IP Library Granted Patent US 12,486,345
Granted Patent B2
US 12,486,345 · App. 18/002,911 · Granted Dec 2, 2025

Ethylene copolymer for biaxial orientation

Inventors: Maryam Fereydoon (Houston, TX); Shivendra Goyal (Calgary, CA); Stephen Brown (Calgary, CA); Owen Lightbody (Calgary, CA); Norman Aubee (Calgary, CA); Bronwyn Gillon (Calgary, CA); Thomas Green (Petrolia, CA); Lison Mark (Bright's Grove, CA); Christian Carello (Calgary, CA)
Assignee: NOVA Chemicals (International) S.A.
C08F210/16C08F2/01C08F4/685C08F2/001C08F2500/04C08F2500/07
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,486,345
App. No.
18/002,911
Granted
Dec 2, 2025
Kind
B2
Abstract

An ethylene copolymer comprising ethylene and at least one alpha olefin having from 4 to 8 carbon atoms has a density f from 0.940 to 0.960 g/cm 3 , a molecular weight distribution, Mw/Mn of from 9 to 12, and a Z-average molecular weight, Mz of greater than 500,000. The ethylene copolymer is made in a multi-zone reactor system under solution phase polymerization conditions and is useful in the preparation of biaxially oriented polyethylene (BOPE) films.

Claims (35)

1 . An ethylene copolymer comprising ethylene and at least one alpha olefin having from 4 to 8 carbon atoms; wherein the ethylene copolymer has a density of 0.940 to 0.960 grams per cubic centimeter (g/cm 3 ); a melt index, I 2 as measured by ASTM D1238 at 190° C. using a 2.16 kilogram load, of from 0.5 to 2.5 grams per 10 minutes (g/10 min); a stress exponent of from 1.75 to 1.95; a number average molecular weight, Mn, of from 11,000 to 15,000; a polydispersity index, (Mw/Mn), of from 9 to 12; and a Z-average molecular weight, Mz, of from 500,000 to 800,000.

2 . The ethylene copolymer of claim 1 , wherein the ethylene copolymer has a composition distribution breadth index, CDBI 25 , of from 40 to 50.

3 . The ethylene copolymer of claim 1 , wherein the ethylene copolymer has a number average molecular weight, Mn, of from 11,000 to 12,500.

4 . The ethylene copolymer of claim 1 , wherein the ethylene copolymer has a number average molecular weight, Mn, of from 11,000 to 12,500.

5 . The ethylene copolymer of claim 1 , wherein the ethylene copolymer has a Z-average molecular weight, Mz, of from 600,000 to 700,000.

6 . The ethylene copolymer of claim 1 , further characterized by containing both titanium and vanadium catalyst residues in an amount of from 0.100 to 1.5 ppm of titanium and from 0.100 to 1.5 ppm of vanadium (based on a weight of the ethylene copolymer).

7 . The ethylene copolymer of claim 1 wherein the ethylene copolymer has a unimodal molecular weight distribution.

8 . The ethylene copolymer of claim 1 , wherein the ethylene copolymer has a density of from 0.940 to 0.956 g/cm 3 .

9 . The ethylene copolymer of claim 1 , wherein the ethylene copolymer has a stress exponent of from 1.80 to 1.90.

10 . The ethylene copolymer of claim 1 wherein the ethylene copolymer comprises polymerized ethylene and 1-butene.

11 . A solution phase polymerization process to make an ethylene copolymer in a multi-zone reactor system,

the multi-zone-reactor system comprising a first, second and third polymerization zone, wherein the first polymerization zone is defined by a first tubular reactor having an inlet and an outlet,

the polymerization process comprising:

feeding solvent, hydrogen, a Ziegler-Natta polymerization catalyst, ethylene, and at least one alpha olefin having 4 to 8 carbon atoms, to the inlet of the first tubular reactor to initiate a polymerization reaction;

feeding hydrogen to at least one location in the first tubular reactor which is downstream from the inlet of the first tubular reactor;

wherein at least 80 weight percent of a total amount of hydrogen added to the multi-zone reactor system, is added to the at least one location in the first tubular reactor which is downstream from the inlet of the first tubular reactor; and

wherein from 20 to 50 weight percent of a total amount of ethylene copolymer made in the multi-zone reactor system is made in the first tubular reactor.

12 . The process of claim 11 , wherein the second polymerization zone is defined by a tank reactor having an inlet and an outlet.

13 . The process of claim 12 , wherein the third polymerization zone is defined by a second tubular reactor having an inlet and an outlet.

14 . The process of claim 13 , wherein the at least one location in the first tubular reactor which is downstream from the inlet of the first tubular reactor is at least one location in the first tubular reactor which is from 35 percent to 65 percent downstream from the inlet along a length of the first tubular reactor.

15 . The process of claim 13 , wherein the at least one location in the first tubular reactor which is downstream from the inlet of the first tubular reactor is at least one location in the first tubular reactor which is from 45 percent to 55 percent downstream from the inlet along a length of the first tubular reactor.

16 . The process of claim 13 , wherein the tank reactor is operated as a plug flow reactor.

17 . The process of claim 13 , wherein the multi-zone reactor system is operated adiabatically.

18 . The process of claim 13 , wherein the inlet of the first tubular reactor is at a temperature of from 30 to 150° C.

19 . The process of claim 13 , wherein the inlet of the first tubular reactor is at a temperature of less than 150° C.

20 . The process of claim 13 , wherein at least 90 weight percent of the ethylene that is fed to the multi-zone reactor system is converted to ethylene copolymer.

21 . The process of claim 13 , wherein the Ziegler-Natta polymerization catalyst comprises titanium, vanadium, and aluminum.

22 . A solution phase polymerization process to make an ethylene copolymer in a multi-zone reactor system,

the multi-zone reactor system comprising a first, second and third polymerization zone, wherein the first polymerization zone is defined by a first tubular reactor having an inlet and an outlet,

the polymerization process comprising:

feeding solvent, hydrogen, a Ziegler-Natta polymerization catalyst, ethylene, and at least one alpha olefin having 4 to 8 carbon atoms, to an inlet of the first tubular reactor to initiate a polymerization reaction;

feeding hydrogen to at least one location in the first tubular reactor which is downstream from the inlet of the first tubular reactor;

wherein at least 80 weight percent of a total amount of hydrogen added to the multi-zone reactor system, is added to at least one location in the first tubular reactor which is downstream from the inlet of the first tubular reactor; and wherein

the ethylene copolymer has a density of 0.940 to 0.960 grams per cubic centimeter (g/cm 3 ); a melt index, I 2 as measured by ASTM D1238 at 190° C. using a 2.16 kilogram load, of from 0.5 to 2.5 grams per 10 minutes (g/10 min); a stress exponent of from 1.75 to 1.95; a number average molecular weight, Mn, of from 11,000 to 15,000; a polydispersity index, (Mw/Mn), of from 9 to 12; and a Z-average molecular weight, Mz, of from 500,000 to 800,000.

23 . A biaxially oriented polyethylene film comprising an ethylene copolymer, the ethylene copolymer comprising ethylene and at least one alpha olefin having from 4 to 8 carbon atoms; wherein the ethylene copolymer has a density of 0.940 to 0.960 grams per cubic centimeter (g/cm 3 ); a melt index, I 2 as measured by ASTM D1238 at 190° C. using a 2.16 kilogram load, of from 0.5 to 2.5 grams per 10 minutes (g/10 min); a stress exponent of from 1.75 to 1.95; a number average molecular weight, Mn, of from 11,000 to 15,000; a polydispersity index, (Mw/Mn), of from 9 to 12; and a Z-average molecular weight, Mz, of from 500,000 to 800,000.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 22, 2022
From: FEREYDOON, MARYAM; GOYAL, SHIVENDRA; BROWN, STEPHEN; LIGHTBODY, OWEN; AUBEE, NORMAN; GILLON, BRONWYN; GREEN, THOMAS; MARK, LISON; CARELLO, CHRISTIAN
To: NOVA CHEMICALS (INTERNATIONAL) S.A.
Reel/Frame 062182/0190 →
Priority Claims (1)
CA 3102574 · Dec 14, 2020 · national
Continuity (2)
Provisional Application 63045383 · Jun 29, 2020
Related Publication 20230235106A1 · Jul 27, 2023
References Cited (118)
US 2862917A · Pont · 1958 [cited by applicant]
US 3380978A · Pont · 1968 [cited by applicant]
US 3663662A · Golike et al. · 1972 [cited by applicant]
US 4383093A · Shiraki et al. · 1983 [cited by applicant]
US 4472330A · Ashcraft · 1984 [cited by applicant]
US 4590020A · Itaba et al. · 1986 [cited by applicant]
US 4870122A · Lu · 1989 [cited by applicant]
US 4916025A · Lu · 1990 [cited by applicant]
US 5043204A · Itaba et al. · 1991 [cited by applicant]
US 5241030A · Barry et al. · 1993 [cited by applicant]
US 5519098A · Brown et al. · 1996 [cited by applicant]
US 5589555A · Zboril · 1996 [cited by examiner]
US 5589561A · Barry et al. · 1996 [cited by applicant]
US 5725962A · Bader et al. · 1998 [cited by applicant]
US 5885721A · Su et al. · 1999 [cited by applicant]
US 5891555A · O'Brien · 1999 [cited by applicant]
US 6084042A · Jaber et al. · 2000 [cited by applicant]
US 6168826B1 · Su et al. · 2001 [cited by applicant]
US 6303233B1 · Amon et al. · 2001 [cited by applicant]
US 6387529B1 · Peet · 2002 [cited by applicant]
US 6479137B1 · Joyner et al. · 2002 [cited by applicant]
US 6518372B1 · Weickert · 2003 [cited by applicant]
US 6689857B1 · Larter et al. · 2004 [cited by applicant]
US 6764751B2 · Poirier · 2004 [cited by applicant]
US 6946203B1 · Lockhart et al. · 2005 [cited by applicant]
US 8080294B2 · Lu · 2011 [cited by applicant]
US 8962755B2 · Wang · 2015 [cited by examiner]
US 9062138B2 · Ker · 2015 [cited by examiner]
US 9074082B2 · Wang · 2015 [cited by examiner]
US 9221966B2 · Wang · 2015 [cited by examiner]
US 9371442B2 · Wang · 2016 [cited by examiner]
US 9475927B2 · Wang · 2016 [cited by examiner]
US 9676169B2 · Paulino · 2017 [cited by applicant]
US 9724901B2 · Lu · 2017 [cited by applicant]
US 9758653B2 · Wang · 2017 [cited by examiner]
US 9783663B2 · Wang · 2017 [cited by examiner]
US 9783664B1 · Wang · 2017 [cited by examiner]
US 9963529B1 · Kazemi · 2018 [cited by examiner]
US 10040261B2 · Mcleod et al. · 2018 [cited by applicant]
US 10071826B2 · Wang · 2018 [cited by examiner]
US 10071895B2 · Wang · 2018 [cited by examiner]
US 10093780B2 · Wang · 2018 [cited by examiner]
US 10189922B2 · Goyal · 2019 [cited by examiner]
US 10239976B2 · Goyal · 2019 [cited by examiner]
US 10329412B2 · Wang et al. · 2019 [cited by applicant]
US 10363700B2 · Yun et al. · 2019 [cited by applicant]
US 10584523B2 · Wang · 2020 [cited by examiner]
US 10625914B2 · Wang · 2020 [cited by examiner]
US 10792899B2 · Pan et al. · 2020 [cited by applicant]
US 11046491B2 · Wang · 2021 [cited by examiner]
US 11046843B2 · Konaganti · 2021 [cited by examiner]
US 11149137B2 · Wang · 2021 [cited by examiner]
US 11279819B2 · Wang · 2022 [cited by examiner]
US 11306196B2 · Wang · 2022 [cited by examiner]
US 11312845B2 · Sadeghi · 2022 [cited by examiner]
US 11339278B2 · Wang · 2022 [cited by examiner]
US 11352485B2 · Wang · 2022 [cited by examiner]
US 11359081B2 · Wang · 2022 [cited by examiner]
US 11560468B2 · Wang · 2023 [cited by examiner]
US 11643531B2 · Wang · 2023 [cited by examiner]
US 11958961B2 · Wang · 2024 [cited by examiner]
US 20010021754A1 · Weber · 2001 [cited by examiner]
US 20040105944A1 · Weber · 2004 [cited by examiner]
US 20060177641A1 · Breese et al. · 2006 [cited by applicant]
US 20100129652A1 · Mcleod · 2010 [cited by applicant]
US 20130209756A1 · Squier et al. · 2013 [cited by applicant]
US 20150094418A1 · Wang · 2015 [cited by examiner]
US 20160031191A1 · Paulino · 2016 [cited by applicant]
US 20190299578A1 · Dou et al. · 2019 [cited by applicant]
US 20200061982A1 · Ambroise · 2020 [cited by applicant]
US 20200270395A1 · Peer et al. · 2020 [cited by applicant]
US 20200369014A1 · Ambroise · 2020 [cited by applicant]
US 20210115206A1 · Toyota et al. · 2021 [cited by applicant]
US 20220402192A1 · Aubee · 2022 [cited by examiner]
CA 703704A · 1965 [cited by applicant]
CA 849081A · 1970 [cited by applicant]
EP 0929583A1 · 1998 [cited by applicant]
EP 1037742A1 · 2000 [cited by applicant]
EP 1819510B1 · 2007 [cited by applicant]
EP 3335874A1 · 2018 [cited by applicant]
JP 2010535273A · 2010 [cited by applicant]
JP 2019143142A · 2019 [cited by applicant]
KR 101085329B1 · 2011 [cited by applicant]
WO WO9722470A1 · 1997 [cited by applicant]
WO WO9814491A1 · 1998 [cited by applicant]
WO WO2008136849A1 · 2008 [cited by applicant]
WO WO2011069240A1 · 2011 [cited by applicant]
WO WO2014106052A1 · 2014 [cited by applicant]
WO WO2018005577A1 · 2018 [cited by applicant]
WO WO2018109112A1 · 2018 [cited by applicant]
WO WO2021079255A1 · 2021 [cited by applicant]
ASTM D1238-04 Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Plastometer—Copyright ASTM International—Current edition approved Mar. 1, 2004. Published Apr. 2004. Originally approved in 1965. Las… [cited by applicant]
Datasheet of Affinity EG 8100G Polyolefin Plastomer, The Dow Chemical Company, Jan. 12, 2016 (2 pages). [cited by applicant]
ASTM D1003-11—Standard Test Method for Haze and Luminous Transmittance of Transparent Plastics—Copyright ASTM International—Current edition approved Apr. 15, 2011. Published Apr. 2011. Originally approved in 1949. Last … [cited by applicant]
ASTM D1238-13—Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Plastometer—Copyright ASTM International—Current edition approved Aug. 1, 2013. Published Aug. 2013. Originally approved in 1965. Las… [cited by applicant]
ASTM D1525-07—Standard Test Method for Vicat Softening Temperature of Plastics—Copyright ASTM International—Current edition approved Mar. 1, 2007. Published Mar. 2007. Originally approved in 1958. Last previous edition … [cited by applicant]
ASTM D1922-09—Standard Test Method for Propagation Tear Resistance of Plastic Film and Thin Sheeting by Pendulum Method—Copyright ASTM International—Current edition approved May 1, 2009. Published Jun. 2009. Originally … [cited by applicant]
ASTM D2457-13—Standard Test Method for Specular Gloss of Plastic Films and Solid Plastics—Copyright ASTM International—Current edition approved Apr. 1, 2013. Published Apr. 2013. Originally approved in 1965. Last previo… [cited by applicant]
ASTM D3985-17—Standard Test Method for Oxygen Gas Transmission Rate Through Plastic Film and Sheeting Using a Coulometric Sensor—Copyright ASTM International—Current edition approved Nov. 15, 2017. Published Dec. 2017. … [cited by applicant]
ASTM D5748-95—Standard Test Method for Protrusion Puncture Resistance of Stretch Wrap Film—Copyright ASTM International—Current edition approved Apr. 1, 2012. Published May 2012. Originally approved in 1995. Last previo… [cited by applicant]
ASTM D6474-12—Standard Test Method for Determining Molecular Weight Distribution and Molecular Weight Averages of Polyolefins by High Temperature Gel Permeation Chromatography—Copyright ASTM International—Current editio… [cited by applicant]
ASTM D6474-99 (Reapproved 2006)—Standard Test Method for Determining Molecular Weight Distribution and Molecular Weight Averages of Polyolefins by High Temperature Gel Permeation Chromatography. Copyright ASTM Internati… [cited by applicant]
ASTM D6988-13—Standard Test Method for Determination of Thickness of Plastic Film Test Specimens—Copyright ASTM International—Current edition approved Apr. 1, 2013. Published Apr. 2013. Originally approved in 2003. Last… [cited by applicant]
ASTM D792-13—Standard Test Methods for Density and Specific Gravity (Relative Density) of Plastics by Displacement—Copyright ASTM International—Current edition approved Nov. 1, 2013. Published Nov. 2013. Originally appr… [cited by applicant]
ASTM D882-12—Standard Test Method for Tensile Properties of Thin Plastic Sheeting—Copyright ASTM International—Current edition approved Aug. 1, 2012. Published Sep. 2012. Originally approved in 1946. Last previous editi… [cited by applicant]
ASTM D972-16—Standard Test Method for Evaporation Loss of Lubricating Greases and Oils—Copyright ASTM International—Current edition approved Apr. 1, 2016. Published May 2016. Originally approved in 1948. Last previous e… [cited by applicant]
ASTM F1249-20—Standard Test Method for Water Vapor Transmission Rate Through Plastic Film and Sheeting Using a Modulated Infrared Sensor—Copyright ASTM International—Current edition approved Jun. 1, 2020. Published Jul.… [cited by applicant]
Bird et al., “Dynamics of Polymer Liquids. Volume 1: Fluid Mechanics”, John Wiley & Sons, 1987, pp. 169-175. [cited by applicant]
Carreau-Yasuda model, K. Yasuda PHD Thesis, IT Cambridge (1979). [cited by applicant]
Deslauriers et al., Quantifying short chain branching microstructures in ethylene 1-olefin copolymers using size exclusion chromatography and Fourier transform infrared spectroscopy (SEC-FTIR), Polymer 43, 2002, pp. 159… [cited by applicant]
Graessley et al., “Effect of Long Branches on the Flow Properties of Polymers”, Acc. Chem. Res., vol. 10, 1977, pp. 332-339. [cited by applicant]
International Search Report & Written Opinion of the International Searching Authority issued in PCT Application No. PCT/IB2020/059816, mailed Jan. 20, 2021. [cited by applicant]
Kanai et al. in the textbook “Film Processing Advances”, Hanser Publishers, 2014, Chapter 7. [cited by applicant]
Kanai et al. in the textbook “Film Processing Advances”, Hanser Publishers, 2014, Chapter 8. [cited by applicant]
Randall et al., “A Review of High Resolution Liquid 13Carbon Nuclear Magnetic Resonance Characterizations of Ethylene-Based Polymers”, JMS—Rev. Macromol. Chem. Phys., 1989, pp. 201-317. [cited by applicant]
Wild et al., “Determination of Branching Distributions in Polyethylene and Ethylene Copolymers”, J. Polym. Sci., Part B, Polym. Phys., vol. 20 (3), pp. 441-455. [cited by applicant]
Yau et al., “Application of Triple-Detector Size Exclusion Chromatography (On-Line Differential Refractometer, Viscometer and Light Scattering Detectors) for the Characterization of Brominated Polystyrene”, Int. J. Poly… [cited by applicant]
International Search Report & Written Opinion of the International Searching Authority issued in PCT Application No. PCT/IB2021/055555, mailed Feb. 24, 2022. [cited by applicant]