A metal complex of the formula (1) TCyLMZ.sub.p (1), wherein M is a group 4 metal, Z is an anionic ligand, p is the number 1 or 2, TCy is a thiophene-fused cyclopentadienyl-type ligand of the formula (2) ##STR00001##
is described. Methods of making and using the metal complex are also described.

Provided in this disclosure are zirconium and hafnium complexes that contain 1) a cyclopentadienyl ligand; 2) an adamantyl-phosphinimine ligand; and 3) at least one other ligand. The use of such a complex, in combination with an activator, as an olefin polymerization catalyst is demonstrated. The catalysts are effective for the copolymerization of ethylene with an alpha olefin (such as 1-butene, 1-hexene, or 1-octene).

This disclosure relates to ethylene interpolymer product having intermediate branching. Intermediate branching was defined as branching that was longer than the branch length due to comonomer and shorter than the entanglement molecular weight (M.sub.e). Intermediately branched ethylene interpolymer products were produced in a continuous solution polymerization process employing an intermediate branching catalyst formulation. Intermediately branched ethylene interpolymer products were characterized by a Non-Comonomer Index Distribution (NCID.sub.i), a melt index from 0.3 to 500 dg/minute, a density from 0.858 to 0.965 g/cm.sup.3, a polydispersity (M.sub.w/M.sub.n) from about 2 to about 25 and a CDBI.sub.50 from about 10% to about 98%. A method based on triple detection cross fractionation chromatography (3D-CFC) was disclosed to measure NCID.sub.i.

A metal complex of the formula (1) InCyLMZp (1), wherein M is a group 4 metal, Z is an anionic ligand, p is number of 1 to 2, InCy is an indole fused cyclopentadienyl-type ligand of the formula (2) wherein R.sup.1 independently is a C1-C4-alkyl, m is a number of 0 to 4, R.sup.2 is a C1-C10-alkyl, C5-C10-cycloalkyl, or a C6-C10-aryl unsubstituted or substituted with C1-C10-alkyl or C1-C4-dialkyl amino, R.sup.3, R.sup.4 and R.sup.5 each is independently selected from hydrogen, C1-C4-alkyl, C6-C10-aryl unsubstituted or substituted with C1-C4-alkyl, halide, or both of C1-C4-alkyl and halide and, L is an amidinate ligand of the formula (3a) wherein the amidine-containing ligand (3a) is bonded to the metal M via the imine nitrogen atom N2, wherein R.sup.7 is independently selected from C1-C4-alkyl and halide and q is a number of 0 to 4, Sub.sub.4 is a cyclic or linear aliphatic or aromatic substituent. ##STR00001##

Embodiments provide bimodal polymerization catalyst systems comprising metallocene olefin polymerization catalysts and biphenylphenol polymerization catalysts made from biphenylphenol polymerization precatalysts of Formula I.

An interpolymer product comprising: a first ethylene interpolymer comprising ethylene and an α-olefin having a weight-average molecular weight (M.sub.w) of greater than 250,000 and a density of less than 0.930 g/cm.sup.3, and a second ethylene interpolymer comprising ethylene and an α-olefin wherein the second ethylene interpolymer comprises a M.sub.w of less than 70,000 and a density of greater than 0.930 g/cm.sup.3; and wherein the interpolymer product comprises an environmental stress crack resistance (ESCR), measured according to ASTM D1693, Condition B, 10% IGEPAL CO-630, of greater than 90 hours. The interpolymer product may be manufactured in a continuous solution polymerization process utilizing at least two reactors employing at least one single site catalyst formulation and at least one heterogeneous catalyst formulation.

Disclosed is a catalyst for olefin polymerization, comprising a main catalyst and a cocatalyst; the main catalyst is a bisphenol metal complex represented by formula I, and the cocatalyst comprises an organoaluminum compound; in formula I, R.sub.1, R.sub.1′, R.sub.2, R.sub.2′ are the same or different, and are each independently selected from hydrogen and a substituted or unsubstituted C.sub.1-C.sub.20 hydrocarbyl; R.sub.3-R.sub.7, R.sub.3′-R.sub.7′ are the same or different, and are each independently selected from hydrogen and a substituted or unsubstituted C.sub.1-C.sub.20 hydrocarbyl; R.sub.8 and R.sub.9 are the same or different, and are each independently selected from hydrogen or a substituted or unsubstituted C.sub.1-C.sub.20 hydrocarbyl; M and M′ are the same or different, and are selected from Group IV metals; and X is halogen;

##STR00001##

Provided are bimodal linear low density polyethylene copolymers (B-LLDPE copolymers) that have a combination of improved properties comprising at least one processability characteristic similar or better than that of an unblended monomodal ZN-LLDPE and a dart impact property similar or better than that of an unblended monomodal MCN-LLDPE. For the various aspects, the B-LLDPE copolymer has a density from 0.8900 to 0.9300 g/cm.sup.3; a melt index (I.sub.2) from 0.1 g/10 min. to 5 g/10 min.; a M.sub.z from 600,000 to 1,900,000 g/mol; and a SHI from 5.35 to 75 η*(1.0)/η*(100). The B-LLDPE copolymer can be further characterized by a first melt flow ratio (I.sub.21/I.sub.2) from 32 to 140 and a first molecular weight ratio (M.sub.z/M.sub.w) from 4.5 to 11.

The disclosure are directed to a process for polymerizing ethylene-based polymers. The process includes polymerizing ethylene and optionally one or more (C.sub.3-C.sub.14)α-olefin monomer, and at least one diene, in the presence of at least one multi-chain catalyst and at least one single-chain catalyst. The process may include a solvent. The multi-chain catalyst in the process includes a plurality of polymerization sites. Long-chain branched polymers are synthesized by connecting the two polymer chains of the multi-chain catalyst with the diene, the joining of the two polymer chains being performed in a concerted manner during the polymerization. The ethylene-based polymers are produced and include at least two molecular weight polymer fractions. The multi-chain catalyst produces the high molecular weight fraction, which is the long-chain branched polymer.

A method of making an attenuated-light-off hybrid catalyst, the method comprising combining a faster-light-off catalyst with an effective amount of a kinetics modifier compound of formula (A.sup.1), (B.sup.1), or (C.sup.1): R.sup.5—C≡C—R.sup.6 (A.sup.1), (R.sup.5).sub.2C═C═C(R.sup.6).sub.2 (B.sup.1), or (R.sup.5)(R.sup.7)C═C(R.sup.6)(R.sup.7) (C.sup.1) as defined herein under effective reaction conditions to give an attenuated hybrid catalyst that exhibits an attenuated light-off kinetics profile (relative to that of the faster-light-off catalyst); wherein the faster-light-off catalyst has been made by activating a hybrid precatalyst (i.e., an unactivated “coordination entity” or “ligand-metal complex”) of structural formula (I): (Cp) (L).sub.k(X).sub.x (I) as defined herein; and related methods, compositions and uses.