Organochromium/metallocene combination catalysts for producing bimodal resins

A method of making a catalyst composition comprising contacting at least one metallocene compound, at least one organochromium compound, at least one chemically-treated solid oxide, and at least one organoaluminum compound, wherein:

• a) the metallocene compound has the following formula:
• (X1)(X2)(X3)(X4)M1,
• wherein M1 is titanium, zirconium, or hafnium;
• wherein (X1) is a cyclopentadienyl, an indenyl, a fluorenyl, a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;
• wherein substituents on (X1) are aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, silyl groups, alkyl halide groups, halides, organometallic groups, phosphorus groups, nitrogen groups, silicon groups, phosphorus groups, boron groups, germanium groups, or hydrogen;
• wherein at least one substituent on (X1) can be a bridging group which connects (X1) and (X2);
• wherein (X3) and (X4) are independently a halide, an aliphatic group, a substituted aliphatic group, a cyclic group, a substituted cyclic group, a combination of an aliphatic group and a cyclic group, a combination of a substituted aliphatic group and a cyclic group, a combination of an aliphatic group and a substituted cyclic group, a combination of a substituted aliphatic group and a substituted cyclic group, an amido group, a substituted amido group, a phosphido group, a substituted phosphido group, an alkyloxide group, a substituted alkyloxide group, an aryloxide group, a substituted aryloxide group, an organometallic group, or a substituted organometallic group;
• wherein (X2) is a cyclopentadienyl, an indenyl, a fluorenyl, a substituted cyclopentadienyl, a substituted indenyl, a substituted fluorenyl, a halide, an aliphatic group, a substituted aliphatic group, a cyclic group, a substituted cyclic group, a combination of an aliphatic group and a cyclic group, a combination of a substituted aliphatic group and a cyclic group, a combination of an aliphatic group and a substituted cyclic group, a combination of a substituted aliphatic group and a substituted cyclic group, an amido group, a substituted amido group, a phosphido group, a substituted phosphido group, an alkyloxide group, a substituted alkyloxide group, an aryloxide group, a substituted aryloxide group, an organometallic group, or a substituted organometallic group;
• wherein substituents on (X2) are aliphatic groups, cyclic groups, combinations of aliphatic groups and cyclic groups, silyl groups, alkyl halide groups, halides, organometallic groups, phosphorus groups, nitrogen groups, silicon groups, boron groups, germanium groups, or hydrogen;
• and
• wherein at least one substituent on (X2) can be a bridging group which connects (X1) and (X2);
• b) the at least one organochromium compound is a compound having the following formula:
• i) CrRn,
• wherein R is a hydrocarbyl having from 1 to about 20 carbon atoms;
• and
• wherein n is an integer from 2 to 4 inclusive;
• or
• ii) Cr(η6-C6R′6)2,
• wherein R′ independently is hydrogen or an alky radical having from 1 to 6 carbon atoms;
• and
• c) the at least one chemically-treated solid oxide comprises a solid oxide treated with at least one electron-withdrawing anion source compound;
• wherein the molar ratio of the at least one metallocene compound to the at least one organochromium compound is from about 100:1 to about 1:100;
• wherein the weight ratio of the at least one metallocene compound to the at least one chemically-treated solid oxide is from about 10:1 to about 0.0001:1;
• and
• wherein the catalyst composition is substantially free of aluminoxanes, organoborons, and ionizing ionic compounds.

A method of polymerizing olefins comprising contacting at least one type of olefin monomer with a catalyst composition under polymerization conditions,

• wherein the catalyst composition comprises the contact product of at least one metallocene compound, at least one organochromium compound, at least one chemically-treated solid oxide, and at least one organoaluminum compound, wherein:
• a) the metallocene compound has the following formula:
• (X1)(X2)(X3)(X4)M1,
• wherein M1 is titanium, zirconium, or hafnium;
• wherein (X1) is a cyclopentadienyl, an indenyl, a fluorenyl, a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl;
• wherein substituents on (X1) are aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, silyl groups, alkyl halide groups, halides, organometallic groups, phosphorus groups, nitrogen groups, silicon groups, phosphorus groups, boron groups, germanium groups, or hydrogen;
• wherein at least one substituent on (X1) can be a bridging group which connects (X1) and (X2);
• wherein (X3) and (X4) are independently a halide, an aliphatic group, a substituted aliphatic group, a cyclic group, a substituted cyclic group, a combination of an aliphatic group and a cyclic group, a combination of a substituted aliphatic group and a cyclic group, a combination of an aliphatic group and a substituted cyclic group, a combination of a substituted aliphatic group and a substituted cyclic group, an amido group, a substituted amido group, a phosphido group, a substituted phosphido group, an alkyloxide group, a substituted alkyloxide group, an aryloxide group, a substituted aryloxide group, an organometallic group, or a substituted organometallic group;
• wherein (X2) is a cyclopentadienyl, an indenyl, a fluorenyl, a substituted cyclopentadienyl, a substituted indenyl, a substituted fluorenyl, a halide, an aliphatic group, a substituted aliphatic group, a cyclic group, a substituted cyclic group, a combination of an aliphatic group and a cyclic group, a combination of a substituted aliphatic group and a cyclic group, a combination of an aliphatic group and a substituted cyclic group, a combination of a substituted aliphatic group and a substituted cyclic group, an amido group, a substituted amido group, a phosphido group, a substituted phosphido group, an alkyloxide group, a substituted alkyloxide group, an aryloxide group, a substituted aryloxide group, an organometallic group, or a substituted organometallic group;
• wherein substituents on (X2) are aliphatic groups, cyclic groups, combinations of aliphatic groups and cyclic groups, silyl groups, alkyl halide groups, halides, organometallic groups, phosphorus groups, nitrogen groups, silicon groups, boron groups, germanium groups, or hydrogen;
• and
• wherein at least one substituent on (X2) can be a bridging group which connects (X1) and (X2);
• b) the at least one organochromium compound is a compound having the following formula:
• i) CrRn,
• wherein R is a hydrocarbyl having from 1 to about 20 carbon atoms;
• and
• wherein n is an integer from 2 to 4 inclusive;
• or
• ii) Cr(η6-C6R′6)2,
• wherein R′ independently is hydrogen or an alky radical having from 1 to 6 carbon atoms;
• and
• c) the at least one chemically-treated solid oxide comprises a solid oxide treated with at least one electron-withdrawing anion source compound;
• wherein the molar ratio of the at least one metallocene compound to the at least one organochromium compound is from about 100:1 to about 1:100;
• wherein the weight ratio of the at least one metallocene compound to the at least one chemically-treated solid oxide is from about 10:1 to about 0.0001:1;
• and
• wherein the catalyst composition is substantially free of aluminoxanes, organoborons, and ionizing ionic compounds.