Preparation method of catalyst for polyolefin polymerization and preparation method of polyolefin

Patent metadata

Field	Value
Publication number	US-9447211-B2
Application number	US-201314390727-A
Country	US
Kind code	B2
Filing date	May 8, 2013
Priority date	Apr 23, 2013
Publication date	Sep 20, 2016
Grant date	Sep 20, 2016

Abstract

A preparation method of a catalyst for polyolefin polymerization capable of polymerizing low-density polyethylene in a single reactor without separately injecting a comonomer to thereby prepare a final product with a low cost through a more simplified process, a catalyst obtained by the preparation method, and a preparation method of a polyolefin using the catalyst are provided.

First claim

What is claimed is:

1. A preparation method of a catalyst for polyolefin polymerization, the preparation method comprising:
supporting an organic chromium compound of the following Chemical Formula 1 on a support including one or more selected from a group consisting of silicia, silica-alumina, and silica-magnesia;
supporting a cocatalyst containing a Group 13 metal on the support on which the organic chromium compound is supported; and
supporting a metallocene catalyst on the support on which the organic chromium compound and the cocatalyst are supported:

in Chemical Formula 1,
R 1 and R 2 are the same or different and are each independently a hydrocarbyl group having 2 to 20 carbon atoms, containing a heteroatom selected from a group consisting of O, N, and P,
R 3 is hydrogen or a hydrocarbyl group having 2 to 20 carbon atoms, containing a heteroatom selected from a group consisting of O, N, and P, and
Y is a halogen, hydrogen, or a hydrocarbyl group having 1 to 4 carbon atoms.

2. The preparation method of claim 1 , wherein in Chemical Formula 1, R 1 and R 2 are each a hydrocarbyl group having 2 to 20 carbon atoms, and containing a t-butoxy group at a terminal of an alkyl group.

3. The preparation method of claim 1 , wherein in Chemical Formula 1, R 3 is hydrogen or a hydrocarbyl group having 2 to 20 carbon atoms, and containing a t-butoxy group at a terminal of an alkyl group.

4. The preparation method of claim 1 , wherein in Chemical Formula 1, Y is a halogen or a methyl group.

5. The preparation method of claim 1 , wherein the metallocene catalyst includes one kind or more selected from a group consisting of compounds of Chemical Formulas 2 and 3:

in Chemical Formula 2,
A 1 and A 2 are the same or different and are each independently one kind of functional group selected from a group consisting of cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, butylcyclopentadienyl, sec-butylcyclopentadienyl, (tert-butyl)(methyl)cyclopentadienyl, trimethylsilylcyclopentadienyl, indenyl, methylindenyl, ethylindenyl, isopropylindenyl, fluorenyl, methylfluorenyl, dimethylfluorenyl, ethylfluorenyl, and isopropylfluorenyl,

in Chemical Formula 3,
A 3 and A 4 are the same or different and are each independently one kind of functional group selected from a group consisting of cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, butylcyclopentadienyl, sec-butylcyclopentadienyl, (tert-butyl)(methyl)cyclopentadienyl, trimethylsilylcyclopentadienyl, indenyl, methylindenyl, ethylindenyl, isopropylindenyl, fluorenyl, methylfluorenyl, dimethylfluorenyl, ethylfluorenyl, isopropylfluorenyl, and —NR 4 —,
R 4 is hydrogen, a straight or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an alkylcycloalkyl group having 4 to 30 carbon atom, substituted with at least one alkyl group having 1 to 10 carbon atoms, and
B is any one selected from a group consisting of an alkylene having 1 to 4 carbon atoms; an alkyl silicon or germanium having 1 to 4 carbon atoms; an alkyl phosphine or amine having 1 to 4 carbon atoms; an arylene group having 6 to 30 carbon atoms; an arylalkylene group having 6 to 30 carbon atoms; an alkylarylene group having 6 to 30 carbon atoms; and a functional group of the following Chemical Formula 31,

in Chemical Formula 31,
B 1 is silicon, germanium, phosphorus, nitrogen, boron, or aluminum,
R 9 is a straight or branched alkyl having 1 to 10 carbon atoms,
R 8 is hydrogen or a straight or branched alkyl having 1 to 10 carbon atoms,
D is oxygen or sulfur,
L is a straight or branched alkyl having 1 to 15 carbon atoms,
* means a binding site,
in Chemical Formulas 2 and 3,
M is a Group 3 to 11 transition metal,
X is selected from a group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, a silylaryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylsiloxyl group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a halogen group, an amine group, and a tetrahydroborate group, and n is an integer of 1 to 5.

6. The preparation method of claim 5 , wherein in Chemical Formula 3,
A 3 and A 4 are the same or different and are each cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, butylcyclopentadienyl, sec-butylcyclopentadienyl, tert-butyl methylcyclopentadienyl, trimethylsilylcyclopentadienyl, indenyl, methylindenyl, ethylindenyl, isopropylindenyl, fluorenyl, methylfluorenyl, dimethylfluorenyl, ethylfluorenyl, or isopropylfluorenyl,
A 3 is —NR 4 —, and A 4 is cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, butylcyclopentadienyl, sec-butylcyclopentadienyl, (tert-butyl)(methyl)cyclopentadienyl, trimethylsilylcyclopentadienyl, indenyl, methylindenyl, ethylindenyl, isopropylindenyl, fluorenyl, methylfluorenyl, dimethylfluorenyl, ethylfluorenyl, or isopropylfluorenyl,
R 4 is hydrogen or a straight or branched alkyl having 1 to 20 carbon atoms,
B is the functional group of Chemical Formula 31,
M is zirconium, titanium, or hafnium,
X is a halogen group, and n is 2.

7. The preparation method of claim 1 , wherein the cocatalyst is one kind or more selected from a group consisting of compounds of Chemical Formulas 4 to 6:
—[Al(R 4 )—O] c -  [Chemical Formula 4]

in Chemical Formula 4, R 4 (s) are the same or different and are each independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a halogen-substituted hydrocarbyl radical having 1 to 20 carbon atoms, and c is an integer of 2 or more,
D(R 5 ) 3   [Chemical Formula 5]

in Chemical Formula 5,
D is aluminum or boron, and R 5 is a hydrocarbyl having 1 to 20 carbon atoms, or a halogen-substituted hydrocarbyl having 1 to 20 carbon atoms,
[L-H] + [Z(E) 4 ] −   [Chemical Formula 6]

in Chemical Formula 6,
L is a neutral Lewis base, [L-H] + is a Bronsted acid,
Z is boron or aluminum in a +3 oxidation state, and
E(s) are each independently an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, in which one or more hydrogen atoms thereof are unsubstituted or substituted with a halogen, a hydrocarbyl having 1 to 20 carbon atoms, an alkoxy functional group, or a phenoxy functional group.

8. The preparation method of claim 1 , wherein based on 100 parts by weight of the support,
1 to 20 parts by weight of the organic chromium compound of Chemical Formula 1;
5 to 100 parts by weight of the cocatalyst; and
1 to 20 parts by weight of the metallocene catalyst are supported.

9. A prepara

Assignees

• Lg Chemical Ltd

Inventors

• Lee Yong Ho
• Lee Ki Soo
• Song Eun Kyoung
• Kwon Heon Yong
• Cho Min Seok
• Hong Dae Sik
• Jeon Man-Seong
• Lim Kyoung-Chan

Classifications

• C08F2420/02

  Cp or analog bridged to a non-Cp X anionic donor · CPC title

• C08F4/025 Primary

  Metal oxides · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F4/6592

  containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring · CPC title

• C08F4/6222

  Component of C08F4/62 containing at least two different metals · CPC title