# US 2019/0169323 A1 · High-processability high-density ethylene-based polymer using hybrid supported metallocene catalyst, and preparation method therefor

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- Number: US 2019/0169323 A1
- Document ID: US20190169323A1
- Status: Published application
- Kind: A1
- Application number: 16/321,114
- Filed: 2017-04-07
- Published: 2019-06-06
- Earliest claimed: 2016-07-28
- Assignees: Hanwha Chemical Corporation
- Applicants: Hanwha Chemical Corporation
- Inventors: In Jun LEE; Won Jun KANG; Dong Ok KIM; Song Hee YANG; Sung Woo LEE; Dong Wook JEONG; Ui Gab JOUNG
- Web page: https://patentgrep.com/patent/US20190169323A1

## CPC

- C08F 4/65904: {in combination with another component of C08F4/64}
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- B01J 31/38: of titanium, zirconium or hafnium
- C07F 17/00: Metallocenes
- C08F 4/646: Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 {(C08F4/64003 - C08F4/64196 take precedence)}
- C08F 4/654: with magnesium or compounds thereof
- C08F 4/659: Component covered by group C08F4/64 containing a transition metal-carbon bond {(C08F4/64003 - C08F4/64196 take precedence)}
- C08F 10/02: Ethene
- C08F 210/02: Ethene
- C08L 23/0815: {with aliphatic 1-olefins containing one carbon-to-carbon double bond}
- B01J 2231/12: Olefin polymerisation or copolymerisation
- B01J 2531/0225: Complexes comprising pentahapto-cyclopentadienyl analogues
- B01J 2531/46: Titanium
- B01J 2531/48: Zirconium
- B01J 2531/49: Hafnium
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 2500/12: Melt flow index or melt flow ratio
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

The present invention relates to a high-density ethylene-based polymer comprising an ethylene homopolymer or a copolymer of ethylene and at least one comonomer selected from the group consisting of an α-olefin, a cyclic olefin, and a straight, branched and cyclic diene. According to the present invention, the high-density polyethylene resin has a wide molecular weight distribution and excellent comonomer distribution characteristics, has excellent melt flowability due to a long chain branched structure, and has excellent mechanical characteristics since the comonomer distribution is concentrated in a high-molecular-weight body. The high-density ethylene polymer of the present invention has excellent molding processability during processing such as extrusion, compression, injection and rotational molding by having excellent mechanical characteristics and melt flowability.

## Claims

### Claim 1

A high-density ethylene-based polymer prepared by polymerizing ethylene and at least one monomer selected from the group consisting of α-olefin-based monomers,
wherein a density is 0.930 g/cm3 to 0.970 g/cm3,
an MI is 0.1 g/10 min to 50 g/10 min,
an MFR is 35 to 100, and
a characteristic relaxation time (λ) is 0.3 s to 2.0 s at 190° C.

### Claim 2 (depends on 1)

The high-density ethylene-based polymer according to claim 1, wherein a relationship between the MI and the characteristic relaxation time (λ) is expressed by Equation 1:
−0.445In(MI)+3.6.23>λ,>−0.323In(MI)+0.696. [Equation 1]

### Claim 3 (depends on 1)

The high-density ethylene-based polymer according to claim 1, wherein the polymer includes a long chain branch (LCB).

### Claim 4 (depends on 1)

The high-density ethylene-based polymer according to claim 1, wherein the α-olefin-based monomer comprises at least one selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-aitosen.

### Claim 5 (depends on 1)

The high-density ethylene-based polymer according to claim 1, wherein, when the high-density ethylene-based polymer is a copolymer of the ethylene and the α-olefin-based monomer, a content of the α-olefin monomer is 0.1 wt % to 10 wt %.

### Claim 6 (depends on 1)

The high-density ethylene-based polymer according to claim 1, wherein the ethylene-based polymer is a material for injection molding, compression molding, or rotational molding.

### Claim 7 (depends on 1)

The high-density ethylene-based polymer according to claim 1, wherein the high-density ethylene-based polymer is polymerized by using a catalyst comprising at least one first metallocene compound represented by Formula 1, at least one second metallocene compound represented by Formula 2, at least one cocatalyst compound, and a carrier:
wherein, in Formula 1,
M1 is a group 4 transition metal of the periodic table of the elements,
X1 and X2 are each independently a halogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, a C7-C40 alkylaryl group, a C7-C40 arylalkyl group, a C1-C20 alkylamido group, a C6-C20 arylamido group, or a C1-C20 alkylidene group,
R1 to R12 are each independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C7-C40 alkylaryl group, a substituted or unsubstituted C7-C40 arylalkyl group, or a substituted or unsubstituted C1-C20 silyl group and are linked to each other to form a ring,
cyclopentadiene linked to R1 to R5 and indene linked to R6 to R12 have an asymmetric structure having different structures, and
the cyclopentadiene and the indene are not linked to each other to form a non-bridge structure:
wherein, in Formula 2,
M2 is a group 4 transition metal of the periodic table of the elements,
X3 and X4 are each independently a halogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, a C7-C40 alkylaryl group, a C7-C40 arylalkyl group, a C1-C20 alkylamido group, a C6-C20 arylamido group, or a C1-C20 alkylidene group,
R13 to R18 are each independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C7-C40 alkylaryl group, a substituted or unsubstituted C7-C40 arylalkyl group, or a substituted or unsubstituted C1-C20 silyl group and are linked to each other to form a ring,
R21 to R26 are each independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C7-C40 alkylaryl group, a substituted or unsubstituted C7-C40 arylalkyl group, or a substituted or unsubstituted C1-C20 silyl group and are linked to each other to form a ring,
R19 and R20 are each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C7-C40 alkylaryl group, a substituted or unsubstituted C7-C40 arylalkyl group, or a substituted or unsubstituted C1-C20 silyl group and are linked to each other to form a ring,
indene linked to R13 to R18 and indene linked to R21 to R26 have the same structure or different structures, and
the indene linked to R13 to R18 and the indene linked to R21 to R26 are linked to Si to form a bridge structure.

### Claim 8 (depends on 7)

The high-density ethylene-based polymer according to claim 7, wherein the first metallocene compound comprises at least one compound selected from the group consisting of compounds having the following structures:

### Claim 9 (depends on 7)

The high-density ethylene-based polymer according to claim 7, wherein the second metallocene compound comprises at least one compound selected from the group consisting of compounds having the following structures:

### Claim 10 (depends on 7)

The high-density ethylene-based polymer according to claim 7, wherein the cocatalyst compound comprises compounds represented by Formulae 3 to 6:
wherein, in Formula 3,
AL is aluminum,
R27 is a halogen atom, a C1-C20 hydrocarbon group, or a C1-C20 hydrocarbon group substituted with halogen, and
a is an integer of 2 or more:
wherein, in Formula 4,
Al is aluminum or boron, and
R28 is a halogen atom, a C1-C20 hydrocarbon group, a C1-C20 hydrocarbon group substituted with halogen, or a C1-C20 alkoxy:
[L1-H]+[Z1(A2)4]− [Formula 5]
[L2]+[Z2(A3)4]− [Formula 6]
wherein, in Formulae 5 and 6,
L1 and L2 are neutral or cationic Lewis acids,
Z1 and Z2 are group 13 elements of the periodic table of the elements, and
A2 and A3 are a substituted or unsubstituted C6-C20 aryl group or a substituted or unsubstituted C1-C20 alkyl group.

### Claim 11 (depends on 10)

The high-density ethylene-based polymer according to claim 10, wherein the cocatalyst compound represented by Formula 3 comprises at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane.

### Claim 12 (depends on 10)

The high-density ethylene-based polymer according to claim 10, wherein the cocatalyst compound represented by Formula 4 comprises at least one compound selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminummethoxide, dimethylaluminumethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and tripentafluorophenylboron.

### Claim 13 (depends on 10)

The high-density ethylene-based polymer according to claim 10, wherein the cocatalyst compound represented by Formula 5 or 6 each independently comprises at least one selected from the group consisting of methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(phenyl)borate, triethylammonium tetrakis(phenyl)borate, tripropylammonium tetrakis(phenyl)borate, tributylammonium tetrakis(phenyl)borate, trimethylammonium tetrakis(p-tolyl)borate, tripropylammonium tetrakis(p-tolyl)borate, trimethylammonium tetrakis(o,p-dimethylphenyl)borate, triethylammonium tetrakis(o,p-dimethylphenyl)borate, trimethylammonium tetrakis(p-trifluoromethylphenyl)borate, tributylammonium tetrakis(p-trifluoromethylphenyl)borate, tributylammonium tetrakis(pentafluorophenyl)borate, diethylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(phenyl)borate, trimethylphosphonium tetrakis(phenyl)borate, N,N-diethylanilinium tetrakis(phenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbonium tetrakis(p-trifluoromethylphenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(phenyl)aluminate, triethylammonium tetrakis(phenyl)aluminate, tripropylammonium tetrakis(phenyl)aluminate, tributylammonium tetrakis(phenyl)aluminate, trimethylammonium tetrakis(p-tolyl)aluminate, tripropylammonium tetrakis(p-tolyl)aluminate, triethylammonium tetrakis(o,p-dimethylphenyl)aluminate, tributylammonium tetrakis(p-trifluoromethylphenyl)aluminate, trimethylammonium tetrakis(p-trifluoromethylphenyl)aluminate, tributylammonium tetrakis(pentafluorophenyl)aluminate, N,N-diethylanilinium tetrakis(phenyl)aluminate, N,N-diethylanilinium tetrakis(phenyl)aluminate, N,N-diethylanilinium tetrakis(pentafluorophenyl)aluminate, diethylammonium tetrakis(pentafluorophenyl)aluminate, triphenylphosphonium tetrakis(phenyl)aluminate, trimethylphosphonium tetrakis(phenyl)aluminate, triethylammonium tetrakis(phenyl)aluminate, and tributylammonium tetrakis(phenyl)aluminate.

### Claim 14 (depends on 7)

The high-density ethylene-based polymer according to claim 7, wherein a ratio of a total mass of a transition metal of the first metallocene compound and a transition metal of the second metallocene compound to a mass of the carrier is 1:1 to 1:1,000, and a mass ratio of the first metallocene compound to the second metallocene compound is 1:100 to 100:1.

### Claim 15 (depends on 10)

The high-density ethylene-based polymer according to claim 10, wherein a mass ratio of the cocatalyst compound represented by Formulae 3 and 4 to the carrier is 1:100 to 100:1, and
a mass ratio of the cocatalyst compound represented by Formulae 5 and 6 to the carrier is 1:20 to 20:1, and

### Claim 16 (depends on 7)

The high-density ethylene-based polymer according to claim 7, wherein the carrier comprises at least one selected from the group consisting of silica, alumina, titanium oxide, zeolite, zinc oxide, and starch,
the carrier has an average particle size of 10 microns to 250 microns,
the carrier has a microporous volume of 0.1 cc/g to 10 cc/g, and
the carrier has a specific surface area of 1 m2/g to 1,000 m2/g.

### Claim 17 (depends on 7)

A method for preparing a high-density ethylene-based polymer, further comprising adding the hybrid supported catalyst according claim 7, at least one α-olefin monomer selected from the group consisting of α-olefins, and ethylene to an autoclave reactor or a gas phase polymerization reactor, and polymerizing a high-density ethylene-based polymer in an environment in which a temperature is 0° C. to 120° C. and a pressure is 1 bar to 150 bar.

### Claim 18 (depends on 17)

The high-density ethylene-based polymer according to claim 17, wherein the α-olefin monomer comprises at least one selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-aitosen.