Supported catalyst for propylene polymerization and method for producing polypropylene resin using same

Patent metadata

Field	Value
Publication number	US-12139566-B2
Application number	US-201917294361-A
Country	US
Kind code	B2
Filing date	Nov 14, 2019
Priority date	Nov 15, 2018
Publication date	Nov 12, 2024
Grant date	Nov 12, 2024

Abstract

The present invention relates to a supported catalyst for propylene polymerization in which a first transition metal compound contributing to the production of crystalline polypropylene and a second transition metal compound contributing to the production of rubbery polypropylene are co-supported, and a method for producing a polypropylene resin using same. By using the supported catalyst, according to the present invention, it is possible to produce, by a single step of propylene polymerization, a polypropylene resin in which crystalline polypropylene and rubbery polypropylene are simultaneously formed.

First claim

The invention claimed is:

1. A supported catalyst for propylene polymerization, comprising:
a first transition metal compound represented by Chemical Formula 1 below;
a second transition metal compound represented by Chemical Formula 3 below; and
a carrier configured to co-support the first and second transition metal compounds,

wherein, in Chemical Formula 1,
M 1 is a group 4 transition metal,
Q 1 and Q 2 are the same or different, and are each independently: a halogen group; 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 1 -C 20 ) alkyl (C 6 -C 20 ) aryl group; a (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl group; a (C 1 -C 20 ) alkylamido group; a (C 6 -C 20 ) arylamido group; or a (C 1 -C 20 ) alkylidene group,
A 1 is a group 14 element,
R 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are the same or different, and are each independently: hydrogen; a (C 1 -C 20 ) alkyl group unsubstituted or substituted with an acetal group or ether group; a (C 2 -C 20 ) alkenyl group unsubstituted or substituted with an acetal group or ether group; a (C 6 -C 20 ) aryl group unsubstituted or substituted with an acetal group or ether group; a (C 1 -C 20 ) alkyl (C 6 -C 20 ) aryl group unsubstituted or substituted with an acetal group or ether group; a (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl group unsubstituted or substituted with an acetal group or ether group; or a (C 1 -C 20 ) silyl group unsubstituted or substituted with an acetal group or ether group,
two or more groups among R 1 , R 2 , R 3 , and R 4 are capable of forming an aliphatic ring or aromatic ring by being bonded to each other,
two or more groups among R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are capable of forming an aliphatic ring or aromatic ring by being bonded to each other, and
R 5 and R 6 are the same or different, and are each independently: hydrogen; 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 1 -C 20 ) alkyl (C 6 -C 20 ) aryl group; a (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl group; a (C 1 -C 20 ) alkylamido group; a (C 6 -C 20 ) arylamido group; or a (C 1 -C 20 ) alkylidene group,

wherein, in Chemical Formula 3,
M 3 is a group 4 transition metal,
Q 5 and Q 6 are the same or different, and are each independently: a halogen group; 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 1 -C 20 ) alkyl (C 6 -C 20 ) aryl group; a (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl group; a (C 1 -C 20 ) alkylamido group; a (C 6 -C 20 ) arylamido group; or a (C 1 -C 20 ) alkylidene group,
R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , and R 33 are the same or different, and are each independently: hydrogen; a (C 1 -C 20 ) alkyl group unsubstituted or substituted with an acetal group or ether group; a (C 2 -C 20 ) alkenyl group unsubstituted or substituted with an acetal group or ether group; a (C 6 -C 20 ) aryl group unsubstituted or substituted with an acetal group or ether group; a (C 1 -C 20 ) alkyl (C 6 -C 20 ) aryl group unsubstituted or substituted with an acetal group or ether group; a (C 6 -C 20 ) aryl (C 1 -C 20 ) alkyl group unsubstituted or substituted with an acetal group or ether group; or a (C 1 -C 20 ) silyl group unsubstituted or substituted with an acetal group or ether group; a (C 1 -C 20 ) alkoxy group; or a (C 6 -C 20 ) aryloxy group, and
two or more groups among R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , and R 27 are capable of forming an aliphatic ring or aromatic ring by being bonded to each other.

2. The supported catalyst of claim 1 , wherein the R 9 is
a (C 6 -C 20 ) aryl group unsubstituted or substituted with an acetal group or ether group; or
a (C 1 -C 20 ) alkyl (C 6 -C 20 ) aryl group unsubstituted or substituted with an acetal group or ether group.

3. The supported catalyst of claim 1 , wherein the A 1 is carbon (C) or silicon (Si), and the R 5 , and the R 6 , are each independently hydrogen or a methyl group.

4. The supported catalyst of claim 1 , wherein the Q 1 , the Q 2 , the Q 5 , and the Q 6 , are each independently:
a halogen group selected from among F, Cl, Br, and I;
a methyl group; or
an ethyl group.

5. The supported catalyst of claim 1 , wherein
the compound represented by Chemical Formula 1 is any one of compounds represented by Chemical Formulas 1-1 to 1-6 below, and
the compound represented by Chemical Formula 3 is any one of compounds represented by Chemical Formulas 3-1 to 3-8 below

6. The supported catalyst of claim 1 , wherein the first transition metal compound and the second transition metal compound are included in a molar ratio ranging from 50:50 to 10:90.

7. The supported catalyst of claim 1 , further comprising one or more cocatalyst compounds selected from the group consisting of a compound having a unit represented by Chemical Formula 5 below, a compound represented by Chemical Formula 6 below, and a compound represented by Chemical Formula 7 below:
Chemical Formula 5
—[Al(Ra)—O] n —,

wherein, in Chemical Formula 5, n is an integer of 2 or more, Al is aluminum, O is oxygen, and Ra is: a halogen group; or a (C 1 -C 20 ) hydrocarbyl group unsubstituted or substituted with a halogen group,
Chemical Formula 6
Q(Rb) 3 ,

wherein, in Chemical Formula 6, Q is: aluminum; or boron, and Rbs are the same or different, and are each independently: a halogen group; or a (C 1 -C 20 ) hydrocarbyl group unsubstituted or substituted with a halogen group,
Chemical Formula 7
[W] + [Z(Rc) 4 ] − ,

wherein, in Chemical Formula 7, [W] + is: a cationic Lewis acid; or a cationic Lewis acid to which a hydrogen atom is bonded, Z is a group 13 element, and Rcs are the same or different, and are each independently: a (C 6 -C 20 ) aryl group substituted with one or more substituents selected from the group consisting of a halogen group, a (C 1 -C 20 ) hydrocarbyl group, an alkoxy group, and a phenoxy group; or a (C 1 -C 20 ) alkyl group substituted with one or more substituents selected from the group consisting of a halogen group, a (C 1 -C 20 ) hydrocarbyl group, an alkoxy group, and a phenoxy group.

8. A method of producing a polypropylene resin, comprising carrying out a propylene polymerization reaction in the presence of the supported catalyst of claim 1 .

9. The method of claim 8 , wherein crystalline polypropylene and rubbery polypropylene are simultaneously formed through the polymerization reaction.

10. The method of claim 9 , wherein the rubbery polypropylene includes one or more selected from the group consisting of:
a rubbery propylene homopolymer, and
a rubbery propylene copolymer polymerized by additionally adding other types of monomers during the polymerization of propylene.

11. The method of claim 10 , wherein the other types of monomers include one or more selected from the group consisting of ethylene, butene, hexene, and octene.

Assignees

• Lotte Chemical Corp

Inventors

• Min Joon Keun
• Shin Eun Hye
• Lee Rai Ha
• Lee Hae In
• Jeong Su Jeong
• Chae Byung Hun

Classifications

• C08F4/76

  selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum · CPC title

• C08F4/02

  Carriers therefor · CPC title

• C07F17/00

  Metallocenes · CPC title

• C08F2420/10

  Heteroatom-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by at least one group that contains a heteroatom · CPC title

• C08F210/06 Primary

  Propene · CPC title