Producing polyolefin products with improved stiffness, toughness, and processability

Patent metadata

Field	Value
Publication number	US-2016347888-A1
Application number	US-201515116250-A
Country	US
Kind code	A1
Filing date	Feb 10, 2015
Priority date	Feb 11, 2014
Publication date	Dec 1, 2016
Grant date	—

Abstract

Polymers, and systems and methods for making and using the same are described herein. A polymer includes ethylene and at least one alpha olefin having from 4 to 20 carbon atoms. The polymer has a melt index ratio (MIR) greater than about 40. The polymer also has a value for Mw1/Mw2 of at least about 2.0, wherein Mw1/Mw2 is a ratio of a weight average molecular weight (Mw) for a first half of a temperature rising elution (TREF) curve from a cross-fractionation (CFC) analysis to an Mw for a second half of the TREF curve. The polymer also has a value for Tw1−Tw2 of less than about −15° C., wherein Tw1−Tw2 is a difference of a weight average elution temperature (Tw) for the first half of the TREF curve to a Tw for the second half of the TREF curve.

First claim

What is claimed is:

1 . A polymer, comprising ethylene and at least one alpha olefin having from 4 to 20 carbon atoms, wherein the polymer has:
a melt index ratio (MIR) greater than about 40; a value for Mw1/Mw2 of at least about 2.0, wherein Mw1/Mw2 is a ratio of a weight average molecular weight (Mw) for a first half of a temperature rising elution (TREF) curve from a cross-fractionation (CFC) analysis to a Mw for a second half of the TREF curve; and a value for Tw1−Tw2 of less than about −15° C., wherein Tw1−Tw2 is a difference of a weight average elution temperature (Tw) for the first half of the TREF curve to a Tw for the second half of the TREF curve.

2 . The polymer of claim 1 , wherein the polymer has:
an average modulus of greater than about 20,000 psi; and a dart impact strength of greater than about 100 g/mil.

3 . The polymer of claim 1 , wherein the polymer has no negative inflection point in a van Gurp Palmen (vGP) plot at a frequency of between about 0.1 rad/s and 300 rad/s at 190° C.

4 . The polymer of claim 1 , wherein the polymer has a relationship between average modulus (M) and dart impact strength in g/mil (DIS) complying with the formula:
DIS≧0.8×[100 +e (11.71−0.000268×M+2.183×10 −9 ×M 2 ) ].

5 . The polymer of claim 1 , comprising:
a lower molecular weight polymer formed by a first catalyst and a higher molecular weight polymer formed by a second catalyst, wherein:
the lower molecular polymer has a density of about 0.02 greater than the density of the higher molecular weight polymer; and
the mol ratio of the first catalyst to the second catalyst is between about 1:1 and 1:10.

6 . The polymer of claim 5 , wherein the lower molecular weight polymer has a peak molecular weight of less than about ¼ of the peak molecular weight of the higher molecular weight polymer.

7 . The polymer of claim 1 , comprising a polymer chain formed by a catalyst system comprising bis(n-propylcyclopentadienyl) hafnium (CH 3 ) 2 .

8 . The polymer of claim 1 , comprising a polymer chain formed by a catalyst system comprising bis(n-butyl, methyl cyclopentadienyl) zirconium (CH 3 ) 2 .

9 . The polymer of claim 1 , comprising a polymer chain formed by a catalyst system comprising bis(1-ethylindenyl) zirconium (CH 3 ) 2 .

10 . The polymer of claim 1 , comprising a polymer chain formed by a catalyst system comprising any one of the compounds represented by the following formulas:

wherein R 1 and R 2 are each, independently, methyl, chloro, fluoro, or a hydrocarbyl group.

11 . The polymer of claim 1 , comprising polymer chains formed by a catalyst system comprising bis(n-propylcyclopentadienyl) hafnium (CH 3 ) 2 and bis(1-ethylindenyl) zirconium (CH 3 ) 2 .

12 . The polymer of claim 1 , comprising polymer chains formed by a catalyst system comprising bis(n-propylcyclopentadienyl) hafnium (CH 3 ) 2 and meso-O(SiMe 2 Ind) 2 ZrMe 2 .

13 . The polymer of claim 1 , comprising polymer chains formed by a catalyst system comprising a compound represented by one of the following formulas:
Cp A Cp B MX n or Cp A (A)Cp B MX n , wherein M is a Group 4, 5, or 6 atom; Cp A and Cp B are each bound to M and are independently selected from the group consisting of cyclopentadienyl ligands, substituted cyclopentadienyl ligands, ligands isolobal to cyclopentadienyl and substituted ligands isolobal to cyclopentadienyl; (A) is a divalent bridging group bound to both Cp A and Cp B selected from the group consisting of divalent C 1 to C 20 hydrocarbyls and C 1 to C 20 heteroatom containing hydrocarbonyls, wherein the heteroatom containing hydrocarbonyls comprise from one to three heteroatoms; X is a leaving group selected from the group consisting of chloride ions, bromide ions, C 1 to C 10 alkyls, and C 2 to C 12 alkenyls, carboxylates, acetylacetonates, and alkoxides; and n is an integer from 1 to 3.

14 . The polymer of claim 1 , comprising polymer chains generated by a catalyst system comprising at least two co-supported catalysts.

15 . The polymer of claim 1 , comprising a ratio of a polymer formed by a first catalyst to a polymer formed by a second catalyst of between about 2:1 and 5:1.

16 . The polymer of claim 1 , comprising a high molecular weight component that is between about 0.02 and about 0.05 less than a density of a low molecular weight component.

17 . A polymer, comprising ethylene and at least one alpha olefin having 4 carbon atoms, wherein the polymer has:
a total haze of less than about 30%; an average modulus of greater than about 30,000 psi; a dart impact strength of greater than about 120 g for a 1 mil film; a melt index ratio (MIR) greater than about 25; and an Elmendorf machine direction tear of greater than about 170 g at 1 mil film gauge.

18 . The polymer of claim 17 , wherein a melt index of between about 0.1 and 5.

19 . The polymer of claim 17 , wherein a density of the polymer is between about 0.915 and about 0.935.

20 . The polymer of claim 17 , wherein the melt index ratio (MIR) is less than about 35.

21 . The polymer of claim 17 , having an absence of a negative inflection point in a van Gurp Palmen (vGP) plot at a frequency of between about 0.1 rad/s and 200 rad/s at 190° C.

22 . The polymer of claim 17 , wherein the polymer has a relationship between average modulus (M) and dart impact strength in g/mil (DIS) complying with the formula:
DIS≧0.8×[100+ e (11.71−0.000268×M+2.183×10 −9 ×M 2 ) ].

23 . The polymer of claim 17 , comprising a polymer chain formed by a catalyst system comprising any one of the compounds represented by the following formulas:

wherein R 1 and R 2 are each, independently, methyl, chloro, fluoro, or a hydrocarbyl group.

24 . A polymer, comprising ethylene and at least one alpha olefin having 4 carbon atoms, wherein the polymer has:
a value for melt index ratio (MIR) of between about 25 and about 35; a value for Mw1/Mw2 of at least about 2.0, wherein Mw1/Mw2 is a ratio of a weight average molecular weight (Mw) for a first half of a temperature rising elution (TREF) curve to a Mw for a second half of the TREF curve; and a value for Tw1−Tw2 of less than about −15° C., wherein Tw1−Tw2 is a difference of a weight average elution temperature (Tw) for the first half of the TREF curve to a Tw for the second half of the TREF curve.

25 . The polymer of claim 17 , comprising a polymer chain formed by a catalyst system comprising any one of the compounds represented by the following formulas:

wherein R 1 and R 2 are each, independently, methyl, chloro, fluoro, or a hydrocarbyl group.

26 . A polymer, comprising ethylene and at least one alpha olefin having from 4 to 20 carbon atoms, wherein the polymer has:
an absence of a negative inflection point in a van Gurp Palmen (vGP) plot at a frequency of between about 0.1 rad/s and 300 rad/s at 190° C.; a melt index ratio (MIR) greater than about 40; a relationship between average modulus (M) and dart impact strength in g/mil (DIS) complying with the formula:
DIS≧0.8×[100

Assignees

• Univation Tech Llc

Inventors

• Lue Ching-Tai
• Rix Francis C
• Boller Timothy M
• Giesbrecht Garth R
• Goode Mark G
• Kao Sun-Chueh
• Li Dongming
• Pequeno R Eric
• Farley James M
• Zilker Jr Daniel P

Classifications

• C08J5/18 Primary

  Manufacture of films or sheets · CPC title

• B32B27/32

  comprising polyolefins {(comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30)} · CPC title

• C08F2/34

  Polymerisation in gaseous state · CPC title

• C08J2323/08

  Copolymers of ethene (C08J2323/16 takes precedence) · CPC title

• C07F17/00

  Metallocenes · CPC title