Olefin polymerization catalyst system comprising mesoporous organosilica support
A catalyst system comprising a combination of: 1) an activator; 2) one or more metallocene catalyst compounds; 3) a support comprising an organosilica material, which may be a mesoporous organosilica material. The organosilica material may be a polymer of at least one monomer of Formula [Z 1 OZ 2 SiCH 2 ] 3 (I), where Z 1 represents a hydrogen atom, a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer and Z 2 represents a hydroxyl group, a C 1 -C 4 alkoxy group, a C 1 -C 6 alkyl group, or an oxygen atom bonded to a silicon atom of another monomer. This invention further relates to processes to polymerize olefins comprising contacting one or more olefins with the above catalyst system.
1. A catalyst system comprising:
one or more olefin polymerization catalyst compounds;
a catalyst support comprising an organosilica material that is a polymer of at least one monomer of Formula [Z 1 OZ 2 SiCH 2 ] 3 (I), wherein Z 1 represents a hydrogen atom, a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer and Z 2 represents a hydroxyl group, a C 1 -C 4 alkoxy group, a C 1 -C 6 alkyl group, or an oxygen atom bonded to a silicon atom of another monomer; and
an activator.
2. The catalyst system of claim 1 , wherein olefin polymerization catalyst compound is a coordination polymerization catalyst compound.
3. The catalyst system of claim 1 , wherein Z 2 represents a hydroxyl group, a C 1 -C 4 alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer, and, optionally, Z 1 represents a hydrogen atom, methyl, ethyl or a bond to a silicon atom of another monomer.
4. The catalyst system of claim 1 , wherein the polymer further comprises a second distinct monomer of Formula [Z 1 OZ 2 SiCH 2 ] 3 (I).
5. The catalyst system of claim 1 , wherein the organosilica material further comprises at least one monomer selected from the group consisting of:
a monomer of Formula Z 3 OZ 4 Z 5 Z 6 Si (II), wherein Z 3 represents a hydrogen atom or a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer; and Z 4 , Z 5 and Z 6 are each independently selected from the group consisting of a hydroxyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, a nitrogen-containing C 1 -C 10 alkyl group, a nitrogen-containing heteroaralkyl group, a nitrogen-containing optionally substituted heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer;
a monomer of Formula Z 7 Z 8 Z 9 Si—R 1 —SiZ 7 Z 8 Z 9 (III), wherein Z 7 represents a hydroxyl group, a C 1 -C 4 alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer; Z 8 and Z 9 each independently represent a hydroxyl group, a C 1 -C 4 alkoxy group, a C 1 -C 4 alkyl group, or an oxygen bonded to a silicon atom of another monomer; and R 1 is selected from the group consisting of a C 1 -C 8 alkylene group, a C 2 -C 8 alkenylene group, a C 2 -C 8 alkynylene group, a nitrogen-containing C 2 -C 10 alkylene group, an optionally substituted C 6 -C 20 aralkylene and an optionally substituted C 4 -C 20 heterocycloalkylene group;
a trivalent metal oxide monomer of Formula M 1 (OZ 10 ) 3 (IV), wherein M 1 represents a Group 13 metal and Z 10 represents a hydrogen atom, a C 1 -C 6 alkyl or a bond to a silicon atom of another monomer;
a trivalent metal oxide monomer of Formula (Z 11 O) 2 M 2 -O—Si(OZ 12 ) 3 (V), wherein M 2 represents a Group 13 metal and Z 11 and Z 12 each independently represent a hydrogen atom, a C 1 -C 6 alkyl group, or a bond to a silicon atom of another monomer;
a cyclic polyurea monomer of Formula
wherein each R 2 is a Z 13 OZ 14 Z 5 SiZ 16 group, wherein Z 13 represents a hydrogen atom, a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer; Z 14 and Z 15 each independently represent a hydroxyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer; and Z 16 represents a C 1 -C 8 alkylene group bonded to a nitrogen atom of the cyclic polyurea; and
combinations thereof.
6. The catalyst system of claim 1 , wherein the catalyst support comprising an organosilica material has:
an average pore diameter between about 2 nm and about 50 nm;
a pore volume about 0.1 cm 3 /g to about 10 cm 3 /g; and/or
a surface area of about 100 m 2 /g to about 2,500 m 2 /g.
7. The catalyst system of claim 1 , wherein the catalyst support comprising the organosilica material has an X-Ray diffraction spectrum exhibiting substantially no peaks above 4 degrees 2θ; and/or is made using substantially no added structure directing agent or porogen.
8. The catalyst system of claim 1 , wherein the olefin polymerization catalyst compound comprises one or more metallocene compounds represented by the formula:
T y Cp m M 6 G n X 5 q
wherein each Cp is, independently, a cyclopentadienyl group which may be substituted or unsubstituted, M 6 is a Group 4 transition metal, G is a heteroatom group represented by the Formula JR* z where J is N, P, O or S, and R* is a linear, branched or cyclic hydrocarbyl group having from one to twenty carbon atoms and z is 1 or 2, T is a bridging group, and y is 0 or 1, X 5 is a leaving group, and m=1 or 2, n=0, 1, 2 or 3, q=0, 1, 2 or 3, and the sum of m+n+q is equal to the oxidation state of the transition metal.
9. The catalyst system of claim 8 , wherein each Cp is a cyclopentadienyl, indenyl or fluorenyl group, which may be substituted or unsubstituted, each M 6 is titanium, zirconium, or hafnium, and each X 5 is, independently, a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group.
10. The catalyst system of claim 8 , wherein y is 1, m is 1, n is 1, J is N, and R* is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl or an isomer thereof.
11. The catalyst system of claim 8 , wherein the at least one metallocene compound comprises one or more of: bis(tetrahydroindenyl)Hf Me 2 ; bis(1-butyl,3-methylcyclopentadienyl)ZrCl 2 ; bis-(n-butylcyclopentadienyl)ZrCl 2 ; (Dimethylsilyl) 2 O bis(indenyl)ZrCl 2 ; dimethylsilyl(3-(3-methylbutyl)cyclopentadienyl)(2,3,4,5-tetramethylcyclopentadienyl)ZrCl 2 ; dimethylsilylbis(tetrahydroindenyl)ZrCl 2 ; dimethylsilyl-(3-phenyl-indenyl)(tetramethylcyclopentadienyl)ZrCl 2 ; dimethylsilyl(3-neopentylcyclopentadienyl)(tetramethylcyclopentadienyl)HfCl 2 ; tetramethyldisilylene bis(4-(3,5-di-tert-butylphenyl)-indenyl)ZrCl 2 ; cyclopentadienyl(1,3-diphenylcyclopentadienyl)ZrCl 2 ; bis(cyclopentadienyl)zirconium dichloride; bis(pentamethyl cyclopentadienyl)zirconiurn dichloride; bis(pentamethylcyclopentadienyl)zirconium dimethyl; bis(pentamethylcyclopentadienyl)hafnium dichloride; bis(pentanmethylcyclopentadienyl)zirconium dimethyl; bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride; bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl; bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride; bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dimethyl; bis(indenyl)zirconium dichloride; bis(indenyl)zirconium dimethyl; bis(tetrahydro-1-indenyl)zirconium dichloride; bis(tetrahydro-1-indenyl)zirconium dimethyl; dimethylsilylbis(tetrahydroindenyl)zirconium dichloride; dimethylsilylbis(tetrahydroindenyl)zirconium dimethyl; dimethylsilylbis(indenyl)zirconium dichloride; dimethylsilyl(bisindenyl)zirconium dimethyl; dimethylsilylbis(cyclopentadienyl)zirconium dichloride; and dimethylsilylbis(cyclopentadienyl)zirconium dimethyl.
12. The catalyst system of claim 1 , wherein the activator comprises an alkylalumoxane and/or a non-coordinating anion.
13. The catalyst system of claim 1 , wherein the one or more olefin polymerization catalyst compounds comprises a Ziegler-Natta catalyst compound.
14. The catalyst system of claim 1 , wherein the one or more olefin polymerization catalyst compounds comprises one or more metallocene compounds of: dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl; dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dichloride; dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dimethyl; dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dichloride; μ-(CH 3 ) 2 Si(cyclopentadienyl)(1-adamantylamido)M 7 (R 15 ) 2 ; μ-(CH 3 ) 2 Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)M 7 (R 15 ) 2 ; μ-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-adamantylamido)M 7 (R 15 ) 2 ; μ-(CH 3 ) 2 C(tetramethylcyclopentadienyl)(1-adamantylamido)M 7 (R 15 ) 2 ; μ-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-tertbutylamido)M 7 (R 15 ) 2 ; μ-(CH 3 ) 2 Si(fluorenyl)(1-tertbutylamido)M 7 (R 15 ) 2 ; μ-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)M 7 (R 15 ) 2 ; or μ-(C 6 H 5 ) 2 C(tetramethylcyclopentadienyl)(1-cyclododecylamido)M 7 (R 15 ) 2 ;
where M 7 is selected from a group consisting of Ti, Zr, and Hf and R 15 is selected from halogen or C 1 -C 5 alkyl.
15. The catalyst system of claim 1 , wherein the one or more olefin polymerization catalyst compounds comprises a first metallocene compound and a second metallocene compound independently selected from the group consisting of: SiMe 2 (Me 4 Cp)(cC 12 N)TiMe 2 and bis(1-Bu,3-Me-Cp) ZrCl 2 ; SiMe 2 (Me 4 Cp)(cC 12 N)TiMe 2 and (SiMe 2 ) bis(indenyl)ZrCl 2 ; SiMe 2 (Me 4 Cp)(cC 12 N)TiMe 2 and (SiMe 2 ) 2 O bis(indenyl)ZrCl 2 ; SiMe 2 (Me 4 Cp)(cC 12 N)TiMe 2 and (SiMe 2 ) 2 O bis(indenyl)ZrMe 2 ; SiMe 2 (Me 4 Cp)(cC 12 N)TiMe 2 and SiMe 2 (3-neopentylCp)((Me 4 Cp)HfCl 2 ; SiMe 2 (Me 4 Cp)(cC 12 N)TiMe 2 and SiMe 2 (3-neopentylcyclopentadienyl)(Me 4 Cp)HfMe 2 ; SiMe 2 (Me 4 Cp)(1-adamantylamido)TiMe 2 and bis(1-Bu,3-MeCp)ZrCl 2 ; and SiMe 2 (Me 4 Cp)(1-t-butylamido)TiMe 2 and bis(1-Bu,3-MeCp)ZrCl 2 .
16. The catalyst system of claim 12 , wherein the activator comprises methylalumoxane, ethylalumoxane, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate or a mixture thereof.
17. A process to produce polymer comprising:
contacting, in the gas phase or slurry phase, one or more olefin monomers with the catalyst system of claim 1 ; and ii) obtaining a polymer.
18. The process of claim 17 , wherein the polymer is an ethylene polymer or a propylene polymer.
19. The process of claim 17 , wherein the process occurs at a temperature of from about 0° C. to about 300° C., at a pressure of from about 0.35 MPa to about 10 MPa, and at a time up to 300 minutes.
20. The process of claim 17 , wherein the one or more olefin monomers comprise ethylene and one or more comonomer selected from propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene or a mixture thereof.
21. The process of claim 17 , wherein the 2) catalyst support comprising an organosilica material comprises a plurality of mesopores having an average pore diameter between about 2 nm and about 50 nm and the polymerization occurs within the mesopores.