Ethylene-based polymers having a density of 0.952 to 0.968 g/cm.sup.3, a ratio of HLMI/MI from 185 to 550, an IB parameter from 1.46 to 1.80, a tan δ at 0.1 sec.sup.−1 from 1.05 to 1.75 degrees, and a slope of a plot of viscosity versus shear rate at 100 sec.sup.−1 from 0.18 to 0.28 are described, with low melt flow versions having a HLMI from 10 to 30 g/10 min and a Mw from 250,000 to 450,000 g/mol, and high melt flow versions having a HLMI from 30 to 55 g/10 min and a Mw from 200,000 to 300,000 g/mol. These polymers have the processability of chromium-based resins, but with improved stress crack resistance and topload strength for bottles and other blow molded products.

Disclosed are a spherelike supermacroporous mesoporous material, a polyolefin catalyst, and a preparation method therefor and an olefin polymerization process. The spherelike supermacroporous mesoporous material has a twodimensional hexagonal ordered pore channel structures. The mesoporous material has an average pore size of 10 nm to 15 nm, a specific surface area of 300 m.sup.2/g to 400 m.sup.2/g, and an average particle size of 1 .Math.m to 3 .Math.m, based on the total mass of the mesoporous material. The mass content of water in the mesoporous material is < 1 ppm. The mass content of oxygen in the mesoporous material is < 1 ppm. When a polyolefin catalyst prepared with the mesoporous material as a carrier is used for an olefin polymerization reaction, the a polyolefin product with a narrow molecular weight distribution and a good melt index can be obtained.

Ethylene-based polymers having a density from 0.94 to 0.96 g/cm.sup.3, a Mn from 5,000 to 14,000 g/mol, a ratio of Mw/Mn from 18 to 40, and at least one of a PENT value at 2.4 MPa of at least 11,500 hr and/or a W90 from 7.5 to 15 wt. % are disclosed. Additional ethylene polymers can have the same density, Mn, and Mw/Mn values, as well as a relaxation time from 0.5 to 3.5 sec, a CY-a parameter from 0.48 to 0.68, a HLMI from 5 to 11 g/10 min, a viscosity at HLMI from 3,000 to 7,500 Pa-sec, and a higher molecular weight component (HMW) and a lower molecular weight (LMW) component, in which a ratio of the number of SCBs at Mp of the HMW component to the number of SCBs at Mp of the LMW component is from 3.5 to 8.

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.

Methods for preparing a metallocene-based catalyst composition that can impact the long chain branching of ethylene homopolymers and copolymers produced using the catalyst composition are described. The catalyst composition can be prepared by contacting a metallocene compound, a hydrocarbon solvent, and a first organoaluminum compound for a first period of time to form a metallocene solution, and then contacting the metallocene solution with an activator-support and a second organoaluminum compound for a second period of time to form the catalyst composition.

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.

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.

Ethylene-based polymers having a density of 0.952 to 0.968 g/cm3. a ratio of HLMI/MI from 185 to 550. an IB parameter from 1.46 to 1.80, a tan δ at 0.1 sec.sup.-1 from 1.05 to 1.75 degrees, and a slope of a plot of viscosity versus shear rate at 100 sec.sup.-1 from 0.18 to 0.28 are described, with low melt flow versions having a HLMI from 10 to 30 g/10 min and a Mw from 250,000 to 450,000 g/mol, and high melt flow versions having a HLMI from 30 to 55 g/10 min and a Mw from 200,000 to 300,000 g/mol. These polymers have the processability of chromium-based resins, but with improved stress crack resistance and topload strength for bottles and other blow molded products.

A complex of formula (I): (I′) M is Hf; each X is a sigma ligand; L is a bridge of formula -(ER.sup.8.sub.2).sub.y—; y is 1 or 2; E is C or Si; each R.sup.8 is independently a C.sub.1-C.sub.20-hydrocarbyl, tri(C.sub.1-C.sub.20-alkyl)silyl, C.sub.6-C.sub.20-aryl, C.sub.7-C.sub.20-arylalkyl or C.sub.7-C.sub.20-alkylaryl or L is an alkylene group such as methylene or ethylene; Ar and Ar′ are each independently an aryl or heteroaryl group optionally substituted by 1 to 3 groups R.sup.1 or R.sup.1′ respectively; R.sup.1 and R.sup.1′ are each independently the same or can be different and are a linear or branched C.sub.1-C.sub.6-alkyl group, C.sub.7-20 arylalkyl, C.sub.7-20 alkylaryl group or C.sub.6-20 aryl group with the proviso that if there are four or more R.sup.1 and R.sup.1′ groups present in total, one or more of R.sup.1 and R.sup.1′ is other than tert butyl; R.sup.2 and R.sup.2′ are the same or are different and are a CH.sub.2—R.sup.9 group, with R.sup.9 being H or linear or branched C.sub.1-C.sub.6-alkyl group, C.sub.3-8 cycloalkyl group, C.sub.6-10 aryl group; each R is a —CH.sub.2—, —CHRx- or C(Rx).sub.2- group wherein Rx is C.sub.1-4 alkyl and where m is 2-6; R.sup.5 is a linear or branched C.sub.1-C.sub.6-alkyl group, C.sub.7-20 arylalkyl, C.sub.7-20 alkylaryl group or C.sub.6-C.sub.20-aryl group; R.sup.6 is a C(R.sup.10).sub.3 group, with R.sup.10 being a linear or branched C.sub.1-C.sub.6 alkyl group; and R.sup.6 and R.sup.7′ are the same or are different and are H or a linear or branched C.sub.1-C.sub.6-alkyl group. Invention relates also to a catalyst in solid form comprising (i) a complex of formula (I) and (ii) a cocatalyst of an aluminium compound and (iii) a cocatalyst of a boron compound. ##STR00001##

A first embodiment which is a bimodal polymer having a weight fraction of a lower molecular weight (LMW) component ranging from about 0.25 to about 0.45, a weight fraction of a higher molecular weight (HMW) component ranging from about 0.55 to about 0.75 and a density of from about 0.931 g/cc to about 0.955 g/cc which when tested in accordance with ASTM D1003 using a 1 mil test specimen displays a haze characterized by equation: % Haze=2145−2216*Fraction.sub.LMW−181*a molecular weight distribution of the LMW component (MWD.sub.LMW)−932*a molecular weight distribution of the HMW component (MWD.sub.HMW)+27*(Fraction.sub.LMW*MWD.sub.LMW)+1019*(Fraction.sub.LMW*MWD.sub.HMW)+73*(MWD.sub.LMW*MWD.sub.HMW) wherein fraction refers to the weight fraction of the component in the polymer as a whole.