with Si-OH groups remaining in the silica. The silica gel may be cooled to room temperature after heating and before mixing with the Group 1 metal to form an M-SG.

[0027] The M-SG's described herein are described as Stage 0, I, II, and III materials. These materials differ in their preparation and chemical reactivity. Each successive stage may be prepared directly using the methods described below or from an earlier stage material. Stage 0 materials may, for example, be prepared using liquid alloys of Na and K which are rapidly absorbed by silica gel under isothermal conditions, for example at or just above room temperature, to form loose black powders that retain much of the reducing ability of the Group 1 metals. It is believed the Stage 0 materials have small clusters of neutral Group 1 metal absorbed in the silica gel pores. Stage I materials may be prepared by heating Stage 0 materials at 140°C overnight. Stage I material is a loose black powder that may be stable in dry air. Subsequent heating to 400 °C produces Stage II materials, which are also loose black powders. Further heating above 400 ^ forms Stage III material with release of some Group 1 metal. Without wishing to be bound by theory, it is believed that Stage I, II and III materials represent reductions of the silica gel after absorption of the Group 1 metal.

[0028] The amount of Group 1 metal loading is dependent upon the pore size and pore density of the silica gel used. Typically, the Group 1 metal may be present in the compositions of the invention up to about 50% by weight; alternatively from 10% to 40%, and alternatively from 30% to 40%, based on the weight of the M-SG. In the Stage I, II, and III materials, loadings above 40% by weight may result in some free metal remaining in the silica gel pores.

[0029] The process may further comprise using a catalyst. The catalyst may be selected from metallic copper (Cu), metallic tin (Sn), metallic Zinc (Zn), phosphorous (P), and combinations of Cu, Sn, Zn, and/or P. Alternatively, the catalyst may comprise one or more salts of Cu, Sn, Zn, or P. Salts are exemplified by halides, e.g., chlorides such as cuprous chloride (CuCI), stannous chloride (SnCl2), stannic chloride (SnCl4), and/or zinc chloride (ZnCl2); and phosphides, such as copper phosphide (CU3P). Alternatively, the catalyst may comprise one or more of copper, phosphorus, tin, zinc, a salt of copper, a salt of phosphorus, a salt of tin, and a salt of zinc. Alternatively, the catalyst may comprise metallic copper or cuprous chloride. The amount of catalyst can vary depending on the type and amount of species selected from the catalyst and the activity of the Group 1 metal. However, the amount of catalyst may range from 1 % to 35%, alternatively 2% to 30%, and alternatively 9% to 25% of the M-SG based on the combined weights of all ingredients in the M-SG. Alternatively, when metallic copper, copper chloride, metallic Zn, and/or metallic Sn are used individually, the amount may range from 5% to 15%, alternatively 9% to 13% of the M-SG. Alternatively, when Zn and/or Sn are used in combination with copper or a copper compound, then the amount of Zn and/or Sn may be 0.1 % to 1 % of the M-SG.

[0030] The process can be performed in any reactor suitable for the combining of gases and solids or any reactor suitable for the combining of liquids and solids. For example, the reactor configuration can be a batch vessel, packed bed, stirred bed, vibrating bed, moving bed, recirculating beds, or a fluidized bed. Alternatively, the reactor for may be a packed bed, a stirred bed, or a fluidized bed. To facilitate reaction, the reactor may have means to control the

temperature of the reaction zone, i.e., the portion of the reactor in which the hydrocarbylating agent and M-SG are in contact.

[0031] The temperature of the reactor in which the hydrocarbylating agent and the M-SG are contacted is at least 300 °C, alternatively 300 ^<C to 700 ^<C; alternatively 300 °C to 600 °C; alternatively 350 °C to 500 °C; alternatively 350 °C to 480 °C; alternatively 350 °C to 450 ^<C; alternatively 350 ^<C to 400 °C; alternatively 370 ^<C to 400 ^<C; and alternatively 300 °C to 400 °C. Without wishing to be bound by theory, it is thought that if temperature is less than 300 'C, then the reaction may not proceed at a sufficient speed to produce the desired product; and if the temperature is greater than 700 °C, then the hydrocarbylating agent and/or hydrocarbyloxysilanes and/or hydrocarbyloxy- functional polyorganosiloxanes in the reaction product may decompose.

[0032] The pressure at which the hydrocarbylating agent and the M-SG are contacted can be sub-atmospheric, atmospheric, or super-atmospheric. For example, the pressure may range from greater than 0 kilopascals absolute (kPa) to 2000 kPa; alternatively 100 kPa to 1000 kPa; and alternatively 101 kPa to 800 kPa.

[0033] The mole ratio of hydrocarbylating agent to M-SG 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 . The amounts of hydrocarbylating agent and M-SG are sufficient to provide the mole ratio described above.

[0034] The residence time for the hydrocarbylating agent is sufficient for the hydrocarbylating agent to contact the M-SG and form the reaction product. For example, a sufficient residence time 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, and alternatively 0.5 s to 10 s. The desired residence time may be achieved by adjusting the flow rate of the hydrocarbylating agent, or by adjusting the total reactor volume, or by any combination thereof.

[0035] The M-SG is used in a sufficient amount. A sufficient amount of M-SG is enough M-SG to form the reaction product, when the hydrocarbylating agent is contacted with the M-SG. The exact amount of M-SG depends upon various factors including the type of reactor used (e.g., batch or continuous), the residence time, temperature, the molar ratio of hydrocarbylating agent to M-SG, and the particular hydrocarbylating agent used. However, a sufficient amount of M-SG may be at least 0.01 milligram per cubic centimeter (mg/cm^) of reactor volume; alternatively at least 0.5 mg/cm^ of reactor volume, and alternatively 1 mg/cm^ of reactor volume to the maximum bulk density of the M-SG, alternatively 1 mg/cm^ to 5,000 mg/cm^ of reactor volume, alternatively 1 mg/cm^ to 1 ,000 mg/cm^ of reactor volume, and alternatively 1 mg/cm^ to 900 mg/cm^ of reactor volume.

[0036] There is no upper limit on the time for which the process is conducted. Without wishing to be bound by theory, it is thought that the process may be performed indefinitely to make the reaction product as the hydrocarbylating agent is contacted with the M-SG, provided sufficient silica gel is added. For example, the process may conducted for at least 0.1 s, alternatively 1 s to 30 hours (h), alternatively 1 s to 5 h, alternatively 1 min to 30 h, alternatively 3 h to 30 h, alternatively 3 h to 8 h, and alternatively 3 h to 5 h.

[0037] The process described herein may also comprise purging before contacting the M-SG and the hydrocarbylating agent. Purging may be conducted to remove unwanted gaseous or liquid materials. Unwanted materials are, for example, air, O2 and/or H2O. Purging may be

accomplished with a gas such as Ar, He, H2, and/or N2; alternatively H2; alternatively an inert gas such as Ar, He, and/or N2. Purging may be performed by feeding the gas into the reactor at ambient or elevated temperature, such as 25 °C to 300 °C.

[0038] The process may further comprise vaporizing the hydrocarbylating agent, such as by known methods, e.g., heating, before contacting with the M-SG. Alternatively, the process may further comprise bubbling a first hydrocarbylating agent (e.g., the hydrocarbylating agent of formula RX) through a second hydrocarbylating agent (such as the carbonate described above) to vaporize the second hydrocarbylating agent before contacting with the M-SG.

[0039] The process may further comprise recovering the reaction product, for example, to purify one or more of the compounds in the reaction product produced. The reaction product may be recovered by, for example, removing gaseous reaction product and any other vapors from the reaction product followed by condensation of the vapors and/or isolation of one or more compounds from any other compounds in the reaction product by a technique such as solvent extraction and/or distillation.

[0040] The reaction product produced by the process described and exemplified herein comprises one or more of organometallic compounds, hydrocarbyloxysilanes (such as

alkoxysilanes) and hydrocarbyloxy-functional polyorganosiloxanes (such as alkoxy-functional polyorganosiloxanes). Examples of organometallic compounds in the reaction product include organotin compounds such as alkyl tin compounds and alkyl, halo tin compounds. The organotin compound may have formula R_aSnXk, where subscript a is 1 or more and subscript b is 0 or more, with the proviso that a quantity (a + b) = 4, R is a hydrocarbyl group as described above, and X is a halogen as described above (e.g., methyl tin compounds of formula Me_aSnClb, where a and b are as described above). Such organofunctional tin compounds may be used, for example, as catalyst for condensation reactions. Examples of hydrocarbyloxysilanes in the reaction product include alkoxysilanes, such as alkylalkoxysilanes and tetraalkoxysilanes, e.g., Me_cSi(OMe)(4__c) and

Si(OMe)4, where subscript c is 1 to 3, alternatively 2. Examples of hydrocarbyloxy-functional polyorganosiloxanes include both oligomers and polymers, such as Me3SiOSiMe3.

[0041] The hydrocarbyloxysilanes (such as alkoxysilanes) and hydrocarbyloxy-functional polyorganosiloxanes (such as alkoxy-functional polyorganosiloxanes) may be used as reactants to make polyorganosiloxane resins with crosslinked siloxane networks. Such polyorganosiloxane resins are useful, for example, as high temperature coatings, as thermal and electrical insulating coatings, as hydrophobic coatings, and/or as matrices for fiber reinforced composites.

EXAMPLES

[0042] 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.

[0043] The alkali metal/silica gel compositions (M-SG) used in these examples were obtained from SiGNa Chemistry, Inc. of New York, NY, USA, or from Sigma-Aldrich Co. LLC of St. Louis, MO, USA. These compositions were stored under an inert atmosphere until they were ready to be used (in N2 glove bag or Ar glove box). These compositions were used without further purification. [0044] Methyl bromide was used as the hydrocarbylating agent. The reactors were glass tubes heated in an aluminum block. Below each reactor, a trap was cooled to allow collection of product exiting the reactors as a liquid. Table 1 shows the M-SG's that were used in these examples. Table 1 . Na-K / silica gel compositions obtained from SiGNa Chemistry LLC.

[0045] The ranking of the relative basicity and reducing power was done upon consultation with SiGNa. Stage II materials were considered the stronger bases and material with the highest atomic percent of alkali metal (i.e., KsNa-SG) were the more powerful reducing agents.

[0046] Samples in the amount of 500 mg of each M-SG were loaded into a reactor under inert conditions. Additional samples were prepared by mixing 500 mg of each M-SG with a catalyst under inert conditions, and loading each resulting mixture (of the M-SG and the catalyst) into a reactor. The reactor was connected to a gas delivery system. The reactor was heated to 327°C. MeBr was then passed either directly through the reactor, or first bubbled through dimethyl carbonate. Reaction times were 6.5 h to 7.5 h. Liquid was collected in cold traps through which the reactor effluent passed, and the liquid was analyzed by GC-MS.

[0047] Tables 2 to 6 compile the main products of the reactions of M-SG's with MeBr and Me₂C03 as detected by GC-MS. The stage I, only sodium containing M-SG (Na/Si02 I), produced methyl-silicon species when P, Sn, Zn, their combinations and the combination with CuCI were used as the catalyst (see Table 2). When tin was used as part of the catalyst package, methyl-tin organometallic compounds dominated the GC-MS spectra. Methoxysilanes including Si(OMe)4 were also observed in the reaction product together with organic compounds (ethers, ketones, saturated and unsaturated hydrocarbons, shown below in Table 8). Without wishing to be bound by theory, it is thought that the presence of organic compounds can be attributed to dehydration, de- oxygenation, dissociation, exchange and decomposition reactions of Me₂C03 in the presence of

MeBr. [0048] The stage II, only sodium containing M-SG (Na/Si02 II) produced methyl-silicon species in the presence of almost all the combinations of catalysts that were tried (see Table 3). Even reactions over Cu and CuCI formed methyl-methoxy silanes and siloxanes. The reactivity of Na/Si02 II with MeBr / Me2C03 seemed to be greater than the reactivity of the Na/Si02 I under the same conditions. As was the case with the Na/Si02 Stage I halo methyl tin organometallic compounds were produced when tin was used as catalyst. In the absence of catalyst, Si(OMe)4 and organic compounds were observed.

[0049] The sodium-potassium alloy containing M-SG's (Na2K/SiC>2, NaK2/SiC>2 and NaKs/SiC^) were all stage I and were thought to increase in reducing power with potassium loading. The results of their reactions with MeBr / Me2C03 are summarized in Tables 4-6. Based on the GC-MS data, Cu alone seemed to be the most effective of the catalyst combinations that were tried with one of these M-SG's. Of the three Na-K alloy containing M-SG's, NaK2 Si02 produced the highest amount of methyl methoxy silanes and methoxy-functional polyorganosiloxanes. Without wishing to be bound by theory, it is thought that the high reducing power of the Nal<2 alloy could be responsible for this reactivity.

Table 2. Summary of reactions of Na/Si02 I materials with MeBr (Me2C03) in the presence of catal sts.

a Clear liquid, milliliters.

[0050] In the tables herein, (< ml) means greater than 0 but less than 1 ml of liquid was recovered, (« ml) means greater than 0 and much less than 1 ml was recovered, and (0) means the sample analyzed was from the gas phase and no liquid was recovered.

Table 3. Summary of reactions of Na/Si02 II materials with MeBr (Me2C03) in the presence of catalysts.

aClear liquid, unless notes otherwise, milliliters. Table 4. Summary of reactions of Na2K/SiC>2 with MeBr (Me2C03) in the presence of catalysts.

aClear liquid, milliliters. Table 5. Summary of reactions of NaK2 Si02 materials with MeBr (Me2C03) in the presence of catalysts.

M-SG Catalyst(s) Reaction GC-MS Results Liq.

Time Recovered (min) (ml)*

NaK₂/Si0₂ Cu 420 Me_cSi(OMe)4-_c, c is 0, 1 or 2; (1 )

methyl and methoxy siloxanes;

some Et, Pr, Vi, EtO, PrO, BuO, OH

groups

NaK₂/Si0₂ Cu, P, Sn, 420 MebSi(OMe)4-b, b is 0 , 1 , 2, or 3; (0.5)

and Zn methyl and methoxy siloxanes;

some Et, Pr, Bu, EtO, PrO, and OH

groups

NaK₂/Si0₂ CuCI 435 MebSi(OMe)4-b, b is 0 , 1 , 2, or 3; (0.5)

methyl and methoxy siloxanes;

some Bu, Pr, Et, BuO, EtO, PrO,

OH groups

NaK₂/Si0₂ CuCI, P, Sn, 450 Si(OMe)₄, MeSi(OMe)₃; some Et, (0)

and Zn EtO, OH silanes; methoxysiloxanes

NaK₂/Si0₂ CuCI, P, Sn, 390 MebSi(OMe)4_b, b is 0 , 1 , 2, or 3; (« ml)

and Zn some Et, Pr, Vi, OH groups, one

siloxane

NaK₂/Si0₂ P, Sn, and 420 MebSi(OMe)4-b, b is 0 , 1 , 2, or 3; (1 )

Zn methyl and methoxy siloxanes;

some Pr, Et, BuO, EtO, PrO groups;

large MeSi(OMe)_3j Si(OMe)₄, and

(MeO)₃SiOSi(OMe)₃

NaK₂/Si0₂ Sn 390 BrbSnMe4_b, b = 0, 1 , 2, or 3, (0)

CISnMe₃, (OSiMe2)4-5 cyclics

NaK₂/Si0₂ P, Sn, Zn, 405 Br_cSnMe4_-c, c is 0, 1 , or 2, (< ml)

and CuCI organics M-SG Catalyst(s) Reaction GC-MS Results Liq.

Time Recovered (min) (ml)^a

NaK₂/Si0₂ Zn 480 Mostly air, organics (0)

NaK₂/Si0₂ No catalyst 390 MebSi(OMe)4-b, b is 0, 1 , 2, or 3; (4)

methyl and methoxy siloxanes,

some Et, Pr, Bu, EtO, PrO, H, and

OH groups

aClear liquid, milliliters.

Table 6. Summary of reactions of Nal<5/Si0₂ materials with MeBr (Me₂C03) in the presence of catalysts.

aClear liquid, milliliters.

Table 7. X- ray diffraction results of M-SG's, Na/SiC>2 I, Na/SiC>2 II and Na2K/SiC>2 and NaK2/SiC>2 with catalyst, before and after reaction with MeBr/Me2C03. Reaction temperature, 327 ^<C. Reaction time, 450 min.

7A1 7B1 7B2 7C1 7D1 7E 7F

Na/Si0₂ I (after Na/Si0₂ II (after Na/Si0₂ II Na₂K/Si0₂ NaK₂/Si0₂ CuCI Promoters reaction) reaction) Standard (after reaction) (after reaction) Standard Standard

NaBr (57%) NaBr (88.3%) Na₂Si0₃ (90.9%) KBr (57.0%) KBr (86.7%) CuCI (86.8%) Cu₃P (69.1 %)

CuOHCI Cu₅Zn₈

Na₂Si0₃ (26.7%) CuBr (9.3%) NaSi₆ (9.1 %) NaBr (39.2%) NaBr (8.6%) (13.2%) (30.9%)

CuClo.75Bro.25

Na0₂ (12.1 %) (2.4%) Cu (3.8%) Cu (4.7%)

Cu (4.2%)

6 The x-ray diffraction pattern of Na/Si02 I, Na2K/Si02, and Nal<2/Si02 solids prior to reaction shows them to be amorphous.

[0051] The XRD results showed that the Na/SiC>2 II contained a crystalline component (9.1 wt% sodium silicide, NaSis) prior to the reaction with MeBr/Me2C03. The Na/SiC>2 I, Na2K/SiC>2 and NaK2/Si02 solids presented an amorphous pattern. After the reaction, the crystalline component of the solids dominated the XRD patterns (see Table 7). The alkali cations were oxidized to Na⁺ and K+ forming salts with Br and S1O3^2" anions.

[0052] Without wishing to be bound by theory, it is thought that the reduced form of silicon in the silica matrix, either via its reaction with the zero-valent metals during the above described methylation experiments or via its preformed silicide form, was the substrate that was methylated because most of the reactions of M-SG with MeBr / Me2C03 resulted in the formation of methyl-silicon species. This theory is supported by the observation that the Na/SiC>2 II composition that contained 9% silicide was the most readily methylated substrate of the group.

Table 8. Organic compounds observed in GC-MS of reactions of Si-SG materials with MeBr (Me2CC>3) in the presence of catalysts.

[0053] These examples show that silica gel that has been impregnated with alkali metals can be methylated with MeCI and Me2CC>3 in the presence of the catalysts under the conditions described above. Without wishing to be bound by theory, it is thought that Group 1 metals reduce portions of the silicate network to form silicides and/or other reduced silicon centers which readily participate in hydrocarbylation (e.g., methylation) reactions.

[0054] A new process can be used for the preparation of hydrocarbyloxysilanes and hydrocarbyloxy-functional polyorganosiloxanes. The process comprises reacting silica- based raw materials, which have been modified by the addition of Group 1 metals, with conventional hydrocarbylating agents in the presence of metal-based catalysts. Group 1 metals such as sodium, potassium, and their alloys are used to impregnate silica at various loadings. The resulting metal-modified silica (and silicates) reacts with hydrocarbylating agents (such as alkyl halides, e.g., methyl chloride or methyl bromide or alkyl carbonates, e.g., dimethyl carbonate) or their combinations at temperatures similar to those used during the Direct Process for the manufacturing of dihydrocarbyldihalosilanes such as

dimethyldichlorosilane. The reaction is assisted by the presence of the catalysts described herein. Without wishing to be bound by theory, it is thought that the process described herein may provide the benefit of eliminating the need for carbothermic reduction to Si⁰ before reacting with a hydrocarbylating agent, such as an alkylating agent.

[0055] 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 and provides adequate support for specific embodiments within the scope of the appended claims. The disclosure of Markush groups includes the entire group and also any individual members and subgroups subsumed therein. For example, disclosure of the Markush group: alkyl, alkenyl, alkynyl, and carbocyclic groups includes the member alkyl individually; the subgroup alkyl and alkenyl; and any other individual member and subgroup subsumed therein.

[0056] 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 "1 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.

[0057] 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.

Claims

1. A process for preparing a reaction product comprises:

Optionally (pre-1 ) purging a reactor containing an alkali metal/silica gel composition, where the alkali metal/silica gel composition comprises

(a) a silica gel, and

(b) a Group 1 metal; and

(1 ) at a temperature of at least 300 °C, combining ingredients comprising

(A) a hydrocarbylating agent,

(B) the alkali metal/silica gel composition, and

optionally (C) a catalyst;

thereby forming the reaction product, where the reaction product comprises an

organometallic compound, a hydrocarbyloxysilane, a hydrocarbyloxy-functional polyorganosiloxane, or a combination thereof.

2. The process of claim 1 , where the Group 1 metal is selected from sodium, potassium, rubidium, cesium, and an alloy of one or more of sodium, potassium, rubidium, and cesium.

3. The process of claim 1 or claim 2, where the catalyst is present in step (1 ), and the catalyst comprises one or more of copper, phosphorus, tin, zinc, a salt of copper, a salt of phosphorus, a salt of tin, and a salt of zinc.

4. The process of any one of the preceding claims where the hydrocarbylating agent is selected from:

(I) a hydrocarbyl halide of formula RX, where R is a hydrocarbyl group and X is a halogen;

(II) an aliphatic hydrocarbyl halide of formula H_xC_yX_z, where subscript x is 0 or more, subscript y is 1 or more, and

(III) a carbonate of formula:

re each R¹ and each R² are independently a hydrocarbyl group; and

(IV) combinations of two or more of (I), (II), and (III).

5. The process of claim 4, where R is alkyl, X is Br or CI, R¹ is alkyl, and R² is alkyl.

6. The process any one of the preceding claims, further comprising forming the alkali metal/silica gel composition before step (1 ) by a technique comprising combining silica gel with the Group 1 metal, and optionally heating the silica gel and Group 1 metal.

7. The process of claim 6, where the process further comprises heating the silica gel to a temperature of 300 °C to 900 °C before forming the alkali metal/silica gel composition, and optionally cooling the silica gel before combining.

8. The process of any one of the preceding claims, further comprising (2) recovering the reaction product.

9. The process of claim 8, where the reaction product comprises at least one of a hydrocarbyloxysilane and a hydrocarbyloxy-functional polyorganosiloxane.

10. A hydrocarbyloxysilane produced by the process of any one of claims 1 to 9.

1 1. Use of the hydrocarbyloxysilane of claim 10 as a reactant for preparing a resin.

12. A hydrocarbyloxy-functional polyorganosiloxane produced by the process of any one of claims 1 -9.

13. Use of the hydrocarbyloxy-functional polyorganosiloxane of claim 12 as a reactant for preparing a resin.

14. An organofunctional tin compound produced by the process of any one of claims 1 -8.

15. Use of the organofunctional tin compound of claim 14 as a catalyst.