Catalyst composition and method of preparing polyolefin using the same

Patent metadata

Field	Value
Publication number	US-10513474-B2
Application number	US-201515551200-A
Country	US
Kind code	B2
Filing date	Dec 11, 2015
Priority date	May 15, 2015
Publication date	Dec 24, 2019
Grant date	Dec 24, 2019

Abstract

Provided are a catalyst composition and a method of oligomerizing olefins using the same. When the catalyst composition according to the present invention is used, oligomerization and copolymerization of olefin monomers may be performed in a single reactor at the same time with high efficiency without a separate process of preparing alpha-olefin. Therefore, costs for preparing or purchasing comonomers which are expensive raw materials may be reduced, thereby reducing the production cost of a final product. Contents of SCB (short chain branch) and LCB (long chain branch) in the polyolefin may be increased without separate feeding of comonomers, thereby producing high-quality linear low-density polyethylene.

First claim

What is claimed is:

1. A catalyst composition, comprising;
a first supported catalyst having one or more organic chromium compounds supported on a support; and
a second supported catalyst having one or more metallocene compounds supported on a support,
wherein the organic chromium compound includes two or more of a group represented by the following Chemical Formula 1 in a molecule, and has a linkage group (L) linking the two or more groups represented by the following Chemical Formula 1 via 4 to 8 carbon atoms in the linkage group (L):

wherein * is a part which binds to the linkage group (L) linking the two or more groups,
R 1 to R 4 are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 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, or an alkoxyaryl group having 7 to 20 carbon atoms;
Y 1 , Y 2 and Y 3 are each independently halogen, hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, or a heterohydrocarbyl group having 1 to 10 carbon atoms, and
wherein the linkage group (L) is a group selected from the group consisting of the following Chemical Formulae:

wherein * is a part which binds to N of Chemical Formula 1,
R's are each independently hydrogen or alkyl having 1 to 5 carbon atoms, p is an integer of 1 to 6, q is an integer of 1 to 5, and a plurality of R's binding to one ring are the same as or different from each other.

2. The catalyst composition of claim 1 , wherein the organic chromium compound is represented by the following Chemical Formula 2:

wherein L is a linkage group linking nitrogen (N) atoms via 4 to 8 carbon atoms in the linkage group, and is an aliphatic group having 2 to 20 carbon atoms, a heteroaliphatic group having 2 to 20 carbon atoms, an alicyclic group having 2 to 20 carbon atoms, a heteroalicyclic group having 2 to 20 carbon atoms, or a group of two or more of the aliphatic group, the heteroaliphatic group, the alicyclic group, and the heteroalicyclic group, which are linked together,
R 1 to R 8 are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 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, or an alkoxyaryl group having 7 to 20 carbon atoms; and
Y 1 to Y 6 are each independently halogen, hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, or a heterohydrocarbyl group having 1 to 10 carbon atoms.

3. The catalyst composition of claim 1 , wherein R 1 to R 4 of the Chemical Formula 1 are phenyl.

4. The catalyst composition of claim 1 , wherein the organic chromium compound is selected from the group consisting of the following Chemical Formulae:

5. The catalyst composition of claim 1 , wherein the metallocene compound includes one or more selected from compounds represented by the following Chemical Formulae 3 to 6:
(Cp 1 R a ) n (Cp 2 R b )M 1 Z 1 3-n   [Chemical Formula 3]

wherein M 1 is a Group 4 transition metal;
Cp 1 and Cp 2 are the same as or different from each other, and each independently any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, which may be substituted with hydrocarbon having 1 to 20 carbon atoms;
R a and R b are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
Z 1 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene, a substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
n is 1 or 0;
(Cp 3 R c ) m B 1 (Cp 4 R d )M 2 Z 2 3-m   [Chemical Formula 4]

wherein M 2 is a Group 4 transition metal;
Cp 3 and Cp 4 are the same as or different from each other, and each independently any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, which may be substituted with hydrocarbon having 1 to 20 carbon atoms;
R c and R d are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
Z 2 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene, a substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
B 1 is one or more of carbon, germanium, silicon, phosphorus, or nitrogen-containing radical, or a combination thereof, which crosslinks a Cp 3 R c ring with a Cp 4 R d ring, or crosslinks one Cp 4 R d ring to M 2 ;
m is 1 or 0;
(Cp 5 R e )B 2 (J)M 3 Z 3 2[ Chemical Formula 5]

wherein M 3 is a Group 4 transition metal;
Cp 5 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-l-indenyl, and fluorenyl radicals, which may be substituted with hydrocarbon having 1 to 20 carbon atoms;
R e is hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
Z 3 is a halogen atom, C1 to C20 alkyl, C2 to C10 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, substituted or unsubstituted C1 to C20 alkylidene, a substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy;
B 2 is any one or more of carbon, germanium, silicon, phosphorus, or nitrogen-containing radical, or a combination thereof, which crosslinks a Cp 5 R e ring with J; and
J is any one selected from the group consisting of NR f , O, PR f and S, wherein R f is C1 to C20 alkyl, aryl, substituted alkyl, or substituted aryl;

wherein A is hydrogen, 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, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
D is —O—, —S—, —N(R)- or —Si(R)(R′)—, wherein R and R′ are the same as or different from each other, and each independently hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;
E is a C1 to C10 linear or branched alkylene group;
B 3 is carbon, silicon, or germanium;
Q is hydrogen, 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;
M is a Group 4 transition metal;
X 1 and X 2 are the same as

Assignees

• Lg Chemical Ltd

Inventors

• Park Jin Young
• Lee Yong Ho
• Lee Seung Mi
• Lee Ki Soo
• Shin Eun Ji
• Sa Seok Pil
• Im Seul Ki

Classifications

• C08F110/00

  Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F4/69

  Chromium, molybdenum, tungsten or compounds thereof · CPC title

• C08F4/6592

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

• B01J31/14

  of aluminium or boron · CPC title

• B01J31/1608

  the ligands containing silicon · CPC title