JPH05138022 | PRODUCTION OF LACTONE |
WO/2019/048404 | CATALYST AND PROCESS FOR THE OXIDATIVE COUPLING OF METHANE |
WO2022108974A1 | 2022-05-27 | |||
WO2016170017A1 | 2016-10-27 |
US11161922B2 | 2021-11-02 | |||
US11161922B2 | 2021-11-02 | |||
US8354485B2 | 2013-01-15 | |||
US9090720B2 | 2015-07-28 | |||
US7910764B2 | 2011-03-22 | |||
US8575284B2 | 2013-11-05 | |||
US5006500A | 1991-04-09 | |||
US4937217A | 1990-06-26 | |||
US20160355618A1 | 2016-12-08 | |||
US20110010938A1 | 2011-01-20 | |||
US7915357B2 | 2011-03-29 | |||
US8129484B2 | 2012-03-06 | |||
US7202313B2 | 2007-04-10 | |||
US6833417B2 | 2004-12-21 | |||
US6841630B2 | 2005-01-11 | |||
US6989344B2 | 2006-01-24 | |||
US7504463B2 | 2009-03-17 | |||
US7563851B2 | 2009-07-21 | |||
US8420754B2 | 2013-04-16 | |||
US8101691B2 | 2012-01-24 | |||
US4543399A | 1985-09-24 | |||
US4588790A | 1986-05-13 | |||
US5028670A | 1991-07-02 | |||
US5317036A | 1994-05-31 | |||
US5352749A | 1994-10-04 | |||
US5405922A | 1995-04-11 | |||
US5436304A | 1995-07-25 | |||
US5453471A | 1995-09-26 | |||
US5462999A | 1995-10-31 | |||
US5616661A | 1997-04-01 | |||
US5668228A | 1997-09-16 |
LUO, JAINHARLAN, ACS ANNUAL MEETING, CONFERENCE ABSTRACTS PMSE 126 AND INOR 1169, 2 April 2017 (2017-04-02)
CHEMICAL AND ENGINEERING NEWS, vol. 63, no. 5, 1985, pages 27
Claims: We claim: 1. A method for preparing a catalyst system comprising: contacting in an organic solvent at least one support material having absorbed water and trimethylaluminum (TMA) to form a supported MAO (catalyst precursor) in-situ; and contacting the supported MAO with at least one catalyst precursor compound having a Group 3 through Group 12 metal atom or lanthanide metal atom, wherein the charged TMA to water ratio and the in-situ sMAO formation temperature are so controlled that the supernate after the in-situ supported MAO formation with optional heating or after the finished catalyst formation contains no detectable TMA or not more than 600 ppm TMA, provided that, a. for a support containing absorbed water 6.5 (mmol/g support) or less, the charged TMA:water ratio is controlled in the range of between 1.31:1 and 1.25:1 and the in-situ supported MAO formation temperature is controlled at between -8°C and -60°C, b. for a support containing absorbed water 5.0 (mmol/g support) or less, the charged TMA:water ratio is controlled in the range of between 1.42:1 and 1.25:1 and the in-situ supported MAO formation temperature is controlled at between -8°C to -60°C, and c. for a support containing absorbed water 7.0 - 10.0 (mmol/g support), the charged TMA:water ratio is controlled in the range of between 1.20:1 and 1.15:1 and the in-situ sMAO formation temperature is controlled at between -12°C and -60°C. 2. A method for preparing a catalyst system comprising: contacting in an organic solvent at least one support material having absorbed water and trimethylaluminum (TMA) to form a supported MAO (catalyst precursor) in-situ; contacting the supported MAO with at least one catalyst precursor compound having a Group 3 through Group 12 metal atom or lanthanide metal atom, wherein TMA to water ratio is in between 1.80:1 to 1.42:1 and the in-situ supported MAO formation temperature is between -6°C to -60°C; and recovering free TMA from a supernate, after the in-situ supported MAO formation or after finished catalyst formation is removed, by adding, to the supernate, a second support containing hydroxyl groups to result in no detectable or not higher than 600 ppm TMA in the supernate. 3. The method of claim 2, wherein the second support containing the hydroxyl groups are water absorbed silica the same as or different from the one used in making the in-situ sMAO or the derived finished catalyst. 4. The method of claim 2, wherein the support containing hydroxyl groups are silica calcined at 150°C to 875°C. 5. The method of one of claims 1 to 4, wherein the at least one catalyst precursor compound having a Group 3 through Group 12 metal atom or lanthanide metal atom comprises at least one substituted or non-substituted cycplopentadienyl ligand to form a bridging or unbridging half-metallocene or metallocene. 6. The method of one of claims 1 to 4, wherein the at least one catalyst precursor compound having a Group 3 through Group 12 metal atom or lanthanide metal atom comprises at least one organic ligand with at least two hetero-atom donors. 7. The method of claim 6, wherein the at least one organic ligand with at least two hetero- atom donors comprises oxygen, nitrogen, or phosphorus donors. 8. A method of producing a polyolefin product, comprising polymerizing an olefin by contacting the olefin with the catalyst system produced from one of Claims 1-6. |
[0100] Unlimited examples of non-bridged metallocenes are: bis(n-propylcyclopentadienyl)hafnium dichloride, bis(n-propylcyclopentadienyl)hafnium dimethyl, bis(n-propylcyclopentadienyl)zirconium dichloride, bis(n-propylcyclopentadienyl)zirconium dimethyl, bis(n-propylcyclopentadienyl)titanium dichloride, bis(n-propylcyclopentadienyl)titanium dimethyl, (n-propylcyclopentadienyl) (pentamethylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl) (pentamethylcyclopentadienyl)zirconium dimethyl, (n-propylcyclopentadienyl) (pentamethylcyclopentadienyl)hafnium dichloride, (n-propylcyclopentadienyl) (pentamethylcyclopentadienyl)hafnium dimethyl, (n-propylcyclopentadienyl) (pentamethylcyclopentadienyl)titanium dichloride, (n-propylcyclopentadienyl) (pentamethylcyclopentadienyl)titanium dimethyl, (n-propylcyclopentadienyl) (tetramethylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl) (tetramethylcyclopentadienyl)zirconium dimethyl, (n-propylcyclopentadienyl) (tetramethylcyclopentadienyl)hafnium dichloride, (n-propylcyclopentadienyl) (tetramethylcyclopentadienyl)hafnium dimethyl, (n-propylcyclopentadienyl) (tetramethylcyclopentadienyl)titanium dichloride, (n-propylcyclopentadienyl) (tetramethylcyclopentadienyl)titanium dimethyl, bis(cyclopentadienyl)hafnium dimethyl, bis(n-butylcyclopentadienyl)hafnium dichloride, bis(n-butylcyclopentadienyl)hafnium dimethyl, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dimethyl, bis(n-butylcyclopentadienyl)titanium dichloride, bis(n-butylcyclopentadienyl)titanium dimethyl, bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride, bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dimethyl, bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride, bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl, bis(1-methyl-3-n-butylcyclopentadienyl)titanium dichloride, and bis(1-methyl-3-n-butylcyclopentadienyl)titanium dimethyl. [0101] The metallocene catalyst compound may be a bridged metallocene catalyst compound represented by the formula: Cp A (A)Cp B M’X’n, wherein each Cp A and Cp B is independently selected from cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl. One or both Cp A and Cp B may contain heteroatoms, and one or both Cp A and Cp B may be substituted by one or more R’’ groups. M’ is selected from Groups 3 through 12 atoms and lanthanide Group atoms. X’ is an anionic leaving group. n is 0 or an integer from 1 to 4. (A) is selected from divalent alkyl, divalent lower alkyl, divalent substituted alkyl, divalent heteroalkyl, divalent alkenyl, divalent lower alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent alkynyl, divalent lower alkynyl, divalent substituted alkynyl, divalent heteroalkynyl, divalent alkoxy, divalent lower alkoxy, divalent aryloxy, divalent alkylthio, divalent lower alkylthio, divalent arylthio, divalent aryl, divalent substituted aryl, divalent heteroaryl, divalent aralkyl, divalent aralkylene, divalent alkaryl, divalent alkarylene, divalent haloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalent heteroalkyl, divalent heterocycle, divalent heteroaryl, a divalent heteroatom-containing group, divalent hydrocarbyl, divalent lower hydrocarbyl, divalent substituted hydrocarbyl, divalent heterohydrocarbyl, divalent silyl, divalent boryl, divalent phosphino, divalent phosphine, divalent amino, divalent amine, divalent ether, divalent thioether. R’’ is selected from alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, alkylthio, lower alkylthio, arylthio, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, a heteroatom-containing group, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, silyl, boryl, phosphino, phosphine, amino, amine, germanium, ether, and thioether. [0102] In at least one embodiment, each of Cp A and Cp B is independently selected from cyclopentadienyl, n-propylcyclopentadienyl, indenyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, and n-butylcyclopentadienyl. [0103] (A) may be O, S, NR', or SiR’2, where each R’ is independently hydrogen or C 1 -C 20 hydrocarbyl. [0104] Unlimited examples of the bridged metallocenes are: ethylene-bis(indenyl)Zr dichloride or dimethyl; dimethylsilandiyl bis(4,5,6,7-indenyl)Zr dichloride or dimethyl; dimethylsilandiyl bis(4,5,6,7-tetrahydro-indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-methyl-(4-(3’,5’-di-tert-butyl-4’- methoxy-phenyl)indenyl)(2-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-ethyl-4-(3',5'-di-tert-butyl-4’-methox yphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-propyl-4-(3',5'-di-tert-butyl-4’-metho xyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-butyl-4-(3',5'-di-tert-butyl-4’-methox yphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-methyl-4-(3',5'-bistrifluoromethyl-4’- methoxyphenyl)indenyl)(2-n-hexyl-4- (o-biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-methyl-4-(3',5'-bistrifluoromethyl-4’- methoxyphenyl)indenyl)(2-n-hexyl-4- (o-biphenyl)indenyl)Zr(CH3)2; dimethylsilandiyl(2-ethyl-4-(3',5'-bistrifluoromethyl-4’-m ethoxyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-propyl-4-(3',5'-bistrifluoromethyl-4’- methoxyphenyl)indenyl)(2-n-hexyl-4- (o-biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-butyl-4-(3',5'-bistrifluoromethyl-4’-m ethoxyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-methyl-4-(3',5'-di-iso-propyl-4’-metho xyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-ethyl-4-(3',5'-di-iso-propyl-4’-methox yphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-propyl-4-(3',5'-di-iso-propyl-4’-metho xyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-butyl-4-(3',5'-di-iso-propyl-4’-methox yphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-methyl-4-(3',5'-di-phenyl-4’-methoxyph enyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-ethyl-4-(3',5'-di-phenyl-4’-methoxyphe nyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-propyl-4-(3',5'-di-phenyl-4’- methoxyphenyl)indenyl)(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; and dimethylsilandiyl(2-butyl-4-(3',5'-di-phenyl-4’-methoxyphe nyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl. dimethylsilandiyl(2-methyl-4-(3',5'-di-tert-butyl-4’-metho xyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-methyl-4-(3',5'-di-tert-butyl-4’-metho xyphenyl)(1,5,6,7-tetrahydro-s- indacenyl))(2-n-hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-methyl-4-phenyl-(1,5,6,7-tetrahydro-s-in dacenyl))(2-isopropyl-4-(4’-t- butylphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-methyl-4-(4’-t-butylphenyl)indenyl)(2- isopropyl-4-(4’-t- butylphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-ethyl-4-(3',5'-di-tert-butyl-4’-methox yphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl) indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-propyl-4-(3',5'-di-tert-butyl-4’-metho xyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-butyl-4-(3',5'-di-tert-butyl-4’-methox yphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-methyl-4-(3',5'-bistrifluoromethyl-4’- methoxyphenyl)indenyl)(2-n-hexyl-4- (o-biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-ethyl-4-(3',5'-bistrifluoromethyl-4’-m ethoxyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-propyl-4-(3',5'-bistrifluoromethyl-4’- methoxyphenyl)indenyl)(2-n-hexyl-4- (o-biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-butyl-4-(3',5'-bistrifluoromethyl-4’-m ethoxyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-methyl-4-(3',5'-di-iso-propyl-4’-metho xyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-ethyl-4-(3',5'-di-iso-propyl-4’-methox yphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-propyl-4-(3',5'-di-iso-propyl-4’-metho xyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-butyl-4-(3',5'-di-iso-propyl-4’-methox yphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-methyl-4-(3',5'-di-phenyl-4’-methoxyph enyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-ethyl-4-(3',5'-di-phenyl-4’-methoxyphe nyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-propyl-4-(3',5'-di-phenyl-4’-methoxyph enyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl(2-butyl-4-(3',5'-di-phenyl-4’-methoxyphe nyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylamidoborane(2-methyl-4-(3',5'-di-tert-butyl-4’-met hoxyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylamidoborane(2-ethyl-4-(3',5'-di-tert-butyl-4’-meth oxyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylamidoborane(2-propyl-4-(3',5'-di-tert-butyl-4’-met hoxyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylamidoborane(2-butyl-4-(3',5'-di-tert-butyl-4’-meth oxyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylamidoborane(2-methyl-4-(3',5'-bistrifluoromethyl-4 -methoxyphenyl)indenyl)(2-n- hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; dimethylamidoborane(2-ethyl-4-(3',5'-bistrifluoromethyl-4’ -methoxyphenyl)indenyl)(2-n-hexyl- 4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; dimethylamidoborane(2-propyl-4-(3',5'-bistrifluoromethyl-4 -methoxyphenyl)indenyl)(2-n-hexyl- 4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; dimethylamidoborane(2-butyl-4-(3',5'-bistrifluoromethyl-4’ -methoxyphenyl)indenyl)(2-n-hexyl- 4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; dimethylamidoborane(2-methyl-4-(3',5'-di-iso-propyl-4’-met hoxyphenyl)indenyl)(2-n-hexyl-4- (o-biphenyl)indenyl)Zr dichloride or dimethyl; dimethylamidoborane(2-ethyl-4-(3',5'-di-iso-propyl-4’-meth oxyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylamidoborane(2-propyl-4-(3',5'-di-iso-propyl-4’-met hoxyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylamidoborane(2-tert-butyl-4-(3',5'-di-iso-propyl-4’ -methoxyphenyl)indenyl)(2-n-hexyl-4- (o-biphenyl)indenyl)Zr dichloride or dimethyl; dimethylamidoborane(2-methyl-4-(3',5'-di-phenyl-4’-methoxy phenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylamidoborane(2-ethyl-4-(3',5'-di-phenyl-4’-methoxyp henyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylamidoborane(2-propyl-4-(3',5'-diphenyl-4’-methoxyp henyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; dimethylamidoborane(2-butyl-4-(3',5'-diphenyl-4’-methoxyph enyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; di-iso-propylamidoborane(2-methyl-4-(3',5'-di-tert-butyl-4 -methoxyphenyl)indenyl)(2-n-hexyl- 4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; di-iso-propylamidoborane(2-ethyl-4-(3',5'-di-tert-butyl-4’ -methoxyphenyl)indenyl)(2-n-hexyl-4- (o-biphenyl)indenyl)Zr dichloride or dimethyl; di-iso-propylamidoborane(2-propyl-4-(3',5'-di-tert-butyl-4 -methoxyphenyl)indenyl)(2-n-hexyl- 4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; di-iso-propylamidoborane(2-butyl-4-(3',5'-di-tert-butyl-4’ -methoxyphenyl)indenyl)(2-n-hexyl-4- (o-biphenyl)indenyl)Zr dichloride or dimethyl; di-iso-propylamidoborane(2-methyl-4-(3',5'-bistrifluoromethy l-4’-methoxyphenyl)indenyl)(2-n- hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; di-iso-propylamidoborane(2-ethyl-4-(3',5'-bistrifluoromethyl -4’-methoxyphenyl)indenyl)(2-n- hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; di-iso-propylamidoborane(2-propyl-4-(3',5'-bistrifluoromethy l-4’-methoxyphenyl)indenyl)(2-n- hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; di-iso-propylamidoborane(2-butyl-4-(3',5'-bistrifluoromethyl -4’-methoxyphenyl)indenyl)(2-n- hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; di-iso-propylamidoborane(2-methyl-4-(3',5'-di-iso-propyl-4 -methoxyphenyl)indenyl)(2-n-hexyl- 4-(o-biphenyl) indenyl)Zr dichloride or dimethyl; di-iso-propylamidoborane(2-ethyl-4-(3',5'-di-iso-propyl-4’ -methoxyphenyl)indenyl)(2-n-hexyl-4- (o-biphenyl) indenyl)Zr dichloride or dimethyl; di-iso-propylamidoborane(2-propyl-4-(3',5'-di-iso-propyl-4 -methoxyphenyl)indenyl)(2-n-hexyl- 4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; di-iso-propylamidoborane(2-tert-butyl-4-(3',5'-di-iso-propyl -4’-methoxyphenyl)indenyl)(2-n- hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; di-iso-propylamidoborane(2-methyl-4-(3',5'-diphenyl-4’-met hoxyphenyl)indenyl)(2-n-hexyl-4- (o-biphenyl)indenyl)Zr dichloride or dimethyl; di-iso-propylamidoborane(2-ethyl-4-(3',5'-di-phenyl-4’-met hoxyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; di-iso-propylamidoborane(2-propyl-4-(3',5'-diphenyl-4’-met hoxyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; di-iso-propylamidoborane(2-butyl-4-(3',5'-diphenyl-4’-meth oxyphenyl)indenyl)(2-n-hexyl-4-(o- biphenyl)indenyl)Zr dichloride or dimethyl; bis(trimethylsilyl)amidoborane(2-methyl-4-(3',5'-di-tert-but yl-4’-methoxyphenyl)indenyl)(2-n- hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; bis(trimethylsilyl)amidoborane(2-ethyl-4-(3',5'-di-tert-buty l-4’-methoxyphenyl)indenyl)(2-n- hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; bis(trimethylsilyl)amidoborane(2-propyl-4-(3',5'-di-t-butyl- 4’-methoxyphenyl)indenyl)(2-n- hexyl-4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; bis(trimethylsilyl)amidoborane(2-butyl-4-(3',5'-di-tert-buty l-4’-methoxyphenyl)indenyl)(2-n- hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; bis(trimethylsilyl)amidoborane(2-methyl-4-(3',5'-bis-trifluo romethyl-4’- methoxyphenyl)indenyl)(2-n-hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; bis(trimethylsilyl)amidoborane(2-ethyl-4-(3',5'-bis-trifluor omethyl-4’-methoxyphenyl)indenyl)(2- n-hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; bis(trimethylsilyl)amidoborane(2-propyl-4-(3',5'-bis-trifluo romethyl-4’- methoxyphenyl)indenyl)(2-n-hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; bis(trimethylsilyl)amidoborane(2-butyl-4-(3',5'-bis-trifluor ometllyl-4’- methoxyphenyl)indenyl)(2-n-hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; bis(trimethylsilyl)amidoborane(2-methyl-4-(3',5'-di-iso-prop yl-4’-methoxyphenyl)indenyl)(2-n- hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; bis(trimethylsilyl)amidoborane(2-ethyl-4-(3',5'-di-iso-propy l-4’-methoxyphenyl)indenyl)(2-n- hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; bis(trimethylsilyl)amidoborane(2-propyl-4-(3',5'-di-iso-prop yl-4’-methoxyphenyl)indenyl)(2-n- hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; bis(trimethylsilyl)amidoborane(2-butyl-4-(3',5'-di-iso-propy l-4’-methoxyphenyl)indenyl)(2-n- hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; bis(trimethylsilyl)amidoborane(2-methyl-4-(3',5'-diphenyl-4 -methoxyphenyl)indenyl)(2-n- hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; bis(trimethylsilyl)amidoborane(2-ethyl-4-(3',5'-diphenyl-4 -methoxyphenyl)indenyl)(2-n- hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; bis(trimethylsilyl)amidoborane(2-propyl-4-(3',5'-diphenyl-4 -methoxyphenyl)indenyl)(2-n- hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; bis(trimethylsilyl)amidoborane(2-butyl-4-(3',5'-diphenyl-4 -methoxyphenyl)indenyl)(2-n- hexane,4-(o-biphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl bis(2-methyl-4-phenyl-indenyl)Zr dichloride or dimethyl; dimethylsilandiyl bis(2-methyl-4-(3’,5-di-t-butylphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl bis(2-methyl-4-(3’,5-di-t-butyl-4-methoxyphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl bis(2-methyl-4-(4’-t-butylphenyl)indenyl) Zr dichloride or dimethyl; dimethylsilandiyl bis(2-ethyl-4-phenyl-indenyl)Zr dichloride or dimethyl; dimethylsilandiyl bis(2-ethyl-4-(3’,5-di-t-butylphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl bis(2-ethyl-4-(3’,5-di-t-butyl-4-methoxyphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl bis(2-ethyl-4-(4’-t-butylphenyl)indenyl) Zr dichloride or dimethyl; dimethylsilandiyl bis(2-propyl-4-phenylindenyl) Zr dichloride or dimethyl; dimethylsilandiyl bis(2-propyl-4-(3’,5-di-t-butylphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl bis(2-propyl-4-(3’,5-di-t-butyl-4-methoxyphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl bis(2-propyl-4-(4’-t-butylphenyl)indenyl) Zr dichloride or dimethyl; dimethylsilandiyl bis(2-isopropyl-4-phenylindenyl) Zr dichloride or dimethyl; dimethylsilandiyl bis(2-isopropyl-4-(3’,5-di-t-butylphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl bis(2-isopropyl-4-(4’-t-butylphenyl)indenyl) Zr dichloride or dimethyl; dimethylsilandiyl bis(2-cyclopropyl-4-phenylindenyl) Zr dichloride or dimethyl; dimethylsilandiyl bis(2-cyclopropyl-4-(3’,5-di-t-butylphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl bis(2-cyclopropyl-4-(4’-t-butylphenyl)indenyl) Zr dichloride or dimethyl; dimethylsilandiyl bis(2-butyl-4-phenylindenyl) Zr dichloride or dimethyl; dimethylsilandiyl bis(2-butyl-4-(3’,5-di-t-butylphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl bis(2-butyl-4-(4’-t-butylphenyl)indenyl) Zr dichloride or dimethyl; dimethylsilandiyl bis(2-methyl-4-(2’-methylphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl bis(2-isopropyl-4-(2’-methylphenyl)indenyl)Zr dichloride or dimethyl; dimethylsilandiyl bis(2-methyl-4-carbozolindenyl)Zr dichloride or dimethyl; and dimethylsilandiyl bis(2-isopropyl-4-carbozolindenyl)Zr dichloride or dimethyl. [0105] In at least one embodiment, many C1 symmetry bis-Cp metallocene catalysts capable of high Tm PP and/or diene incorporation can be represented by bridging substituted cyclopentadienyl and substituted indenyl catalyst precursor compounds as the formula (C1a): wherein: M is a transition metal atom; T is a bridging group; each of X 1 and X 2 is a univalent anionic ligand, or X 1 and X 2 are joined to form a metallocycle ring; R 1 is hydrogen, a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R''- SiR' 3 , where R'' is C 1 -C 10 alkyl and each R' is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl; R 3 is an unsubstituted C 4 -C 62 cycloalkyl, a substituted C 4 -C 62 cycloalkyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, or a substituted C 4 -C 62 heteroaryl; each of R 2 and R 4 is independently hydrogen, a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, -NR' 2 , -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R''-SiR'3, wherein R'' is C 1 -C 10 alkyl and each R' is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl; each of R 5 , R 6 , R 7 , and R 8 is independently hydrogen, a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 , or -R''-SiR' 3 , wherein R'' is C 1 -C 10 alkyl and each R' is hydrogen, halogen, C 1 -C 10 alkyl, or C6-C10 aryl, or one or more of R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 can be joined to form a substituted or unsubstituted C 4 -C 62 saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof; and each of J 1 and J 2 is joined to form a substituted or unsubstituted C 4 -C 62 saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof. [0106] In some embodiments of the present disclosure, M is a transition metal such as a transition metal of Group 3, 4, or 5 of the Periodic Table of Elements, such as a Group 4 metal, for example Zr, Hf, or Ti. [0107] In some embodiments of the present disclosure, each of X 1 and X 2 is independently an unsubstituted C 1 -C 40 hydrocarbyl (such as an unsubstituted C 2 -C 20 hydrocarbyl), a substituted C 1 -C 40 hydrocarbyl (such as a substituted C 2 -C 20 hydrocarbyl), an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, ether, and a combination thereof, for example each of X 1 and X 2 is independently a halide or a C 1 -C 5 alkyl, such as methyl. In some embodiments, each of X 1 and X 2 is independently chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl. In some embodiments of the present disclosure, X 1 and X 2 form a part of a fused ring or a ring system. [0108] In some embodiments, T is represented by the formula, (R*2G)g, wherein each G is C, Si, or Ge, g is 1 or 2, and each R* is, independently, hydrogen, halogen, an unsubstituted C 1 -C 20 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), a substituted C 1 -C 20 hydrocarbyl, or the two or more R* may join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. In some embodiments of the present disclosure, T is a bridging group and is represented by R'2C, R'2Si, R'2Ge, R'2CCR'2, R'2CCR'2CR'2, R'2CCR'2CR'2CR'2, R'C=CR', R'C=CR'CR' 2 , R' 2 CCR'=CR'CR' 2 , R'C=CR'CR'=CR', R'C=CR'CR' 2 CR' 2 , R' 2 CSiR' 2 , R'2SiSiR'2, R2CSiR'2CR'2, R'2SiCR'2SiR'2, R'C=CR'SiR'2, R'2CGeR'2, R'2GeGeR'2, R' 2 CGeR' 2 CR' 2 , R' 2 GeCR' 2 GeR' 2 , R' 2 SiGeR' 2 , R'C=CR'GeR' 2 , R'B, R' 2 C–BR', R' 2 C–BR'–CR' 2 , R'2C–O–CR'2, R'2CR'2C–O–CR'2CR'2, R'2C–O–CR'2CR'2, R'2C–O–CR'=CR', R'2C–S–CR'2, R' 2 CR' 2 C–S–CR' 2 CR' 2 , R' 2 C–S–CR' 2 CR' 2 , R' 2 C–S–CR'=CR', R' 2 C–Se–CR' 2 , R' 2 CR' 2 C–Se– CR'2CR'2, R'2C–Se–CR2CR'2, R'2C–Se–CR'=CR', R'2C–N=CR', R'2C–NR'–CR'2, R'2C–NR'– CR' 2 CR' 2 , R' 2 C–NR'–CR'=CR', R' 2 CR' 2 C–NR'–CR' 2 CR' 2 , R' 2 C–P=CR', or R' 2 C–PR'–CR' 2 where each R' is independently hydrogen or an unsubstituted C 1 -C 20 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), a substituted C 1 -C 20 hydrocarbyl, a C 1 -C 20 halocarbyl, a C 1 -C 20 silylcarbyl, or a C 1 -C 20 germylcarbyl substituent, or two or more adjacent R' join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. In some embodiments of the present disclosure, T is a bridging group that includes carbon or silicon, such as dialkylsilyl, for example T is a CH2, CH2CH2, C(CH3)2, (Ph)2C, (p-(Et)3SiPh)2C, SiMe 2 , SiPh 2 , SiMePh, Si(CH 2 ) 3 , Si(CH 2 ) 4 , or Si(CH 2 ) 4 . [0109] In some embodiments, R 1 is hydrogen, a substituted C 1 -C 20 hydrocarbyl, or an unsubstituted C 1 -C 20 hydrocarbyl, such as a substituted C 1 -C 12 hydrocarbyl or an unsubstituted C 1 -C 12 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), for example hydrogen, a substituted C 1 -C 6 hydrocarbyl, or an unsubstituted C 1 -C 6 hydrocarbyl. [0110] In some embodiments, each of R 2 and R 4 is independently hydrogen, a substituted C 1 -C 20 hydrocarbyl, or an unsubstituted C 1 -C 20 hydrocarbyl, such as a substituted C 1 -C 12 hydrocarbyl or an unsubstituted C 1 -C 12 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), for example hydrogen, a substituted C 1 -C 6 hydrocarbyl, or an unsubstituted C 1 -C 6 hydrocarbyl. [0111] In some embodiments, each of R 5 , R 6 , R 7 , and R 8 is independently hydrogen, a substituted C 1 -C 20 hydrocarbyl, or an unsubstituted C 1 -C 20 hydrocarbyl, such as a substituted C 1 -C 12 hydrocarbyl or an unsubstituted C 1 -C 12 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), such as a substituted C 1 -C 6 hydrocarbyl, or an unsubstituted C 1 -C 6 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, or hexyl), or one or more of R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 can be joined to form a substituted or unsubstituted C 4 -C 20 saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof. [0112] In some embodiments, one or more of R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 can be joined to form a substituted or unsubstituted C 5 -C 8 saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof. [0113] In some embodiments, R 3 is an unsubstituted C 4 -C 20 cycloalkyl (e.g., cyclohexane, cyclypentane, cycloocatane, adamantane), or a substituted C 4 -C 20 cycloalkyl. [0114] In some embodiments, R 3 is a substituted or unsubstituted phenyl, benzyl, carbazolyl, naphthyl, or fluorenyl. [0115] In some embodiments, R 3 is a substituted or unsubstituted aryl group represented by the formula: , wherein each of R 9 , R 10 , R 11 , R 12 , and R 13 is independently hydrogen, an unsubstituted C 1 -C 40 hydrocarbyl, a substituted C 1 -C 40 hydrocarbyl, a heteroatom, a heteroatom-containing group, or two or more of R 9 , R 10 , R 11 , R 12 , and R 13 are joined together to form a C 4 -C 62 cyclic or polycyclic ring structure, or a combination thereof. [0116] In some embodiments of the present disclosure,, each of R 9 , R 10 , R 11 , R 12 , and R 13 is independently hydrogen, a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a substituted C 1 -C 40 hydrocarbyl, an unsubstituted C 4 -C 62 aryl (such as an unsubstituted C 4 -C 20 aryl, such as a phenyl), a substituted C 4 -C 62 aryl (such as a substituted C 4 -C 20 aryl), an unsubstituted C 4 -C 62 heteroaryl (such as an unsubstituted C 4 -C 20 heteroaryl), a substituted C 4 -C 62 heteroaryl (such as a substituted C 4 -C 20 heteroaryl), -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 , or -R''-SiR' 3 , where R'' is C 1 -C 10 alkyl and each R' is hydrogen, halogen, C 1 -C 10 alkyl, or C6-C10 aryl. For example, each of R 9 , R 10 , R 11 , R 12 , and R 13 is independently hydrogen, a substituted C 1 -C 20 hydrocarbyl, or an unsubstituted C 1 -C 20 hydrocarbyl, such as a substituted C 1 -C 12 hydrocarbyl or an unsubstituted C 1 -C 12 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), such as a substituted C 1 -C 6 hydrocarbyl, or an unsubstituted C 1 -C 6 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, or hexyl), or two or more of R 9 , R 10 , R 11 , R 12 , and R 13 can be joined to form a substituted or unsubstituted C 4 -C 20 saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof. [0117] In some embodiments of the present disclosure, at least one of R 9 , R 10 , R 11 , R 12 , and R 13 is a phenyl. [0118] In some embodiments of the present disclosure, each of J 1 and J 2 is joined form an unsubstituted C 4 -C 20 cyclic or polycyclic ring, either of which may be saturated, partially saturated, or unsaturated. In some embodiments each J joins to form a substituted C 4 -C 20 cyclic or polycyclic ring, either of which may be saturated or unsaturated. Examples include: . [0119] In at least one embodiment, C1 symmetry bis-Cp metallocene catalysts can also be represented by bridging substituted cyclopentadienyl and substituted indenyl catalyst precursor compounds as the formula (C1b): wherein M, T, J 1 , J 2 , X 1 , X 2 , R 1 , R 2 , and R 4 -R 13 are described above. [0120] In at least one embodiment, C1 symmetry bis-Cp metallocene catalysts can also be represented by bridging substituted cyclopentadienyl and substituted indenyl catalyst precursor compounds as the formula (C1c):
wherein: each of R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 is independently hydrogen, an unsubstituted C 1 -C 40 hydrocarbyl, a substituted C 1 -C 40 hydrocarbyl, a heteroatom, a heteroatom-containing group, or two or more of R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 are joined together to form a cyclic or polycyclic ring structure, or a combination thereof; and M, T, X 1 , X 2 , R 1 , R 2 , and R 4 -R 13 are described above. [0121] In some embodiments, each of R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 is independently hydrogen, a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a substituted C 1 -C 40 hydrocarbyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 , or -R''-SiR' 3 , where R'' is C 1 -C 10 alkyl and each R' is hydrogen, halogen, C 1 -C 10 alkyl, or C6-C10 aryl. For example, each of R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 is independently hydrogen, a substituted C 1 -C 20 hydrocarbyl, or an unsubstituted C 1 -C 20 hydrocarbyl, such as a substituted C 1 -C 12 hydrocarbyl or an unsubstituted C 1 -C 12 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), such as a substituted C 1 -C 6 hydrocarbyl, or an unsubstituted C 1 -C 6 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, or hexyl), or two or more of R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 can be joined to form a substituted or unsubstituted C 4 -C 20 saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof. [0122] In at least one embodiment, C1 symmetry bis-Cp metallocene catalysts that can also be represented by bridging substituted cyclopentadienyl and substituted indenyl catalyst precursor compounds as the formula (C1d):
wherein: each of R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 is independently hydrogen, an unsubstituted C 1 -C 40 hydrocarbyl, a substituted C 1 -C 40 hydrocarbyl, a heteroatom, a heteroatom-containing group, or two or more of R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 are joined together to form a cyclic or polycyclic ring structure, or a combination thereof; and M, T, X 1 , X 2 , R 1 , R 2 , and R 4 -R 13 are described above. [0123] In some embodiments, each of R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 is independently hydrogen, a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a substituted C 1 -C 40 hydrocarbyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, -NR' 2 , -SR', -OR, -SiR' 3 , -OSiR' 3 , -PR' 2 , or -R''-SiR' 3 , where R'' is C 1 -C 10 alkyl and each R' is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl. For example, each of R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 is independently hydrogen, a substituted C 1 -C 20 hydrocarbyl, or an unsubstituted C 1 -C 20 hydrocarbyl, such as a substituted C 1 -C 12 hydrocarbyl or an unsubstituted C 1 -C 12 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), such as a substituted C 1 -C 6 hydrocarbyl, or an unsubstituted C 1 -C 6 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, or hexyl), or two or more R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 can be joined to form a substituted or unsubstituted C 4 -C 20 saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof. [0124] Useful examples of bridging C1 metallocenes used for polyolefin products especially for propylene and diene polymerization and copolymerization include but are not limited to:
[0125] In another embodiment, the metallocene catalyst compound is represented by the formula: TyCpmMGnXq , where Cp is independently a substituted or unsubstituted cyclopentadienyl ligand or substituted or unsubstituted ligand isolobal to cyclopentadienyl such as indenyl, fluorenyl and indacenyl. M is a Group 4 transition metal, such as Hf, Ti or Zr. 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 C 1 -C 20 hydrocarbyl. z is 1 or 2. T is a bridging group. y is 0 or 1. X is a leaving group. m=1, n=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, preferably 2, 3, or 4, preferably 4. [0126] In at least one embodiment, 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. Preferred JR*z groups include t-butyl amido and cyclododecylamido. [0127] Preferred examples for the bridging group T include CH 2 , CH 2 CH 2 , SiMe 2 , SiPh 2 , SiMePh, Si(CH2)3, Si(CH2)4, O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me 2 SiOSiMe 2 , and PBu. In a preferred embodiment of the invention in any embodiment of any formula described herein, T is represented by the formula ER d d 2 or (ER 2 )2 , where E is C, Si, or Ge, and each R d is, independently, hydrogen, halogen, C 1 to C 20 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a C 1 to C 20 substituted hydrocarbyl, and two R d can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system. [0128] Each X is independently selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, aryls, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (two Xs may form a part of a fused ring or a ring system), preferably each X is independently selected from halides, aryls and C 1 to C 5 alkyl groups, preferably each X is a phenyl, methyl, ethyl, propyl, butyl, pentyl, or chloro group. [0129] The half-metallocene catalyst precursor compound may be selected from: dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl; dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dichloride; dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dimethyl; dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dichloride; dimethylsilyl (cyclopentadienyl)(l-adamantylamido)M(R) 2 ; dimethylsilyl (3-tertbutylcyclopentadienyl)(1-adamantylamido)M(R)2; dimethylsilyl (tetramethylcyclopentadienyl)(1-adamantylamido)M(R) 2 ; dimethylsilyl (tetramethylcyclopentadienyl)(1-adamantylamido)M(R)2; µ-(CH 3 ) 2 C(tetramethylcyclopentadienyl)(1-adamantylamido)M(R) 2 ; dimethylsilyl (tetramethylcyclopentadienyl)(1-tertbutylamido)M(R)2; dimethylsilyl (fluorenyl)(1-tertbutylamido)M(R) 2 ; (tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R)2; µ-(C 6 H 5 ) 2 C(tetramethylcyclopentadienyl)(1-cyclododecylamido)M(R ) 2 ; and dimethylsilyl (η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(te rtbutylamido)M(R)2; where M is selected from Ti, Zr, and Hf; and each R is selected from halogen or C 1 to C 5 alkyl (preferably chloro, bromo, methyl, ethyl, propyl, butyl, pentyl or isomers thereof). [0130] In at least one embodiment, the catalyst precursor compound can be a post- metallocene single-site catalyst compound, such as a Group 3 through Group 12 transition metal directly binding to at least two hetero-atoms (e.g., O, N, P, S, CN, etc.) on at least one organic ligand through σ and/or coordination bondings, optionally having σ bonding between carbon on the organic ligand and the transition metal center as well, for example: having one ligand with two nitrogen donors forming one N-Hf σ ^bond and one N-Hf coordination bond, whereas having one ligand with two nitrogen donors to form one N-Hf σ ^bond and one N-Hf coordination bond plus one C-Hf σ bond. The two of the at least two hetero-atoms on the organic ligand may form a 4, 5, 6, 7, 8 or more membered ring with the transition metal center, for example, the two compounds above have a 5 membered ring formed through two N and two C atoms on the ligand, and the metal center; for example, the compounds with the formula below has two 6 membered rings formed through N, O, three C atoms, and the metal center: 1 5 (R to R are independently H or C 1 to C 20 organic groups, M is Ti, Zr, or Hf, and X is halide such as Cl or alkyl such as Me); for example, the two Hf compounds below have two 7 membered rings plus one 6 membered ring formed through two O and three or four C atoms on the ligand and the metal center:
(Bz = benzyl); for example, the three compounds below have two 8 membered rings formed through N, O, and five C atoms on the ligand and the metal center: (M = Ti, Zr, or Hf; X = halide such as Cl or alkyl such as Me of Bz); and the like. [0131] Multiple catalyst precursors can also be used; for example, one bridged metallocene with one unbridged metallocene, one metallocene plus one half metallocene, one metallocene with one post-metallocene, or two post-metallocenes. Catalyst System Formation [0132] Embodiments of the present disclosure include methods for preparing a catalyst system including contacting in an organic solvent the in-situ supported MAO with at least one catalyst precursor compound having a Group 3 through Group 12 metal atom or lanthanide metal atom. The catalyst precursor compound having a Group 3 through Group 12 metal atom or lanthanide metal atom can be a metallocene or post-metallocene catalyst precursor compound comprising a Group 4 metal. [0133] In at least one embodiment, the in-situ supported MAO is heated prior to contact with the catalyst precursor compound. [0134] The in-situ supported MAO formed as a slurry in an organic solvent can be immediately contacted with at least one catalyst precursor compound, or can be stored as is or isolated as a solid supported MAO for later use, to make the finished catalysts. The catalyst precursor compound can also be added as a solid or as a slurry of an organic solvent to the in- situ supported MAO. In at least one embodiment, the slurry of the in-situ supported MAO is contacted with the catalyst precursor compound for a period of time between about 0.02 hours and about 24 hours, such as between about 0.1 hours and 1 hour, 0.2 hours and 0.6 hours, 2 hours and about 16 hours, or between about 4 hours and about 8 hours. [0135] The mixture of the catalyst precursor compound and the in-situ supported MAO may be heated to between about 30°C and about 100°C, such as between about 45°C and about 70°C, or without heating, such as at the room temperature. Contact times may be between about 0.02 hours and about 24 hours, such as between about 0.1 hours and 1 hour, 0.2 hours and 0.6 hours, 2 hours and about 16 hours, or between about 4 hours and about 8 hours. [0136] Useful organic solvents are materials in which all or part of the reactants used herein, e.g., the in-situ supported MAO and the catalyst precursor compound, are at least partially soluble (or in the case of the solid support, suspended) and which are liquid at reaction temperatures. Non-limiting example solvents are non-cyclic alkanes with formula CnH(n+2) where n is 3 to 30, such as propane, isobutane, butane, isopentane, hexane, n-heptane, octane, nonane, decane and the like, and cycloalkanes with formula CnHn where n is 5 to 30, such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane and the like. Suitable organic solvents also include mixtures of any of the above. Although aromatic solvents such as benzene or toluene can also be used to make the finished catalyst with good performance, they are not preferred because non-anchored MAO on support is more soluble in these solvents and may cause high level MAO residue in the supernate that needs to be removed before contacting the catalyst precursor compound to make the finished catalyst to avoid catalyst operability issue and before the solvent can be reused. [0137] If the in-situ supported MAO is isolated as a solid for later use, to make a finished catalyst using the isolated in-situ supported MAO solid, a solvent can be charged into a reactor, followed by the solid supported MAO. A catalyst precursor compound can then be charged into the reactor, such as a solution in an organic solvent or as a solid. The mixture can be stirred at a temperature, such as room temperature. Additional solvent may be added to the mixture to form a slurry having a desired consistency, such as from about 2 cc/g of silica to about 20 cc/g silica, such as about 4 cc/g. The solvent is then removed. Removing solvent dries the mixture and may be performed under a vacuum atmosphere, purged with inert atmosphere, heating of the mixture, or combinations thereof. For heating of the mixture, any suitable temperature can be used that evaporates the organic solvent. It is to be understood that reduced pressure under vacuum will lower the boiling point of the organic solvent depending on the pressure of the reactor. Solvent removal temperatures can be from about 10°C to about 100°C, such as from about 60°C to about 90°C, such as from about 60°C to about 80°C, for example about 75°C or less, such as about 65°C or less. In at least one embodiment, removing solvent includes applying heat, applying vacuum, and applying nitrogen purged from bottom of the vessel by bubbling nitrogen through the mixture. The mixture is dried. Methods to Obtain Supernate Free of or Low in TMA [0138] Embodiments of the present disclosure include methods for preparing an in-situ supported MAO or the derived finished catalyst system with the supernate after the formation of the in-situ supported MAO or the derived finished catalyst free of or low in free TMA in order to: 1) eliminate or reduce the potential fouling factor caused by the free TMA in the supernate reacting with the catalyst precursor compound to form non-supported soluble low activity species; and 2) enable the direct reuse of the supernate as solvent without futher treatment. [0139] The term charged TMA:water (or water:TMA) ratio refers to the ratio of TMA and water raw starting materials charged into the in-situ sMAO formation reaction equipment. The term TMA:water uptake ratio refers to the indirect measurement of the ratio of the charged water and TMA reacted to form MAO molecules loaded on silica, which is estimated through the H 1 NMR quantification of free TMA left in the supernate after the in-situ sMAO formation reaction, which can be calculated as below: TMA:water uptake ratio = (Charged TMA – Residual TMA):Charged water, by assuming that all water molecules are converted to MAO molecules due to more water reactive Al-Me units than the reactive OH units of the charged water. E.g., for charged TMA:water ratio = 1.30:1, the water reactive Al-Me units on TMA (AlMe3) are 1.30x3eq = 3.90eq and the OH units of water are 2eq. Method 1 [0140] For a support containing absorbed water 6.5 (mmol/g support) or less, when the charged TMA:water ratio is controlled in the range of between 1.31:1 and 1.25:1, and the in- situ supported MAO formation temperature is controlled at not higher than -8°C, e.g., -10±2°C -12±4°C, -15±7°C, -20±12°C, or not higher than -8°C and not lower than -60°C, the supernate of the in-situ sMAO or the derived finished catalyst slurry free of TMA (H 1 NMR undetectable) or with a TMA concentration not more than 600 ppm (quantified with H 1 NMR method described in Example 22) can be obtained, as indicated in Table 2 Entries 1-4. Although the Table 2 data are generated from the catalysts made from the TMA concentration at about 20 wt% and a water absorbed silica slurry at about 22 wt%, higher or lower concentrations of the two ingredients, e.g., TMA concentration at 30-80 wt% or 1-3 wt% and the water absorbed silica slurry at 23-25 wt% or 1-10 wt%, can also be used. The water absorbed silica may also be added as a solid. Method 2 [0141] For a support containing absorbed water 5.0 (mmol/g support) or less, when the charged TMA:water ratio is controlled in the range of between 1.42:1 and 1.25:1, and the in-situ supported MAO formation temperature is controlled at not higher than -12°C, e.g., -14±2°C -20±8°C, -30±18°C, or not higher than -12°C and not lower than -60°C, the supernate of the finished catalyst slurry free of TMA (H 1 NMR undetectable) or with a TMA concentration not more than 600 ppm (quantified with H 1 NMR method described in Example 22) can be obtained, as indicated in Table 2 Entries 5-13. Although the Table 2 data are generated from the catalysts made from the TMA concentration at about 20 wt% and a water absorbed silica slurry at about 22 wt%, higher or lower concentrations of the two ingredients, e.g., TMA concentration at 30 wt% - 80 wt% or 1 wt% - 3 wt% and the water absorbed silica slurry at 23 wt% - 25 wt% or 1 wt% - 10 wt%, can also be used. The water absorbed silica may also be added as a solid. Method 3 [0142] For a support containing absorbed water 7.0 -10.0 (mmol/g support), e.g., 7.0, 7.5, 8.0, 9.0, or 10.0 (mmol/g silica), when the charged TMA:water ratio is 1.20:1 or less, e.g., 1.15:1, and the in-situ sMAO formation temperature is controlled at not higher than -12°C or lower, the supernate of the finished catalyst slurry free of TMA (1H NMR undetectable) or with a TMA concentration not more than 600 ppm (quantified with H 1 NMR method described in Example 22) can be obtained, provided that the higher the water content, the lower the cooling temperature required. For example, for 7.8 (mmol water/g support) loading, the sMAO formation temperature should be controlled at -12°C or lower, and for 9.0 (mmol water/g support) loading, the sMAO formation temperature should be controlled at -20°C or lower, as indicated in Table 2 Entries 15-16. Although the Table 2 data are generated from the catalysts made from the TMA concentration at about 20 wt% and from a water absorbed silica slurry of about 22 wt%, higher or lower concentrations of the two ingredients, e.g., TMA concentration at 30 wt% - 80 wt% or 1 wt% - 3 wt% and the water absorbed silica slurry at 23 wt% - 25 wt% or 1 wt% - 10 wt%. The water absorbed silica may also be added as a solid. Method 4 [0143] In some in-situ sMAO preparation cases, the sMAO containing both supported MAO (e.g., siloxy anchored MAO as sketched in Eq. 4 species C, a simplified structure C in the introduction section for better chemistry understanding purpose) and unsupported MAO (unanchored free MAO, as sketched in Eq. 4 species A, a simplified structure A in the introduction section for better chemistry understanding purpose) may need to be heated at a higher temperature, e.g., 85°C, 92°C, 100°C, or 110°C, presumably to form the MAO dimer to limit the soluble MAO portion for the derived catalysts used in slurry polymerization to prevent MAO leaching fouling, presumably due to species A becoming soluble in the solvent phase of the slurry polymerization media. The heating step may cause the generation of free TMA likely through Eq.3: [0144] The heating generated free TMA can be removed by an additional matching amount of the same water absorbed silica for the preparation of the in-situ sMAO and therefore the total charged TMA:water ratio is decreased; e.g., under the conditions of Method 2 where the charged TMA:water is 1.42:1, additional 5% of water absorbed silica added to remove free TMA released by heating may decrease the charged TMA:water ratio, e.g., to 1.35:1, or 1.31:1. Method 5 [0145] Similar to Method 4 but instead of adding additional water absorbed silica, a calcined silica with controlled hydroxyl residue is used to add to remove free TMA left in the supernate after the in-situ sMAO formation, including the heating generated TMA. 150°C - 875°C calcined silica can be used with the amount so controlled that the amount of reactive hydroxyl residue on the silica matches the free TMA amount. A raw silica can also be used but the amount of water absorbed on the silica may be first quantified, e.g., through Grignard titration or LOD (loss on drying) methods, to determine the active protons and TMA matching. Polymerization Processes [0146] In at least one embodiment of the present disclosure, a method includes polymerizing olefins to produce a polyolefin composition by contacting at least one olefin with a catalyst system of the present disclosure and obtaining the polyolefin composition. Polymerization may be conducted 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/or at a time up to about 400 minutes. [0147] Embodiments of the present disclosure include polymerization processes where monomer (such as ethylene or propylene), and optionally comonomer, are contacted with a catalyst system comprising at least one catalyst compound and an activator, as described above. The at least one catalyst compound and activator may be combined in any order, and are combined typically prior to contact with the monomer. [0148] Slurry and gas phase polymerizations may be conducted in the presence of an aliphatic hydrocarbon solvent/diluent/condensing agent (such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; preferably aromatics are present in the solvent/diluent/condensing agent at less than 1 wt%, preferably less than 0.5 wt%, preferably at 0 wt% based upon the weight of the solvents/diluent/condensing agent). [0149] In preferred embodiments, solvents/diluents used in the polymerizations are not aromatic, preferably aromatics are present in the solvent/diluent at less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0 wt% based upon the weight of the solvents/diluents. [0150] Monomers useful herein include substituted or unsubstituted C 2 to C 40 alpha olefins, preferably C 2 to C 20 alpha olefins, preferably C2 to C12 alpha olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof. In a preferred embodiment, olefins include a monomer that is propylene and one or more optional comonomers comprising one or more ethylene or C 4 to C 40 olefin, preferably C4 to C 20 olefin, or preferably C6 to C12 olefin. The C4 to C 40 olefin monomers may be linear, branched, or cyclic. The C 4 to C 40 cyclic olefin may be strained or unstrained, monocyclic or polycyclic, and may include one or more heteroatoms and/or one or more functional groups. In another preferred embodiment, olefins include a monomer that is ethylene and an optional comonomer comprising one or more of C3 to C 40 olefin, preferably C 4 to C 20 olefin, or preferably C 6 to C 12 olefin. The C 3 to C 40 olefin monomers may be linear, branched, or cyclic. The C 3 to C 40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may include heteroatoms and/or one or more functional groups. [0151] Exemplary C 2 to C 40 olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and substituted derivatives thereof, preferably norbornene, norbornadiene, and dicyclopentadiene. [0152] In at least one embodiment, one or more dienes are present in a polymer produced herein at up to about 10 wt%, such as from about 0.00001 wt% to about 1.0 wt%, such as from about 0.002 wt% to about 0.5 wt%, such as from about 0.003 wt% to about 0.2 wt%, based upon the total weight of the composition. In at least one embodiment, about 500 ppm or less of diene is added to the polymerization, such as about 400 ppm or less, such as about 300 ppm or less. In at least one embodiment, at least about 50 ppm of diene is added to the polymerization, or about 100 ppm or more, or 150 ppm or more. [0153] Diolefin monomers include any hydrocarbon structure, preferably C 4 to C 30 , having at least two unsaturated bonds, wherein at least two of the unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non-stereospecific catalyst(s). It is further preferred that the diolefin monomers be selected from alpha, omega-diene monomers (i.e., di-vinyl monomers). In at least one embodiment, the diolefin monomers are linear di-vinyl monomers, such as those containing from 4 to 30 carbon atoms. Non-limiting examples of dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and low molecular weight polybutadienes (Mw less than 1000 g/mol). Non-limiting example cyclic dienes include cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions. [0154] In at least one embodiment, where butene is the comonomer, the butene source may be a mixed butene stream comprising various isomers of butene. The 1-butene monomers are expected to be preferentially consumed by the polymerization process as compared to other butene monomers. Use of such mixed butene streams will provide an economic benefit, as these mixed streams are often waste streams from refining processes, for example, C4 raffinate streams, and can therefore be substantially less expensive than pure 1-butene. [0155] Polymerization processes of the present disclosure can be carried out in any suitable manner. Any suitable slurry or gas phase polymerization process can be used. Such processes can be run in a batch, semi-batch, or continuous mode. [0156] Preferred polymerizations can be run at any temperature and/or pressure suitable to obtain the desired polyolefins. Typical temperatures and/or pressures include a temperature from about 0°C to about 300°C, such as from about 20°C to about 200°C, such as from about 35°C to about 150°C, such as from about 40°C to about 120°C, such as from about 65°C to about 95°C; and at a pressure from about 0.35 MPa to about 10 MPa, such as from about 0.45 MPa to about 6 MPa, or preferably from about 0.5 MPa to about 4 MPa. [0157] In a typical polymerization, the run time of the reaction is up to about 400 minutes, such as from about 5 minutes to about 250 minutes, such as from about 10 minutes to about 120 minutes. [0158] Hydrogen, may be added to a reactor for molecular weight control of polyolefins. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of from about 0.001 psig and 50 psig (0.007 kPa to 345 kPa), such as from about 0.01 psig to about 25 psig (0.07 kPa to 172 kPa), such as from about 0.1 psig and 10 psig (0.7 kPa to 70 kPa). In one embodiment, 600 ppm or less of hydrogen is added, or 500 ppm or less of hydrogen is added, or 400 ppm or less or 300 ppm or less. In other embodiments, at least 50 ppm of hydrogen is added, or 100 ppm or more, or 150 ppm or more. [0159] In an alternative embodiment, the activity of the catalyst is at least about 50 g/mmol/hour, such as about 500 or more g/mmol/hour, such as about 5,000 or more g/mmol/hr, such as about 750,000 or more g/mmol/hr where the amount of metallocene catalyst is in the denominator. In an alternative embodiment, the conversion of olefin monomer is at least about 10%, based upon polymer yield (weight) and the weight of the monomer entering the reaction zone, such as about 20% or more, such as about 30% or more, such as about 50% or more, such as about 80% or more. [0160] Preferably, alumoxane is present at a molar ratio of aluminum to transition metal of a catalyst compound of less than about 500:1, such as less than about 300:1, such as less than about 100:1, such as less than about 1:1. [0161] In a preferred embodiment, little or no scavenger is used in the process to produce the polyolefin composition. Preferably, scavenger (such as tri alkyl aluminum) is present at zero mol%. Alternatively, the scavenger is present at a molar ratio of scavenger metal to transition metal of the catalyst of less than about 100:1, such as less than about 50:1, such as less than about 15:1, such as less than about 10:1. [0162] In a preferred embodiment, the polymerization: 1) is conducted at temperatures of 0°C to 300°C (preferably 25°C to 150°C, preferably 40°C to 120°C, preferably 45°C to 80°C); 2) is conducted at a pressure of atmospheric pressure to 10 MPa (preferably 0.35 MPa to 10 MPa, preferably from 0.45 MPa to 6 MPa, preferably from 0.5 MPa to 4 MPa); 3) wherein the catalyst system used in the polymerization comprises alumoxane at a molar ratio of aluminum to transition metal of a catalyst compound of less than 200:1, preferably 75:1 to 160:1, preferably 90:1 to 150:1, such as 95:1 to 125:1; 4) the polymerization preferably occurs in one reaction zone; 5) the productivity of the catalyst compound is at least 80,000 g/mmol/hr (preferably at least 150,000 g/mmol/hr, preferably at least 200,000 g/mmol/hr, preferably at least 250,000 g/mmol/hr, preferably at least 300,000 g/mmol/hr); 6) optionally scavengers (such as trialkyl aluminum compounds) are absent (e.g., present at zero mol%). Alternatively, the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, preferably less than 50:1, preferably less than 15:1, preferably less than 10:1; and 8) optionally hydrogen is present in the polymerization reactor at a partial pressure of 0.001 psig to 50 psig (0.007 kPa to 345 kPa) (preferably from 0.01 psig to 25 psig (0.07 kPa to 172 kPa), more preferably 0.1 psig to 10 psig (0.7 kPa to 70 kPa)). In a preferred embodiment, the catalyst system used in the polymerization comprises no more than one catalyst compound. A "reaction zone", also referred to as a "polymerization zone", is a vessel where polymerization takes place, for example a batch reactor. When multiple reactors are used in either series or parallel configuration, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in both a batch reactor and a continuous reactor, each polymerization stage is considered as a separate polymerization zone. The polymerization can occur in one or more reaction zones. [0163] Other additives may also be used in the polymerization, as desired, such as one or more scavengers, promoters, modifiers, chain transfer agents (such as diethyl zinc), reducing agents, oxidizing agents, hydrogen, aluminum alkyls, or silanes. [0164] Chain transfer agents may be alkylalumoxanes, a compound represented by the formula AlR 3 , ZnR 2 (where each R is, independently, a C 1 -C 8 aliphatic radical, preferably methyl, ethyl, propyl, butyl, penyl, hexyl, heptyl, octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof. [0165] Gas phase polymerization: Gas phase polymerization processes may be used herein. Generally, in a fluidized gas bed process used for producing polymers, a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer. (See, for example, U.S. Patent Nos. 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661; and 5,668,228; all of which are fully incorporated herein by reference.) [0166] Slurry phase polymerization: Slurry phase polymerization processes may be used herein. A slurry polymerization process generally operates between 1 to about 50 atmosphere pressure range (15 psi to 735 psi, 103 kPa to 5068 kPa) or even greater and temperatures of 0 ^C to about 120 ^C. In a slurry polymerization, a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which monomer and comonomers, along with catalysts, are added. The suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor. The liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, preferably a branched alkane. The medium employed should be liquid under the conditions of polymerization and relatively inert. When a propane medium is used, the process should be operated above the reaction diluent critical temperature and pressure. Preferably, a hexane or an isobutane medium is employed. In another embodiment, the diluent is not aromatic, preferably aromatics are present in the diluent at less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0 wt% based upon the weight of the diluents employed. Polyolefin Products [0167] The present disclosure also relates to polyolefin compositions, such as resins, produced by the catalyst systems of the present disclosure. Polyolefins of the present disclosure can have no detectable aromatic solvent. [0168] In at least one embodiment, a process includes utilizing a catalyst system of the present disclosure to produce propylene homopolymers or propylene copolymers, such as propylene-ethylene and/or propylene-alphaolefin (preferably C3 to C 20 ) copolymers (such as propylene-hexene copolymers or propylene-octene copolymers) having an Mw/Mn of greater than about 1, such as greater than about 2, such as greater than about 3, such as greater than about 4. [0169] In at least one embodiment, a process includes utilizing a catalyst system of the present disclosure to produce olefin polymers, preferably polyethylene and polypropylene homopolymers and copolymers. In at least one embodiment, the polymers produced herein are homopolymers of ethylene or copolymers of ethylene preferably having from about 0 mol% and 25 mol% of one or more C 3 to C 20 olefin comonomer (such as from about 0.5 mol% and 20 mol%, such as from about 1 mol% to about 15 mol%, such as from about 3 mol% to about 10 mol%). Olefin comonomers may be C 3 to C 12 alpha-olefins, such as one or more of propylene, butene, hexene, octene, decene, or dodecene, preferably propylene, butene, hexene, or octene. Olefin monomers may be one or more of ethylene or C 4 to C 12 alpha-olefin, preferably ethylene, butene, hexene, octene, decene, or dodecene, preferably ethylene, butene, hexene, or octene. [0170] Polymers produced herein may have an Mw of from about 5,000 g/mol to about 1,000,000 g/mol (such as from about 25,000 g/mol to about 750,000 g/mol, such as from about 50,000 g/mol to about 500,000 g/mol), and/or an Mw/Mn of from about 1 to about 40 (such as from about 1.2 to about 20, such as from about 1.3 to about 10, such as from about 1.4 to about 5, such as from about 1.5 to about 4, such as from about 1.5 to about 3) as determined by GPC-4D as described in the Experimental section below. [0171] The polyolefins produced herein contain 0 ppm of aromatic hydrocarbon. Preferably, the polyolefins produced herein contain 0 ppm of toluene. Experimental Materials [0172] Chemicals: T rimethylaluminum was purchased from Sigma Aldrich (St. Louis, MO) or AkzoNobel (now Nouryon) and used as obtained, unless stated otherwise. Spray-dried silica ES70™ was purchased from PQ Corporation (now Ecovyst) and non spray-dried silica DM-L403 was purchased from AGC Chemicals. ES70X and ES70 are ES70™ silica that has been calcined at either 200°C, 400°C, or 875°C for four hours. DM-L 403 silica is calcined at 200°C for four hours. The silica parameters provided by vendors are summarized below: Table 1. Silica Parameters [0173] Isohexane (in house plant grade solvent) and heptane (purchased from Sigma Aldrich anhydrous grade) were sparged with dry N 2 and then stored with activated 3 Angstrom molecular sieves in a container with 5 wt% -10 wt% molecular sieves at least for overnight before use. Water used is a lab deionized water. All reactions were performed under an inert nitrogen atmosphere, unless otherwise stated. All deuterated solvents were obtained from Cambridge Isotopes (Cambridge, MA) and dried over 3 Angstrom molecular sieves before use. [0174] Equipment: Ace Glass 600mL and 4L jacketed filter reactors with a Lauda chiller with Kryo 20 coolant capable of controlling temperature range from -30°C to 150°C. The water absorbed silica slurry is charged into the well-sealed 600 mL reactor and metered into the 4L reactor through a Teflon tubing with additional rate controlled with positive N 2 pressure through a needle valve. [0175] In-situ supported MAO silica calcined at 200°C, 400°C, or 875°C with a water loading in the range of 4.3-9.1mmol/g and the charged TMA:water ratio in the range of 12.7:1 to 1.31:1 were used to investigate TMA residue in supernate (Table 2). Three metallocene catalyst precursor compounds representing different ligand structures and different metal centers were used to make the finished catalyst for activity comparisons: non-bridged zirconocene bis(1-methyl-3-butylcyclopentadienyl)zirconium dichloride (M1); bridged zirconocene dimethylsilyl-bis(4,5,6,7-tetrahydroindenyl)zirconium dimethyl (M2), and non- bridged hafnocene bis(proylcyclopentadienyl)hafnium dimethyl (M3). M1 has very good solubility in an aliphatic solvent, whereas M2 and M3 dichloride versions are significantly less soluble. Their methylated versions have higher solubility in preferred aliphatic solvents and are thus used. Table 2. sMAO Formation Conditions, Supernate TMA Contents, and Finished Catalyst Activities 1 Standard catalysts are M1, M2, and M3 metallocenes supported on the same silica derived supported regular MAO (W. R. Grace 30% MAO solution in toluene) with MAO loading of 6.2mmol Al/g silica, to give activities of 2,912, 3,389, and 6,294g/g cat/hr, respectively; 2 before heating because the heating was applied on solid. [0176] Example 1 (M3, 400°C calcined ES70 silica, in-situ sMAO solid heated at 92°C) 1. In the drybox, each of the 3 bottles (1L volume) was charged with 100 g of silica ES70 (400°C), 360 g of isohexane, and 11.7 g of water. The 3 bottles containing total 300 g silica, 1080 g isohexane, and 35.1 g (1.95 mol) water were capped and sealed well with electrical tapes. The 3 bottles were taken out of the drybox and placed on a roller set at 80 rpm to roll for 2 hours. After 2 hours, the 3 bottles were brought back into the drybox. 2. 760 g of dry isohexane (3A molecular sieves overnight) was charged into the 4L reactor equipped with an anchor stir blade. The Lauda chiller was turned on with the temperature controller set at -30°C. The stirrer was turned on and set to 170 rpm. 3. After the isohexane was cooled to -1°C, the filtration cap at the reactor bottom was checked to ensure no leaking, 184.2 g (2.55 mol) of neat TMA was added to the reactor. The TMA:water ratio is 2.55:1.95 or 1.31:1. 4. While waiting for the TMA solution to reach -15°C, 1 of the 3 bottles of water absorbed silica slurry was transferred to the 600 mL reactor and cooled to about -5°C and stirred to ensure a good mixing. 5. After the TMA solution temperature reach -15°C, started the addition of the water absorbed silica in a rate that maintained the reaction temperature between -9°C to -12°C under 250 rpm. 6. After the addition of silica slurry, the agitation was adjusted to 170 rpm, the jacket temperature was increased to 1°C and maintained for 30 minutes and then to ambient. 7. The agitation was stopped and the solvent was removed through the reactor bottom filter under vacuum. An 1 H-NMR spectrum was acquired for the filtrate in THF-d8 (deuterated tetrahydrofuran) and showed neither MAO nor TMA. 8. The wet solid was dried in the 4L jacketed filter reactor at ambient for 2 hours, and then set heating temperature at 100°C to allow solid temperature at 92°C for 4 hours. Yield: 441.5 g. 9. 1.0 g sMAO from above was slurried into 4 g isohexane in a 20 mL vial and then added 19.0 mg M3 metallocene. 10. The slurry was placed on a shaker to shake for 1 hour, filtered through a frit, and then vacuum dried for 1 hour. Yield 1.0 g. The catalyst was tested for gas-phase ethylene polymerization in a 2L autoclave salt-bed reactor with procedure described in Example 22. [0177] Example 2 (M3, 200°C calcined ES70 silica, in-situ sMAO slurry heated at 92°C) 1. In the drybox, each of the 3 bottles (1L volume) was charged with 100 g of silica ES70 (200°C), 360 g of heptane, and 11.7 g of water. The 3 bottles containing total 300 g silica, 1080 g heptane, and 35.1 g (1.95 mol) water were capped and sealed well with electrical tapes. The 3 bottles were taken out of the drybox and placed on a roller set at 80 rpm to roll for 2 hours. After 2 hours, the 3 bottles were brought back into the drybox. 2. 760 g of dry heptane (3A molecular sieves overnight) was charged into the 4L reactor equipped with an anchor stir blade. The Lauda chiller was turned on with the temperature controller set at -30°C. The stirrer was turned on and set to 170 rpm. 3. After the heptane was cooled to -1°C, the filtration cap at the reactor bottom was checked to ensure no leaking, 184.2 g (2.55 mol) of neat TMA was added to the reactor. The TMA:water ratio is 2.55:1.95 or 1.31:1. 4. While waiting for the TMA solution to reach -15°C, 1 of the 3 bottles of water absorbed silica slurry was transferred to the 600 mL reactor and cooled to about -5°C and stirred to ensure a good mixing. 5. After the TMA solution temperature reach -15°C, started the addition of the water absorbed silica in a rate that maintained the reaction temperature between -9°C to -12°C under 250 rpm. 6. After the addition of silica slurry, the agitation was adjusted to 170 rpm, the jacket temperature was increased to 1°C and maintained for 30 minutes and then to ambient. 7. The agitation was stopped to allow the solid to settle. An 1 H-NMR spectrum was acquired for the filtrate in THF-d8 (deuterated tetrahydrofuran) and showed neither MAO nor TMA. 8. The stirrer was turned on again and set at 170 rpm slurry was then heated by setting the heater to 96°C to allow the reaction temperature to be 92°C - 93°C and maintained for 4 hours. 9. After heating, the slurry was cooled to 25°C and the stirrer was increased to 300 rpm, 8.45 g M3 metallocene was added. 10. After the M3 addition, the stirrer was reduced to 170 rpm for 2 hours. 11. The slurry was filtered, washed with 2x 1L isohexane, and dried overnight under vacuum at ambient. Yield: 445.5 g. The catalyst was tested for gas-phase ethylene polymerization in a 2L autoclave salt-bed reactor with procedure described in Example 22. [0178] Example 3 (M3, 200°C calcined ES70 silica, in-situ sMAO slurry heated at 65°C) 1. In the drybox, each of the 3 bottles (1L volume) was charged with 100 g of silica ES70 (200°C), 360 g of heptane, and 11.7 g of water. The 3 bottles containing total 300 g silica, 1080 g heptane, and 35.1 g (1.95 mol) water were capped and sealed well with electrical tapes. The 3 bottles were taken out of the drybox and placed on a roller set at 80 rpm to roll for 2 hours. After 2 hours, the 3 bottles were brought back into the drybox. 2. 715 g of dry heptane (3A molecular sieves overnight) was charged into the 4L reactor equipped with an anchor stir blade. The Lauda chiller was turned on with the temperature controller set at -30°C. The stirrer was turned on and set to 200 rpm. 3. After the heptane was cooled to -1°C, the filtration cap at the reactor bottom was checked to ensure no leaking, 184.2 g (2.55 mol) of neat TMA was added to the reactor. The TMA:water ratio is 2.55:1.95 or 1.31:1. 4. While waiting for the TMA solution to reach -15°C, 1 of the 3 bottles of water absorbed silica slurry was transferred to the 600 mL reactor and cooled to about -5°C and stirred to ensure a good mixing. 5. After the TMA solution temperature reach -15°C, started the addition of the water absorbed silica in a rate that maintained the reaction temperature between -9°C to -12°C under 300 rpm. 6. After the addition of silica slurry, the agitation was adjusted to 200 rpm, the jacket temperature was increased to 1°C and maintained for 30 minutes and then to ambient. 7. The slurry was then heated by setting the heater to 68°C to allow the reaction temperature to be about 65°C and maintained for 4 hours. 8. The temperature was then reduced to ambient (~21°C). The stirrer was turned off to allow the solid to settle. An 1 H-NMR spectrum was acquired for the supernate in THF-d8 (deuterated tetrahydrofuran) and showed neither MAO nor TMA. 9. The stirrer was turned on and set at 60 rpm for overnight. 10. The stirrer was increased to 300 rpm, 8.84 g M3 metallocene was added. 11. After the M3 addition, the stirrer was reduced to 200 rpm for 2 hours. 12. The slurry was filtered, washed with 2x 1L isohexane, and dried overnight under vacuum at ambient. Yield: 459 g. The catalyst was tested for gas-phase ethylene polymerization in a 2L autoclave salt-bed reactor with procedure described in Example 22. [0179] Example 4 (M3, 400°C calcined ES70 silica, in-situ sMAO slurry heated at 92°C) 1. In the drybox, each of the 3 bottles (1L volume) was charged with 100 g of silica ES70 (400°C), 360 g of heptane, and 11.7 g of water. The 3 bottles containing total 300 g silica, 1080 g heptane, and 35.1 g (1.95 mol) water were capped and sealed well with electrical tapes. The 3 bottles were taken out of the drybox and placed on a roller set at 80 rpm to roll for 2 hours. After 2 hours, the 3 bottles were brought back into the drybox. 2. 700 g of dry heptane (3A molecular sieves overnight) was charged into the 4L reactor equipped with an anchor stir blade. The Lauda chiller was turned on with the temperature controller set at -30°C. The stirrer was turned on and set to 200 rpm. 3. After the heptane was cooled to -1°C, the filtration cap at the reactor bottom was checked to ensure no leaking, 184.2 g (2.55 mol) of neat TMA was added to the reactor. The TMA:water ratio is 2.55:1.95 or 1.31:1. 4. While waiting for the TMA solution to reach -15°C, 1 of the 3 bottles of water absorbed silica slurry was transferred to the 600 mL reactor and cooled to about -5°C and stirred to ensure a good mixing. 5. After the TMA solution temperature reach -15°C, started the addition of the water absorbed silica in a rate that maintained the reaction temperature between -9°C to -12°C under 300 rpm. 6. After the addition of silica slurry, the agitation was adjusted to 200 rpm, the jacket temperature was increased to 1°C and maintained for 30 minutes and then to ambient. 7. The slurry was then heated by setting the heater to 96°C to allow the reaction temperature to be 92°C - 93°C and maintained for 4 hours. 8. The temperature was then reduced to ambient (~21°C). The stirrer was turned off to allow the solid to settle. An 1 H-NMR spectrum was acquired for the supernate in THF-d8 (deuterated tetrahydrofuran) and showed 170 ppm TMA. 9. The stirrer was turned on and set at 60 rpm for overnight. 10. The stirrer was increased to 300 rpm, 8.45g M3 metallocene was added. 11. After the M3 addition, the stirrer was reduced to 200 rpm for 2 hours. 12. The slurry was filtered, washed with 2x 1L isohexane, and dried overnight under vacuum at ambient. Yield: 458.8 g. The catalyst was tested for gas-phase ethylene polymerization in a 2L autoclave salt-bed reactor with procedure described in Example 21. [0180] Example 5 (M3, 200°C calcined ES70X silica, in-situ sMAO slurry heated at 92°C) 1. In the drybox, each of the 3 bottles (1L volume) was charged with 100 g of silica ES70X (200°C), 360 g of heptane, and 11.7 g of water. The 3 bottles containing total 300 g silica, 1080 g heptane, and 35.1 g (1.95 mol) water were capped and sealed well with electrical tapes. The 3 bottles were taken out of the drybox and placed on a roller set at 80 rpm to roll for 2 hours. After 2 hours, the 3 bottles were brought back into the drybox. 2. 760 g of dry heptane (3A molecular sieves overnight) was charged into the 4L reactor equipped with an anchor stir blade. The Lauda chiller was turned on with the temperature controller set at -30°C. The stirrer was turned on and set to 170 rpm. 3. After the isohexane was cooled to -1°C, the filtration cap at the reactor bottom was checked to ensure no leaking, 184.2 g (2.55 mol) of neat TMA was added to the reactor. The TMA:water ratio is 2.55:1.95 or 1.31:1. 4. While waiting for the TMA solution to reach -15°C, 1 of the 3 bottles of water absorbed silica slurry was transferred to the 600 mL reactor and cooled to about -5°C and stirred to ensure a good mixing. 5. After the TMA solution temperature reach -15°C, started the addition of the water absorbed silica in a rate that maintained the reaction temperature between -9°C to -12°C under 250 rpm. 6. After the addition of silica slurry, the agitation was adjusted to 170 rpm, the jacket temperature was increased to 1°C and maintained for 30 minutes and then to ambient. 7. The slurry was then heated by setting the heater to 96°C to allow the reaction temperature to be 92°C - 93°C and maintained for 5 hours. 8. The reaction temperature was reduced to ambient. The agitation was stopped to allow the solid to settle. An 1 H-NMR spectrum was acquired for the supernate in THF-d8 (deuterated tetrahydrofuran) and showed 270 ppm TMA. 9. The stirrer was turned back on and set at 170 rpm, 8.63 g M3 catalyst precursor compound was added at once and the slurry was stirred for 2 hours. 10. The slurry was then filtered, washed with 2x 1L isohexane, and dried overnight under vacuum at ambient. Yield: 471.5 g. The catalyst was tested for gas-phase ethylene polymerization in a 2L autoclave salt-bed reactor with procedure described in Example 21. [0181] Examples 6 - 21 (Preparation of finished catalysts from silica with different calcinated temperature and water content and from M1 and M2 metallocenes) [0182] Example 6-15, 17-21 finished catalysts were prepared with procedures similar to Example 5, and Example 16 similar to Example 1, with variations in Table 3: Table 3. Preparation of Finished Catalysts for Examples 6-21 1 Standard catalysts are M1, M2, and M3 metallocenes supported on the same silica derived supported regular MAO (W. R. Grace 30% MAO solution in toluene) with MAO loading of 6.2mmol Al/g silica, to give activities of2,912, 3,389, and 6,294g/g cat/hr, respectively; 2 Silica and water were charged in a 2L round bottom flask and sealed well with a rubber septum and electrical tapes; the round bottom flask was placed in a balance to record the weight before it was place in an oven set at 55oC to heat for 5hr; the flask was taken out of the oven and cooled to ambient and weighted again to make sure no significant weight loss before the solvent was added and mixed well; the slurry was then added to the 600mL jacketed reactor as 3 equal portions. Example 22 (Polymerization tests) [0183] A lab scale 2L salt-bed gas-phase polymerization reactor, in which a 2L autoclave reactor was heated to 110°C and purged with N 2 for at least 30 minutes. It was charged with dry NaCl (350 g; Fisher, S271-10 dehydrated at 180°C and subjected to pump/purge cycles and finally passed through a 16 mesh screen prior to use) and TIBAL treated silica (5 g at 105°C) and stirred for 30 minutes. The temperature was adjusted to 85°C. At a pressure of 2 psig N 2 d drryy a anndd d deeggaasssseedd 11--hheexxeennee ( (CC66 = , see Table 4 for different volumes for different catalysts) was added to the reactor with a syringe and then the reactor was charged with N 2 to a pressure of 20 psig. A mixture of H2 and N2 was flowed into the reactor (See Table 4 for pre-charge H 2 ; 10% H2 in N2 in use) while stirring the bed. Catalysts indicated in the Table 4 below were injected into the reactor with ethylene (C2 = ) at a pressure of 220 psig. C2 = was allowed to flow over the course of the run to maintain constant pressure in the reactor. C6 = was fed into the reactor as a ratio to ethylene as indicated in Table 4. H 2 was fed to the reactor at a ratio to C2 = as indicated in Table 4. The H2 and C2 = ratios were measured by on-line GC analysis. Polymerizations were halted after 1 hour by venting the reactor, cooling to about 23°C, and exposing the reactor to air. The salt was removed by washing with water two times. The polymer was isolated by filtration, briefly washed with acetone, and dried in air for at least for two days. Catalyst activities are reported in the Table 2 above. Table 4. 2L Salt-Bed Reactor for Gas-Phase Ethylene (C2 = )-Hexene (C6 = ) Copolymerization Example 23 (H 1 -NMR Method for Quantification of TMA Content in Supernate) [0184] Into a 5mm NMR tube are charged about 0.5 inch of the supernate of interest and about 1 inch of THF-d8. The mixture is mixed well. An H 1 NMR spectrum is required on a Brucker 400MHz instrument using ns = 8 and D1 = 1s. The solvent peaks including CH 3 , CH 2 , and CH 1 signals (~0.3ppm to ~2.5ppm area including THF-d8 1.73ppm peak (too small, no subtraction)) and TMA (sharp singlet peak in between -0.9 to -1.0ppm) are integrated and the solvent integral is set to 1400 (for iC6, 14H) or 1600 (for heptane, 16H). If the integral of TMA is x, the TMA concentration y can be calculated as: y = (72.1*x/9)/(72.1*x/9 + 86.2*100) for iC6 as solvent y = (72.1*x/9)/(72.1*x/9 + 100.2*100) for heptane as solvent . [0185] For example, Example 3 shows no TMA detected whereas Example 4 shows detected TMA with integral 0.21; the concentration y in heptane is therefore: y = 72.1*0.21/9/(72.1*0.21/9 + 100.2*100) = 0.000168 or 168 ppm . The Figure provides a spectrum showing the TMA for Examples 3 and 4. Example 24 (Standard Catalyst Preparation from Supported Regular MAO) [0186] 10.0 g ES70X (600°C calcination) or ES70 (875°C calcination) silica was added in a 100 mL cel-stir reactor with 40 g toluene. To this slurry was slowly added MAO (30% toluene solution from W. R. Grace) 12.4 g (62.0 mmol Al based on Al in MAO solution 13.5 wt% or 5.0 mmol/g) at ambient. After the MAO addition, the mixture was stirred at ambient for 1 hour. [0187] The solid supported MAO was isolated by filtering through a frit, washing with 2x 40 g iC6, and drying under vacuum for 2 hours. Yield: 13.9g. [0188] M1 finished catalyst (sMAO on ES70X (600°C)): 2.0 g sMAO from above procedure was charged in a 20 mL vial, following by 8 g toluene. 35 mg (40 μmol/g sMAO) M1 was mixed with the slurry, which was shaken on a shaker for 1 hour. The solid supported catalyst was isolated by filtering through a frit, washing with 2x 10 g iC6, and drying under vacuum for 1 hour. Yield: 2.0g. [0189] M2 finished catalyst (sMAO on ES70X (600°C)): 2.0 g sMAO from above procedure was charged in a 20 mL vial, following by 8 g toluene. 33 mg (35 μmol/g sMAO) M2 was mixed with the slurry, which was shaken on a shaker for 1 hour. The solid supported catalyst was isolated by filtering through a frit, washing with 2x 10 g iC6, and drying under vacuum for 1 hour. Yield: 2.0 g. [0190] M3 finished catalyst (sMAO on ES70 (875°C)): 2.0 g sMAO from above procedure was charged in a 20 mL vial, following by 8 g toluene. 38 mg (45 μmol/g sMAO) M3 was mixed with the slurry, which was shaken on a shaker for 1 hour. The solid supported catalyst was isolated by filtering through a frit, washing with 2x 10 g iC6, and drying under vacuum for 1 hour. Yield: 2.0 g. [0191] All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while some embodiments have been illustrated and described, various modifications can be made without departing from the spirit and scope of the disclosure. Accordingly, it is not intended that the disclosure be limited thereby. Likewise, the term "comprising" is considered synonymous with the term "including." Likewise, whenever a composition, an element or a group of elements is preceded with the transitional phrase "comprising", it is understood that we also contemplate the same composition or group of elements with transitional phrases "consisting essentially of," "consisting of", "selected from the group of consisting of," or "is" preceding the recitation of the composition, element, or elements and vice versa.