Synthesis of organohalosilane monomers via enhanced cleavage of direct process residue
View Patent ↗Discloses herein is a catalytic process for producing organohalosilane monomers from a high-boiling residue resulting from the Direct Reaction of an organohalide with silicon. The high-boiling residue contains more conventionally cleavable compounds than conventionally uncleavable compounds. The process includes heating the residue in the presence of a catalyst comprising (1) one or more heterocyclic amines and/or one or more heterocyclic ammonium halides, and (2) one or more quaternary Group 15 onium compounds.
1. A catalytic process for producing an organohalosilane monomer composition from a high-boiling residue resulting from the Direct Reaction of an organohalide with silicon, said process comprising
(A) heating the high-boiling residue in the presence of a catalyst comprising (1) one or more heterocyclic amines and/or one or more heterocyclic ammonium halides, and (2) one or more quaternary Group 15 onium compounds,
optionally in the presence of an organohalide and/or a hydrogen halide and/or an inert gas, at a temperature within the range of about 75° C. to about 300° C. under atmospheric pressure or superatmospheric pressure
to convert the high-boiling residue to an organohalosilane monomer composition containing at least one organohalosilane monomer having a general formula selected from the group consisting of R 1 SiHX 2 , R 1 2 SiHX, R 1 2 SiX 2 and R 1 3 SiX, R 1 being an aromatic, aliphatic, alkaryl or cycloaliphatic univalent hydrocarbyl group, X being a halogen atom selected from the group consisting of fluorine, chlorine, bromine, and iodine, and
(B) optionally recovering the catalyst,
wherein the high-boiling residue comprises (1) a cleavable component containing at least one of diorganotetrahalodisilanes and triorganotrihalodisilanes and (2) optionally an uncleavable component containing at least one of carbosilanes, polysilanes, hexaorganodisilanes, pentaorganohalodisilanes and tetraorganodihalodisilanes, with the proviso that if present, the uncleavable component has a concentration no greater than that of the cleavable component; and
wherein the quaternary Group 15 onium compound is of the general formula, R 4 Q + X − , wherein each R is independently an alkyl, cycloalkyl, aryl or alkaryl group of from 1 to 30 carbon atoms, Q is phosphorus, arsenic, antimony or bismuth, and X is a halide selected from the group consisting of F, Cl, Br and I.
2. The process of claim 1 wherein the heterocyclic amine has at least one nitrogen atom in at least one 4- to 8-membered hydrocarbon ring, wherein the ring atoms adjacent to the nitrogen are carbon or nitrogen, and the hydrocarbon ring or rings are, independently of one another, aromatic or non-aromatic hydrocarbon rings.
3. The process of claim 2 wherein the heterocyclic amine has a pKa of about 6.9 to about 7.9.
4. The process of claim 2 wherein the heterocyclic amine contains a five-membered ring with 1 to 3 nitrogen atoms.
5. The process of claim 4 wherein the heterocyclic amine is selected from the group consisting of imidazole, 1-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropyl-imidazole, 4-methylimidazole, 2,4-dimethylimidazole, 2-(2-imidazolyl)imidazole, 2-phenylimidazole, imidazoline, imidazolidine, pyrazole, 3-methylpyrazole, pyrrolidone, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidone, 1,2,3-triazole, and 1,2,4-triazole.
6. The process of claim 1 wherein the heterocyclic ammonium halide is derived from a heterocyclic amine having at least one nitrogen atom in at least one 4- to 8-membered hydrocarbon ring, wherein the ring atoms adjacent to the nitrogen are independently carbon or nitrogen atoms, and the hydrocarbon ring or rings are, independently of one another, aromatic or non-aromatic hydrocarbon rings, wherein the halide is fluoride, chloride, bromide or iodide.
7. The process of claim 6 wherein the heterocyclic ammonium halide is derived from a heterocyclic amine with 1 to 3 nitrogen atoms in a five-membered ring, and the halide is fluoride, chloride, bromide or iodide.
8. The process of claim 7 wherein the heterocyclic ammonium halide is 1,2-dimethyl-3-(n-propyl)-imidazolium chloride, 1-ethyl-3-methylimidazolium bromide, 1,2-dimethyl-3-(n-butyl)imidazolium chloride, 1-butyl-3-methyl-imidazolium chloride, 1-(3-cyanopropyl)-3-methylimidazolium chloride, or 1-methylimidazolium chloride.
9. The process of claim 6 wherein the heterocyclic ammonium halide is an ionic liquid selected from the group consisting of 1-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, and 1-(3-cyanopropyl)-3-methylimidazolium chloride.
10. The process of claim 1 wherein the quaternary Group 15 onium compound, R 4 Q + X − , is tetra(n-butyl)phosphonium chloride, tetra(n-butyl)phosphonium bromide, trihexyl(tetradecyl)phosphonium bromide, methyltri(isobutyl)phosphonium bromide, methyltri(isobutyl)phosphonium chloride, tetra(n-octyl)phosphonium chloride, tri(n-butyl)tetradecylphosphonium chloride, or octyltri(butyl)phosphonium chloride.
11. The process of claim 10 wherein the quaternary Group 15 onium compound is an ionic liquid selected from the group consisting of tri(n-hexyl)tetradecylphosphonium chloride, tetra(n-butyl)phosphonium bromide, tetra(n-butyl)phosphonium chloride, tri(n-butyl)tetradecylphosphonium chloride, and methyltri(isobutyl)phosphonium chloride.
12. The process of claim 1 wherein the step (A) is conducted in the presence of an organohalide being methyl chloride or methyl bromide.
13. The process of claim 1 wherein the step (A) is conducted in the presence of a hydrogen halide being HCl or HBr.
14. The process of claim 1 wherein the step (A) is conducted in the presence of an inert gas being nitrogen or argon.
15. The process of claim 1 wherein the high-boiling residue resulted from the Direct Reaction of methylchlorosilanes, ethylchlorosilanes, phenylchlorosilanes, methylbromosilanes, ethylbromosilanes or phenylbromosilanes; and wherein R 1 is methyl, ethyl or phenyl and X is chloride or bromide.
16. The process of claim 1 wherein the gravimetric ratio (R 1 SiHX 2 +R 1 2 SiHX+R 1 2 SiX 2 +R 1 3 SiX)/R 1 SiX 3 is greater than or equal to 2.
17. The process of claim 1 wherein the organohalosilane monomer composition comprises (CH 3 ) 2 SiHCl, CH 3 SiHCl 2 , (CH 3 ) 3 SiCl, (CH 3 ) 2 SiCl 2 , and CH 3 SiCl 3 , and wherein the content of (CH 3 ) 2 SiCl 2 and CH 3 SiHCl 2 , individually or collectively, exceeds that of CH 3 SiCl 3 .
18. The process of claim 1 wherein the high-boiling residue is heated under a superatmospheric pressure of up to 7 MPa at about 150° C. to about 250° C. for a period of 30 to 150 minutes.
19. The process of claim 1 wherein the high-boiling residue is heated under ambient atmospheric pressure at about 140° C. to about 250° C.
20. The process of claim 1 wherein the catalyst comprises from about 0.01 wt % to about 99.95 wt % of (1) the heterocyclic amine and/or heterocyclic ammonium halide; and from about 0.05 wt % to about 99.9 wt % of (2) the quaternary Group 15 onium compound based on the total weight of components (1) and (2).
21. The process of claim 20 wherein the weight ratio of the heterocyclic amine and/or heterocyclic ammonium halide relative to the quaternary Group 15 onium compound is from about 1:9 to about 9:1.
22. The process of claim 21 wherein the catalyst comprises 2-methylmidazole and tetra(n-butyl)phosphonium and wherein the molar ratio of 2-methylmidazole to tetra(n-butyl)phosphonium chloride is from 1.1 to 100.
23. The process of claim 1 wherein the weight of the catalyst is 1 to 50 percent of the weight of the high-boiling residue.
24. The process of claim 1 wherein multiple batches of the high-boiling residue are converted to the organohalosilane monomer composition on a single catalyst charge, and the ultimate catalyst usage, defined as 100×(weight of the catalyst/total weight of the high-boiling residue), is about 0.1 to about 5 weight percent.
25. The process of claim 1 wherein the catalytic process comprises at least one reaction selected from the group consisting of disproportionation, redistribution, silylene extrusion, and silylene insertion.
26. The process of claim 25 wherein the reactions are conducted batchwise or continuously in ionic liquids in a mechanically-stirred reactor, a gas-sparged reactor or a bubble column.