IP Library Granted Patent US 7,645,715
Granted Patent B2
US 7,645,715 · App. 11/738,697 · Granted Jan 12, 2010

Bis-arylaryloxy catalytic system for producing ethylene homopolymers or ethylene copolymers with alpha-olefins

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Quick Facts
Patent No.
US 7,645,715
App. No.
11/738,697
Granted
Jan 12, 2010
Kind
B2
Abstract

The present invention relates to a bis-arylaryloxy catalyst system for the production of ethylene homopolymers or copolymers with α-olefins, which has high catalytic activity. More particularly, it relates to a transition metal catalyst comprising a group-IV transition metal as a central metal, a cyclopentadiene derivative around the central metal, and two aryloxide ligands substituted with aryl derivatives at the ortho-positions, the ligands not being bridged to each other, as well as a catalyst system comprising said catalyst and an aluminoxane co-catalyst or a boron compound co-catalyst, and a method for producing high-molecular-weight ethylene homopolymers or copolymers with α-olefins using the same.

Claims (14)

1. A bis-arylaryloxy transition metal catalyst shown in Formula 1, which comprises a cyclopentadienyl group containing ligand around a transition metal and two aryloxide ligands substituted with aryl derivatives at the ortho-positions, the ligands not being bridged to each other:

wherein M is a group-IV transition metal in the periodic table; Cp is cyclopentadienyl or a derivative thereof, which forms an η 5 bond with the central metal; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 on the arylphenoxide ligands are each independently a hydrogen atom, a halogen atom, a C1-C20 linear or nonlinear alkyl group optionally substituted with at least one halogen atoms, a silyl group containing a C1-C20 linear or nonlinear alkyl group optionally substituted with at least one halogen atoms, a C6-C30 aryl group optionally substituted with at least one halogen atom, a C7-C30 arylalkyl group optionally substituted with at least one halogen atom, an alkoxy group having a C1-C20 linear or nonlinear alkyl group optionally substituted with at least one halogen atoms, a siloxy group having C3-C20 alkyl or C6-C20 aryl, an amido or phosphido group having a C1-C20 hydrocarbon group, or a mercapto group having C1-C20 alkyl, or a nitro group, and these substituents ma y also optionally bind to each other to form a ring; and X is selected from the group consisting of an halogen atom, a C1-C20 alkyl group other than a Cp derivative, a C7-C30 arylalkyl group, an alkoxy group having a C1-C20 alkyl group, a siloxy group substituted with C3-C20 alkyl, and an amido group having a C1-C20 hydrocarbon group.

2. The bis-arylaryloxy transition metal catalyst of claim 1 , wherein said M is titanium.

3. The bis-arylaryloxy transition metal catalyst of claim 1 , wherein said Cp is selected from among cyclopentadienyl and pentamethylcyclopentadienyl.

4. The bis-arylaryloxy transition metal catalyst of claim 1 , wherein said R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 R 8 and R 9 on the arylphenoxide ligands are each individually selected from among a hydrogen atom, a methyl group and an isopropyl group.

5. The bis-arylaryloxy transition metal catalyst of claim 1 , wherein said X is selected from among a chlorine atom, a methyl group, a methoxy group, an isopropoxy group and a dimethylamino group.

6. A bis-arylaryloxy catalyst system for producing ethylene homopolymers or ethylene and α-olefin copolymers, comprising: a bis-arylaryloxy transition metal catalyst of Formula 1 containing a cyclopentadienyl group containing ligand around a transition metal and two aryloxide ligands substituted with aryl derivatives at the ortho-positions, the ligands not being bridged to each other; and an aluminoxane co-catalyst or a boron compound cocatalyst:

wherein M is a group-IV transition metal in the periodic table; Cp is cyclopentadienyl or a derivative thereof, which forms an η 5 bond with the central metal; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 on the arylphenoxide ligands are each independently a hydrogen atom, a halogen atom, a C1-C20 linear or nonlinear alkyl group optionally substituted with at least one halogen atoms, a silyl group containing a C1-C20 linear or nonlinear alkyl group optionally substituted with at least one halogen atoms, a C6-C30 aryl group optionally substituted with at least one halogen atom, a C7-C30 arylalkyl group optionally substituted with at least one halogen atom, an alkoxy group having a C1-C20 linear or nonlinear alkyl group optionally substituted with at least one halogen atom, a siloxy group having C3-C20 alkyl or C6-C20 aryl, an amido or phosphido group having a C1-C20 hydrocarbon group, or a mercapto group having C1-C20 alkyl, or a nitro group, and these substituents ma y also optionally bind to each other to form a ring; and X is selected from the group consisting of an halogen atom, a C1-C20 alkyl group other than a Cp derivative, a C7-C30 arylalkyl group, an alkoxy group having a C1-C20 alkyl group, a siloxy group substituted with C3-C20 alkyl, and an amido group having a C1-C20 hydrocarbon group.

7. The bis-arylaryloxy catalyst system of claim 6 , wherein the aluminoxane cocatalyst is methylaluminoxane, and is used in a molar ratio of central metal:aluminum of 1:50 to 1:5,000.

8. The bis-arylaryloxy catalyst system of claim 6 , wherein the boron compound co-catalyst is selected from among N,N-dimethylanilinium tetrakispentafluorophenylborate and triphenylmethylanilinium tetrakispentafluorophenylborate.

9. The bis-arylaryloxy catalyst system of claim 6 , wherein the boron compound co-catalyst is used in a mixture with aluminoxane or organoalkylaluminum such that the molar ratio of central metal:boron atom:aluminum atom is 1:0.5-5: 25-500.

10. The bis-arylaryloxy catalyst system of claim 9 , wherein the aluminoxane is methylaluminoxane, and the organoalkylaluminium is selected from among triethylaluminum and triisobutylaluminum.

11. A method for producing a copolymer of ethylene with α-olefin using the bisarylaryloxy catalyst system of claim 6 , in which the comonomer α-olefin for polymerization with ethylene is at least one selected from the group consisting of 1-butene, 1-hexene, 1-octene, and 1-decene, and the content of ethylene in the ethylene/α-olefin copolymer is more than 60 wt %.

12. A method for producing an ethylene homopolymer or an ethylene copolymer with α-olefin using the bis-arylaryloxy transition metal catalyst of claim 1 , in which the pressure of the ethylene monomer in a reactor is 10-150 atm, and the polymerization of the ethylene monomer is conducted at 80-250° C.

Assignments (3)
CORRECTIVE ASSIGNMENT TO CORRECT THE INCORRECT PATENT NUMBER 7448700 AND REPLACE IT WITH 7488700 PREVIOUSLY RECORDED ON REEL 026619 FRAME 0330. ASSIGNOR(S) HEREBY CONFIRMS THE CHANGE OF NAME. Recorded Apr 11, 2016
From: SK ENERGY CO., LTD.
To: SK INNOVATION CO., LTD.
Reel/Frame 038406/0201 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 23, 2015
From: SK INNOVATION CO., LTD.
To: SABIC SK NEXLENE COMPANY PTE. LTD.
Reel/Frame 036635/0906 →
CHANGE OF NAME Recorded Jul 14, 2011
From: SK ENERGY CO., LTD.
To: SK INNOVATION CO., LTD.
Reel/Frame 026619/0330 →