Process for the direct synthesis of trialkoxysilane
View Patent ↗The Direct Synthesis of trialkoxysilane is carried out by conducting the Direct Synthesis reaction of silicon and alcohol, optionally in solvent, in the presence of a catalytically effective amount of Direct Synthesis catalyst and an effective catalyst-promoting amount of Direct Synthesis catalyst promoter, said promoter being an organic or inorganic compound possessing at least one phosphorus-oxygen bond.
1. A process for the Direct Synthesis of trialkoxysilane which comprises conducting the Direct Synthesis reaction of silicon and alcohol, optionally in solvent, in the presence of a mixture of a catalytically effective amount of Direct Synthesis catalyst precursor and an effective catalyst-promoting amount of Direct Synthesis catalyst promoter, said promoter being a mixture of organic and inorganic compound possessing at least one phosphorus-oxygen bond wherein a Direct Synthesis catalyst is produced in-situ by the reaction of the Direct Synthesis catalyst precursor with silicon.
2. The process of claim 1 wherein the trialkoxysilane possesses the general formula HSi(OR) 3 wherein each R is the same or different alkyl of from 1 to 6 carbon atoms.
3. The process of claim 2 wherein R is methyl, ethyl, propyl or isopropyl.
4. The process of claim 2 resulting in at least one additional reaction product selected from the group consisting of Si(OR) 4 , RSi(OR) 3 , (RO) 3 SiOSi(OR) 3 , H(RO) 2 SiOSi(OR) 2 H, HSi(RO) 2 SiOSi(OR) 3 , (RO) 3 SiOSi(OR) 2 R, (RO) 3 SiOSi(RO) 2 OSi(RO) 3 , (RO) 3 SiOSi(OR)HOSi(OR) 3 , (RO) 3 SiOSi(OR)ROSi(OR) 3 , (RO)Si[OSi(OR) 3 ] 3 , (RO) 3 SiOSi(OR)(OSi(RO) 3 )OSi(OR) 3 and [OSi(OR) 2 ] n , wherein n is at least 4.
5. The process of claim 1 wherein the Direct Synthesis catalyst is obtained by contacting silicon and at least one member of the group consisting of copper and copper-containing compound.
6. The process of claim 1 wherein the Direct Synthesis catalyst is at least one member selected from the group consisting of copper-silicon alloy, intermetallic of copper and silicon, silicon containing diffused copper, reaction product of silicon and copper-containing compound.
7. The process of claim 5 wherein the copper-containing compound is at least one member of the group consisting of copper (I) oxide, copper (II) oxide, copper (I) chloride, copper (II) chloride, copper (II) hydroxide, mixed hydrous oxides, basic copper carbonate, copper carboxylate, copper alkoxide and copper siloxide.
8. The process of claim 6 wherein the copper-containing compound is at least one member of the group consisting of copper (I) oxide, copper (II) oxide, copper (I) chloride, copper (II) chloride, copper (II) hydroxide, mixed hydrous oxides, basic copper carbonate, copper carboxylate, copper alkoxide and copper siloxide.
9. The process of claim 1 wherein the Direct Synthesis catalyst possesses a particle size within the range of from about 0.1 to about 100 nanometers.
10. The process of claim 5 wherein the Direct Synthesis catalyst possesses a particle size within the range of from about 0.1 to about 100 nanometers.
11. The process of claim 6 wherein the Direct Synthesis catalyst possesses a particle size within the range of from about 0.1 to about 100 nanometers.
12. The process of claim 1 wherein the Direct Synthesis catalyst is substantially anhydrous.
13. The process of claim 5 wherein the Direct Synthesis catalyst is substantially anhydrous.
14. The process of claim 6 wherein the Direct Synthesis catalyst is substantially anhydrous.
15. The process of claim 1 wherein the Direct Synthesis catalyst promoter possessing at least one phosphorus-oxygen bond is at least one phosphorus-containing compound selected from the group consisting of phosphate salt, phosphate ester, polyphosphate, metaphosphate, pyrophosphate, phosphonate and phosphite.
16. The process of claim 15 wherein the phosphorus-containing compound contains at least one PO 4 3− , P 2 O 7 2− , P 3 O 10 5− , P n+1 O 3n+4 (n+3)− wherein n is at least 4 and P x O 3x x− wherein x is at least 3.
17. The process of claim 15 wherein the phosphorus-containing compound is at least one copper-containing compound selected from the group consisting of copper orthophosphate, copper metaphosphate and copper polyphosphate.
18. The process of claim 1 wherein the Direct Synthesis catalyst promoter possesses a particle size within the range of from about 0.1 to about 600 nanometers.
19. The process of claim 15 wherein the Direct Synthesis catalyst promoter possesses a particle size within the range of from about 0.1 to about 600 nanometers.
20. The process of claim 9 wherein the Direct Synthesis catalyst promoter possesses a particle size within the range of from about 0.1 to about 600 nanometers.
21. The process of claim 1 wherein the Direct Synthesis catalyst promoter is substantially anhydrous.
22. The process of claim 12 wherein the Direct Synthesis catalyst promoter is substantially anhydrous.
23. The process of claim 4 wherein the Direct Synthesis catalyst promoter is present in the reaction medium in an amount effective to limit Si(OR) 4 formation to below about 6 weight percent and to provide HSi(OR) 3 formation of greater than about 85 weight percent based on the total weight of silane products.
24. The process of claim 1 , wherein the effective catalyst-promoting amount of Direct Synthesis catalyst promoter is from 3 to 30 weight percent, based on the weight of copper catalyst precursor.
25. A process for the Direct Synthesis of trialkoxysilane which comprises conducting the Direct Synthesis reaction of silicon and alcohol, optionally in solvent, in the presence of a mixture of a catalytically effective amount of Direct Synthesis catalyst precursor selected from the group consisting of copper (I) oxide, copper (II) oxide, copper (I) carbonate, copper carboxylate, copper alkoxide and copper siloxide and an effective catalyst-promoting amount of Direct Syntheses catalyst promoter, said promoter being a mixture of organic and inorganic compounds possessing at least on phosphorus-oxygen bond is at least one phosphorus-containing compound selected from the group consisting of phosphate salt, phosphate ester, polyphosphate, metaphosphate, pyrophosphate, phosphonate and phosphite, wherein the Direct Synthesis catalyst promoter is from 3 to 30 weight percent based upon the weight of copper catalyst precursor, wherein a Direct Synthesis catalyst is produced in-situ by the reaction of the Direct Synthesis catalyst precursor with silicon.
26. The process of claim 25 wherein the phosphorus-containing Compound contains at least one PO 4 3− , P 2 O 7 2− , P 3 O 10 5− , P n+1 O 3n+4 (n+3)− ion wherein n is at least 4 and P x O 3x x− wherein x is at least 3.
27. The process according to claim 25 wherein the Direct Synthesis catalyst promoter is of the general formula:
(RO) n (OH) 3−n PO
wherein R is C 1 to C 20 alkyl, cylcoaliphatic or alkaryl and n is an integer from 0 to 3.
28. The process according to claim 25 wherein the Direct Synthesis catalyst promoter is of the general formula:
MD x D* y M
wherein M is (CH 3 ) 3 SiO 1/2 ; D is (CH 3 ) 2 SiO 2/2 ; D* is (CH 3 )SiZO 2/2 ; Z is a phosphorlyated oxyalkylene group; and x and y are greater than zero.
29. The process according to claim 25 wherein the Direct Synthesis catalyst promoter is of the general formula:
M*D u D* y M*
wherein M* is Z(CH 3 ) 2 SiO 1/2 ; D is (CH 3 ) 2 SiO 2/2 ; D* is (CH 3 )SiZO 2/2 ; Z is phosphorlyated oxyalkylene group; u is greater than zero; and v is greater than or equal to zero.
30. The process according to claim 25 wherein the Direct Synthesis catalyst promoter is of the general formula:
(ROSi) w (R′OP═O) z
wherein R is C 1 to C 20 alkyl, cylcoaliphatic or alkaryl; R′ is C 1 to C 20 alkyl, cylcoaliphatic or alkaryl; and each w and z is an integer from 0.5 to 25.
31. The process according to claim 25 wherein the Direct Synthesis catalyst promoter is of the general formula:
(RO) m P 2 O 3 (OH) 4−m
wherein R is C 1 to C 20 alkyl, cylcoaliphatic or alkaryl; and m is greater than or equal to 2.
32. The process according to claim 25 wherein the trialkoxysilane possesses the general formula HSi(OR) 3 wherein each R is the same or different alkyl of from 1 to 6 carbon atoms.
33. The process of claim 32 wherein R is methyl.
34. The process of claim 25 wherein the catalytically effective amount of Direct Synthesis catalyst precursor is from about 0.01 to about 5 parts by weight of catalyst precursor per 100 parts by weight of silicon metal.