Preparation of catalyst system
Improved preparation process for supported catalyst systems, which comprise a specific class of metallocene complexes in combination with a boron containing cocatalyst and an aluminoxane cocatalyst and use of the new, improved catalyst system.
1 . A process for the preparation of a supported catalyst system, wherein the catalyst system comprises:
(i) a metallocene complex;
(ii) a cocatalyst system comprising a boron containing cocatalyst and an aluminoxane cocatalyst; and
(iii) a porous inorganic silica support;
whereby the process comprises the steps of:
a) treating the porous inorganic support with the aluminoxane cocatalyst in a hydrocarbon solvent, optionally followed by thermal treatment of the aluminoxane treated support;
b) combining the metallocene complex with the boron containing cocatalyst and optionally with the aluminoxane cocatalyst in the hydrocarbon solvent;
c) loading the solution of step b) onto the treated support of step a);
wherein the amount of aluminoxane cocatalyst added in step a) is 75.0 to 100.0 wt % of the total amount of aluminoxane cocatalyst and the amount of aluminoxane cocatalyst added in step b) is 0.0 to 25.0 wt % of the total amount of aluminoxane cocatalyst; and
wherein the metallocene complex is of formula (VI):
wherein
each X independently is a sigma-donor ligand,
M is a group 4 metal;
L is a carbon, silicon, or germanium based bridge in which one to four backbone atoms link the ligands; and
each Ind is a substituted or unsubstituted indenyl, or a substituted or unsubstituted fused indenyl; and
wherein the boron containing cocatalyst is either of formula (B) or a borate containing an anion of formula (C):
BY 3 (B)
(Z) 4 B— (C)
wherein
each Y independently is a hydrogen atom, an alkyl group of from 1 to about 20 carbon atoms, an aryl group of from 6 to about 15 carbon atoms, alkylaryl, arylalkyl, haloalkyl or haloaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6-20 carbon atoms in the aryl radical or fluorine, chlorine, bromine or iodine; or
Z is an optionally substituted phenyl derivative, said substituent being a halo-C 1-6 -alkyl or halo group, and as counterions protonated amine or aniline derivatives.
2 . The process as claimed in claim 1 , wherein the metallocene complex is of formula (IV):
wherein
each X independently is a sigma-donor ligand;
M is Zr or Hf;
L is a carbon, silicon, or germanium based divalent bridge in which one or two backbone atoms link the ligands;
each Ar independently is an aryl or heteroaryl group having 3 to 20 carbon atoms, such as a phenyl ring or a 5 or 6 membered heteroaryl ring;
each R 1 independently is hydrogen, a linear or branched C 1 -C 6 -alkyl group, a C 7-20 -arylalkyl group, a C 7-20 -alkylaryl group, a C 6-20 -aryl group, or an OY group, wherein Y is a C 1-10 -hydrocarbyl group, or wherein two adjacent R 1 taken together with the phenyl carbons to which they are bonded form a ring;
each R 2 independently is a CHR 8′ —R 8 group, with R 8 being H, a linear or branched C 1-6 -alkyl group, a C 3-8 -cycloalkyl group, a C 6-10 -aryl group, or a heteroaryl group having 3 to 20 carbon atoms optionally substituted by one to three groups R 11 , and R 8′ is H or a C 1-6 alkyl;
R 3 is a linear or branched C 1 -C 6 -alkyl group, a C 7-20 -arylalkyl group, a C 7-20 -alkylaryl group, or C 6 -C 20 -aryl group;
R 4 is a C(R 9 ) 3 group, with R 9 being a linear or branched C 1 -C 6 -alkyl group;
R 5 and R 6 are each independently hydrogen or an aliphatic C 1 -C 20 -hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16 of the periodic table of elements, or wherein R 5 and R 6 taken together form a 5 membered saturated carbon ring which is optionally substituted by n groups R 10 , n being from 0 to 4, and each R 10 independently is a C 1 -C 20 -hydrocarbyl group, or a C 1 -C 20 -hydrocarbyl radical optionally containing one or more heteroatoms belonging to groups 14-16 of the periodic table of elements;
R 7 is H or a linear or branched C 1 -C 6 -alkyl group or an aryl or heteroaryl group having 3 to 20 carbon atoms optionally substituted by one to three groups R 11 ; and
each R 11 independently is hydrogen, a linear or branched C 1 -C 6 -alkyl group, a C 7-20 -arylalkyl group, a C 7-20 -alkylaryl group, a C 6-20 -aryl group, or an OY group, wherein Y is a C 1-10 -hydrocarbyl group.
3 . The process as claimed in claim 1 , wherein the metallocene complex is C2 symmetric.
4 . The process as claimed in claim 1 , wherein the metallocene complex is of formula (XIX):
wherein
each X independently is a sigma-donor ligand;
M is Zr or Hf;
L is —R′ 2 Si—; wherein each R′ is independently a C 1 -C 6 -alkyl, C 5-6 -cycloalkyl, C 1-10 -alkyl-O—C 1-10 alkyl, or C 6 -aryl group;
each R 1 independently is hydrogen, or a linear or branched C 1 -C 6 -alkyl group;
each R 2 independently is a CH 2 —R 8 group, with R 8 being H or a linear or branched C 1-6 -alkyl group;
R 6 is an O—C 1 -C 6 -alkyl group;
R 5 is a C(R 9 )3 group, with R 9 being a linear or branched C 1 -C 6 alkyl group;
R 5′ is an O—C 1 -C 6 -alkyl group;
R 6′ is a C(R 9 )3 group, with R 9 being a linear or branched C 1 -C 6 alkyl group; or
R 5 and R 6 can be taken together to form a 5 membered saturated carbon ring; or
R 5′ and R 6′ can be taken together to form a 5 membered saturated carbon ring; and
R 7 is H or a phenyl group optionally substituted by one to 3 groups R 11 , each R 11 independently is hydrogen, or a linear or branched C 1 -C 6 -alkyl group.
5 . The process according to claim 1 , wherein the metallocene (i) is:
rac-dimethylsilanediyl-bis-[2-methyl-4-(3′5′dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,
rac-anti-dimethylsilanediyl[2-methyl-4-(4′-tert.-butylphenyl)-inden-1-yl][2-methyl-4-(4′-tert.-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,
rac-anti-dimethylsilanediyl[2-methyl-4-(4′-tert.-butylphenyl)-inden-1-yl][2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,
rac-anti-dimethylsilanediyl[2-methyl-4-(3′,5′-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3′,5′-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,
rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(4′-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3′,5′-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,
rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3′,5′-dimethylphenyl)-1,5,6,7-tetrahydro-s indacen-1-yl][2-methyl-4-(3′,5′-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,
rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3′,5′-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3′,5′-ditert-butyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride,
rac-dimethylsilanediylbis[2-methyl-4-(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride,
rac-dimethylsilanediylbis[2-methyl-4-(3,5-ditertbutylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride,
rac-dimethylsilanediylbis[2-methyl-4-(4′-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride,
or their hafnium analogues.
6 . The process according to claim 1 , wherein in step a) the support/solvent/aluminoxane mixture is heated at a temperature of from 60° C. to 120° C. before step b).
7 . The process according to claim 1 , wherein the aluminoxane cocatalyst is of formula (A):
wherein
n is from 6 to 20, and
R is C 1 -C 10 -alkyl.
8 . The process according to claim 1 , wherein the boron containing cocatalyst is:
triphenylcarbeniumtetrakis(pentafluorophenyl) borate,
N,N-dimethylaniliniumtetrakis(pentafluorophenyl) borate,
N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate, or
N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate.
9 . The process according to claim 1 , wherein the metallocene complex includes a metal ion M and the metallocene complex, the boron containing cocatalyst, and the aluminoxane cocatalyst are each provided in an amount such that the molar ratio of boron to the metal ion M in the metallocene complex is in the range of 0.1:1 to 10:1 mol/mol, and the molar ratio of aluminum in the aluminoxane cocatalyst to the metal ion M in the metallocene complex is in the range of 1:1 to 2000:1 mol/mol.
10 . The process according to claim 1 , wherein the porous inorganic support has an average particle size of from 10 to 100 μm, an average pore size of from 10 to 100 nm, a pore volume of 1 to 3 mL/g, or a combination thereof.
11 . The process according to claim 1 , wherein the catalyst system comprises from 5 to 500 mol of zirconium or hafnium per gram of the porous inorganic support and from 5 to 15 mmol of Al per gram of the porous inorganic support.
12 . The process according to claim 1 , wherein 97.1 to 100 wt % of the aluminoxane cocatalyst is added in step a).
13 . The process according to claim 1 , wherein in step b):
the boron containing cocatalyst, the aluminoxane cocatalyst, and the metallocene complex are combined simultaneously;
the aluminoxane cocatalyst is added to a combination of the metallocene complex and the boron containing cocatalyst; or
the aluminoxane cocatalyst and the boron containing cocatalyst are combined and added to the metallocene complex.
14 . The process according to claim 1 , wherein in step a) the aluminoxane cocatalyst treated support is washed one or more times with toluene and optionally one more times with heptane at an elevated temperature of from 70° C. to 115° C. with a subsequent drying step.
15 . The process according to claim 1 , wherein in step a) 77.0 to 95.0 wt % of the total amount of the aluminoxane cocatalyst is added and 5.0 to 23.0 wt % of the total amount of aluminoxane cocatalyst is added in step b).