Process for producing ethylene/α-olefin copolymer

Patent metadata

Field	Value
Publication number	US-9969827-B2
Application number	US-201515117015-A
Country	US
Kind code	B2
Filing date	Feb 10, 2015
Priority date	Feb 13, 2014
Publication date	May 15, 2018
Grant date	May 15, 2018

Abstract

A process capable of producing an ethylene/α-olefin copolymer having a high molecular weight even under the conditions of a high polymerization temperature is provided. The process for producing an ethylene/α-olefin copolymer includes copolymerizing ethylene and an α-olefin having 3 or more carbon atoms in the presence of an olefin polymerization catalyst including a crosslinked metallocene compound (A) represented by the following general formula [I] and a cocatalyst component (B). In the general formula [I], Y is selected from a carbon atom, etc., M is a hafnium atom or the like, R 1 to R 12 are each selected from a hydrogen atom, a hydrocarbon group, etc., R 13 and R 14 are each a substituted aryl group or the like, at least one of R 13 and R 14 is a substituted aryl group having one or more electron-donating substituents having a Hammett substituent constant σ of not more than −0.2, Q is selected from a halogen atom, etc., and j is an integer of 1 to 4.

First claim

The invention claimed is:

1. A process for producing an ethylene/α-olefin copolymer, comprising copolymerizing ethylene and an α-olefin having 3 or more carbon atoms in the presence of an olefin polymerization catalyst comprising:
(A) a bridged metallocene compound represented by the following general formula [I], and
(B) at least one compound selected from (B-1) an organometallic compound, (B-2) an organoaluminum oxy-compound and (B-3) a compound which reacts with the bridged metallocene compound (A) to form an ion pair,

wherein Y is selected from a carbon atom, a silicon atom, a germanium atom and a tin atom,
M is a titanium atom, a zirconium atom or a hafnium atom,
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, and are optionally the same as or different from each other,
adjacent substituents of R 1 to R 12 are optionally bonded to each other to form a ring,
R 13 and R 14 are each an aryl group or a substituted aryl group, and are optionally the same as or different from each other when being both substituted aryl groups,
at least one of R 13 and R 14 is a substituted aryl group, said substituted aryl group being a substituted aryl group in which one or more hydrogen atoms of an aryl group are each substituted with an electron-donating substituent having a Hammett substituent constant σ of not more than −0.2, wherein when the substituted aryl group has a plurality of the electron-donating substituents, these electron-donating substituents are the same as or different from each other, said substituted aryl group optionally having a substituent which is a substituent other than the electron-donating substituent and is selected from a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, wherein when the substituted aryl group has a plurality of the substituents, these substituents are the same as or different from each other,
Q is selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand and a neutral ligand capable of coordination with a lone pair of electrons, in a combination of the same or different kinds, and
j is an integer of 1 to 4, and,
wherein polymerization is carried out in such a manner as to obtain an ethylene-based polymer in which the proportion of constituent units derived from ethylene is not less than 50% by mol when the total of constituent units derived from monomers in the polymer is 100% by mol.

2. The process for producing an ethylene/α-olefin copolymer as claimed in claim 1 , wherein R 1 , R 2 , R 3 and R 4 in the general formula [I] are all hydrogen atoms.

3. The process for producing an ethylene/α-olefin copolymer as claimed in claim 1 , wherein Y in the general formula [I] is a carbon atom.

4. The process for producing an ethylene/α-olefin copolymer as claimed in claim 1 , wherein the electron-donating substituent is a group selected from a nitrogen-containing group and an oxygen-containing group.

5. The process for producing an ethylene/α-olefin copolymer as claimed in claim 4 , wherein R 13 and R 14 in the general formula [I] are the same substituted aryl group.

6. The process for producing an ethylene/α-olefin copolymer as claimed in claim 4 , wherein R 13 and R 14 in the general formula [I] are each a substituted phenyl group containing, as the electron-donating substituent, a group selected from a nitrogen-containing group and an oxygen-containing group at the meta position and/or the para position with respect to bonding to Y.

7. The process for producing an ethylene/α-olefin copolymer as claimed in claim 4 , wherein R 13 and R 14 in the general formula [I] are each a substituted phenyl group containing, as the electron-donating substituent, a nitrogen-containing group represented by the following general formula [II]:

wherein R 15 and R 16 are each an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group and a halogen-containing group, are optionally the same as or different from each other, and are optionally bonded to each other to form a ring, and a line drawn on the right-hand side of N represents bonding to the phenyl group.

8. The process for producing an ethylene/α-olefin copolymer as claimed in claim 4 , wherein R 13 and R 14 in the general formula [I] are each a substituted phenyl group containing, as the electron-donating substituent, an oxygen-containing group represented by the following general formula [III]:
R 17 —O—  [III]

wherein R 17 is an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group and a halogen-containing group, and a line drawn on the right-hand side of 0 represents bonding to the phenyl group.

9. The process for producing an ethylene/α-olefin copolymer as claimed in claim 1 , wherein R 5 , R 8 , R 9 and R 12 in the general formula [I] are all hydrogen atoms.

10. The process for producing an ethylene/α-olefin copolymer as claimed in claim 1 , wherein at least two of R 6 , R 7 , R 10 and R 11 in the general formula [I] are each a substituent selected from a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group.

11. The process for producing an ethylene/α-olefin copolymer as claimed in claim 10 , wherein R 6 and R 7 , and/or R 10 and R 11 in the general formula [I] are bonded to each other to form a ring.

12. The process for producing an ethylene/α-olefin copolymer as claimed in claim 11 , wherein R 6 and R 7 , and R 10 and R 11 in the general formula [I] are both bonded to each other to form a ring.

13. The process for producing an ethylene/α-olefin copolymer as claimed in claim 12 , wherein the rings formed by bonding of R 6 and R 7 , and R 10 and R 11 in the general formula [I] to each other are each a five-membered to seven-membered ring.

14. The process for producing an ethylene/α-olefin copolymer as claimed in claim 13 , wherein the rings formed by bonding of R 6 and R 7 , and R 10 and R 11 in the general formula [I] to each other are each a six-membered ring.

15. The process for producing an ethylene/α-olefin copolymer as claimed in claim 14 , wherein ethylene and an α-olefin are copolymerized in the presence of an olefin polymerization catalyst comprising a bridged metallocene compound represented by the following general formula [IV]:

wherein M is a titanium atom, a zirconium atom or a hafnium atom,
R 13 and R 14 are each a substituted phenyl group containing, as the electron-donating substituent, a nitrogen-containing group represented by the general formula [II], or are each a substituted phenyl group containing, as the electron-donating substituent, an oxygen-containing group re

Assignees

• Mitsui Chemicals Inc

Inventors

• Endo Koji
• Hiwara Mayumi
• Matsuura Sadahiko
• Kosugi Yoko
• Yamamura Yuichi
• Mizobuchi Yusuke

Classifications

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F2/44

  Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers · CPC title

• C08F210/16 Primary

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

• C08F210/06

  Propene · CPC title