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

Patent metadata

Field	Value
Publication number	US-10975173-B2
Application number	US-201716321114-A
Country	US
Kind code	B2
Filing date	Apr 7, 2017
Priority date	Jul 28, 2016
Publication date	Apr 13, 2021
Grant date	Apr 13, 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 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.

First claim

The invention claimed is:

1. A high-density ethylene-based polymer prepared by polymerizing ethylene and at least one α-olefin monomer,
wherein a density is 0.930 g/cm 3 to 0.970 g/cm 3 ,
an MI is 0.1 g/10 min to 50 g/10 min,
an MFR is 35 to 100, and
a characteristic relaxation time (k) is 0.3 s to 2.0 s at 190° C.

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

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

4. The high-density ethylene-based polymer according to 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.

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

6. 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.

7. The high-density ethylene-based polymer according to claim 1 , wherein the high-density ethylene-based polymer is polymerized in the presence of 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,
X 1 and X 2 are each independently a halogen atom, a C 1 -C 20 alkyl group, a C 2 -C 20 alkenyl group, a C 2 -C 20 alkynyl group, a C 6 -C 20 aryl group, a C 7 -C 40 alkylaryl group, a C 7 -C 40 arylalkyl group, a C 1 -C 20 alkylamido group, a C 6 -C 20 arylamido group, or a C 1 -C 20 alkylidene group,
R 1 to R 12 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 7 -C 40 alkylaryl group, a substituted or unsubstituted C 7 -C 40 arylalkyl group, or a substituted or unsubstituted C 1 -C 20 silyl group, and the two adjacent R 1 to R 12 are optionally linked to each other to form a ring,
cyclopentadienyl linked to R 1 to R 5 and indenyl linked to R 6 to R 12 have an asymmetric structure, and
the cyclopentadienyl and the indenyl 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,
X 3 and X 4 are each independently a halogen atom, a C 1 -C 20 alkyl group, a C 2 -C 20 alkenyl group, a C 2 -C 20 alkynyl group, a C 6 -C 20 aryl group, a C 7 -C 40 alkylaryl group, a C 7 -C 40 arylalkyl group, a C 1 -C 20 alkylamido group, a C 6 -C 20 arylamido group, or a C 1 -C 20 alkylidene group,
R 13 to R 18 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 7 -C 40 alkylaryl group, a substituted or unsubstituted C 7 -C 40 arylalkyl group, or a substituted or unsubstituted C 1 -C 20 silyl group, and the two adjacent R 13 to R 18 are optionally 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 20 alkyl group, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 7 -C 40 alkylaryl group, a substituted or unsubstituted C 7 -C 40 arylalkyl group, or a substituted or unsubstituted C 1 -C 20 silyl group, and the two adjacent R 21 to R 26 are optionally 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, a substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 7 -C 40 alkylaryl group, a substituted or unsubstituted C 7 -C 40 arylalkyl group, or a substituted or unsubstituted C 1 -C 20 silyl group, and the two adjacent R 19 to R 20 are optionally 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 bridge structure,
wherein the substituted C 1 -C 20 alkyl group, the substituted C 2 -C 20 alkenyl group, the substituted C 6 -C 20 aryl group, the substituted C 7 -C 40 alkylaryl group, the substituted C 7 -C 40 arylalkyl group, and the substituted C 1 -C 20 silyl group are a C 1 -C 20 alkyl group, a C 2 -C 20 alkenyl group, a C 6 -C 20 aryl group, a C 7 -C 40 alkylaryl group, a C 7 -C 40 arylalkyl group, and a C 1 -C 20 silyl group where a hydrogen atom is substituted with a substituent comprising a halogen atom, a C 1 -C 20 hydrocarbon group, a C 1 -C 20 alkoxy group, and a C 6 -C 20 aryloxy group, respectively.

8. The high-density ethylene-based polymer according to claim 7 , wherein the first metallocene compound is selected from the group consisting of compounds having the following structures:

9. The high-density ethylene-based polymer according to claim 7 , wherein the second metallocene compound is selected from the group consisting of compounds having the following structures:

10. The high-density ethylene-based polymer according to claim 7 , wherein the cocatalyst compound is 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:

wherein, in Formula 4,
Al is aluminum or boron, and

Assignees

• Hanwha Chemical Corp

Inventors

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

Classifications

• C08F210/16 Primary

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

• C08F4/65916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title

• C08F4/654

  with magnesium or compounds thereof · CPC title

• B01J31/38

  of titanium, zirconium or hafnium · CPC title

• C08F10/02

  Ethene · CPC title