IP Library Granted Patent US 10,023,706
Granted Patent B2
US 10,023,706 · App. 15/609,051 · Granted Jul 17, 2018

Rotomolded articles

Inventors: Celine Bellehumeur (Calgary, CA); Brian Molloy (Airdrie, CA); Hamidreza Khakdaman (Houston, TX); XiaoChuan Wang (Calgary, CA); Tieqi Li (Calgary, CA); Christopher Dobbin (Calgary, CA); Fazle Sibtain (Calgary, CA); Kenneth Taylor (Sarnia, CA)
Assignee: NOVA Chemicals (International) S.A.
C08J5/18B29C41/04B29C41/22B32B3/266B32B7/12B32B27/08B32B27/327B32B27/34C08F2/001C08F2/06C08F4/6555C08F4/6583C08F4/6585C08F4/6592C08F4/65904C08F210/16C08J5/00C08L23/08C08L23/0815C08L23/14C08L23/20B29K2023/08B29K2105/0058B29K2105/0085B29K2105/0094B29K2905/02B29K2995/0063B29K2995/0088B32B2307/7265B32B2439/40C08F4/65908C08F4/65912C08F210/14C08F2420/01C08F2420/04C08F2500/03C08F2500/09C08F2500/11C08F2500/12C08F2500/13C08F2500/17C08F2500/18C08F2500/26C08J2323/06C08J2323/08C08J2323/20C08J2323/24C08J2423/08C08J2423/20C08J2423/24C08L2203/16C08L2205/025C08L2205/03C08L2205/06C08L2314/02C08L2314/06
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Quick Facts
Patent No.
US 10,023,706
App. No.
15/609,051
Granted
Jul 17, 2018
Kind
B2
Abstract

This disclosure relates to rotomolded articles, having a wall structure, where the wall structure contains at least one layer containing an ethylene interpolymer product, or a blend containing an ethylene interpolymer product and an ethylene polymer, where the ethylene interpolymer product has a Dilution Index (Y d ) greater than 0 and improved Environmental Stress Crack Resistance (ESCR). The ethylene interpolymer product has a melt index from about 0.5 to about 15 dg/minute, a density from about 0.930 to about 0.955 g/cm 3 , a polydispersity (M w /M n ) from about 2 to about 6 and a CDBI 50 from about 50% to about 98%. 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.

Claims (46)

1. A rotomolded article comprising a wall structure; wherein said wall structure comprises at least one layer comprising an ethylene interpolymer product comprising:

(i) a first ethylene interpolymer;

(ii) a second ethylene interpolymer, and;

(iii) optionally a third ethylene interpolymer;

wherein said ethylene interpolymer product has a Dilution Index, Y d , greater than 0;

wherein a plaque molded from said ethylene interpolymer product has (a) and/or (b),

(a) passes an ESCR test Condition A100 and a comparative plaque

fails said ESCR test Condition A100, wherein said ESCR test Condition A100 is passed if a failure time (F A 50 ) is ≥1000 hr or said ESCR test Condition A100 is failed if said failure time (F A 50 ) is <1000 hr;

(b) passes an ESCR test Condition B100 and said comparative

plaque fails said ESCR test Condition B100, wherein said ESCR test Condition B100 is passed if a failure time (F B 50 ) is ≥1000 hr or said ESCR test Condition B100 is failed if said failure time (F B 50 ) is <1000 hr;

wherein said comparative plaque comprises a comparative ethylene interpolymer product comprising a comparative first ethylene interpolymer, a comparative second ethylene interpolymer and optionally a comparative third ethylene interpolymer;

wherein said ethylene interpolymer product has a TREF weight fraction eluting below 85° C., wtF <85 , that is at least 10% higher relative to a comparative TREF weight fraction eluting below 85° C., wtF c <85 , of said comparative ethylene interpolymer product;

wherein said first ethylene interpolymer has a weight average molecular weight, 1 st M w , that is at least 20% higher relative a comparative weight average molecular weight of said comparative first ethylene interpolymer, 1 st (M w ) c ;

wherein said failure times (F A 50 ) and (F B 50 ) are estimated graphically as described in Annex Al of ASTM D1693.

2. The rotomolded article of claim 1 , wherein said ethylene interpolymer product has ≥0.03 terminal vinyl unsaturations per 100 carbon atoms.

3. The rotomolded article of claim 1 , wherein said ethylene interpolymer product has ≥3 parts per million (ppm) of a total catalytic metal.

4. The rotomolded article of claim 1 , wherein said ethylene interpolymer product has ≥0.03 terminal vinyl unsaturations per 100 carbons and ≥3 parts per million (ppm) of total catalytic metal.

5. The rotomolded article of claim 1 , wherein said ethylene interpolymer product has a Dimensionless Modulus from about −0.16 to about −0.08.

6. The rotomolded article of claim 1 having a melt index from about 0.5 to about 15 dg/minute; wherein melt index is measured according to ASTM D1238 (2.16 kg load and 190° C.).

7. The rotomolded article of claim 1 having a density from about 0.930 to about 0.955 g/cc; wherein density is measured according to ASTM D792.

8. The rotomolded article of claim 1 having a M w /M n from about 2 to about 6.

9. The rotomolded article of claim 1 having a CDBI 50 from about 50% to about 98%.

10. The rotomolded article of claim 1 ; wherein

(i) said first ethylene interpolymer is 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/minute and a density from about 0.89 g/cm 3 to about 0.975 g/cc, and;

(ii) said second ethylene interpolymer is 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/minute and a density from about 0.89 g/cm 3 to about 0.975 g/cc, and;

(iii) optionally said third ethylene interpolymer is 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/minute and a density from about 0.89 to about 0.975 g/cc;

wherein weight percent is the weight of said first, or said second or said optional third ethylene interpolymer 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 density is measured according to ASTM D792.

11. The rotomolded article of claim 1 ; wherein said ethylene interpolymer product is synthesized using a solution polymerization process.

12. The rotomolded article of claim 1 further comprising from 0.1 to about 2.0 mole percent of one or more α-olefin.

13. The rotomolded article of claim 12 ; wherein said one or more α-olefin are C 3 to C 10 α-olefins.

14. The rotomolded article of claim 12 ; wherein said one or more α-olefin is 1-hexene, 1-octene or a mixture of 1-hexene and 1-octene.

15. The rotomolded article of claim 1 ; wherein said first ethylene interpolymer is synthesized using a single-site catalyst formulation.

16. The rotomolded article of claim 1 ; wherein said second ethylene interpolymer is synthesized using a first heterogeneous catalyst formulation.

17. The rotomolded article of claim 1 ; wherein said third ethylene interpolymer is synthesized using a first heterogeneous catalyst formulation or a second heterogeneous catalyst formulation.

18. The rotomolded article of claim 1 wherein said second ethylene interpolymer is synthesized using a first in-line Ziegler Natta catalyst formulation or a first batch Ziegler-Natta catalyst formulation; optionally, said third ethylene interpolymer is synthesized using said first in-line Ziegler Natta catalyst formulation or said first batch Ziegler-Natta catalyst formulation.

19. The rotomolded article of claim 1 wherein said third ethylene interpolymer is synthesized using a second in-line Ziegler Natta catalyst formulation or a second batch Ziegler-Natta catalyst formulation.

20. The rotomolded article of claim 1 , having ≤1 part per million (ppm) of a metal A; wherein said metal A originates from a single site catalyst formulation used to synthesize said first ethylene interpolymer.

21. The rotomolded article of claim 20 ; wherein said metal A is titanium, zirconium or hafnium.

22. The rotomolded article of claim 1 having 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 a first heterogeneous catalyst formulation used to synthesize said second ethylene interpolymer and optionally said metal C originates from a second heterogeneous catalyst formulation used to synthesize said third ethylene interpolymer; optionally said metal B and said metal C are the same metal.

23. The rotomolded article of claim 22 ; 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.

24. The rotomolded article of claim 1 wherein said first ethylene interpolymer has a first M w /M n , said second ethylene interpolymer has a second M w /M n and said optional third ethylene interpolymer has a third M w /M n ; wherein said first M w /M n is lower than said second M w /M n and said optional third M w /M n .

25. The rotomolded article of claim 24 ; 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 larger than said second M w /M n .

26. The rotomolded article of claim 24 wherein said second M w /M n and said optional third M w /M n are ≤4.0.

27. The rotomolded article of claim 1 ; wherein said first ethylene interpolymer has a first CDBI 50 from about 70 to about 98%, said second ethylene interpolymer has a second CDBI 50 from about 45 to about 98% and said optional third ethylene interpolymer has a third CDBI 50 from about 35 to about 98%.

28. The rotomolded article of claim 27 ; wherein said first CDBI 50 is higher than said second CDBI 50 ; optionally said first CDBI 5 O is higher than said third CDBI 50 .

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 13, 2017
From: BELLEHUMEUR, CELINE; MOLLOY, BRIAN; KHAKDAMAN, HAMIDREZA; WANG, XIAOCHUAN; DOBBIN, CHRISTOPHER; SIBTAIN, FAZLE; TAYLOR, KENNETH
To: NOVA CHEMICALS (INTERNATIONAL) S.A.
Reel/Frame 042992/0926 →
Priority Claims (1)
CA 2868640 · Oct 21, 2014 · national
Continuity (3)
Continuation In Part 15335485 · Oct 27, 2016
Continuation 14918964 · Oct 21, 2015
Related Publication 20170267822A1 · Sep 21, 2017
Cited By (3)
US 12,378,393 US 12,617,883 US 12,742,062