Metallocene complex and method for producing olefin polymer

Patent metadata

Field	Value
Publication number	US-9963522-B2
Application number	US-201515126344-A
Country	US
Kind code	B2
Filing date	Mar 17, 2015
Priority date	Mar 20, 2014
Publication date	May 8, 2018
Grant date	May 8, 2018

Abstract

The present invention provides a metallocene complex capable of producing a homopolypropylene having a high melting point in the homopolymerization of propylene, and a production method of an olefin polymer using the same. The metallocene complex of the present invention is represented by formula [I].

First claim

The invention claimed is:

1. A metallocene complex represented by the following formula [I]:

in which M is Ti, Zr, or Hf;
Q is a carbon atom, a silicon atom, or a germanium atom;
each of X 1 and X 2 is independently a halogen atom, an alkyl group having a carbon number of 1 to 6, an aryl group having a carbon number of 6 to 18, an amino group substituted with an alkyl group having a carbon number of 1 to 6, an alkoxy group having a carbon number of 1 to 6, a halogen-containing alkyl group having a carbon number of 1 to 6, or a halogen-containing aryl group having a carbon number of 6 to 18;
R 1 and R 11 are the same or different and are a hydrogen atom, an alkyl group having a carbon number of 1 to 6, an alkoxy group having a carbon number of 1 to 6, a furyl group, a thienyl group, a furyl group having a substituent, or a thienyl group having a substituent, and one or both of R 1 and R 11 are selected from a furyl group, a thienyl group, a furyl group having a substituent, or a thienyl group having a substituent;
R 7 and R 17 are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to 6, an alkoxy group having a carbon number of 1 to 6, a halogen-containing alkyl group having a carbon number of 1 to 6, a trialkylsilyl group-containing alkyl group having a carbon number of 1 to 6, a silyl group containing a hydrocarbon group having a carbon number of 1 to 6, an aryl group having a carbon number of 6 to 18, or a halogen-containing aryl group having a carbon number of 6 to 18, and when either one of R 7 or R 17 is a hydrogen atom, the other is a substituent except for a hydrogen atom;
R 8 and R 18 are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to 6, an alkoxy group having a carbon number of 1 to 6, a halogen-containing alkyl group having a carbon number of 1 to 6, a trialkylsilyl group-containing alkyl group having a carbon number of 1 to 6, a silyl group containing a hydrocarbon group having a carbon number of 1 to 6, an aryl group having a carbon number of 6 to 18, or a halogen-containing aryl group having a carbon number of 6 to 18;
adjacent substituents out of R 7 , R 8 , R 17 , and R 18 are optionally bonded together to form a 5- to 7-membered ring, and the 5- to 7-membered ring optionally contains an unsaturated bond;
R 2 , R 3 , R 4 , R 5 , R 6 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 19 are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to 6, an alkoxy group having a carbon number of 1 to 6, a halogen-containing alkyl group having a carbon number of 1 to 6, a trialkylsilyl group-containing alkyl group having a carbon number of 1 to 6, an aryl group having a carbon number of 6 to 18, a halogen-containing aryl group having a carbon number of 6 to 18, a furyl group, a thienyl group, a furyl group having a substituent, or a thienyl group having a substituent;
adjacent substituents out of R 2 , R 3 , R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , R 15 , and R 16 are optionally bonded together to form a 5- to 7-membered ring, and the 5- to 7-membered ring optionally contains an unsaturated bond;
A is a divalent hydrocarbon group having a carbon number of 3 to 12 and forming a ring together with Q to which it is bonded, and optionally contains an unsaturated bond;
R 10 is a substituent on A and is an alkyl group having a carbon number of 1 to 6, a halogen-containing alkyl group having a carbon number of 1 to 6, a trialkylsilyl group-containing alkyl group having a carbon number of 1 to 6, a silyl group containing a hydrocarbon group having a carbon number of 1 to 6, an aryl group having a carbon number of 6 to 18, or a halogen-containing aryl group having a carbon number of 6 to 18; and
m represents an integer of 0 to 24, and when m is 2 or more, R 10 s optionally combine with each other to form a new ring structure.

2. The metallocene complex according to claim 1 , wherein in the formula [I], R 7 and R 17 are optionally the same or different and are selected from alkyl groups having a carbon number of 1 to 6.

3. The metallocene complex according to claim 1 , wherein in the formula [I], R 8 and R 18 are optionally the same or different and are selected from alkyl groups having a carbon number of 1 to 6.

4. The metallocene complex according to claim 1 , wherein in the formula [I], A is a divalent hydrocarbon group having a carbon number of 3 to 6 and forms a 4- to 7-membered ring, and m is an integer of 0 to 6.

5. The metallocene complex according to claim 1 , wherein in the formula [I], R 2 , R 6 , R 9 , R 12 , R 16 and R 19 is each a hydrogen atom.

6. The metallocene complex according to claim 1 , wherein the formula [I] is represented by the following formula [II]:

in which Z is an oxygen atom or a sulfur atom,
R 30 , R 31 , R 32 , and R 33 are optionally the same or different and are a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to 6, an alkoxy group having a carbon number of 1 to 6, a halogen-containing alkyl group having a carbon number of 1 to 6, a silyl group containing a hydrocarbon group having a carbon number of 1 to 6, or an aryl group having a carbon number of 6 to 18,
adjacent substituents out of R 30 , R 31 , R 32 , and R 33 are optionally bonded together to form a 5- to 7-membered ring, the 5- to 7-membered ring optionally contains an unsaturated bond, and each of M, X 1 , X 2 , Q, R 2 to R 10 , R 12 to R 19 , and m has the same meaning as in formula [I].

7. A catalyst for olefin polymerization, comprising the metallocene complex according to claim 1 .

8. A catalyst for olefin polymerization, comprising each of the following components (A), (B), and (C):
component (A): the metallocene complex according to claim 1 ,
component (B): a compound reacting with the component (A) to form an ion pair, or an ion-exchange layered silicate, and
component (C): an organoaluminum compound.

9. The catalyst for olefin polymerization according to claim 8 , wherein the component (B) is an ion-exchange layered silicate.

10. A method for producing an olefin polymer, comprising performing a polymerization or copolymerization of olefin by using the catalyst for olefin polymerization according to claim 7 .

11. A method for producing a propylene-based polymer by using the catalyst for olefin polymerization according to claim 7 , comprising:
(i) polymerizing propylene in a ratio of 90 to 100 wt % and ethylene or α-olefin in a ratio of 0 to 10 wt %, relative to all monomer components; and
(ii) polymerizing propylene in a ratio of 10 to 90 wt % and ethylene and/or α-olefin having a carbon number of 4 or more in a ratio of 10 to 90 wt %, relative to all monomer components.

12. A method for producing a propylene-based polymer by using the catalyst for olefin polymerization according to claim 7 , comprising:
(i) polymerizing propylene in a ratio of 90 to 100 wt % and ethylene or α-olefin in a ratio of 0 to 10 wt %, relative to all monomer components, by bulk polymerization using propylene as a solvent or gas phase polymerization of maintaining the monomers in a gas state; and
(ii) gas phase polymerizing propylene in a ratio of 10 to 90 wt % and ethylene or α-olefin in a ratio of 10 to 90 wt %, relative to all monomer components.

Assignees

• Japan Polypropylene Corp

Inventors

• Suzuki Toshinori
• Kashimoto Masami
• Nakano Masato
• Uchino Hideshi
• Tayano Takao

Classifications

• C07F17/00

  Metallocenes · CPC title

• C08F2420/06

  Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/65916 Primary

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

• C08F10/00

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title