Polyethylene composition

Patent metadata

Field	Value
Publication number	US-11142597-B2
Application number	US-201716346245-A
Country	US
Kind code	B2
Filing date	Oct 25, 2017
Priority date	Nov 8, 2016
Publication date	Oct 12, 2021
Grant date	Oct 12, 2021

Abstract

A bimodal linear polyethylene composition, products made therefrom, methods of making and using same, and articles containing same.

First claim

The invention claimed is:

1. A bimodal linear medium density polyethylene composition comprising a lower molecular weight (LMW) polyethylene component and a higher molecular weight (HMW) polyethylene component, wherein each of the LMW and HMW polyethylene components comprises ethylene-derived monomeric units and (C 3 -C 20 )alpha-olefin-derived comonomeric units; and wherein the bimodal linear medium density polyethylene composition is characterized by each of limitations (a) to (d): (a) a resolved bimodality showing in a chromatogram of gel permeation chromatography (GPC) of the bimodal linear medium density polyethylene composition, wherein the chromatogram shows a peak representing the HMW polyethylene component, a peak representing the LMW polyethylene component, and a resolved bimodal molecular weight distribution characterized by a local minimum in a range of Log(molecular weight) (“Log(MW)”) 1.5 to 5.0 between the peak representing the HMW polyethylene component and the peak representing the LMW polyethylene component, measured according to Bimodality Test Method; (b) a molecular mass dispersity (M w /M n ), Ð M , from 5 to 30.1, measured according to Gel Permeation Chromatography (GPC) Test Method; (c) no measurable amount of long chain branching per 1,000 carbon atoms (“LCB Index”), measured according to LCB Test Method; and (d) a density from 0.930 to 0.950 gram per cubic centimeter (g/cm 3 ), measured according to ASTM D792-13 Method B.

2. The bimodal linear medium density polyethylene composition of claim 1 described by any one of limitations (i) to (iii): (i) a melt index (190° C., 2.16 kilograms (kg), “MI 2 ”) from 0.1 to 5.0 grams per 10 minutes (g/10 min), measured according to Melt Index MI 2 Test Method; (ii) a tan delta (tan δ) from 5 to 35, measured at 190° C. and 0.1000 radians per second (rad/s) according to Tan Delta Test Method; (iii) both (i) and (ii).

3. The bimodal linear medium density polyethylene composition of claim 1 described by any one of limitations (i) to (iii): (i) a melt index (190° C., 2.16 kilograms (kg), “MI 2 ”) from 0.1 to 5.0 grams per 10 minutes (g/10 min), measured according to Melt Index MI 2 Test Method; (ii) a molecular mass dispersity (M w /M n ), Ð M , of at least one of the LMW and HMW polyethylene components of from >2.0 to <3.0, measured according to the GPC Test Method after deconvoluting the LMW and HMW polyethylene components of the bimodal linear medium density polyethylene composition according to Deconvoluting Test Method; (iii) both (i) and (ii).

4. The bimodal linear medium density polyethylene composition of claim 1 described by any one of limitations (i) to (xii): (i) a flow index (190° C., 21.6 kg, “FI 21 ”) from 4 to 500 g/10 min, measured according to the Flow Index FI 21 Test Method; (ii) a melt flow ratio (190° C., “MI 21 /MI 2 ”) 20.0 to 50.0, calculated according to the Melt Flow Ratio Test Method; (iii) a shear thinning index value from 1.5 to 10, measured according to the Shear Thinning Index Test Method; (iv) a number-average molecular weight (M n ) from 5,000 to 25,000 grams per mole (g/mol) measured according to GPC Test Method; (v) both (i) and (ii); (vi) both (i) and (iii); (vii) both (i) and (iv); (viii) both (ii) and (iii); (ix) both (ii) and (iv); (x) both (iii) and (iv); (xi) any three of (i) to (iv); and (xii) each of (i) to (iv).

5. The bimodal linear medium density polyethylene composition of claim 1 described by any one of limitations (i) to (iv): (i) the (C 3 -C 20 )alpha-olefin-derived comonomeric units are derived from 1-butene; (ii) the (C 3 -C 20 )alpha-olefin-derived comonomeric units are derived from 1-hexene; (iii) the (C 3 -C 20 )alpha-olefin-derived comonomeric units are derived from 1-octene; and (iv) the (C 3 -C 20 )alpha-olefin-derived comonomeric units are derived from a combination of any two of 1-butene, 1-hexene, and 1-octene.

6. A manufactured article comprising a shaped form of the bimodal linear medium density polyethylene composition of claim 1 .

7. The manufactured article of claim 6 selected from the group consisting of coatings, films, sheets, extruded articles, and injection molded articles.

8. The manufactured article of claim 6 selected from the group consisting of a coated metal pipe, agricultural film, food packaging, garment bags, grocery bags, heavy-duty sacks, industrial sheeting, pallet and shrink wraps, bags, buckets, freezer containers, lids, and toys.

9. The manufactured article of claim 6 comprising a coated steel pipe.

10. A bimodal linear medium density polyethylene composition made by copolymerizing ethylene (monomer) and at least one (C 3 -C 20 )alpha-olefin (comonomer) with a mixture of a bimodal catalyst system and a trim solution in the presence of molecular hydrogen gas (H 2 ) and an inert condensing agent (ICA) in a polymerization reactor under (co)polymerizing conditions; wherein prior to being mixed together the trim solution consists essentially of a (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium complex and an inert liquid solvent and the bimodal catalyst system consists essentially of an activator species, a bis(2-pentamethylphenylamido)ethyl)amine zirconium complex and a (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium complex, all disposed on a solid support; and wherein the (co)polymerizing conditions comprise a reaction temperature from 80° C. to 110° C., a molar ratio of the molecular hydrogen gas to the ethylene (H2/C2 molar ratio) from 0.001 to 0.050; and a molar ratio of the comonomer to the ethylene (Comonomer/C2 molar ratio) from 0.005 to 0.10.

11. A method of making a bimodal linear medium density polyethylene composition, the method comprising contacting ethylene and at least one (C 3 -C 20 )alpha-olefin with a mixture of a bimodal catalyst system and a trim solution in the presence of H 2 gas and an inert condensing agent in a polymerization reactor under (co)polymerizing conditions, thereby making the bimodal linear medium density polyethylene composition; wherein prior to being mixed together the trim solution consists essentially of a (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium complex and an inert liquid solvent and the bimodal catalyst system consists essentially of an activator species, a non-metallocene ligand-Group 4 metal complex and a metallocene ligand-Group 4 metal complex, all disposed on a solid support; and wherein the (co)polymerizing conditions comprise a reaction temperature from 80° C. to 110° C. a molar ratio of molecular hydrogen gas to the ethylene from 0.001 to 0.050; and a molar ratio of comonomer to the ethylene from 0.005 to 0.10.

12. The bimodal linear medium density polyethylene composition of claim 10 described by of any one of limitations (i) to (vi): (i) wherein the bimodal catalyst system consists essentially of a bis(2-pentamethylphenylamido)ethyl)amine zirconium complex and a (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium complex in a molar ratio thereof from 1.0:1.0 to 5.0:1.0, respectively, and a methylaluminoxane species, all disposed by spray-drying onto the solid support; (ii) wherein the bimodal catalyst system further consists essentially of mineral oil and the solid support is a hydrophobic fumed silica; (iii) wherein the mixture is a suspension of the bimodal catalyst system in mineral oil and the trim solution and the mixture is premade and then fed into the polymerization reactor; (iv) wherein the trim solution is made by dissolving (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dimethyl in the inert liquid solvent to give the trim solution; (v) wherein the polymerization reactor is one fluidized bed gas phase reactor

Assignees

• Univation Tech Llc

Inventors

• Chandak Swapnil B
• Borse Nitin
• Bafna Ayush A
• Zhang Yi
• Lynn Timothy R
• Kuhlman Roger L
• Szul John F

Classifications

• C08L23/08

  Copolymers of ethene (C08L23/16 takes precedence) · CPC title

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F10/00

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F10/02 Primary

  Ethene · CPC title

• C08F210/02

  Ethene · CPC title