Selective 1,2-hydrosilylation of terminally unsaturated 1,3-dienes using iron catalysts
The present invention is directed to a selective and efficient process for the hydrosilylation of compounds containing terminally unsaturated 1,3-dienes using iron-based hydrosilylation catalysts. The resulting 1,2-addition products are useful as precursors for various silicone materials or silane- or silyl/silicone-functionalized polyolefins.
1. A process for the hydrosilylation of a compound containing a terminally unsaturated 1,3-diene, the process comprising (i) contacting a composition containing a silyl hydride and a compound containing a terminally unsaturated 1,3-diene with a complex of Formula (Ia) or (Ib), optionally in the presence of a solvent, to cause the silyl hydride to react with the compound containing a terminally unsaturated 1,3-diene to produce selectively a 1,2-hydrosilylation product containing said complex, and (ii) optionally removing the complex from the 1,2-hydrosilylation product;
wherein the compound containing a terminally unsaturated 1,3-diene has the formula CH 2 ═CH—CR═CHR′ where R and R′ independently is a saturated or unsaturated alkyl or aryl group or a halogen radical, with the proviso that R′ is H for isoprene and chloroprene; and
wherein the complexes of Formula (Ia) and (Ib) are
wherein:
G is Fe;
each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 is independently hydrogen, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent, wherein R 2 -R 9 , other than hydrogen, optionally contain at least one heteroatom;
each occurrence of R 23 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R 23 optionally contains at least one heteroatom;
optionally any two neighboring R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 23 groups taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure.
2. The process of claim 1 , wherein R 23 is
wherein R 1 , R 2 , R 4 , R 5 and R 6 are as defined in claim 1 .
3. The process of claim 1 , wherein R 1 and R 2 are both methyl, ethyl, propyl or isopropyl groups.
4. The process of claim 1 , wherein R 3 is methyl.
5. The process of claim 1 , wherein R 1 and R 2 are both methyl, R 4 , R 5 , and R 6 are hydrogen, and R 23 is 2,6-xylyl.
6. The process of claim 1 , wherein the complex of Formula (Ia) is [( Me PDI)FeN 2 ] 2 (μ 2 -N 2 ) or the complex of Formula (Ib) is ( Me PDI)Fe(N 2 ) 2 .
7. The process of claim 1 , wherein the complex is immobilized on a support.
8. The process of claim 7 , wherein the support is selected from the group consisting of carbon, silica, alumina, MgCl 2 , zirconia, polyethylene, polypropylene, polystyrene, poly(aminostyrene), dendrimers, and combinations thereof.
9. The process of claim 7 , wherein at least one of R 1 -R 9 contains a functional group that covalently bonds with the support.
10. The process of claim 1 , further comprising the step of removing the complex from the hydrosilylation product by magnetic separation and/or filtration.
11. The process of claim 1 , wherein the silyl hydride is selected from the group consisting of R a SiH 4-a , (RO) a SiH 4-a , Q u T v T p H D w D H x M H y M z , and combinations thereof, wherein Q is SiO 4/2 , T is R′SiO 3/2 , T H is HSiO 3/2 , D is R′ 2 SiO 2/2 D H is R′HSiO 2/2 , M H is HR′ 2 SiO 1/2 , M is R′ 3 SiO 1/2 , each occurrence of R and R′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, wherein R and R′ optionally contain at least one heteroatom, each occurrence of a independently has a value of from 1 to 3, g has a value of from 0 to 3, each of p, u, v, y and z is independently from 0 to 20, w and x are independently from 0 to 500, provided that p+x+y equals 1 to 500, and the valences of the all the elements in the silyl hydride are satisfied.
12. The process of claim 11 , wherein each of p, u, v, y, and z is independently from 0 to 10, w and x are independently from 0 to 100, wherein p+x+y equals 1 to 100.
13. The process of claim 1 , wherein the silyl hydride is MD H M.
14. The process of claim 1 , wherein the compound containing the terminally unsaturated 1,3-diene is isoprene, 1,3-hexadiene, myrcene, or chloroprene.
15. The process of claim 1 , wherein the catalyst is present in an amount of from about 0.05 mol % to about 5 mol %.
16. The process of claim 1 , wherein the catalyst is present in an amount of about 0.25 mol %.
17. The process of claim 1 , wherein the reaction is conducted over a period of from about 1 hour to about 24 hours.
18. The process of claim 1 , wherein the reaction is conducted over a period of about 24 hours.
19. A 1,2-hydrosilylation product produced from the process of claim 1 , wherein the compound containing the terminally unsaturated 1,3-diene is isoprene, 1,3-hexadiene, myrcene, or chloroprene, and wherein the product comprises (i) about 5 mol % or less of a 1,4-hydrosilylation product, an internal adduct, and/or an isomerization by-product, and (ii) the complex of (Ia) or (Ib).