Granted Patent B2

US 9,249,165 · App. 14/471,625 · Granted Feb 2, 2016

Abstract

Claims (25)

1. A process for the synthesis of organohalosilane monomers, comprising the steps of:

(1) forming a slurry of cyclone fines, ultra fines and/or spent contact mass in a thermally stable solvent and reacting the agitated slurry with at least one organohalide of the formula R 1 X and optionally organohalosilane and/or hydrogen halide in the presence of an additive selected from the group consisting of dialkylpolyethers, podands, secondary amines, terpenes, diterpenes, triterpenes, nitrohydrocarbons, nitriles, hexamethyldisiloxane, polydimethylsiloxanes having a viscosity of from 5 to 100 cSt, and mixtures thereof for a reaction time and at a temperature and pressure sufficient to produce organohalosilane monomers having the formulae R 1 SiHX 2 , R 1 2 SiHX, R 1 3 SiX, R 1 SiX 3 , and R 1 2 SiX 2 or mixtures thereof;

wherein R 1 is a saturated or unsaturated aromatic group, a saturated or unsaturated aliphatic group, alkaryl group, or cycloaliphatic hydrocarbyl group, and X is a halogen; and

(2) recovering said organohalosilane monomers from said solvent.

2. The process of claim 1 , wherein R 1 is methyl, ethyl, phenyl, cyclohexyl, allyl, vinyl, methallyl, phenyl, or benzyl.

3. The process of claim 1 wherein the slurry is a slurry of cyclone fines and wherein R 1 is allyl or methallyl and the organohalosilane monomers are of the formulae R 1 SiX 3 or mixtures of R 1 SiX 3 and R 1 SiHX 2 and wherein the optional hydrogen halide is present and where the molar ratio of allyl halide to hydrogen halide in the mixture of step (1) is greater than or equal to one.

4. The process of claim 1 wherein X is fluorine, chlorine, bromine, or iodine.

5. The process of claim 1 , wherein the organohalide is selected from the group consisting of methyl chloride, methyl bromide, ethyl chloride, vinyl chloride, allyl chloride, chlorobenzene, and mixtures thereof.

6. The process of claim 1 , wherein the solvent is selected from the group consisting of linear or branched paraffins, naphthenes, alkylated benzenes, dialkylated benzenes, aromatic ethers, polyaromatic hydrocarbons, hydrochloric acid and mixtures thereof.

7. The process of claim 1 , wherein said additive is selected from the group consisting of tetra(ethyleneglycol)dimethyl ether, tri(ethyleneglycol)dimethyl ether, diphenylamine, hexamethyldisiloxane, polydimethylsiloxanes having a viscosity of from 5 to 100 cSt, turpentine, squalene, nitrobenzene, trivinylcyclohexane, adiponitrile, 1,6-dicyanohexane, and mixtures thereof.

8. The process of claim 1 , wherein said temperature is greater than about 180° C.

9. The process of claim 1 , wherein said temperature ranges from about 250° C. to about 450° C. when the organohalide is methyl chloride, methyl bromide, ethyl chloride and chlorobenzene.

10. The process of claim 1 , wherein the reaction pressure ranges from about atmospheric pressure to about 10 atmospheres.

11. The process of claim 1 , wherein the reaction time is within the range from about 0.1 to about 100 hours.

12. The process of claim 1 , further comprising combining said slurry and said organohalide in the presence of a foam control agent.

13. The process of claim 1 , further comprising the step of recovering the solvent for reuse in step (1).

14. The process of claim 1 , further comprising introducing additional cyclone fines, ultra fines and/or spent mass into the reaction slurry after the initial charge has been partially or fully converted, and continuing the reaction with the organohalide to produce organohalosilane monomers without first recovering and/or remediating the solvent.

15. A process for the synthesis of organohalosilane monomers, comprising the steps of:

(1) forming a slurry of cyclone fines, ultra fines and/or spent contact mass in a thermally stable solvent and reacting the agitated slurry with methyl chloride and optionally organohalosilane and/or hydrogen halide in the presence of tetraglyme for a reaction time and at a temperature of from 240° C. to about 350° C. and at a pressure of from about 1 to about 5 atmospheres to produce organohalosilane monomers having the formulae R 1 SiHX 2 , R 1 2 SiHX, R 1 3 SiX, R 1 SiX 3 , and R 1 2 SiX 2 or mixtures thereof;

wherein R 1 is methyl, and X is Cl; and

(2) recovering said organohalosilane monomers from said solvent and wherein the initial solvent to solids gravimetric ratio is in the range from about 1 to about 3.

16. The process of claim 1 wherein the organohalide is allyl chloride, allyl bromide, methallyl chloride or methallyl bromide, and the reaction is conducted at about 200 to about 280° C.

17. The process of claim 16 wherein the organohalide is allyl chloride, initial solvent to solids gravimetric ratio is about 1 to about 3, the additives are methyltrichlorosilane, tetraglyme, or combinations thereof, the temperature is about 200 to about 280° C. and the pressure is about 1 to about 5 atmospheres.

18. The process of claim 16 wherein products of general formula, R 1 SiX 3 , and/or R 1 SiHX 2 , are produced with greater selectivity than al least one of the products of general formulae, R 1 2 SiX 2 , R 1 3 SiX, R 1 2 SiXH and R 1 SiHX 2 when R 1 is unsaturated.

19. The process of claim 1 wherein the products of the general formula R 1 2 SiX 2 are produced with greater selectivity than products of the general formula R 1 SiX 3 when R 1 is saturated.

Assignments (16)