# US 10,870,712 B2 · Method for preparing polyolefin

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- Number: US 10,870,712 B2
- Document ID: US10870712B2
- Status: Granted
- Kind: B2
- Application number: 15/552,658
- Filed: 2016-06-10
- Published: 2018-02-08
- Granted: 2020-12-22
- Earliest claimed: 2015-06-15
- Assignees: LG Chem, Ltd.
- Applicants: LG Chem, Ltd.
- Inventors: Eun Kyoung Song; Yong Ho Lee; Kyung Jin Cho; Yi Young Choi; Ki Soo Lee; Heon Yong Kwon; Young Suk You
- Web page: https://patentgrep.com/patent/US10870712B2

## CPC

- C08F 4/61922: {containing at least two cyclopentadienyl rings, fused or not}
- C08F 110/02: Ethene
- C08F 4/02: Carriers therefor
- C08F 4/649: organic
- C08F 4/659: Component covered by group C08F4/64 containing a transition metal-carbon bond {(C08F4/64003 - C08F4/64196 take precedence)}
- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 2410/01: Additive used together with the catalyst, excluding compounds containing Al or B
- C08F 2410/03: Multinuclear procatalyst, i.e. containing two or more metals, being different or not
- C08F 2420/02: Cp or analog bridged to a non-Cp X anionic donor
- C08F 2420/07: Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom
- C08F 2420/10: Heteroatom-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by at least one group that contains a heteroatom
- C08F 2500/04: Broad molecular weight distribution, i.e. Mw/Mn > 6
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

The present invention provides a method for preparing a polyolefin having a broad molecular weight distribution. More specifically, the present invention provides a method for preparing a polyolefin having a broad molecular weight distribution and an ultra-high molecular weight in which an organometallic complex containing a specific Ti—Al complex structure is used as a molecular weight controller (i.e., molecular weight enhance) in the polymerization of an olefin monomer, thereby enabling both solution polymerization and slurry polymerization, particularly enabling the molecular weight distribution to be more readily and effectively controlled.

## Claims

### Claim 1

A method for preparing a polyolefin comprising:
providing a metallocene catalyst comprising a metallocene compound, a cocatalyst and a compound of Chemical Formula 1, which are supported on a support selected from the group consisting of silica, silica-alumina, and silica-magnesia in a single solvent-containing reactor, and
polymerizing an olefin monomer in the presence of the metallocene catalyst:
wherein, in Chemical Formula 1, R1 to R10 are each independently hydrogen, a linear or branched alkyl, alkoxy or alkoxyalkyl having 1 to 10 carbon atoms,
R11 is a linear or branched alkylene group having 1 to 10 carbon atoms, or halogen,
R12 and R13 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, or halogen, and
X is a halogen atom,
wherein, in the metallocene catalyst, the compound of Chemical Formula 1 is included in a molar ratio of 0.05 to 1 with respect to 1 mole of a transition metal contained in the metallocene compound,
wherein an amount of hydroxyl group on the surface of the support is 0.1 to 10 mmol/g,
wherein a weight ratio of the total transition metal included in the metallocene compound to the support is 1:10 to 1:1,000,
wherein a weight ratio of the cocatalyst to the support is 1:1 to 1:100,
wherein the step of polymerizing the olefin monomer includes solution polymerization including a step of performing slurry polymerization including a step of injecting a metallocene-supported catalyst in which the metallocene compound, the cocatalyst and the compound of Chemical Formula 1 are supported on the support, in the reactor, and performing slurry polymerization while adding the olefin-based monomer to the reactor.

### Claim 2 (depends on 1)

The method for preparing a polyolefin according to claim 1, wherein at least one of R1 to R10 in Chemical Formula 1 is an alkoxyalkyl having 1 to 10 carbon atoms.

### Claim 3 (depends on 1)

The method for preparing a polyolefin according to claim 1, wherein at least one of R1 to R10 in Chemical Formula 1 is an alkoxyalkyl having 8 to 10 carbon atoms.

### Claim 4 (depends on 1)

The method for preparing a polyolefin according to claim 1, wherein, in Chemical Formula 1, R11 is a branched alkylene group having 4 to 10 carbon atoms, and R12 and R13 are each independently an alkyl group having 4 to 10 carbon atoms.

### Claim 5 (depends on 1)

The method for preparing a polyolefin according to claim 1, wherein the compound of Chemical Formula 1 is prepared by reacting a compound of Chemical Formula 2 with an organoaluminum compound of Chemical Formula 3 in a solvent:
wherein, in Chemical Formula 2, R1 to R10 are each independently hydrogen, a linear or branched alkyl, alkoxy or alkoxyalkyl having 1 to 10 carbon atoms, and
X is halogen;
R11R12R13Al [Chemical Formula 3]
wherein, in Chemical Formula 3,
R11, R12 and R13 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms or a halogen, and at least one of R11, R12 and R13 is a linear or branched alkyl group having 1 to 10 carbon atoms.

### Claim 6 (depends on 1)

The method for preparing a polyolefin according to claim 1, wherein the metallocene compound contained in the metallocene catalyst is selected from the compounds represented by the following Chemical Formulas 4 to 6:
(Cp1Ra)n(Cp2Rb)M1Z13-n [Chemical Formula 4]
wherein, in Chemical Formula 4,
M1 is a Group 4 transition metal;
Cp1 and Cp2 are the same as or different from each other and are each independently any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical, each of which may be substituted with hydrocarbon having 1 to 20 carbon atoms;
Ra and Rb are the same as or different from each other and are each independently hydrogen, a C1-C20 alkyl, a C1-C10 alkoxy, a C2-C20 alkoxyalkyl, a C6-C20 aryl, a C6-C10 aryloxy, a C2-C20 alkenyl, a C7-C40 alkylaryl, a C7-C40 arylalkyl, a C8-C40 arylalkenyl, or a C2-C10 alkynyl;
Z1 is a halogen atom, a C1-C20 alkyl, a C2-C10 alkenyl, a C7-C40 alkylaryl, a C1-C40 arylalkyl, a C6-C20 aryl, a substituted or unsubstituted C1-C20 alkylidene, a substituted or unsubstituted amino group, a C2-C20 alkylalkoxy, or a C7-C40 arylalkoxy; and
n is 1 or 0;
(Cp3Rc)mB1(Cp4Rd)M2Z23-m [Chemical Formula 5]
wherein, in Chemical Formula 5,
M2 is a Group 4 transition metal;
Cp3 and Cp4 are the same as or different from each other and are each independently any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical, each of which may be substituted by hydrocarbon having 1 to 20 carbon atoms;
Rc and Rd are the same as or different from each other and are each independently hydrogen, a C1-C20 alkyl, a C1-C10 alkoxy, a C2-C20 alkoxyalkyl, a C6-C20 aryl, a C6-C10 aryloxy, a C2-C10 alkenyl, a C7-C40 alkylaryl, a C7-C40 arylalkyl, a C8-C40 arylalkenyl, or a C2-C10 alkynyl;
Z2 is a halogen atom, a C1-C20 alkyl, a C2-C10 alkenyl, a C7-C40 alkylaryl, a C7-C40 arylalkyl, a C6-C20 aryl, a substituted or unsubstituted C1-C20 alkylidene, a substituted or unsubstituted amino group, a C2-C20 alkylalkoxy, or a C7-C40 arylalkoxy;
B1 is at least one of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals, or a combination thereof, which crosslinks Cp3Rc ring and Cp4Rd ring or crosslinks one Cp4Rd ring to M2; and
m is 1 or 0;
(Cp5Rc)B2(J)M3Z32 [Chemical Formula 6]
wherein, in Chemical Formula 6,
M3 is a Group 4 transition metal;
Cp5 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical, each of which may be substituted with hydrocarbon having 1 to 20 carbon atoms;
Rc is hydrogen, a C1-C20 alkyl, a C1-C10 alkoxy, a C2-C20 alkoxyalkyl, a C6-C20 aryl, a C6-C10 aryloxy, a C2-C20 alkenyl, a C7-C40 alkylaryl, a C7-C40 arylalkyl, a C8-C40 arylalkenyl, or a C2-C10 alkynyl;
Z3 is a halogen atom, a C1-C20alkyl, a C2-C10 alkenyl, a C7-C40 alkylaryl, a C7-C40 arylalkyl, a C6-C20 aryl, a substituted or unsubstituted C1-C20 alkylidene, a substituted or unsubstituted amino group, a C2-C20 alkylalkoxy, or a C7-C40 arylalkoxy;
B2 is at least one of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals, or a combination thereof, which crosslinks Cp5Rc ring and J; and
J is any one selected from the group consisting of NRf, O, PRf and S, where the Rf is C1-C20 alkyl, aryl, substituted alkyl or substituted aryl.

### Claim 7 (depends on 1)

The method for preparing a polyolefin according to claim 1, wherein the cocatalyst contained in the metallocene catalyst includes one or more selected from the group consisting of compounds represented by Chemical Formula 7:
R30—[Al(R29)—O]n—R31
wherein, in Chemical Formula 7, R29, R30 and R31 are each independently any one of hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen, and
n is an integer of 2 or more.

### Claim 8 (depends on 1)

The method for preparing a polyolefin according to claim 1, wherein the olefin-based monomer includes at least one monomer selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-decene, 1-undecene, 1-dodecene, norbornene, ethylidenenorbornene, styrene, alpha-methylstyrene and 3-chloromethylstyrene.

### Claim 9 (depends on 1)

The method for preparing a polyolefin according to claim 1, wherein the weight average molecular weight of the polyolefin is 100,000 to about 3,000,000 g/mol.

### Claim 10 (depends on 1)

The method for preparing a polyolefin according to claim 1, wherein the molecular weight distribution is 2 to 20.