High activity catalyst for hydrosilylation reactions and methods of making the same
A heterogeneous catalyst comprising a metal-containing polymer matrix covalently bonded to a support material and a method of making and using such catalysts. The metal-containing polymer matrix comprises metal nano-particles encapsulated in a polymer matrix, e.g., a siloxane. In one aspect, the metal-containing polymer matrix can be bonded to the support material via a hydrophobic group attached to the support material. The catalyst can be recovered after being used in a metal catalyzed reaction and exhibit excellent catalytic activity upon reuse in subsequent reactions.
1. A heterogeneous catalyst comprising a metal-containing siloxane polymer matrix covalently bonded to a support material,
wherein the support material is chosen from silicon, a sodium silicate, a borosilicate, a calcium aluminum silicate, clay, silica, calcium carbonate, barium carbonate, a metal oxide, and mixtures of two or more thereof;
wherein the support material comprises a functional group chosen from silanol, alkoxy, acetoxy, silazane, oximino-functional silyl group, hydroxyl, acyloxy, ketoximino, amine, aminoxy, alkylamide, hydrogen, an aliphatic olefinic group, aryl, hydrosulfide, or a combination of two or more thereof;
wherein the metal-containing siloxane polymer matrix comprises metal nanoparticles encapsulated in a siloxane polymer matrix, wherein the polymer matrix comprises a crosslinked or partially crosslinked network of hydrosiloxanes with a vinyl silicone compound, wherein the hydrosiloxanes are chosen from a silicon hydride-containing polyorganohydrosiloxane of the general formula:
M 1 a M 2 b D 1 c D 2 d T 1 e T 2 f Q J
wherein: M 1 =R 1 R 2 R 3 SiO 1/2 ; M 2 =R 4 R 5 R 6 SiO 1/2 ; D 1 =R 7 R 8 SiO 2/2 ; D 2 =R 9 R 10 SiO 2/2 ; T 1 =R 11 SiO 3/2 ; T 2 =R 12 SiO 3/2 ; Q=SiO 4/2 ; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are aliphatic, aromatic or fluoro monovalent hydrocarbon having from 1 to 60 carbon atoms; at least one of R 9 or R 12 is hydrogen; and the subscript a, b, c, d, e, f, and j are zero or positive subject to the following limitations: 2≤a+b+c+d+e+f+j≤6000, and b+d+f>0;
wherein the covalent bond is formed between the functional group present on the support material and the siloxane polymer matrix.
2. The catalyst of claim 1 , wherein the metal nanoparticles are chosen from nanoparticles of aluminum, iron, silver, zinc, gold, copper, cobalt, nickel, platinum, manganese, rhodium, ruthenium, palladium, titanium, vanadium, chromium, molybdenum, cadmium, mercury, calcium, zirconium, iridium, cerium, oxides and sulfides of such metal, or combinations of two or more thereof.
3. The catalyst of 1 wherein the metal-containing polymer matrix has a ratio of polymer to metal of from about 1:1000 to about 100:1.
4. The catalyst of claim 1 , wherein the metal-containing polymer matrix has a weight ratio of polymer to metal of from about 1:1 to about 20:1.
5. The catalyst of claim 1 , wherein the metal-containing polymer matrix has a weight ratio of polymer to metal of from about 10:1 to about 20:1.
6. The catalyst of claim 1 , wherein the metal-containing polymer matrix has a weight ratio of polymer to metal of from about 12:1 to about 16:1.
7. The catalyst of claim 1 wherein the metal particles have a particle size of from about 1 to about 100 nanometers.
8. The catalyst of claim 1 wherein the metal loading ranges from about 0.05 to about 5 percent by weight of the support material.
9. The catalyst of claim 1 wherein the metal loading ranges from about 0.1 to about 1 percent by weight of the support material.
10. The catalyst of claim 1 , wherein the support material comprises a functional group chosen from —Si—CH═CH 2 , —Si—OH, —Si—(CH 2 ) n C≡CH, —Si—(CH 2 ) n —NH 2 , —Si—(CH 2 ) n —OH, —Si—(CH 2 ) n —SH, or a combination of two or more thereof, and n is 1-26.
11. The catalyst of claim 1 wherein the metal-containing polymer matrix is covalently bonded to the support material via a hydrophobic functional group attached to the support material.
12. The catalyst of claim 11 wherein the hydrophobic functional group is chosen from a silazane-containing functional group.
13. A method of synthesizing supported nanoparticle catalysts, the method comprising:
(a) forming a metal-containing polymer matrix comprising metal nanoparticles by forming a colloidal suspension of metal nano-particles by reacting metal complexes with a silicon hydride-containing polyorganohydrosiloxane solution to form a colloidal suspension of metal nano-particles and subsequently reacting the suspension to form a polymer matrix and encapsulate the metal nano-particles in a siloxane matrix, wherein the polymer matrix comprises a crosslinked or partially crosslinked network of hydrosiloxanes with a vinyl silicone compound, and the hydrosiloxanes are chosen from a silicon hydride-containing polyorganohydrosiloxane of the general formula:
M 1 a M 2 b D 1 c D 2 d T 1 e T 2 f Q J
wherein: M 1 =R 1 R 2 R 3 SiO 1/2 ; M 2 =R 4 R 5 R 6 SiO 1/2 ; D 1 =R 7 R 8 SiO 2/2 ; D 2 =R 9 R 10 SiO 2/2 ; T 1 =R 11 SiO 3/2 ; T 2 =R 12 SiO 3/2 ; Q=SiO 4/2 ; R 1 , R 2 , R 3 ,R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are aliphatic, aromatic or fluoro monovalent hydrocarbon having from 1 to 60 carbon atoms; at least one of R 9 or R 12 is hydrogen; and the subscript a, b, c, d, e, f, and j are zero or positive subject to the following limitations: 2≤a+b+c+d+e+f+j≤6000, and b+d+f>0; and
(b) attaching the metal-containing polymer matrix to a support material via covalent chemical bonds, wherein the support material is chosen from silicon, a sodium silicate, a borosilicate, a calcium aluminum silicate, clay, silica, metal oxide, and mixtures of two or more thereof; and wherein the support material comprises a functional group chosen from silanol, alkoxy, acetoxy, silazane, oximino-functional silyl group, hydroxyl, acyloxy, ketoximino, amine, aminoxy, alkylamide, hydrogen, an aliphatic olefinic group, aryl, hydrosulfide, or a combination of two or more thereof.
14. The method of claim 13 wherein the reacting of the metal complexes with a silicon hydride-containing polyorganohydrosiloxane solution in solvent is under nitrogen atmosphere.
15. The method of claim 14 , wherein the metal complex is selected from a metal salt chosen from PtCl 2 , H 2 PtCl 6 , Pt 2 (dba) 3 , Pt 2 (dvs) 3 , Pt(OAc) 2 Pt(acac) 2 , Na 2 PtCl 6 , K 2 PtCl 6 , platinum carbonate, platinum nitrate, 1,5-cycooctadienedimethylplatinum(II), platinum perchlorate, amine complexes of the platinum ammonium hexachloropalladate(IV), palladium(II) chloride, AuCl 3 , Au 2 O 3 , NaAuO 2 , AgCl, AgNO 3 , CuSO 4 , CuO, Cu(NO 3 ) 2 , CuCl 2 , Ru 2 O 3 , RuCl 2 , FeCl 2 .6H 2 O, ZnCl 2 , CoCl 2 .6H 2 O, NiCl 2 .6H 2 O, MnCl 2 .4H 2 O, TiCl 4 , vanadium chloride, cadmium chloride, calcium chloride, zirconium tetrachloride, mercuric chloride complexes, or a combination of two or more thereof.
16. The method of claim 14 , wherein encapsulating the metal nano-particles in the siloxane matrix comprises exposing the colloidal suspension to the presence of oxygen for a time period of from about 10 to about 30 minutes.
17. The method of claim 14 further comprising an optional step of removing at least about 50% of the solvent from the colloidal solution.
18. The method claim 13 , wherein the ratio of polymer to metal complex ranges from about 0.001 to about 100.
19. The catalyst of claim 1 , wherein the molecular weight of the polysiloxanes range from 100 to 50000, and the Si—H content of the polysiloxanes ranges from 0.001 to 99 mole percent.
20. The method claim 13 , wherein the nanoparticles are chosen from at least one of aluminum, iron, silver, zinc, gold, copper, cobalt, nickel, platinum, manganese, rhodium, ruthenium, palladium, titanium, vanadium, chromium, molybdenum, cadmium, mercury, calcium, zirconium, iridium, cerium, oxides and sulfides thereof.
21. The method of claim 13 , wherein the step of (b) is carried out at a temperature between about 5 degree C. to about 150 degree C., and at a pressure ranging from 0.001 bar to 10 bar.
22. The method of claim 13 , wherein said nanoparticles have a size in the range of from about 1 to about 100 nanometers.
23. The method of claim 13 , wherein the reaction to form the colloidal suspension is carried out in the presence of a solvent.
24. The method claim 13 , further comprising drying the supported nanoparticle catalysts.
25. The method of claim 13 , wherein said support material comprises particles having a size in the range from 50 to 1000 micrometers.
26. The method of claim 13 , wherein the ratio of metal loading to support material ranges from about 0.001 to 20 percent by weight.
27. The method of claim 13 wherein the support material comprises a functional group chosen from —Si—CH═CH 2 , —Si—OH, —Si—(CH 2 ) n C≡CH, —Si—(CH 2 ) n —NH 2 , —Si—(CH 2 ) n —OH, —Si—(CH 2 ) n —SH, or a combination of two or more thereof, and n is 1-26.
28. The method of claim 13 , wherein the support material is functionalized with a hydrophobic group chosen from an alkyldisilazane, a vinyl-containing silazane, trimethyl disilazane, tetramethyl disilazane, pentamethyl disilazane, hexamethyl disilazane, octamethyl trisilazane, hexamethylcyclo trisilazane, tetraethyltetramethylcyclo tetrasilazane, tetraphenyldimethyl disilazane, dipropyltetramethyl disilazane, dibutyltetramethyl di silazance, dihexyltetramethyl disilazane, dioctyltetramethyl disilazane, diphenyltetramethyl disilazane, octamethylcyclo tetrasilazane, or a combination of two or more thereof.
29. A process comprising:
(a) conducting a metal catalyzed reaction with a catalyst comprising a metal-containing polymer matrix of metal nanoparticles encapsulated in a siloxane polymer matrix covalently bonded to a support material,
wherein the siloxane polymer matrix comprises a crosslinked or partially crosslinked network of hydrosiloxanes with a vinyl silicone compound, the hydrosiloxanes are chosen from a silicon hydride-containing polyorganohydrosiloxane of the formula
M 1 a M 2 b D 1 c D 2 d T 1 e T 2 f Q j
wherein: M 1 =R 1 R 2 R 3 SiO 1/2 ; M 2 =R 4 R 5 R 6 SiO 1/2 ; D 1 =R 7 R 8 SiO 2/2 ; D 2 =R 9 R 10 SiO 2/2 ; T 1 =R 11 SiO 3/2 ; T 2 =R 12 SiO 3/2 ; Q=SiO 4/2 ; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are aliphatic, aromatic or fluoro monovalent hydrocarbon having from 1 to 60 carbon atoms; at least one of R 9 or R 12 is hydrogen; and the subscript a, b, c, d, e, f, and j are zero or positive subject to the following limitations: 2≤a+b+c+d+e+f+j≤6000, and b+d+f>0, or (b) a monomer having a general formula R′ m H n SiX 4−m−n , where each R′ is independently selected from the group consisting of alkyls comprising one to 20 carbon atoms, cycloalkyls comprising four to 12 carbon atoms, and aryls; m=0 to 3, n=1 to 3, and m+n=1 to 4; each X is independently selected from a OR′ group or a halide;
(b) recovering the catalyst; and
(c) conducting a subsequent metal catalyzed reaction with the recovered catalyst.
30. The process of claim 29 , wherein the metal catalyzed reaction is chosen from hydrosilylation, hydroxylation, silaesterification, hydrogenation, oxidation, Heck and Suzuki coupling, dehydrocoupling.
31. The process according to claim 30 wherein the metal catalyzed reaction is a hydrosilylation reaction comprising a reaction of the silicon hydride and an unsaturated reactant.
32. The process of claim 31 , wherein the silicon hydride is chosen from trimethylsilane, dimethylsilane, triethylsilane, dichlorosilane, trichlorosilane, methyldichlorosilane, dimethylchlorosilane, ethyldichlorosilane, cyclopentlydichlorosilane, methylphenylchlorosilane, (3,3,3-trifluoropropyl), heptamethyltrisiloxane hydride, triethoxysilane, trimethoxysilane, hydrogen terminated polydimethylsiloxane, monochlorosilane, or a combination of two or more thereof.
33. A process according to claim 31 , wherein the unsaturated reactant is selected from the group consisting of a hydrocarbon compound or an unsaturated polyether.
34. The process of claim 31 , wherein the unsaturated reactant is chosen from (CH 2 ═CH(CH 2 ) g ) h R′ i Si(OR′) 4−h−i and (CH 2 ═CH(CH 2 ) g R′ i SiCl 4−h−i , where R′ is independently selected from the group consisting of alkyls comprising one to 20 carbon atoms, cycloalkyls comprising four to 12 carbon atoms, and aryls; g is 0 to 20, h is 1 to 3, I is 0-3, and h+i is 1 to 4.
35. The process of claim 33 , where the hydrocarbon compounds is chosen from 1-hexene and 1-5 hexadiene, trans-2hexene, styrene, allylmethoxytriglycol, alpha-methylstyrene, eugenol, 1-octene, allyl glycidylether, trivinylcyclohexane, allylmethacrylate, allylamine, trichloroethylene, ally and vinyl ethers, dichlorostyrene, or a combination of two or more thereof.
36. The process of claim 33 , wherein the unsaturated polyether is chosen from a blocked or random polyoxyalkylenes having at least one of the general formulas:
R 1 (OCH 2 CH 2 ) z (OCH 2 CH[R 3 ]) w OR 2 (X);
R 2 O(CH[R 3 ]CH 2 O) w (CH 2 CH 2 O) z CR 4 2 C≡CCR 4 2 (OCH 2 CH 2 ) z (OCH 2 CH[R 3 ])w R 2 (Y);
or
H 2 C═CCH 2 [R 4 ](OCH 2 CH 2 ) z (OCH 2 CH[R 3 ]) w CH 2 [R 4 ]C═CH 2 (Z)
where R 1 denotes an unsaturated organic group containing from 3 to 10 carbon atoms; R 2 is hydrogen, or a polyether capping group of from 1 to 8 carbon atoms chosen from an alkyl group, an acyl group, or a trialkylsilyl group; R 3 and R 4 are monovalent hydrocarbon groups chosen from a C 1 -C 20 alkyl group, an aryl group, an alkaryl group, or a cycloalkyl group; R 4 can also be hydrogen; z is 0 to 100 inclusive and w is 0 to 100 inclusive, with the proviso that z+w>0.
37. The process of claim 29 , comprising repeating steps (b) and (c) two or more times.
38. The process of claim 29 , wherein the recovered catalyst has a catalytic activity that is at least 85% of the catalytic activity of the catalyst in step (a).
39. The process of claim 29 , wherein the recovered catalyst has a catalytic activity that is at least 95% of the catalytic activity of the catalyst in step (a).
40. The process of claim 29 , wherein the recovered catalyst has a catalytic activity that is at least 99% of the catalytic activity of the catalyst in step (a).
41. The process according to claim 29 , wherein the reaction is carried out in a batch, semi batch, or continuous mode at a temperature between about 0 degree C. to 500 degree C. and a pressure ranging from 0.01 bar to 100 bar.
42. The process of claim 29 , wherein recovering the catalyst is accomplished by filtration.
43. The catalyst of claim 1 , wherein the support material comprises particle having a size in the range of 50 to 1000 micrometers.
44. The catalyst of claim 1 , wherein the support material is chosen from alumina, titania, zirconia, carbon nanotubes, synthetic zeolites, or natural zeolites.
45. The catalyst of claim 1 , wherein the support material comprises a functional group chosen from allyl or vinyl.
46. The catalyst of claim 13 , wherein the support material is chosen from alumina, titania, zirconia, carbon nanotubes, synthetic zeolites, or natural zeolites.
47. The catalyst of claim 13 , wherein the support material comprises a functional group chosen from allyl or vinyl.