This disclosure relates to ethylene interpolymer compositions and films prepared therefrom. Specifically: ethylene interpolymer products having: a dimensionless nonlinear rheology network parameter, Δ.sub.int., greater than or equal to 0.01, satisfying 0.01×(Z−50).sup.0.78≤Δ.sub.int.≤0.01×(Z−60).sup.0.78 inequality wherein Z is a normalized molecular weight defined by $Z=\frac{M_w}{M_e}$
where M.sub.w and M.sub.e are the weight average and entanglement molecular weights, and; a residual catalytic metal of from ≥0.03 to ≤5 ppm of hafnium. The disclosed ethylene interpolymer products have a melt index from about 0.3 to about 500 dg/minute, a density from about 0.855 to about 0.975 g/cc, a polydispersity, $\frac{M_w}{M_n},$
from about 1.7 to about 25 and a Composition Distribution Breadth Index (CDBI.sub.50) from about 1% to about 98%.

This disclosure relates to ethylene interpolymer compositions and films prepared therefrom. Specifically: ethylene interpolymer products having: a dimensionless nonlinear rheology network parameter, Δ.sub.int., greater than or equal to 0.01, satisfying 0.01×(Z−50).sup.0.78≤Δ.sub.int.≤0.01×(Z−60).sup.0.78 inequality wherein Z is a normalized molecular weight defined by $Z=\frac{M_w}{M_e}$
where M.sub.w and M.sub.e are the weight average and entanglement molecular weights, and; a residual catalytic metal of from ≥0.03 to ≤5 ppm of hafnium. The disclosed ethylene interpolymer products have a melt index from about 0.3 to about 500 dg/minute, a density from about 0.855 to about 0.975 g/cc, a polydispersity, $\frac{M_w}{M_n},$
from about 1.7 to about 25 and a Composition Distribution Breadth Index (CDBI.sub.50) from about 1% to about 98%.

The present invention relates to a continuous high-pressure polymerization process for the preparation of a liquid ethylene copolymer which comprises in polymerized form 20 to 60 wt % of ethylene; and at least 20 wt % of an acrylate, which is selected from C.sub.1-C.sub.22 alkyl (meth)acrylate, where a monomer feed comprising the ethylene and the acrylate is polymerized in the presence of at least 2 wt % of a chain transfer agent. The invention further relates to the liquid ethylene copolymer obtainable by the polymerization process; and to a lubricant comprising the liquid ethylene copolymer obtainable by the polymerization process; and to a method for reducing friction between moving surfaces comprising the step of contacting the surfaces with the lubricant or with the ethylene copolymer.

The present invention relates to a continuous high-pressure polymerization process for the preparation of a liquid ethylene copolymer which comprises in polymerized form 20 to 60 wt % of ethylene; and at least 20 wt % of an acrylate, which is selected from C.sub.1-C.sub.22 alkyl (meth)acrylate, where a monomer feed comprising the ethylene and the acrylate is polymerized in the presence of at least 2 wt % of a chain transfer agent. The invention further relates to the liquid ethylene copolymer obtainable by the polymerization process; and to a lubricant comprising the liquid ethylene copolymer obtainable by the polymerization process; and to a method for reducing friction between moving surfaces comprising the step of contacting the surfaces with the lubricant or with the ethylene copolymer.

A method for producing gradient copolymers can include polymerizing a reaction mixture comprising a monomer and a comonomer in the presence of a metallocene catalyst in a loop reactor, wherein in the loop reactor a gradient monomer weight percent in the reaction mixture is about 3 wt % to about 50 wt %, thereby forming a gradient copolymer.

A method for producing gradient copolymers can include polymerizing a reaction mixture comprising a monomer and a comonomer in the presence of a metallocene catalyst in a loop reactor, wherein in the loop reactor a gradient monomer weight percent in the reaction mixture is about 3 wt % to about 50 wt %, thereby forming a gradient copolymer.

This disclosure provides new methods for the design and development of ethylene polymerization catalysts, including Group 4 metallocene catalysts such as zirconocenes, which are based on an improved ability to adjust co-monomer incorporation into the polymer. Computational analyses with and without dispersion corrections revealed that designing catalyst scaffolds which induce stabilizing non-covalent dispersion type interactions with incoming α-olefin co-monomers can be used to modulate co-monomer selectivity into the polyethylene chain. Demonstrated herein is a lack of correlation of computed ΔΔG.sup.‡ values against experimental ΔΔG.sup.‡ values when the dispersion correction (D3BJ) was disabled, and B3LYP was used in the absence of Grimme's D3 dispersion and Becke-Johnson (BJ) dampening, but a correlation of computed against experimental ΔΔG.sup.‡ with B3LYP+D3BJ, which are used to design new catalyst scaffolds.

This disclosure provides new methods for the design and development of ethylene polymerization catalysts, including Group 4 metallocene catalysts such as zirconocenes, which are based on an improved ability to adjust co-monomer incorporation into the polymer. Computational analyses with and without dispersion corrections revealed that designing catalyst scaffolds which induce stabilizing non-covalent dispersion type interactions with incoming α-olefin co-monomers can be used to modulate co-monomer selectivity into the polyethylene chain. Demonstrated herein is a lack of correlation of computed ΔΔG.sup.‡ values against experimental ΔΔG.sup.‡ values when the dispersion correction (D3BJ) was disabled, and B3LYP was used in the absence of Grimme's D3 dispersion and Becke-Johnson (BJ) dampening, but a correlation of computed against experimental ΔΔG.sup.‡ with B3LYP+D3BJ, which are used to design new catalyst scaffolds.

What is disclosed is a Ziegler-Natta catalyzed ethylene and alpha-olefin LLDPE copolymer having a unique composition distribution and long chain-branching. The polymers of the present invention inherently exhibit outstanding melt strength with great bubble stability, sufficient flexibility, excellent gel performance, as well as desirable mechanical properties such as balanced toughness and stiffness, which are desirable properties for thick gauge film applications. Specifically, the polymers of the present invention.

What is disclosed is a Ziegler-Natta catalyzed ethylene and alpha-olefin LLDPE copolymer having a unique composition distribution and long chain-branching. The polymers of the present invention inherently exhibit outstanding melt strength with great bubble stability, sufficient flexibility, excellent gel performance, as well as desirable mechanical properties such as balanced toughness and stiffness, which are desirable properties for thick gauge film applications. Specifically, the polymers of the present invention.