A method comprising a) contacting a solvent, a carboxylic acid, and a peroxide-containing compound to form an acidic mixture wherein a weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) contacting a titanium-containing compound and the acidic mixture to form a solubilized titanium mixture wherein an equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4 and an equivalent molar ratio of titanium-containing compound to peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) contacting a chromium-silica support comprising from about 0.1 wt. % to about 20 wt. % water and the solubilized titanium mixture to form an addition product and drying the addition product by heating to a temperature in a range of from about 50° C. to about 150° C. and maintaining the temperature in the range of from about 50° C. to about 150° C. for a time period of from about 30 minutes to about 6 hours to form a pre-catalyst.

Ethylene-based polymers are characterized by a density from 0.92 to 0.955 g/cm.sup.3, a HLMI of less than 35 g/10 min, and a ratio of a number of short chain branches (SCBs) per 1000 total carbon atoms at Mz to a number of SCBs per 1000 total carbon atoms at Mn in a range from 11.5 to 22. These polymers can have a higher molecular weight (HMW) component and a lower molecular weight (LMW) component, in which a ratio of a number of SCBs per 1000 total carbon atoms at Mn of the HMW component to a number of SCBs per 1000 total carbon atoms at Mn of the LMW component is in a range from 10.5 to 22. These ethylene polymers can be produced using a dual catalyst system containing an unbridged metallocene compound with an indenyl group having at least one halogen-substituted hydrocarbyl substituent with at least two halogen atoms, and a single atom bridged metallocene compound with a fluorenyl group and a cyclopentadienyl group.

Ethylene-based polymers are characterized by a density from 0.92 to 0.955 g/cm.sup.3, a HLMI of less than 35 g/10 min, and a ratio of a number of short chain branches (SCBs) per 1000 total carbon atoms at Mz to a number of SCBs per 1000 total carbon atoms at Mn in a range from 11.5 to 22. These polymers can have a higher molecular weight (HMW) component and a lower molecular weight (LMW) component, in which a ratio of a number of SCBs per 1000 total carbon atoms at Mn of the HMW component to a number of SCBs per 1000 total carbon atoms at Mn of the LMW component is in a range from 10.5 to 22. These ethylene polymers can be produced using a dual catalyst system containing an unbridged metallocene compound with an indenyl group having at least one halogen-substituted hydrocarbyl substituent with at least two halogen atoms, and a single atom bridged metallocene compound with a fluorenyl group and a cyclopentadienyl group.

Disclosed herein are ethylene-based polymers generally characterized by a melt index of less than 15 g/10 min, a density from 0.91 to 0.945 g/cm.sup.3, a CY-a parameter at 190° C. from 0.2 to 0.6, an average number of long chain branches per 1,000,000 total carbon atoms of the polymer in a molecular weight range of 500,000 to 2,000,000 g/mol of less than 5, and a maximum ratio of η.sub.E/3η at an extensional rate of 0.03 sec.sup.−1 in a range from 3 to 15. The ethylene polymers have substantially no long chain branching in the high molecular weight fraction of the polymer, but instead have significant long chain branching in the lower molecular weight fraction, such that polymer melt strength and bubble stability are maintained for the fabrication of blown films and other articles of manufacture. These ethylene polymers can be produced using a dual catalyst system containing a single atom bridged metallocene compound with an indenyl group and a cyclopentadienyl group, and an unbridged hafnium metallocene compound with two cyclopentadienyl groups.

Disclosed are support-activators and catalyst compositions comprising the support-activators for polymerizing olefins in which the support-activator includes clay heteroadduct, prepare from a colloidal phyllosilicate such as a colloidal smectite clay, which is chemically-modified with a heterocoagulation agent. By limiting the amount of heterocoagulation reagent relative to the colloidal smectite clay as described herein, the smectite heteroadduct support-activator is a porous and amorphous solid which can be readily isolated from the resulting slurry by a conventional filtration process, and which can activate metallocenes and related catalysts toward olefin polymerization. Related compositions and processes are disclosed.

Disclosed are catalyst systems, processes for making the catalyst systems, and processes for polymerizing at least one olefin monomer comprising ethylene to form a low-density polyethylene (LDPE). The polymerization process uses a catalyst system that can include: at least one diimine complex having the formula I: ##STR00001##
wherein M is Ni, Pd, or Pt; a first activator such as an organoaluminum compound; and a second activator including a solid oxide chemically-treated with an electron withdrawing anion, such as fluoride silica-alumuina. It was discovered that such the complexes could be activated in a manner to provide an active catalyst system that polymerized ethylene to form a low-density polyethylene (LDPE).

Disclosed herein are methods for preparing fluorided solid oxides by contacting an acidic fluorine-containing compound with an inorganic base to form an aqueous mixture having a pH of at least 4, followed by contacting a solid oxide with the aqueous mixture to produce the fluorided solid oxide. Also disclosed are methods for preparing fluorided solid oxides by contacting an acidic fluorine-containing compound with a solid oxide to produce a mixture, followed by contacting the mixture with a inorganic base to produce the fluorided solid oxide at a pH of at least about 4. The fluorided solid oxide can be used as an activator component in a catalyst system for the polymerization of olefins.

Catalyst compositions containing a metallocene compound, a solid activator, and a co-catalyst, in which the solid activator or the supported metallocene catalyst has a d50 average particle size of 15 to 50 μm and a particle size distribution of 0.5 to 1.5, can be contacted with an olefin in a loop slurry reactor to produce an olefin polymer. A representative ethylene-based polymer produced using the catalyst composition has excellent dart impact strength and low gels, and can be characterized by a HLMI from 4 to 10 g/10 min, a density from 0.944 to 0.955 g/cm.sup.3, a higher molecular weight component with a Mn from 280,000 to 440,000 g/mol, and a lower molecular weight component with a Mw from 30,000 to 45,000 g/mol and a ratio of Mz/Mw ranging from 2.3 to 3.4.

Disclosed are support-activators and catalyst compositions comprising the support-activators for polymerizing olefins in which the support-activator includes clay heteroadduct, prepare from a colloidal phyllosilicate such as a colloidal smectite clay, which is chemically-modified with a heterocoagulation agent. By limiting the amount of heterocoagulation reagent relative to the colloidal smectite clay as described herein, the smectite heteroadduct support-activator is a porous and amorphous solid which can be readily isolated from the resulting slurry by a conventional filtration process, and which can activate metallocenes and related catalysts toward olefin polymerization. Related compositions and processes are disclosed.

A partial oxidative coupling catalyst has a structure in which a component represented by M.sub.2ZrO.sub.3 is supported on a support, where M represents an alkali metal.