Supported hybrid catalyst

Patent metadata

Field	Value
Publication number	US-10865260-B2
Application number	US-201816090763-A
Country	US
Kind code	B2
Filing date	Jan 25, 2018
Priority date	Jan 25, 2017
Publication date	Dec 15, 2020
Grant date	Dec 15, 2020

Abstract

The present disclosure provides a supported hybrid catalyst which facilitates the preparation of polyolefins having improved bubble stability and exhibiting excellent processability for a blown film while maintaining high transparent haze and improved melt strength, and a method for preparing the same.

First claim

The invention claimed is:

1. A supported hybrid catalyst, comprising at least one first transition metal compound selected from compounds represented by the following Chemical Formula 1;
at least one second transition metal compound selected from compounds represented by the following Chemical Formula 2; and
a support on which the first and second transition metal compounds are supported,

wherein, in Chemical Formula 1,
M 1 is a Group 4 transition metal;
X 1 and X 2 are the same as or different from each other, and are each independently any one of a halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH 3 , a C1 to C30 hydrocarbyl(oxy)silyl group, a C1 to C30 sulfonate group, and a C1 to C30 sulfone group;
R 1 and R 3 to R 10 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, and a C2 to C30 hydrocarbyloxyhydrocarbyl group;
R 2 is selected from the group consisting of a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, and a C2 to C30 hydrocarbyloxyhydrocarbyl group;
Q 1 and Q 2 are the same as or different from each other, and are each independently any one of hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH 3 , a C1 to C30 hydrocarbyl(oxy)silyl group, a C1 to C30 hydrocarbyl group substituted with a halogen, and —NR a R b ; and
R a and R b are the same as or different from each other, and are each independently any one of hydrogen and a C1 to C30 hydrocarbyl group, or may be connected with each other to form an aliphatic or aromatic ring,

wherein, in Chemical Formula 2,
M2 is a Group 4 transition metal;
X 3 and X 4 are the same as or different from each other, and are each independently any one of a halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH 3 , a C1 to C30 hydrocarbyl(oxy)silyl group, a C1 to C30 sulfonate group, and a C1 to C30 sulfone group;
R 11 to R 24 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, and a C2 to C30 hydrocarbyloxyhydrocarbyl group;
Q 3 and Q 4 are the same as or different from each other, and are each independently any one of hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH 3 , a C1 to C30 hydrocarbyl(oxy)silyl group, a C1 to C30 hydrocarbyl group substituted with a halogen, and —NR a′ R b′ ; and
R a′ and R b′ are the same as or different from each other, and are each independently any one of hydrogen and a C1 to C30 hydrocarbyl group, or may be connected with each other to form an aliphatic or aromatic ring.

2. The supported hybrid catalyst of claim 1 ,
wherein R 1 and R 3 to R 6 are each hydrogen, and
R 2 each are any one of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 arylalkyl group, and a C7 to C20 alkylaryl group.

3. The supported hybrid catalyst of claim 1 ,
wherein M 1 is Ti, Zr, or Hf,
X 1 and X 2 are the same as or different from each other, and are each independently any one of a halogen, a C1 to C20 alkyl group, and a C1 to C20 alkoxy group,
R 1 and R 3 to R 6 are each hydrogen,
R 2 is a C1 to C20 alkyl group, or a C6 to C20 aryl group,
R 7 to R 10 are the same as or different from each other, and are each independently any one of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, and a C2 to C20 alkenyl group, and
Q 1 and Q 2 are each independently any one of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C6 to C20 aryl group, a C7 to C20 arylalkyl group, and a C7 to C20 alkylaryl group.

4. The supported hybrid catalyst of claim 1 , wherein the first transition metal compound is any one of compounds represented by the following structural formulae:

5. The supported hybrid catalyst of claim 1 ,
wherein M 2 is Ti, Zr, or Hf,
X 3 and X 4 are the same as or different from each other, and are each independently any one of a halogen, a C1 to C20 alkyl group, and a C1 to C20 alkoxy group,
R 11 and R 12 are the same as or different from each other, and are each independently any one of hydrogen, a C1 to C20 alkyl group, a C1 to C20 alkoxy group, and a C2 to C20 alkenyl group,
R 13 to R 20 are each independently any one of hydrogen, a C1 to C20 alkyl group, a C1 to C20 alkoxy group, and a C2 to C20 alkenyl group, or one or more pairs of neighboring substituents of R 13 to R 20 may be connected with each other to form a substituted or unsubstituted aliphatic ring,
R 21 to R 24 are the same as or different from each other, and are each independently any one of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, and a C2 to C20 alkenyl group, and
Q 3 and Q 4 are each independently any one of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C6 to C20 aryl group, a C7 to C20 arylalkyl group, and a C7 to C20 alkylaryl group.

6. The supported hybrid catalyst of claim 1 , wherein the second transition metal compound is any one of compounds represented by the following structural formulae:

7. The supported hybrid catalyst of claim 1 , wherein the first transition metal compound and the second transition metal compound are contained in a molar mixing ratio of 1:1 to 1:15.

8. The supported hybrid catalyst of claim 1 , wherein the support comprises any one or a mixture of two or more selected from the group consisting of silica, alumina, and magnesia.

9. The supported hybrid catalyst of claim 1 , further comprising at least one cocatalyst selected from the group consisting of compounds represented by the following Chemical Formulae 3 to 5:
R 26 —[Al(R 25 )—O] n —R 27   [Chemical Formula 3]

wherein, in Chemical Formula 3,
R 25 , R 26 , and R 27 are each independently any one of hydrogen, a halogen, a C1 to C20 hydrocarbyl group, and a halogen-substituted C1 to C20 hydrocarbyl group; and
n is an integer of 2 or more,
D(R 28 ) 3   [Chemical Formula 4]

wherein, in Chemical Formula 4,
D is aluminum or boron; and
R 28 are each independently any one of a halogen, a C1 to C20 hydrocarbyl group, a C1 to C20 hydrocarbyloxy group, and a halogen-substituted C1 to C20 hydrocarbyl group;
[L-H] + [W(A) 4 ] − or [L] + [W(A) 4 ] −   [Chemical Formula 5]

wherein, in Chemical Formula 5,
L is a neutral or cationic Lewis base; H is a hydrogen atom;
W is a Group 13 element; and
A are each independently any one of a C1 to C20 hydrocarbyl group; a C1 to C20 hydrocarbyloxy group; and a substituent in which at least one hydrogen atom of these substituents is substituted with at least one

Assignees

• Lg Chemical Ltd

Inventors

• Lee Jin Young
• Park Sung Ho
• Kwon Heon Yong
• Kwon Hyun Jee
• Cho Sol
• Kwon Oh Joo
• Lee Ki Soo
• Hong Dae Sik

Classifications

• C08F2420/07

  Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom · CPC title

• C08F2500/11

  Melt tension or melt strength · CPC title

• C08F210/02

  Ethene · CPC title

• C08F4/65922 Primary

  containing at least two cyclopentadienyl rings, fused or not · CPC title

• C08F4/65916

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