Means for increasing the molecular weight and decreasing the density of ethylene interpolymers employing homogeneous and heterogeneous catalyst formulations

Patent metadata

Field	Value
Publication number	US-10442920-B2
Application number	US-201715491264-A
Country	US
Kind code	B2
Filing date	Apr 19, 2017
Priority date	Apr 19, 2017
Publication date	Oct 15, 2019
Grant date	Oct 15, 2019

Abstract

A continuous solution polymerization process is disclosed wherein at least two catalyst formulations are employed. A first homogeneous catalyst formulation is employed in a first reactor to produce a first ethylene interpolymer and a first heterogeneous catalyst formulation is employed in a second reactor to produce a second ethylene interpolymer. Optionally a third ethylene interpolymer is formed in a third reactor. The resulting ethylene interpolymer products possess desirable properties in a variety of end use applications, for example in film applications. A means for increasing the molecular weight of the first ethylene interpolymer is disclosed and/or a means for increasing the temperature of the first reactor, relative to a third homogeneous catalyst formulation. A means for reducing the (α-olefin/ethylene) weight ratio in the first reactor is disclosed and/or reducing the density of the first ethylene interpolymer, relative to a third homogeneous catalyst formulation.

First claim

What is claimed is:

1. An ethylene interpolymer product comprising:
(i) a first ethylene interpolymer,
(ii) a second ethylene interpolymer, and
(iii) optionally a third ethylene interpolymer;
wherein the ethylene interpolymer product has a dimensionless Long Chain Branching Factor, LCBF, greater than or equal to about 0.001;
wherein the ethylene interpolymer product has from about 0.0015 ppm to about 2.4 ppm of hafnium, and;
wherein the ethylene interpolymer product has from about 0.1 ppm to about 11.4 ppm of titanium.

2. The ethylene interpolymer product according to claim 1 , further comprising one or more of the following:
(i) greater than or equal to about 0.02 terminal vinyl unsaturations per 100 carbon atoms;
(ii) greater than or equal to about 0.12 parts per million (ppm) of a total catalytic metal.

3. The ethylene interpolymer product according to claim 1 having a melt index from about 0.3 to about 500 dg/minute; wherein melt index is measured according to ASTM D1238 (2.16 kg load and 190° C.).

4. The ethylene interpolymer product according to claim 1 having a density from about 0.862 to about 0.975 g/cc; wherein density is measured according to ASTM D792.

5. The ethylene interpolymer product according to claim 1 having a M w /M n from about 2 to about 25.

6. The ethylene interpolymer product according to claim 1 having a CDBI 50 from about 20% to about 98%.

7. The ethylene interpolymer product according to claim 1 , wherein:
(i) the first ethylene interpolymer is from about 5 to about 60 weight percent of the ethylene interpolymer product,
(ii) the second ethylene interpolymer is from about 20 to about 95 weight percent of the ethylene interpolymer product, and
(iii) optionally the third ethylene interpolymer is from about 0 to about 30 weight percent of the ethylene interpolymer product;
wherein weight percent is the weight of the first ethylene interpolymer, the second ethylene interpolymer, or the optional third ethylene interpolymer, individually, divided by the weight of the ethylene interpolymer product.

8. The ethylene interpolymer product according to claim 1 , wherein:
(i) the first ethylene interpolymer has a melt index from about 0.01 to about 200 dg/minute;
(ii) the second ethylene interpolymer has melt index from about 0.3 to about 1000 dg/minute; and
(iii) optionally the third ethylene interpolymer has a melt index from about 0.5 to about 2000 dg/minute;
wherein melt index is measured according to ASTM D1238 (2.16 kg load and 190° C.).

9. The ethylene interpolymer product according to claim 1 , wherein:
(i) the first ethylene interpolymer has a density from about 0.855 g/cm 3 to about 0.975 g/cm 3 ;
(ii) the second ethylene interpolymer has a density from about 0.89 g/cm 3 to about 0.975 g/cm 3 ; and
(iii) optionally the third ethylene interpolymer has density from about 0.855 g/cm 3 to about 0.975 g/cm 3 ;
wherein density is measured according to ASTM D792.

10. The ethylene interpolymer product according to claim 1 manufactured using a solution polymerization process.

11. The ethylene interpolymer product according to claim 1 further comprising from 0 to about 10 mole percent of one or more α-olefin.

12. The ethylene interpolymer product according to claim 11 , wherein the one or more α-olefin are C 3 to C 10 α-olefins.

13. The ethylene interpolymer product according to claim 11 , wherein the one or more α-olefin is 1-hexene, 1-octene, or a mixture thereof.

14. The ethylene interpolymer product according to claim 1 , wherein the first ethylene interpolymer is produced using at least one homogeneous catalyst formulation.

15. The ethylene interpolymer product according to claim 13 , wherein the first ethylene interpolymer is produced using a first homogeneous catalyst formulation.

16. The ethylene interpolymer product according to claim 15 , wherein the first homogeneous catalyst formulation is a bridged metallocene catalyst formulation.

17. The ethylene interpolymer product according to claim 16 , wherein the bridged metallocene catalyst formulation comprises a component A defined by Formula (I):

wherein M is a metal selected from titanium, hafnium, and zirconium; G is the element carbon, silicon, germanium, tin, or lead; X represents a halogen atom; each R 6 group is independently selected from a hydrogen atom, a C 1-20 hydrocarbyl radical, a C 1-20 alkoxy radical, or a C 6-10 aryl oxide radical, these radicals may be linear, branched or cyclic or further substituted with halogen atoms, C 1-10 alkyl radicals, C 1-10 alkoxy radicals, C 6-10 aryl or aryloxy radicals; R 1 is a hydrogen atom, a C 1-20 hydrocarbyl radical, a C 1-20 alkoxy radical, or a C 6-10 aryl oxide radical; R 2 and R 3 are independently selected from a hydrogen atom, a C 1-20 hydrocarbyl radical, a C 1-20 alkoxy radical, or a C 6-10 aryl oxide radical; and R 4 and R 5 are independently selected from a hydrogen atom, a C 1-20 hydrocarbyl radial, a C 1-20 alkoxy radical, or a C 6-10 aryl oxide radical.

18. The ethylene interpolymer product according to claim 17 , wherein the second ethylene interpolymer is produced using a first heterogeneous catalyst formulation.

19. The ethylene interpolymer product according to claim 18 , wherein the optional third ethylene interpolymer is produced using the first heterogeneous catalyst formulation or a second heterogeneous catalyst formulation.

20. The ethylene interpolymer product according to claim 19 , wherein the first and the second heterogeneous catalyst formulations are a first and a second in-line Ziegler-Natta catalyst formulation; optionally, the first and the second in-line Ziegler-Natta catalyst formulations are the same formulation.

21. The ethylene interpolymer product according to claim 19 , wherein the first and the second heterogeneous catalyst formulations are a first and a second batch Ziegler-Natta catalyst formulation; optionally, the first and the second batch Ziegler-Natta catalyst formulations are the same formulation.

22. The ethylene interpolymer product according to claim 18 , wherein the optional third ethylene interpolymer is produced using a fifth homogeneous catalyst formulation.

23. The ethylene interpolymer product according to claim 22 , wherein the fifth homogeneous catalyst formulation is the bridged metallocene catalyst formulation, a third homogeneous catalyst formulation, or a fourth homogeneous catalyst formulation.

24. The ethylene interpolymer product according to claim 23 , wherein the third homogeneous catalyst formulation is an unbridged single site catalyst formulation comprising a component C defined by Formula (II)
(L A ) a M(Pl) b (Q) n    (II)

wherein M is a metal selected from titanium, hafnium, and zirconium; L A is selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyland substituted fluorenyl; 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 the 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

Assignees

• Nova Chem Int Sa

Inventors

• Zhang Zengrong
• Kazemi Niousha
• Salomons Stephen
• Kleczek Monika
• Keshtkar Mehdi
• Molloy Brian
• Wang Qinyan
• Zoricak Peter
• Carter Charles
• Wang Xiaochuan
• Dobbin Christopher
• Sibtain Fazle
• Taylor Kenneth
• Vanasseldonk Lawrence
• Khakdaman Hamidreza

Classifications

• C08L2207/07

  Long chain branching · CPC title

• C08L2203/16

  used for films · CPC title

• C08F2410/01

  Additive used together with the catalyst, excluding compounds containing Al or B · CPC title

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title