Olefin polymer and preparation method thereof

Patent metadata

Field	Value
Publication number	US-11746168-B2
Application number	US-202117541434-A
Country	US
Kind code	B2
Filing date	Dec 3, 2021
Priority date	Dec 20, 2016
Publication date	Sep 5, 2023
Grant date	Sep 5, 2023

Abstract

The present disclosure provides an olefin polymer having excellent film processability and physical properties, and a preparation method of the same.

First claim

The invention claimed is:

1. A preparation method of an olefin polymer, the preparation method comprising the step of polymerizing olefinic monomers in the presence of a supported catalyst,
wherein the supported catalyst comprises a support, and a first transition metal compound represented by Chemical Formula 1 and a second transition metal compound represented by Chemical Formula 2 which are supported on the support:

in Chemical Formula 1,
M is Ti, Zr or Hf,
X 1 and X 2 are each independently selected from the group consisting of halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a silyl group, a C1 to C20 alkylsilyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C1 to C20 sulfonate group, and a C1 to C20 sulfone group,
T is C, Si, Ge, Sn or Pb,
Q 1 and Q 2 are each independently selected from the group consisting of hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 heterocycloalkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a C1 to C20 carboxylate, and a C2 to C20 alkenyl group,
R is selected from the group consisting of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a silyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 silyloxyalkyl group, a C2 to C20 alkenyl group, and a C6 to C20 aryl group, and
R 1 to R 9 are each independently selected from the group consisting of hydrogen, a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a silyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 silyloxyalkyl group, a C2 to C20 alkenyl group, and a C6 to C20 aryl group,

in Chemical Formula 2,
M′ is Ti, Zr or Hf,
X 3 and X 4 are each independently selected from the group consisting of halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a silyl group, a C1 to C20 alkylsilyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C1 to C20 sulfonate group, and a C1 to C20 sulfone group, and
R 11 to R 20 are each independently selected from the group consisting of hydrogen, a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a silyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 silyloxyalkyl group, a C2 to C20 alkenyl group, and a C6 to C20 aryl group, or one or more pairs of neighboring substituents of R 11 to R 20 are optionally connected with each other to form a substituted or unsubstituted aliphatic or aromatic ring.

2. The preparation method of claim 1 , wherein in the Chemical Formula 1 of the first transition metal compound,
R is selected from the group consisting of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a silyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 silyloxyalkyl group, a C2 to C20 alkenyl group, and a C6 to C20 aryl group,
R 1 to R 4 are each independently hydrogen, or a C1 to C20 alkyl group, and
R 5 to R 9 are hydrogen.

3. The preparation method of claim 1 , wherein in the first transition metal compound, R is a C1 to C10 alkyl group, R 1 to R 4 are each independently hydrogen, or a C1 to C10 alkyl group, and R 5 to R 9 are hydrogen.

4. The preparation method of claim 1 , wherein the second transition metal compound is a compound represented by Chemical Formula 2a:

in Chemical Formula 2a,
R 21 to R 24 are each independently selected from the group consisting of hydrogen, a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a silyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 silyloxyalkyl group, a C2 to C20 alkenyl group, and a C6 to C20 aryl group.

5. The preparation method of claim 1 , wherein the support comprises silica, alumina, magnesia, or a mixture thereof.

6. The preparation method of claim 1 , wherein the olefinic monomers are ethylene and alpha-olefin.

7. The preparation method of claim 6 , wherein the alpha-olefin is selected from the group consisting of 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, and a mixture thereof.

8. The preparation method of claim 1 , wherein the first transition metal compound is a compound represented by Chemical Formula 1a:

in Chemical Formula 1a,
Q 1 and Q 2 are each independently selected from the group consisting of hydrogen, a C1 to C10 alkyl group, a C1 to C10 alkoxy group, and a C2 to C10 alkoxyalkyl group,
R is selected from the group consisting of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a silyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 silyloxyalkyl group, a C2 to C20 alkenyl group, and a C6 to C20 aryl group,
R 1 to R 4 are each independently a C1 to C10 alkyl group, and
R 5 to R 9 are hydrogen.

9. The preparation method of claim 1 , wherein the first transition metal compound is a compound represented by Chemical Formula 1a-1:

10. The preparation method of claim 1 , wherein the second transition metal compound is a compound represented by Chemical Formula 2a-1:

11. The preparation method of claim 1 , wherein the second transition metal compound is a compound represented by Chemical Formula 2b:

in Chemical Formulae 2b,
R 25 to R 28 are each independently selected from the group consisting of halogen, a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C2 to C20 alkoxyalkyl group, a silyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 silyloxyalkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, and a C7 to C20 arylalkyl group.

12. The preparation method of claim 1 , wherein the supported catalyst further comprises a cocatalyst selected from the group consisting of the compounds represented by Chemical Formulae 3 to 5, and a mixture thereof:
R 31 —[Al(R 32 )—O] n —R 33   [Chemical Formula 3]

in Chemical Formula 3,
R 31 , R 32 and R 33 are each independently selected from the group consisting of hydrogen, 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 34 ) 3   [Chemical Formula 4]

in Chemical Formula 4,
D is aluminum or boron, and
R 34 are each independently selected from the group consisting of halogen, a C1 to C20 hydrocarbyl group, and a halogen-substituted C1 to C20 hydrocarbyl group,
[L-H] + [Z(A) 4 ] − or [L] + [Z(A) 4 ] −   [Ch

Assignees

• Lg Chemical Ltd

Inventors

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

Classifications

• C08F210/16 Primary

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F4/65904

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

• C08F4/65916

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

• C08F4/65925

  two cyclopentadienyl rings being mutually non-bridged · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title