The present disclosure provides bridged metallocene catalyst compounds comprising —Si—Si— bridges, catalyst systems comprising such compounds, and uses thereof. Catalyst compounds of the present disclosure can be hafnium-containing compounds having one or more cyclopentadiene ligand(s) substituted with one or more silyl neopentyl groups and linked with an Si—Si-containing bridge. In another class of embodiments, the present disclosure is directed to polymerization processes to produce polyolefin polymers from catalyst systems comprising one or more olefin polymerization catalysts, at least one activator, and an optional support.

Processes of synthesizing long-chain branched polymers. The processes include contacting together one or more C.sub.2-C.sub.14 alkene monomers, at least one diene, optionally a solvent, and a multi-chain catalyst optionally in the presence of hydrogen, wherein the multi-chain catalyst comprises a plurality of polymerization sites; producing at least two polymer chains of the C.sub.2-C.sub.14 alkene monomers, each polymer chain polymerizing at one of the polymerization sites; synthesizing the long-chain branched polymers by connecting the two polymer chains with the diene, the joining of the two polymer chains being performed in a concerted manner during the polymerization; and producing tri-functional long chain branches and tetra-functional long chain branches from the diene, wherein the long-chain branched polymers have a ratio of tri-functional to tetra-functional long chain branches from 0.05:1 to 100:0; and adjusting the ratio of tri-functional and tetra-functional long chain branches. The diene has a structure according to formula (I):

##STR00001##

Processes of synthesizing long-chain branched polymers. The processes include contacting together one or more C.sub.2-C.sub.14 alkene monomers, at least one diene, optionally a solvent, and a multi-chain catalyst optionally in the presence of hydrogen, wherein the multi-chain catalyst comprises a plurality of polymerization sites; producing at least two polymer chains of the C.sub.2-C.sub.14 alkene monomers, each polymer chain polymerizing at one of the polymerization sites; synthesizing the long-chain branched polymers by connecting the two polymer chains with the diene, the joining of the two polymer chains being performed in a concerted manner during the polymerization; and producing tri-functional long chain branches and tetra-functional long chain branches from the diene, wherein the long-chain branched polymers have a ratio of tri-functional to tetra-functional long chain branches from 0.05:1 to 100:0; and adjusting the ratio of tri-functional and tetra-functional long chain branches. The diene has a structure according to formula (I):

##STR00001##

This invention relates to a supported catalyst system comprising: (i) at least one first catalyst component comprising a group 4 bis(phenolate) complex; (ii) at least one second catalyst component comprising a 2,6-bis(imino)pyridyl iron complex; (iii) activator; and (iv) support. The catalyst system may be used for preparing polyolefins, such a bimodal polyethylene, typically in a gas phase polymerization.

This invention relates to a supported catalyst system comprising: (i) at least one first catalyst component comprising a group 4 bis(phenolate) complex; (ii) at least one second catalyst component comprising a 2,6-bis(imino)pyridyl iron complex; (iii) activator; and (iv) support. The catalyst system may be used for preparing polyolefins, such a bimodal polyethylene, typically in a gas phase polymerization.

This invention relates to metallocene compounds represented by the formula: ##STR00001##
catalyst systems comprising said metallocene compound and an activator or a reaction product of the metallocene compound with the at least one activator, and polymerization processes using such metallocene compounds and activators, where Cp.sub.a and Cp.sub.b are optionally-substituted cyclopentadienyl rings; A is bridging group; q is zero or 1; Q is O, O(CR.sup.3R.sup.4).sub.m, (CR.sup.3R.sup.4).sub.mO, or (CR.sup.3R.sup.4).sub.m; m is 0 to 18; Z is (CR.sup.3R.sup.4).sub.2; LA is a Lewis acid; M is a transition metal; X.sup.1 and X.sup.2 are independently R.sup.5 or OR.sup.5; R.sup.1 and R.sup.2 are independently selected from optionally-substituted hydrocarbyl groups; R.sup.3 and R.sup.4 are independently selected from the group consisting of H, halogen, and an optionally-substituted hydrocarbyl group; and R.sup.5 is alkyl, aryl, perfluoroalkyl, or perfluoroaryl.

This invention relates to metallocene compounds represented by the formula: ##STR00001##
catalyst systems comprising said metallocene compound and an activator or a reaction product of the metallocene compound with the at least one activator, and polymerization processes using such metallocene compounds and activators, where Cp.sub.a and Cp.sub.b are optionally-substituted cyclopentadienyl rings; A is bridging group; q is zero or 1; Q is O, O(CR.sup.3R.sup.4).sub.m, (CR.sup.3R.sup.4).sub.mO, or (CR.sup.3R.sup.4).sub.m; m is 0 to 18; Z is (CR.sup.3R.sup.4).sub.2; LA is a Lewis acid; M is a transition metal; X.sup.1 and X.sup.2 are independently R.sup.5 or OR.sup.5; R.sup.1 and R.sup.2 are independently selected from optionally-substituted hydrocarbyl groups; R.sup.3 and R.sup.4 are independently selected from the group consisting of H, halogen, and an optionally-substituted hydrocarbyl group; and R.sup.5 is alkyl, aryl, perfluoroalkyl, or perfluoroaryl.

The present invention relates to a branched modifier and a composition comprising more than 25 wt % (based on the weight of the composition) of one or more linear ethylene polymers having a g′.sub.vis of 0.97 or more and an Mw of 20,000 g/mol or more and at least 0.1 wt % of a branched modifier where the modifier has a) a g′.sub.vis of 0.70 or less; b) an Mw of 100,000 g/mol or more; c) an Mw/Mn of 4.0 or more; d) a shear thinning ratio of 110 or more, e) a melt strength of 10 cN or more; f) a complex viscosity at 0.1 rad/sec at 190° C. of at least 130,000 Pa.Math.s; and g) a phase angle of Z° or less where Z=138.3G*.sup.(−0.142), where G* is the complex modulus reported in Pascals measured at 190° C. and the phase angle units are reported in degrees, wherein the G* is from 1,000 to 1,000,000 Pa.

The present invention relates to a branched modifier and a composition comprising more than 25 wt % (based on the weight of the composition) of one or more linear ethylene polymers having a g′.sub.vis of 0.97 or more and an Mw of 20,000 g/mol or more and at least 0.1 wt % of a branched modifier where the modifier has a) a g′.sub.vis of 0.70 or less; b) an Mw of 100,000 g/mol or more; c) an Mw/Mn of 4.0 or more; d) a shear thinning ratio of 110 or more, e) a melt strength of 10 cN or more; f) a complex viscosity at 0.1 rad/sec at 190° C. of at least 130,000 Pa.Math.s; and g) a phase angle of Z° or less where Z=138.3G*.sup.(−0.142), where G* is the complex modulus reported in Pascals measured at 190° C. and the phase angle units are reported in degrees, wherein the G* is from 1,000 to 1,000,000 Pa.

The present disclosure provides polymerization processes to produce polymeric materials, such as olefin terpolymers, using transition metal catalysts having bridged phenolate ligands. The polymerization process includes contacting a transition metal complex with a mixture olefin monomers that contain ethylene, propylene, and a cyclic diene to produce an olefin polymer and recovering the olefin polymer. The mixture of olefin monomers can include specified weight ratios for the various olefin monomers. The transition metal complex includes a bridged phenolate ligand bonded to a metal atom via covalent bonds by two oxygens, a coordinate covalent bond by a Group 15 atom, and a coordinate covalent bond by a Group 15 or 16 atom. The transition metal complex provides relatively high endocyclic alkene/vinyl selectivity to minimize hyperbranching during the production of olefin polymeric materials, such as EPDM and other terpolymers that are free or substantially free of gels.