# US 10,501,563 B2 · Method of preparing supported metallocene catalyst

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- Number: US 10,501,563 B2
- Document ID: US10501563B2
- Status: Granted
- Kind: B2
- Application number: 15/566,098
- Filed: 2016-06-13
- Published: 2018-04-05
- Granted: 2019-12-10
- Earliest claimed: 2015-06-15
- Assignees: LG Chem, Ltd.
- Applicants: LG Chem, Ltd.
- Inventors: Young Suk You; Kyung Jin Cho; Hyuck Ju Kwon; Yi Young Choi; Ki Soo Lee; Eun Kyoung Song; Woo Ri Kim
- Web page: https://patentgrep.com/patent/US10501563B2

## CPC

- C08F 4/6592: containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F 2/38: Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation}
- C08F 4/02: Carriers therefor
- C08F 10/02: Ethene
- C08F 10/06: Propene
- C08F 10/14: Monomers containing five or more carbon atoms
- C08F 110/02: Ethene
- C07F 7/00: Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C08F 2/06: Organic solvent
- C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 4/65925: {two cyclopentadienyl rings being mutually non-bridged}
- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- 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 2420/04: Cp or analog not bridged to a non-Cp X ancillary anionic donor
- C08F 2420/06: Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom
- 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: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

A method of preparing a supported metallocene catalyst capable of more effectively preparing a polyolefin which may be preferably used for blow molding, etc., because its molecular weight distribution is such that polymer elasticity is increased to improve swell, is provided.

## Claims

### Claim 1

A method of preparing a supported metallocene catalyst, comprising:
preparing a molecular weight modifier composition by mixing a cyclopentadienyl metal compound of the following Chemical Formula 1 and an organic aluminum compound of the following Chemical Formula 2 and stirring a resulting mixture at room temperature for 50 hours to 108 hours; and
supporting one or more metallocene compounds represented by any one of the following Chemical Formulae 3 to 6 and the molecular weight modifier composition on a support,
wherein the molecular weight modifier composition is supported in an amount of about 1 mol % to 85 mol %, based on the total weight of the metallocene compound:
(R1—Cp1)(R2-Cp2)M4X2 Chemical Formula 1
in Chemical Formula 1,
Cp1 and Cp2 are each independently a ligand comprising a cyclopentadienyl group, an indenyl group, or a fluorenyl group; R1 and R2 are substituents of Cp1 and Cp2, and are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a heteroalkenyl group having 2 to 20 carbon atoms, a heteroalkylaryl group having 6 to 20 carbon atoms, a heteroarylalkyl group having 6 to 20 carbon atoms, or a heteroaryl group having 5 to 20 carbon atoms; M4 is a Group 4 transition metal element; and X is a halogen,
R3R4R5Al Chemical Formula 2
in Chemical Formula 2,
R3, R4, and R5 are each independently an alkyl group having 4 to 20 carbon atoms or a halogen, and at least one of R3, R4, and R5 is an alkyl group having 4 to 20 carbon atoms,
(Cp5Ra)n(Cp6Rb)M1Z13-n Chemical Formula 3
in Chemical Formula 3,
M1 is a Group 4 transition metal;
Cp5 and Cp6 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 radicals-which are optionally substituted with a 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 to C20 alkyl, a C1 to C10 alkoxy, a C2 to C20 alkoxyalkyl, a C6 to C20 aryl, a C6 to C10 aryloxy, a C2 to C20 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C8 to C40 arylalkenyl, or a C2 to C10 alkynyl;
Z1 is a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene, a substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy; and
n is 1 or 0,
(Cp7Rc)mB1(Cp8Rd)M2Z23-m Chemical Formula 4
in Chemical Formula 4,
M2 is a Group 4 transition metal;
Cp7 and Cp8 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 radicals, and these are substituted with a 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 to C20 alkyl, a C1 to C10 alkoxy, a C2 to C20 alkoxyalkyl, a C6 to C20 aryl, a C6 to C10 aryloxy, a C2 to C20 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C8 to C40 arylalkenyl, or a C2 to C10 alkynyl;
Z2 is a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene, a substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;
B1 is any one or more of carbon, germanium, silicon, phosphorus, or nitrogen atom-containing radicals, which crosslink a Cp3Rc ring and a Cp4Rd ring or crosslink one Cp4Rd ring to M2, or a combination thereof; and
m is 1 or 0,
(Cp9Re)B2(J)M3Z32 Chemical Formula 5
in Chemical Formula 5,
M3 is a Group 4 transition metal;
Cp9 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, and these are substituted with a hydrocarbon having 1 to 20 carbon atoms;
Re is hydrogen, a C1 to C20 alkyl, a C1 to C10 alkoxy, a C2 to C20 alkoxyalkyl, a C6 to C20 aryl, a C6 to C10 aryloxy, a C2 to C20 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C8 to C40 arylalkenyl, or a C2 to C10 alkynyl;
Z3 is a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene, a substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;
B2 is any one or more of carbon, germanium, silicon, phosphorus, or nitrogen atom-containing radicals, which crosslink a Cp5Re ring to J, or a combination thereof;
J is any one selected from the group consisting of NRf, O, PRf and S; and Rf is a C1 to C20 alkyl, aryl, substituted alkyl, or substituted aryl,
in Chemical Formula 6,
A is hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
D is —O—, —S—, —N(R)—, or —Si(R)(R′)—, in which R and R′ are the same as or different from each other, and are each independently hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;
L is a C1 to C10 straight or branched alkylene group;
B is carbon, silicon, or germanium;
Q is hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;
M is a Group 4 transition metal;
X1 and X2 are the same as or different from each other, and are each independently a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group, a C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;
C1 and C2 are the same as or different from each other, and are each independently represented by any one of the following Chemical Formula 7a, Chemical Formula 7b, and Chemical Formula 7c, excluding that both C1 and C2 are Chemical Formula 7c,
in Chemical Formulae 7a, 7b, and 7c,
R1 to R17 and R1′ to R9′ are the same as or different from each other, and are each independently hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, and two or more neighboring groups of R10 to R17 are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

### Claim 2 (depends on 1)

The method of preparing the supported metallocene catalyst of claim 1, wherein the supporting is performed by mixing the support, the metallocene catalyst, and the molecular weight modifier composition, and stirring a resulting mixture at a temperature of 30° C. to 100° C. for 1 hour to 12 hours.

### Claim 3 (depends on 1)

The method of preparing the supported metallocene catalyst of claim 1, wherein R1 and R2 in Chemical Formula 1 are each independently selected from the group consisting of hydrogen, methyl, ethyl, butyl, and t-butoxy hexyl.

### Claim 4 (depends on 1)

The method of preparing the supported metallocene catalyst of claim 1, wherein R3, R4, and R5 in Chemical Formula 2 are each independently an isobutyl group.

### Claim 5 (depends on 1)

The method of preparing the supported metallocene catalyst of claim 1, wherein M4 in Chemical Formula 1 is selected from the group consisting of titanium, zirconium, and hafnium.

### Claim 6 (depends on 1)

The method of preparing the supported metallocene catalyst of claim 1, wherein the molecular weight modifier composition comprises a compound represented by the following Chemical Formula 8, Chemical Formula 9, Chemical Formula 10, or Chemical Formula 11:

### Claim 7 (depends on 1)

The method of preparing the supported metallocene catalyst of claim 1, wherein the support is selected from the group consisting of silica, silica-alumina, and silica-magnesia.

### Claim 8 (depends on 1)

The method of preparing the supported metallocene catalyst of claim 1, wherein the support is one on which a first aluminum-containing cocatalyst of the following Chemical Formula 12 is supported:
-[-Al(R18)—O-]n- Chemical Formula 12
in Chemical Formula 12,
each R18 is independently a halogen, or a halogen-substituted or unsubstituted hydrocarbyl having 1 to 20 carbon atoms, and n is an integer of 2 or more.

### Claim 9 (depends on 8)

The method of preparing the supported metallocene catalyst of claim 8, wherein the molecular weight modifier composition is supported immediately after supporting the metallocene compound onto the first cocatalyst-supported support.

### Claim 10 (depends on 1)

The method of preparing the supported metallocene catalyst of claim 1, wherein a second borate-based cocatalyst of the following Chemical Formula 13 is further supported:
T+[BQ4]− Chemical Formula 13
in Chemical Formula 13,
T+ is a positive monovalent (+1) polyatomic ion, B is boron having an oxidation state of +3, each Q is independently selected from the group consisting of a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryloxide group, a hydrocarbyl group, a halocarbyl group, and a halo-substituted hydrocarbyl group, in which Q has 20 or fewer carbon atoms, provided that only one or fewer of Q is a halide group.

### Claim 11 (depends on 1)

A method of preparing a polyolefin, comprising polymerizing olefinic monomers in the presence of the supported metallocene catalyst prepared according to claim 1.

### Claim 12 (depends on 11)

The method of preparing the polyolefin of claim 11, wherein the polymerizing of olefinic monomers is performed by slurry polymerization of olefinic monomers in the presence of a supported metallocene catalyst which is obtained by supporting a metallocene compound on a support, together with a molecular weight modifier composition comprising a reaction product of a cyclopentadienyl metal compound and an organic aluminum compound.

### Claim 13 (depends on 11)

The method of preparing the polyolefin of claim 11, wherein the olefinic monomer comprises one or more monomers selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undencene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.