Group 4 transition metal compound and use thereof

Patent metadata

Field	Value
Publication number	US-10364302-B2
Application number	US-201515536553-A
Country	US
Kind code	B2
Filing date	Dec 23, 2015
Priority date	Dec 23, 2014
Publication date	Jul 30, 2019
Grant date	Jul 30, 2019

Abstract

The present invention relates to a novel Group 4 transition metal compound, a method for preparing the compound, a catalyst composition comprising the compound, and a method for preparing a polyolefin comprising performing a polymerization reaction of olefin monomers, in the presence of the catalyst composition. Since the Group 4 transition metal compound of the present invention exhibits an excellent catalytic activity in polyolefin synthesis reactions, as well as having excellent thermal stability, it can be used for polyolefin synthesis reactions at high temperatures, and by changing the type of a central metal and ligand, the weight average molecular weight of synthesized polyolefins and the octene content in the polymer can be controlled. Therefore, it can be effectively used in polyolefin synthesis processes in which grades are controlled.

First claim

The invention claimed is:

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

wherein, in Formula 1, M is a Group 4 transition metal of Ti, Zr, or Hf;
each of X 1 and X 2 is 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 alkylamido, C 6-20 arylamido, or C 1-20 alkylidene;
each of R 1 to R 6 is independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 7-40 alkylaryl, substituted or unsubstituted C 7-40 arylalkyl, or substituted or unsubstituted C 1-20 silyl, or
R 2 and R 3 , or R 4 and R 5 are linked together to form a substituted or unsubstituted C 5-14 ring, or R 1 and R 2 , or R 5 and R 6 are linked together to form a substituted or unsubstituted C 5-14 aliphatic ring,
wherein each substituent is 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 alkylamido, C 6-20 arylamido, or C 1-20 alkylidene;
each of G 1 and G 2 is independently an element of Group 5 or Group 6 of the Periodic Table; and
each of Q 1 to Q 6 is independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 7-40 alkylaryl, substituted or unsubstituted C 7-40 arylalkyl, or substituted or unsubstituted C 1-20 silyl, or
any two of Q 1 to Q 3 or any two of Q 4 to Q 6 may be linked together to form a substituted or unsubstituted C 5-14 ring comprising or not comprising a heteroelement,
with the proviso that, when G 1 is an element of Group 6 of the Periodic Table, then Q 3 is absent, and when G 2 is an element of Group 6 of the Periodic Table, then Q 6 is absent,
wherein each substituent is 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 alkylamido, C 6-20 arylamido, or C 1-20 alkylidene.

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

wherein, in Formula 2, each of R 7 and R 8 is independently hydrogen, or substituted or unsubstituted C 1-20 alkyl.

3. The Group 4 transition metal compound of claim 2 , wherein each of X 1 and X 2 is independently halogen.

4. The Group 4 transition metal compound of claim 3 , wherein X 1 and X 2 are both chlorine.

5. The Group 4 transition metal compound of claim 2 , wherein each of R 7 and R 5 is identical to or different from each other, and is independently selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, butyl, and phenyl.

6. The Group 4 transition metal compound of claim 2 , wherein G 1 and G 2 are both nitrogen or both oxygen.

7. The Group 4 transition metal compound of claim 2 , wherein each of Q 1 , Q 2 , Q 4 and Q 5 is independently hydrogen or methyl, and Q 3 or Q 6 is independently absent, hydrogen, or methyl.

8. The Group 4 transition metal compound according to claim 6 , wherein:
i) when G 1 and G 2 are both nitrogen, and
when any one of Q 1 to Q 3 is hydrogen and any one of Q 4 to Q 6 is hydrogen, the remaining two are both methyl, respectively,
ii) when G 1 and G 2 are both oxygen,
Q 1 and Q 2 , and Q 4 and Q 5 are linked together to form a tetrahydrofuran ring by comprising the oxygen.

9. The Group 4 transition metal compound of claim 1 , wherein the compound is selected from the group consisting of

wherein, in the above formulas, M is a Group 4 transition metal of Ti, Zr, or Hf; Me is methyl; and THF is tetrahydrofuran.

10. A method for preparing a compound represented by Formula 1 below, comprising reacting a compound represented by Formula 3 below and a compound represented by Formula 4 below:

wherein, in the above formulae, M is a Group 4 transition metal of Ti, Zr, or Hf;
each of X 1 , X 2 and X 3 is 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 alkylamido, C 6-20 arylamido, or C 1-20 alkylidene;
each of R 1 to R 6 is independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 7-40 alkylaryl, substituted or unsubstituted C 7-40 arylalkyl, or substituted or unsubstituted C 1-20 silyl, or
R 2 and R 3 , or R 4 and R 5 are linked together to form a substituted or unsubstituted C 5-14 ring, or R 1 and R 2 , or R 5 and R 6 are linked together to form a substituted or unsubstituted C 5-14 aliphatic ring,
wherein each substituent is 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 alkylamido, C 6-20 arylamido, or C 1-20 alkylidene;
each of G 1 and G 2 is independently an element of Group 5 or Group 6 of the Periodic Table; and
each of Q 1 to Q 6 is independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 7-40 alkylaryl, substituted or unsubstituted C 7-40 arylalkyl, or substituted or unsubstituted C 1-20 silyl, or
any two of Q 1 to Q 3 or any two of Q 4 to Q 6 may be linked together to form a substituted or unsubstituted C 5-14 ring comprising or not comprising a heteroelement,
with the proviso that, when G 1 is an element of Group 6 of the Periodic Table, then Q 3 is absent, and when G 2 is an element of Group 6 of the Periodic Table, then Q 6 is absent,
wherein each substituent is 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 alkylamido, C 6-20 arylamido, or C 1-20 alkylidene; 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.

11. The method of claim 10 , wherein the compound represented by Formula 4 is a 1,2,3,4,7,8,9,10-octahydro-1,10-phenanthroline derivative.

12. The method of claim 10 , wherein the compound represented by Formula 3 and the compound represented by Formula 4 are reacted at an equivalent ratio of 1:0.9 to 1:1.5.

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

14. Th

Assignees

• Hanwha Chemical Corp

Inventors

• Joung Ui Gab
• Sagong Kil
• Jun Sung Hae
• Kim Dong Ok
• Park Hye Ran
• Lee In Jun

Classifications

• C07F7/00 Primary

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

• C08F4/64

  Titanium, zirconium, hafnium or compounds thereof · CPC title

• C08F4/64044 Primary

  NN · CPC title

• C08F297/08

  polymerising mono-olefins · CPC title

• C08F210/16

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