Group 4 transition metal compound and use thereof

Patent metadata

Field	Value
Publication number	US-10160775-B2
Application number	US-201515502721-A
Country	US
Kind code	B2
Filing date	Aug 28, 2015
Priority date	Aug 28, 2014
Publication date	Dec 25, 2018
Grant date	Dec 25, 2018

Abstract

The present invention relates to a novel group 4 transition metal compound, a method for preparing the compound, a catalyst composition containing the compound, and a method for preparing a polyolefin, comprising a step for forming a polymerization reaction of olefin monomers in the presence of the catalyst composition. The group 4 transition metal compound of the present invention exhibits an excellent catalytic activity and has excellent thermal stability in a polyolefin synthesis reaction, and thus can be used even in a polyolefin synthesis reaction at a high temperature. In addition, the compound of the present invention can be advantageously used in the synthesis process of grade-controlled polyolefin since the weight average molecular weight of the synthesized polyolefin and the octane content in the polymer can be adjusted by varying the kinds of center metal and ligand.

First claim

The invention claimed is:

1. A Group 4 transition metal compound represented by the following Formula 1:

wherein,
M is a Group 4 transition metal of Ti, Zr, or Hf;
X 1 to X 3 are each independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 7-40 alkylaryl, C 7-40 arylalkyl, C 1-20 dialkylamido, C 6-20 diarylamido, or C 1-20 alkylidene, or
X 1 and X 2 are linked to each other and coordinated to a metal Min the form of

and
R 1 to R 8 and R 1 ′ to R 8 ′ are each independently hydrogen, or substituted or unsubstituted C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 7-40 alkylaryl, C 7-40 arylalkyl, or C 1-20 silyl, and
R 1 and R 2 , R 2 and R 3 , R 4 and R 5 , or R 6 and R 7 are optionally linked together to form a substituted or unsubstituted C 5-14 ring, and
R 7 and R 8 together form a double bond with the nitrogen atom, to which R 7 and R 8 are bonded, wherein the double bond is linked to R 6 to form a substituted or unsubstituted C 5-14 conjugated ring comprising the nitrogen atom as a heteroatom, and optionally comprising an additional heteroatom of O or N,
wherein the substituent is each independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 7-40 alkylaryl, C 7-40 arylalkyl, C 1-20 dialkylamindo, C 6-20 diarylamido, or C 1-20 alkylidene.

2. The Group 4 transition metal compound of claim 1 , wherein the compound is represented by the following Formula 2:

wherein,
R 9 to R 11 are each independently hydrogen, or substituted or unsubstituted C 1-20 alkyl.

3. The Group 4 transition metal compound of claim 2 , wherein X 1 to X 3 are all benzyl.

4. The Group 4 transition metal compound of claim 2 , wherein R 1 and R 11 are the same or different, and are each independently selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, butyl, and phenyl.

5. The Group 4 transition metal compound of claim 4 , wherein the compound is represented by a formula selected from the group consisting of

where in M is a group transition metal of Ti, Zr, or Hf; Ph is phenyl; and Bn is benzyl.

6. A method for preparing the compound of claim 1 , comprising a step of reacting a compound of Formula 3 and a Group 4 transition metal compound of Formula 4:

wherein,
and
X 4 is halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 7-40 alkylaryl, C 7-40 arylalkyl, C 1-20 alkylamido, C 6-20 arylamido, or C 1-20 alkylidene.

7. The method of claim 6 , wherein the compound of Formula 3 is a phenanthroline derivative.

8. The method of claim 6 , wherein X 1 to X 4 are all benzyl.

9. The method of claim 6 , wherein the compound of Formula 3 and the compound of Formula 4 are reacted at a mole ratio of 1:0.9 to 1:1.2.

10. The method of claim 6 , wherein the reaction is carried out in a hydrocarbon solvent selected from the group consisting of a C 5-10 aliphatic or aromatic cyclic hydrocarbon unsubstituted or substituted with halogen, a C 1-10 saturated or unsaturated acyclic hydrocarbon unsubstituted or substituted with halogen, and a mixture thereof.

11. The method of claim 10 , wherein the hydrocarbon solvent is pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, dichloromethane, chloroethane, dichloroethane, chlorobenzene, or a mixture thereof.

12. The method of claim 10 , wherein the hydrocarbon solvent is present in an amount of 100 to 1000 parts by weight based on 100 parts by weight of the total combined amount of the compound of Formula 3 and the compound of Formula 4.

13. A catalyst composition comprising the Group 4 transition metal compound of claim 1 ; and at least one compound selected from the group consisting of a compound of Formula 5, a compound of Formula 6, a compound of Formula 7, and a compound of Formula 8:

wherein,
R a is hydrogen, halogen, e C 1-20 alkyl, C 3-20 cycloalkyl, C 6-40 aryl or C 6-40 alkylaryl unsubstituted or substituted with halogen;
n is an integer of at least 2;
D is aluminum or boron;
R b to R d are the same or different, and are each independently hydrogen, halogen, C 1-20 alkyl, C 3-20 cycloalkyl, C 1-20 alkoxy, C 6-40 aryl, C 6-40 alkylaryl or C 6-40 arylalkyl unsubstituted or substituted with halogen;
L is a neutral or cationic Lewis acid;
L′ is a Lewis base;
Z is a Group 13 element; and
A is substituted or unsubstituted C 6-20 aryl or substituted or unsubstituted C 1-20 alkyl.

14. The catalyst composition of claim 13 , wherein the composition comprises the compound of Formula 5, the compound of Formula 6 or a mixture thereof; and the compound of Formula 7 or 8.

15. The catalyst composition of claim 14 , comprising the compound of Formula 1; the compound of Formula 5, the compound of Formula 6, or a mixture thereof; and the compound of Formula 7 or 8 at a molar ratio of 1:1 to 5:20 to 500.

16. A method for preparing a polyolefin, comprising a step of carrying out polymerization of an olefin monomer in the presence of the catalyst composition of claim 13 .

17. The method for preparing the polyolefin of claim 16 , wherein the olefin monomer is at least one compound selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 1-octene, and 1-decene.

Assignees

• Hanwha Chemical Corp

Inventors

• Joung Ui Gab
• Kim Dong Ok
• Kim Dong Wook
• Kim Ah Reum
• Park Hye Ran
• Sagong Kil
• Jun Sung Hae
• Lee Chun Sun
• Hwang Eun Yeong

Classifications

• C07F7/00 Primary

  Compounds containing elements of Groups 4 or 14 of the Periodic Table · CPC title

• C08F4/16

  of silicon, germanium, tin, lead, titanium, zirconium or hafnium · CPC title

• C08F4/64044

  NN · CPC title

• C08F210/16 Primary

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