CATALYST SYSTEM FOR MULTI-BLOCK COPOLYMER FORMATION

• US 20200131283A1
• Filed: 03/14/2018
• Published: 04/30/2020
• Est. Priority Date: 03/15/2017
• Status: Active Grant

• Current Assignee: Dow Global Technologies LLC (Dow, Inc.)
• Original Assignee: Dow Global Technologies LLC (Dow, Inc.)
• Inventors: Young, Andrew, Do, Hien Q., Bailey, Brad C., Christianson, Matthew D., Munro, Jeffrey C., Camahan, Edmund M.
• Granted Patent: US 11,459,409 B2
• Time in Patent Office: Days
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2410/01 Additive used together with the catalyst, excluding compounds containing Al or B
• CPC Class Codes: C08F 2410/04 Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
• CPC Class Codes: C08F 2500/08 Low density, i.e. < 0.91 g/cm3
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 297/086 the block polymer contains at least three blocks
• CPC Class Codes: C08F 4/64044 NN
• CPC Class Codes: C08F 4/64172 Neutral ligand
• CPC Class Codes: C08F 4/64193 OOOO

Abstract

The present disclosure relates to a catalyst system for use in forming a multi-block copolymer, said copolymer containing therein two or more segments or blocks differing in chemical or physical properties, a polymerization process using the same, and the resulting polymers, wherein the composition comprises the admixture or reaction product resulting from combining: (A) a first olefin polymerization procatalyst, (B) a second olefin polymerization procatalyst capable of preparing polymers differing in chemical or physical properties from the polymer prepared by procatalyst (A) under equivalent polymerization conditions, (C) an activator, and (D) a chain shuttling agent.

Claims

1. An olefin polymerization catalyst system comprising:

(A) a first olefin polymerization procatalyst,

(B) a second olefin polymerization procatalyst, and

(C) a chain shuttling agent,

wherein the second olefin polymerization procatalyst comprises a metal-ligand complex of Formula (I);

2. The catalyst system of claim 1, further comprising (D) an activator.

3. The catalyst system of claim 1, wherein each Z1 independently is Me, Bn, or Cl.

4. The catalyst system of claim 1, wherein Q¹ and Q¹⁰ are substituted phenyl groups, as shown in Formula (II):

5. The catalyst system of claim 4, wherein J¹, J⁵, J⁶ and J¹⁰ are each independently selected from the group consisting of halogen atoms, (C₁-C₈)alkyl groups, and (C₁-C₈)alkoxyl groups.

6. The catalyst system of claim 1, wherein Q⁵ and Q⁶ are each independently (C₁-C₄₀) primary or secondary alkyl groups.

7. The catalyst system of claim 1, wherein Q⁵ and Q⁶ are each independently propyl, isopropyl, neopentyl, hexyl, and benzyl.

8. The catalyst system of claim 1, wherein said metal-ligand complex of Formula (I) is selected from the group consisting of:

9. The catalyst system of claim 1, wherein M is zirconium or hafnium.

10. The catalyst system of claim 1, wherein the first olefin polymerization procatalyst (A) and the second olefin polymerization procatalyst (B) have respective reactivity ratios r_1A and r_1B, such that the ratio (r_1A/r_1B) under polymerization conditions is 0.5 or less.

11. The catalyst system of claim 1, wherein the first olefin polymerization procatalyst (A) comprises a metal-ligand complex of Formula (III):

12. The catalyst system of claim 1, wherein said metal-ligand complex of Formula (III) has the following structure:

13. The catalyst system of claim 1, wherein said metal-ligand complex of Formula (III) has the following structure:

14. The catalyst system of claim 1, wherein said metal-ligand complex of Formula (III) is selected from the group consisting of:

15. A process for preparing a multi-block copolymer comprising contacting one or more addition polymerizable monomers under addition polymerization conditions with a catalyst system according to claim 1, wherein the process is a continuous solution process carried out at a temperature of greater than 125°

C.

16. The process of claim 15, wherein the process is carried out at a temperature of about 150°

C. and comprises a combined catalyst efficiency of above 400 kg_polymer/g_metal.

17. The process of claim 15, wherein the process is carried out at a temperature from about 150°

C. to about 170°

C. and comprises a combined catalyst efficiency of above 200 kg_polymer/g_metal.

18. A multi-block copolymer prepared by the process according to claim 15, wherein the multi-block copolymer comprises, in polymerized form, ethylene and one or more copolymerizable comonomers, said copolymer containing therein two or more segments or blocks differing in comonomer content, crystallinity, tacticity, homogeneity, density, melting point or glass transition temperature.

19. The multi-block copolymer of claim 18, wherein the copolymer comprises a molecular weight distribution, Mw/Mn, of less than 3.0.

20. The multi-block copolymer of claim 18, wherein the copolymer comprises a melt index of less than 1.0 (ASTM D 1238 (190°

C./2.16 kg)).

21. (canceled)