Ethylene interpolymer films

Patent metadata

Field	Value
Publication number	US-10053565-B2
Application number	US-201615341386-A
Country	US
Kind code	B2
Filing date	Nov 2, 2016
Priority date	Oct 21, 2014
Publication date	Aug 21, 2018
Grant date	Aug 21, 2018

Abstract

This disclosure relates to multilayer films having improved caulkability. These multilayer films have at least one layer containing an ethylene interpolymer product, or a blend containing an ethylene interpolymer product, where the ethylene interpolymer product has: a Dilution Index (Y d ) greater than 0; total catalytic metal ≥3.0 ppm; ≥0.03 terminal vinyl unsaturations per 100 carbon atoms, and; optionally a Dimensionless Modulus (X d ) greater than 0. The ethylene interpolymer products have a melt index from about 0.4 to about 100 dg/minute, a density from about 0.950 to about 0.970 g/cm 3 , a polydispersity (M w /M n ) from about 2 to about 25 and a CDBI 50 from about 55% to about 97%. Further, the ethylene interpolymer products are a blend of at least two ethylene interpolymers; where one ethylene interpolymer is produced with a single-site catalyst formulation and at least one ethylene interpolymer is produced with a heterogeneous catalyst formulation.

First claim

What is claimed is:

1. A film comprising at least one layer, wherein said layer comprises an ethylene interpolymer product comprising:
(I) a first ethylene interpolymer;
(II) a second ethylene interpolymer, and;
(III) optionally a third ethylene interpolymer; wherein said first ethylene interpolymer is produced using a single site catalyst formulation comprising a component (i) defined by the formula
(L A ) a M(Pl) b (Q) n

wherein L A is selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl;
M is a metal selected from the group consisting of titanium, hafnium and zirconium;
Pl is a phosphinimine ligand;
Q is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C 1-10 hydrocarbyl radical, a C 1-10 alkoxy radical and a C 5-10 aryl oxide radical; wherein each of said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted or further substituted by a halogen atom, a C 1-18 alkyl radical, a C 1-8 alkoxy radical, a C 6-10 aryl or aryloxy radical, an amido radical which is unsubstituted or substituted by up to two C 1-8 alkyl radicals or a phosphido radical which is unsubstituted or substituted by up to two C 1-8 alkyl radicals;
wherein a is 1; b is 1; n is 1 or 2; and (a+b+n) is equivalent to the valence of the metal M, and;
wherein said second ethylene interpolymer is produced using a first in-line Ziegler-Natta catalyst formulation;
wherein said third ethylene interpolymer is produced using said first in-line Ziegler-Natta catalyst formulation or a second in-line Ziegler-Natta catalyst formulation, and;
wherein said ethylene interpolymer product has a Dilution Index, Y d , greater than 0.

2. The film of claim 1 , wherein said single site catalyst formulation further comprises: an alumoxane co-catalyst; a boron ionic activator, and; optionally a hindered phenol.

3. The film of claim 2 , wherein said alumoxane co-catalyst is methylalumoxane (MAO) and said boron ionic activator is trityl tetrakis (pentafluoro-phenyl) borate.

4. The film of claim 1 , wherein said ethylene interpolymer product is further characterized as having one or more of:
a) ≥0.03 terminal vinyl unsaturations per 100 carbon atoms;
b) ≥3 parts per million (ppm) of a total catalytic metal;
c) a Dimensionless Modulus, X d , greater than 0.

5. The film of claim 1 , wherein said ethylene interpolymer product has a melt index from about 0.4 to about 12 dg/minute; wherein melt index is measured according to ASTM D1238 (2.16 kg load and 190° C.).

6. The film of claim 1 , wherein said ethylene interpolymer product has a density from about 0.900 to about 0.935 g/cc; wherein density is measured according to ASTM D792.

7. The film of claim 1 , wherein said ethylene interpolymer product has a M w /M n from about 2 to about 25.

8. The film of claim 1 , wherein said ethylene interpolymer product has a CDBI 50 from about 20% to about 98%.

9. The film of claim 1 ; wherein
(I) said first ethylene interpolymer constitutes from about 15 to about 60 weight percent of said ethylene interpolymer product and has a melt index from about 0.01 to about 200 dg/min and a density from about 0.855 to about 0.975 g/cc;
(II) said second ethylene interpolymer constitutes from about 30 to about 85 weight percent of said ethylene interpolymer product and has a melt index from about 0.3 to about 1000 dg/min and a density from about 0.89 to about 0.975 g/cc;
(III) said third ethylene interpolymer constitutes from about 0 to about 30 weight percent of said ethylene interpolymer product and has a melt index from about 0.5 to about 2000 dg/min and a density from about 0.89 to about 0.975 g/cc;
wherein weight percent is the weight of said first, said second or said third ethylene interpolymer, individually, divided by the weight of said ethylene interpolymer product;
wherein melt index is measured according to ASTM D1238 (2.16 kg load and 190° C.), and;
wherein density is measured according to ASTM D792.

10. The film of claim 1 ; wherein said ethylene interpolymer product is synthesized using a solution polymerization process.

11. The film of claim 1 , wherein said ethylene interpolymer product further comprises from 0.1 to about 10 mole percent of one or more C 3 to C 10 α-olefins.

12. The film of claim 1 , wherein said ethylene interpolymer product has ≤1 part per million (ppm) of a metal A; wherein said metal A originates from said component (i).

13. The film of claim 1 , wherein said ethylene interpolymer product contains a metal B and optionally a metal C and the total amount of said metal B plus said metal C is from about 3 to about 11 parts per million; wherein said metal B originates from said first in-line Ziegler-Natta catalyst formulation and said metal C originates from said second in-line Ziegler-Natta catalyst formulation; optionally said metal B and said metal C are the same metal.

14. The film of claim 13 ; wherein said metal B and said metal C, are independently selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium or osmium.

15. The film of claim 1 ; wherein
(I) said first ethylene interpolymer has a first CDBI 50 from about 70 to about 98%;
(II) said second ethylene interpolymer has a second CDBI 50 from about 45 to about 98%, and;
(III) said optional third ethylene interpolymer has a third CDBI 50 from about 35 to about 98%.

16. The film of claim 15 ; wherein said first CDBI 50 is higher than said second CDBI 50 and said first CDBI 50 is higher than said third CDBI 50 .

17. The film of claim 1 , wherein
(I) said first ethylene interpolymer has a first M w /M n from about 1.7 to about 2.8;
(II) said second ethylene interpolymer has a second M w /M n from about 2.2 to 4.4, and;
(III) said third ethylene interpolymer has a third M w /M n from about 2.2 to 5.0;
wherein said first M w /M n is lower than said second M w /M n and said third M w /M n .

18. The film of claim 17 ; wherein the blending of said second ethylene interpolymer and said third ethylene interpolymer forms a heterogeneous ethylene interpolymer blend having a fourth M w /M n ; wherein said fourth M w /M n is not broader than said second M w /M n .

19. The film of claim 1 ; wherein said film is a multilayer film, wherein said multilayer film has a sealant layer, wherein said sealant layer comprises said ethylene interpolymer product and said multilayer film has a hole size ≥95 μm and ≤115 μm;
wherein hole size is determined in a caulkability test.

20. The film of claim 19 ; wherein said multilayer film has from 2 to 11 layers.

Assignees

• Nova Chem Int Sa

Inventors

• Ward Daniel
• Li Michael
• Wang Xiaochuan
• Li Tieqi
• Dobbin Christopher John Brooke
• Sibtain Fazle
• Taylor Kenneth Edward
• Khakdaman Hamidreza

Classifications

• C08L2205/025

  containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure · CPC title

• C08L2203/10

  used for bottles · CPC title

• C08L23/0815 Primary

  with aliphatic 1-olefins containing one carbon-to-carbon double bond · CPC title

• C08L2314/02

  Ziegler natta catalyst · CPC title

• C08J5/18

  Manufacture of films or sheets · CPC title