Supported hybrid metallocene catalyst, and method for preparing polyolefin using the same

Patent metadata

Field	Value
Publication number	US-10544247-B2
Application number	US-201715773748-A
Country	US
Kind code	B2
Filing date	Nov 3, 2017
Priority date	Dec 19, 2016
Publication date	Jan 28, 2020
Grant date	Jan 28, 2020

Abstract

The present disclosure relates to a supported hybrid metallocene catalyst and a method for preparing a polyolefin using the same. When the supported hybrid metallocene catalyst according to the present disclosure is used, a polyolefin with a multimodal molecular weight distribution and excellent environmental stress crack resistance can be prepared.

First claim

What is claimed is:

1. A supported hybrid metallocene catalyst, comprising:
a first metallocene compound represented by the following Chemical Formula 1;
a second metallocene compound which is represented by the following Chemical Formula 2 and one of C 1 and C 2 of Chemical Formula 2 is represented by the following Chemical Formula 3a;
a third metallocene compound which is represented by the following Chemical Formula 2 and one of C 1 and C 2 of Chemical Formula 2 is represented by the following Chemical Formula 3b;
a cocatalyst; and
a support:

in Chemical Formula 1,
at least one of R 1 to R 8 is —(CH 2 ) n —OR, wherein R is a C1 to C6 linear or branched alkyl group, and n is an integer of 2 to 10, and the others are the same as or different from each other, and are each independently hydrogen, 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 1 is a Group 4 transition metal, and
X 1 and X 2 are the same as or different from each other, and are each independently a halogen or a C1 to C20 alkyl group,

in Chemical Formula 2,
M 2 is a Group 4 transition metal,
X 3 and X 4 are the same as or different from each other, and are each independently a halogen or a C1 to C20 alkyl group,
B is carbon, silicon, or germanium,
at least one of Q 1 and Q 2 is —(CH 2 ) m —OR′, wherein R′ is a C1 to C6 linear or branched alkyl group, and m is an integer of 2 to 10, and the others 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 C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, and
one of C 1 and C 2 is represented by the following Chemical Formula 3a or 3b, and the other is represented by the following Chemical Formula 3c,

in Chemical Formulae 3a to 3c,
R 9 to R 27 are the same as or different from each other, and are each independently hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkoxy group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group.

2. The supported hybrid metallocene catalyst of claim 1 ,
wherein at least one of R 1 and R 5 of Chemical Formula 1 is —(CH 2 ) n —OR, wherein R is a C1 to C6 linear or branched alkyl group, and n is an integer of 2 to 10.

3. The supported hybrid metallocene catalyst of claim 1 ,
wherein R 10 of Chemical Formula 3a is a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkoxy group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group.

4. The supported hybrid metallocene catalyst of claim 1 ,
wherein at least one of R 24 and R 27 of Chemical Formula 3c is a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkoxy group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group.

5. The supported hybrid metallocene catalyst of claim 1 ,
wherein the first metallocene compound is selected from the group consisting of the following structural formulae:

6. The supported hybrid metallocene catalyst of claim 1 ,
wherein the second metallocene compound is selected from the group consisting of the following structural formulae:

7. The supported hybrid metallocene catalyst of claim 1 ,
wherein the third metallocene compound is represented by the following structural formula:

8. The supported hybrid metallocene catalyst of claim 1 ,
wherein a molar mixing ratio of the first metallocene compound to the second metallocene compound to the third metallocene compound is 1:0.1 to 5:0.1 to 5.

9. The supported hybrid metallocene catalyst of claim 1 ,
wherein the cocatalyst comprises at least one selected from the group consisting of a first cocatalyst represented by the following Chemical Formula 4 and a second cocatalyst represented by the following Chemical Formula 5:
—[Al(R 28 )—O—] k —  [CHEMICAL FORMULA 4]

in Chemical Formula 4, each R 28 is the same as or different from each other, and each is independently a halogen, or a C1 to C20 hydrocarbyl group substituted or unsubstituted with a halogen, and k is an integer of 2 or more,
T + [BG 4 ] −   [CHEMICAL FORMULA 5]

in Chemical Formula 5, T + is a polyatomic ion having a valence of +1, B is boron in a +3 oxidation state, and each G is independently selected from the group consisting of hydride, dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, halocarbyl, and halo-substituted hydrocarbyl, and G has 20 or fewer carbons, provided that G is a halide in one or fewer positions.

10. A method for preparing a polyolefin, comprising the step of polymerizing olefinic monomers in the presence of the supported hybrid metallocene catalyst of claim 1 .

11. The method of claim 10 , wherein the olefinic monomers include at least one 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-undecene, 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.

Assignees

• Lg Chemical Ltd

Inventors

• Kim Sun Mi
• Choi Yi Young
• Lee Ki Soo
• Hong Bog Ki
• Lee Sung Min
• Sun Soon Ho
• Park Jin Young

Classifications

• C08F2420/06

  Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom · CPC title

• C08F4/65916

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

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F4/65904

  in combination with another component of C08F4/64 · CPC title