Method for making an organoaminosilane; a method for making a silylamine from the organoaminosilane
A method of making an organoaminosilane compound, comprising i) combining A) a compound comprising a primary or secondary amine, B) monosilane (SiH 4 ), and C) a catalyst, where the catalyst comprises magnesium or boron, where A), B) and C) are combined under sufficient conditions to form the organoaminosilane compound and hydrogen. A method of making a silylamine, the method comprising: i) forming an organoaminosilane compound by i) combining A) a compound comprising a primary or secondary amine, B) monosilane (SiH 4 ), and C) a catalyst, where the catalyst comprises magnesium or boron, and ii) combining ammonia and the organoaminosilane compound produced in i) under sufficient conditions to form a silylamine product and a byproduct, where the byproduct is a primary or secondary amine.
1. A method of making an organoaminosilane compound, the method comprising:
combining
A) a compound comprising a primary or secondary amine,
B) monosilane (SiH 4 ), and
C) a catalyst, where the catalyst comprises magnesium or boron, wherein the catalyst comprising magnesium has the formula (R 5 2 N) 2 Mg, wherein each R 5 independently is a hydrocarbyl group having from 1 to 20 carbon atom, and wherein the catalyst comprising boron has the formula BR 4 3 , where each R 4 independently is a C 1-10 substituted or unsubstituted hydrocarbyl,
where A), B) and C) are combined under sufficient conditions to form the organoaminosilane compound and hydrogen.
2. A method as in claim 1 , where the organoaminosilane is according to formula (I)
R 1 N(R 2 ) a (H) c (SiH 3 ) 2-a-c (I),
where R 1 is an organic polymer, C 1-20 hydrocarbyl, or —SiR 3 3 , where R 3 is C 1-6 hydrocarbyl, R 2 is C 1-20 hydrocarbyl, H, —SiH 3 , or SiR 3 3 , where R 3 is as defined above, subscript a is 0 or 1, c is 0 or 1, and a+c<2,
provided that the organoaminosilane produced in i) has at least one more nitrogen-bonded —SiH 3 groups than the compound comprising the primary or secondary amine.
3. A method as in claim 1 , wherein the compound comprising a primary or secondary amine is according to formula (III)
R 1 N(R 2 ) a H 2-a (III),
where R 1 is an organic polymer, C 1-20 hydrocarbyl, or —SiR 3 3 , where R 3 is C 1-6 hydrocarbyl, R 2 is C 1-20 hydrocarbyl, H, —SiH 3 , or SiR 3 3 , where R 3 is as defined above, and subscript a is 0 or 1.
4. A method as in claim 3 wherein the compound comprising a primary or secondary amine according to formula (III) is an organic polymer comprising one or more groups according to formula (II)
—N(R 2 ) a (H) b (SiH 3 ) 2-a-b (II)
where R 2 is C 1-20 hydrocarbyl, H, —SiH 3 , or —SiR 3 3 , where R 3 is C 1-6 hydrocarbyl, subscript a is 0 or 1, subscript b is 1 or 2, a+b<3, and where the groups according to formula (II) are in pendant, terminal, or pendant and terminal positions on the organic polymer,
and the organoaminosilane compound is an organic polymer comprising one or more groups according to formula (IV)
—N(R 2 ) a (H) c (SiH 3 ) 2-a-c (IV)
where each R 2 and each subscript a are independently as defined above, subscript c is 0 or 1, a+c is 0 or 1, and the groups according to formula (IV) are in pendant, terminal, or pendant and terminal positions on the organic polymer.
5. A method as in claim 2 , wherein each R 1 independently is a branched alkyl having 3 to 6 carbon atoms, and each R 2 =R 1 .
6. A method as in claim 1 wherein the conditions are a temperature from −20° C. to 150° C. and a pressure above 102 kPa.
7. A method of making a silylamine, the method comprising:
i) combining
A) a compound comprising a primary or secondary amine,
B) monosilane (SiH 4 ), and
C) a catalyst, where the catalyst comprises magnesium or boron,
where A), B) and C) are combined under sufficient conditions to form an organoaminosilane compound and hydrogen, and
ii) combining ammonia and the organoaminosilane compound produced in i) under sufficient conditions to form a silylamine product and a byproduct, where the byproduct is a primary or secondary amine.
8. A method of making a silylamine as in claim 7 , wherein the organoaminosilane is according to formula (I)
R 1 N(R 2 ) a (SiH 3 ) 2-a (I),
where R 1 is an organic polymer, a C 1-20 hydrocarbyl group or —SiR 3 3 , where each R 3 independently is C 1-6 hydrocarbyl, each R 2 independently is a C 1-20 hydrocarbyl group, H, or —SiR 3 3 1 , where each R 3 independently is as defined above, subscript a is 0 or 1, and R 1 and R 2 may be the same or different.
9. A method as in claim 7 , wherein the silylamine product is trisilylamine, N(SiH 3 ) 3 .
10. A method as in claim 7 , wherein the sufficient conditions to form a silylamine product are a temperature from −20° C. to 150° C. and a pressure greater than 102 kPa.
11. A method as in claim 10 , wherein the temperature is from 0° C. to 75° C.
12. A method as in claim 7 , wherein R 1 is alkyl and each R 2 is independently R 1 or H.
13. A method as in claim 12 , wherein R 1 is branched alkyl having 3 to 6 carbon atoms, and each R 2 is independently R 1 or H.
14. A method as in claim 8 , wherein the compound according to formula (I) is an organic polymer comprising one or more groups according to formula (II)
—N(R 2 ) a (H) b (SiH 3 ) 2-a-b (II)
where each R 2 independently is H, C 1-20 hydrocarbyl, or —Si(R 3 ) 3 , where each R 3 independently is C 1-6 hydrocarbyl, subscript a and b independently are 0 or 1, and a+b<2, where the groups according to formula (II) are in pendant, terminal, or pendant and terminal positions on the organic polymer.
15. A method according to claim 7 , wherein a solvent is combined with the ammonia and the organoaminosilane compound.
16. A method as in claim 7 , further comprising iii) combining the byproduct formed in ii) in i), wherein the byproduct formed in ii) is combined in i) as A) the compound comprising a primary or secondary amine.
17. A method as in claim 7 , wherein the catalyst comprising magnesium has the formula (R 5 2 N) 2 Mg, wherein each R 5 independently is a hydrocarbyl group having from 1 to 20 carbon atom, and wherein the catalyst comprising boron has the formula BR 4 3 , wherein each R 4 independently is a C 1-10 substituted or unsubstituted hydrocarbyl.
18. A method as in claim 1 , wherein the catalyst comprising magnesium is selected from the group consisting of bis(dimethylamino) magnesium, bis(diethylamino) magnesium, bis(diispropylamino) magnesium, bis(dipropylamino) magnesium, bis(di-1-methylpropylamino) magnesium, bis(dipentylamino) magnesium, bis(di-1-methylbutylamino) magnesium, bis(dihexylamino) magnesium, bis(dicyclohexylamino) magnesium, bis(diheptylamino) magnesium, dioctylamino) magnesium, bis(dinonylamino) magnesium, bis(didecylamino) magnesium, bis(diundecylamino) magnesium, bis(dodecylamino) magnesium, bis(dipentadecylamino) magnesium, bis(dioctadecylamino) magnesium, and bis(dicosylamino) magnesium.
19. A method as in claim 1 , wherein the catalyst comprising boron is selected from the group consisting of trimethylborane, triethylborane, triphenylborane and tris(pentafluorophenyl)borane.
20. A method as in claim 19 , wherein the catalyst is boron tris-pentafluorobenzene.