High-density ethylene-based polymer using hybrid supported metallocene catalyst, and preparation method

Patent metadata

Field	Value
Publication number	US-10934375-B2
Application number	US-201716096795-A
Country	US
Kind code	B2
Filing date	Feb 10, 2017
Priority date	Apr 27, 2016
Publication date	Mar 2, 2021
Grant date	Mar 2, 2021

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 α-olefins, cyclic olefins and linear, branched and cyclic dienes. According to the present invention, the high-density ethylene-based polymer 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.

First claim

The invention claimed is:

1. A high-density ethylene-based polymer prepared by polymerizing ethylene and at least one monomer selected from the group consisting of α-olefin monomers,
wherein a density is 0.940 g/cm 3 to 0.970 g/cm 3 ,
a melt index (MI) is 0.1 g/10 min to 10 g/10 min,
a melt flow ratio MFR is 37 to 100 and satisfies Equation 1,
Izod impact strength is 4 kJ/m 2 to 30 kJ/m 2 and satisfies Equation 2,
a stress is 600,000 dyn/cm 2 to 1,000,000 dyn/cm 2 at 150° C., an elongation of 1 (1/s), and a Hencky strain of 2.5,
a broad orthogonal comonomer distribution index (BOCDI) value is 0.1 to 1, and
the high-density ethylene-based polymer has a unimodal molecular weight distribution:
−10.11ln(MI)+51.744>MFR>−12.25ln(MI)+65.457  [Equation 1]

93.655ln(MFR)−332.52>Izod impact strength>39.395ln(MFR)+140.74.  [Equation 2]

2. The high-density ethylene-based polymer of claim 1 , wherein a time for which five cracks occur in environmental stress cracking resistance measured according to ASTM D1693 in the high-density ethylene-based polymer is 16 hours to 100 hours when the density is 0.950 g/cm 3 to 0.960 g/cm 3 and the MI is 1.0 g/10 min to 3 g/10 min,
the time is 10 hours to 80 hours when the density is 0.950 g/cm 3 to 0.965 g/cm 3 and the MI is 6.0 g/10 min to 7.0 g/10 min, and
the time is 9 hours to 75 hours when the density is 0.955 g/cm 3 to 0.960 g/cm 3 and the MI is 8.0 g/10 min to 9 g/10 min.

3. The high-density ethylene-based polymer of claim 1 , 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, and 1-hexadecene.

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

5. The high-density ethylene-based polymer of claim 1 , wherein the high-density ethylene-based polymer is prepared 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 elements,
X 1 and X 2 are each independently one of halogen atoms,
R 1 to R 12 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 6 -C 20 aryl group, or a substituted or unsubstituted C 7 -C 40 alkylaryl group and are linked to each other to form a ring, and
cyclopentadienyl and indenyl are not linked to each other:

wherein, in Formula 2,
M2 is a group 4 transition metal of the periodic table of elements,
X 3 and X 4 are each independently one of halogen atoms,
R 13 to R 18 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 6 -C 20 aryl group, or a substituted or unsubstituted C 7 -C 40 alkylaryl group and are linked to each other to form a ring,
R 21 to R 26 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 6 -C 20 aryl group, or a substituted or unsubstituted C 7 -C 40 alkylaryl group and are linked to each other to form a ring,
R 19 and R 20 are each independently a substituted or unsubstituted C 1 -C 20 alkyl group or may be linked to each other to form a ring,
indenyl linked to R 13 to R 18 and indenyl linked to R 21 to R 26 have the same structure or different structures, and
the indenyl linked to R 13 to R 18 and the indenyl linked to R 21 to R 26 are linked to Si to form a bridged structure.

6. The high-density ethylene-based polymer of claim 5 , wherein the first metallocene compound comprises at least one compound selected from the group consisting of compounds having the following structures:

7. The high-density ethylene-based polymer of claim 5 , wherein the second metallocene compound comprises at least one compound selected from the group consisting of compounds having the following structures:

8. The high-density ethylene-based polymer of claim 5 , wherein the cocatalyst compound comprises at least one compound selected from compounds represented by Formulae 3 to 6:

wherein, in Formula 3,
AL is aluminum,
R 27 is a halogen atom, a C 1 -C 20 hydrocarbon group, or a C 1 -C 20 hydrocarbon group substituted with halogen, and
a is an integer of 2 or more and Formula 3 is a repeating unit,

wherein, in Formula 4,
Al is aluminum or boron, and
R 28 each independently is a halogen atom, a C 1 -C 20 hydrocarbon group, a C 1 -C 20 hydrocarbon group substituted with halogen, or a C 1 -C 20 alkoxy group,
[L1-H] + [Z1(A2) 4 ] −   [Formula 5]

[L2] + [Z2(A3) 4 ] −   [Formula 6]

wherein, in Formulae 5 and 6,
[L1-H] + and [L2] + are neutral or cationic Lewis acids,
Z1 and Z2 are group 13 elements of the periodic table of elements, and
A2 and A3 are a substituted or unsubstituted C 6 -C 20 aryl group or a substituted or unsubstituted C 1 -C 20 alkyl group.

9. The high-density ethylene-based polymer of claim 8 , wherein the cocatalyst compound represented by Formula 3 comprises at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane.

10. The high-density ethylene-based polymer of claim 8 , 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 tris(pentafluorophenyl)boron.

11. The high-density ethylene-based polymer of claim 8 , 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 tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetrakis(p-tolyl)borate, tripropylammonium tetrakis(p-tolyl)borate, trimethylammonium tetrakis(o,p-dimet

Assignees

• Hanwha Chemical Corp

Inventors

• Joung Ui Gab
• Jeong Dong Wook
• Kang Won Jun
• Kim Dong Ok
• Yang Song Hee
• Lee In Jun

Classifications

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F4/659

  Component covered by group C08F4/64 containing a transition metal-carbon bond {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F4/646

  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)} · CPC title

• C08F4/642

  Component covered by group C08F4/64 with an organo-aluminium compound {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08F4/02

  Carriers therefor · CPC title