Hydrosilylation synthesis of haloalkylorganosilanes using peroxide promoters
View Patent ↗This invention is directed to a process for producing a haloorganoalkoxysilane product comprising reacting an olefinic halide, an alkoxysilane, a catalytically effective amount of ruthenium-containing catalyst; and a reaction-promoting effective amount of a peroxy compound, optionally in the presence of an electron-deficient aromatic compound.
1. A process for producing a haloorganoalkoxysilane product of Formula (I),
(R 1 ) y (R 2 O) 3-y SiCH 2 CHR 3 CR 4 R 5 X (I)
comprising reacting at a temperature of from about 50° C. to about 130° C.
(a) an olefinic halide having the formula H 2 C═CR 3 CR 4 R 5 X;
(b) an alkoxysilane having the formula (R 1 ) y (R 2 O) 3-y SiH;
(c) a catalytically effective amount of ruthenium-containing catalyst; and
(d) a reaction-promoting effective amount of a peroxy compound selected from the group consisting of (i) a hydroperoxide having a decomposition rate with a half-life of 1 hour at a temperature of from 30° C. to 200° C., (ii) a Group 14 hydroperoxide having a decomposition rate with a half-life of 1 hour at a temperature of from 30° C. to 200° C., (iii) a Group 14 peroxide having a decomposition rate with a half-life of 1 hour at a temperature of from 30° C. to 200° C., (iv) a ketone peroxide having a decomposition rate with a half-life of 1 hour at a temperature of from 30° C. to 200° C., (v) a peroxide having the general formula R—O—O—R, wherein R is a C1 to C25 group that is linear or branched, saturated or unsaturated, cyclic, aromatic or alkaryl and having a decomposition rate with a half-life of 1 hour at a temperature of from 100° C. to 160° C., (vi) a diacyl peroxide having a decomposition rate with a half-life of 1 hour at a temperature of from 40° C. to 100° C., (vii) a peroxy dicarbonate having a decomposition rate with a half-life of 1 hour at a temperature of from 50° C. to 75° C., (viii) a peroxy ester having a decomposition rate with a half-life of 1 hour at a temperature of from 50° C. to 100° C. and (ix) a peroxy ketal having a decomposition rate with a half-life of 1 hour at a temperature of from 100° C. to 150° C., provided, where any of peroxy compounds (i)-(ix) contains a cyclic group, such group is monocyclic, optionally in the presence of an electron-donating aromatic compound, to produce the haloorganoalkoxysilane product,
wherein
R 1 and R 2 are alkyl groups of from 1 to 6 carbon atoms;
R 3 is an alkyl group of from 1 to 6 carbon atoms or hydrogen;
R 4 is an alkyl group of from 1 to 6 carbon atoms, hydrogen or halogen;
R 5 is hydrogen or an alkyl group of from 1 to 6 carbon atoms;
X is a halogen; and
y is 0,1 or 2; and, wherein the peroxy compound (d) is pre-mixed with the olefinic halide (a).
2. The process of claim 1 , wherein the olefinic halide is selected from the group consisting of allyl chloride, methallyl chloride, 3-chloro-1-butene, 3,4-dichloro-1-butene, 2-chloropropene, and combinations thereof.
3. The process of claim 1 , wherein said alkoxysilane is selected from the group consisting of trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, ethyldiethoxysilane, dicthylethoxysilane, and combinations thereof.
4. The process of claim 1 , wherein said reaction-promoting effective amount of said peroxy compound ranges from about 1 to about 2000 ppm, based on the total weight of the reaction mass.
5. The process of claim 1 , wherein said reaction-promoting effective amount of said peroxy compound is from 350 to 6000 ppm for t-butylperoxy-3,5,5-trimethylhexanoate, from 20 to 100 ppm for allyl hydroperoxide, from 50 to 1000 ppm for t-butyl hydroperoxide, from 50 to 1000 ppm for cumene hydroperoxide, from 3 to 300 ppm for di-tert-butyl peroxide, from 50 to 1000 ppm for dicumyl peroxide, from 50 to 2500 ppm for dibenzoyl peroxide, from 50 to 3500 ppm for di(n-peropyl)peroxydicarbonate or from 50 to 3500 ppm for di(2-ethylhexyl)peroxydicarbonate, based on the total weight of the reaction mass.
6. The process of claim 1 , wherein said hydroperoxides(i) and (ii) have the formula R—O—O—H or R 2 C(O—O—H) 2 , wherein R is a C1 to C25 group that is linear or branched, saturated or unsaturated, cyclic, aromatic or alkaryl.
7. The process of claim 6 , wherein said hydroperoxides (i) and (ii) are selected from the group consisting of t-butyl hydroperoxide, t-amyl hydroperoxide, cumene hydroperoxide, allyl hydroperoxide, tetrahydrofuryl hydroperoxide, limonene hydroperoxides, terpene hydroperoxides, steroidal hydroperoxides, 2,5-dihydroperoxy-2,5-dimethylhexane, and combinations thereof.
8. The process of claim 1 , wherein said Group 14 hydroperoxides (ii) and Group 14 peroxides (iii) have the formula Z—O—O—H, wherein Z is a silyl, germyl or stannyl moiety.
9. The process of claim 8 , wherein said Group 14 hydroperoxides (ii) and Group 14 peroxides (iii) are selected from the group consisting of trimethylsilylhydroperoxide, tribenzylsilylhydro-peroxide, tert-butyldimethylsilylhydroperoxide, methyldiphenylsilylhydroperoxide, triphenylsilyihydroperoxide, and combinations thereof.
10. The process of claim 1 , wherein said peroxides (v) are selected from the group consisting of di-t-butyl peroxide, di-t-amyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and combinations thereof.
11. The process of claim 1 , wherein said diacyl peroxides (vi) have the general formula (RC(O)O) 2 , wherein R is a linear or branched, cyclic, aromatic or alkaryl group having 1-25 carbon atoms.
12. The process of claim 11 , wherein said diacyl peroxides (vi) are selected from the group consisting of didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, and combinations thereof.
13. The process of claim 1 , wherein said peroxy esters (viii) have the general formula, RC(O)O—OR, wherein each occurrence of R is a linear or branched, cyclic, aromatic or alkaryl group containing 1-25 carbon atoms.
14. The process of claim 13 , wherein said peroxy esters (viii) are selected from the group consisting of cumyl peroxyneodecanoate, t-amyl peroxypivalate, t-butyl peroxy-3,5,5-trimethylhexanoate, and combinations thereof.
15. The process of claim 1 , wherein said peroxy dicarbonates (vii) have the general formula (ROC(O)O) 2 , wherein R is a linear or branched, cyclic, aromatic or alkaryl group containing 1-25 carbon atoms.
16. The process of claim 15 , wherein said peroxy dicarbonates (vii) are selected from the group consisting of di(n-propyl)peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, and combinations thereof.
17. The process of claim 1 , wherein said peroxy ketals (ix) have the general formula, R 2 C(O—O—R′) 2 , wherein R and R′ are each individually linear or branched, cyclic, aromatic or alkaryl groups containing 1-25 carbon atoms.
18. The process of claim 17 , wherein said peroxy ketals (ix) are selected from the group consisting of ethyl-3,3-di(t-butylperoxy)butyrate, 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-butyl-peroxy)3,3,5-trimethylcyclohexane, and combinations thereof.
19. The process of claim 1 , wherein said ruthenium-containing catalyst is selected from the group consisting of particulate ruthenium, ruthenium halides, zinc-reduced or tin reduced reaction products of ruthenium halides, cycloolefin complexes of ruthenium, amine complexes of ruthenium, and combinations thereof.
20. The process of claim 19 , wherein said ruthenium-containing catalyst is selected from the group consisting of RuCl 3 , RuBr 3 , MRuCl 3 , M 2 Ru 5 Cl 12 , M 4 Ru 4 Cl 12 , where M═H, or alkali metal; ZnRu 5 Cl 12 and SnRu 5 Cl 12 ; RuO 2 , Ru 3 (CO) 12 , [Ru(CO) 3 Cl 2 ] 2 ; cycloolefin complexes of ruthenium Ru(COD)(COT), COD—RuCl 2 , [COD—RuCl 2 ] where COD is cyclooctadiene and COT is cyclooctatriene; bis(6,6-dimethylcyclopentadienyl)ruthenium, bis(η 5 -2,4-dimethylpentadienyl)ruthenium, bis(1,3-dimethylcyclopentadienyl)ruthenium Ru(AcAc) 3 where AcAc is an acetylacetonate ligand; (π-arene) ruthenium complexes such as (p-cymene) ruthenium (II) chloride dimer and (benzene) ruthenium (II) chloride dimer, [Ru(NH 3 ) 6 ]X 2 and [Ru(NH 3 ) 6 ]X 3 where X is a halogen; and, combinations thereof.
21. The process of claim 1 , wherein said electron-donating aromatic compound is selected from the group consisting of benzene, ethylbenzene, diethylbenzene, triethylbenzene, η-butylbenzene, di-t-butylbenzene, bibenzyl, toluene, t-butyltoluene, anisole, 1-phenylhexane, 1-phenyldodecane, mixtures of n-alkylbenzenes with alkyl groups of from C 8 to C 20 , mixtures of diphenylalkanes and bibenzyl isomers, mixtures of benzyl toluenes and dibenzyl toluenes, m-xylene, mesitylene, p-cymene, diphenylmethane, triphenylmethane, phenyl ether, phenothiazine, biphenyl, and combinations thereof.
22. The process of claim 1 , wherein component (b) is present in said process in molar excess relative to component (a).
23. The process of claim 1 , wherein said ruthenium-containing catalyst is substantially-free of phosphine.
24. The process of claim 1 , wherein component (a) is allyl chloride, component (b) is trimethoxysilane, component (c) is RuCl 3 , and component (d) is di(t-butyl)peroxide.
25. The process of claim 1 , wherein said ruthenium-containing catalyst is a zinc-reduced reaction products of ruthenium halides or tin reduced reaction products of ruthenium halides.
26. The process of claim 1 , wherein the ruthenium-containing catalyst (c) is sparged with oxygen before contact of the catalyst (c) with the peroxy compound (d).