Production method for olefin-based polymer, and olefin polymerization catalyst

Patent metadata

Field	Value
Publication number	US-10150825-B2
Application number	US-201515302442-A
Country	US
Kind code	B2
Filing date	Apr 10, 2015
Priority date	Apr 11, 2014
Publication date	Dec 11, 2018
Grant date	Dec 11, 2018

Abstract

Provided is a production method for an olefin-based polymer, including polymerizing an olefin raw material using (A) a transition metal compound, (B) a boron compound capable of forming an ion pair with the component (A), (C) a specific organoaluminum compound, and (D) a specific aluminoxane in presence of at least one or more kinds of (N) a nonpolymerizable unsaturated hydrocarbon in the olefin raw material or a polymerization solvent.

First claim

The invention claimed is:

1. A method of producing an olefin-based polymer, the method comprising polymerizing an olefin raw material by contacting components (A) to (D) in the presence of component (N) in the olefin raw material or a polymerization solvent:
(A) a transition metal compound;
(B) a boron compound capable of forming an ion pair with the component (A);
(C) an organoaluminum compound represented by a formula (VIII):
R 17 v AlJ 3-v   (VIII)

(D) an aluminoxane represented by a formula (i) or (ii):

(N) a nonpolymerizable unsaturated hydrocarbon;
wherein: i
R 17 represents an alkyl group having 1 to 20 carbon atoms;
J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom;
v represents an integer of from 1 to 3, and when v represents 2 or more, R 17 's may be identical to or different from each other, provided that at least one R 17 represents an alkyl group having 1 to 20 carbon atoms;
Ra represents an alkyl group having 1 to 20 carbon atoms, Ra's may be identical to or different from each other;
n represents an integer of from 1 to 50;
the transition metal compound (A) is a double crosslinked metallocene complex represented by a formula (I):

M represents a metal element of Groups 3 to 10 of the periodic table or the lanthanoid series;
E 1 and E 2 each represent a ligand selected from a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group, and a silicon-containing group, form a crosslinked structure via A 1 and A 2 , and may be identical to or different from each other;
X represents a σ-bonding ligand, and when a plurality of X's are present, the plurality of X's may be identical to or different from each other, and X may be crosslinked with any other X, E 1 , E 2 , or Y;
Y represents a Lewis base, and when a plurality of Y's are present, the plurality of Y's may be identical to or different from each other, and Y may be crosslinked with any other Y, E 1 , E 2 , or X;
A 1 and A 2 each represent a divalent crosslinking group for bonding two ligands, and each represent a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, —O—, —CO—, —S—, —SO 2 —, —Se—, —NR 1 —, —PR 1 —, —P(O)R 1 —, —BR 1 —, or —AlR 1 —, wherein R 1 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and may be identical to or different from each other;
q represents an integer of from 1 to 5 representing [(valence of M)−2]; and
r represents an integer of from 0 to 3.

2. The method according to claim 1 , wherein a molar ratio [(D)/(A)] of a molar quantity of an aluminum atom in the component (D) to a molar quantity of a transition metal in the component (A) is more than 2.

3. The method according to claim 1 , wherein a molar ratio [(C)/(D)] of a molar quantity of an aluminum atom in the component (C) to a molar quantity of an aluminum atom in the component (D) is 0.01 or more.

4. The method according to claim 1 , wherein the component (C) is represented by a formula (iii):

wherein in the formula (iii), Rb represents an alkyl group having 1 to 20 carbon atoms, and Rb's may be identical to or different from each other.

5. The method according to claim 1 , wherein the olefin raw material comprises an α-olefin having 3 to 30 carbon atoms, ethylene, or both.

6. The method according to claim 1 , wherein the nonpolymerizable unsaturated hydrocarbon (N) comprises a disubstituted olefin, a trisubstituted olefin, or a tetrasubstituted olefin represented by a formula (iv), or an alkyne compound represented by a formula (v):

wherein:
R a to R d each independently represent hydrogen or a hydrocarbon group having 1 or more carbon atoms, provided that at least two selected from R a to R d each represent the hydrocarbon group; and
R e and R f each independently represent hydrogen or a hydrocarbon group having 1 or more carbon atoms.

7. The method according to claim 1 , wherein a molar ratio [(N)/(A)] of a molar quantity of the component (N) to a molar quantity of a transition metal in the component (A) is 500 or more.

8. An olefin polymerization catalyst, which is obtained by contacting components (A) to (D) with each other:
(A) a transition metal compound;
(B) a boron compound capable of forming an ion pair with the component (A);
(C) an organoaluminum compound represented by a formula (VIII):
R 17 v AlJ 3-v   (VIII)

(D) an aluminoxane represented by a formula (i) or (ii):

wherein:
R 17 represents an alkyl group having 1 to 20 carbon atoms;
J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom;
v represents an integer of from 1 to 3, and when v represents 2 or more, R 17 's may be identical to or different from each other, provided that at least one R 17 represents an alkyl group having 1 to 20 carbon atoms;
Ra represents an alkyl group having 1 to 20 carbon atoms, Ra's may be identical to or different from each other, and n represents an integer of from 1 to 50;
the transition metal compound (A) is a double crosslinked metallocene complex represented by a formula (I):

M represents a metal element of Groups 3 to 10 of the periodic table or the lanthanoid series;
E 1 and E 2 each represent a ligand selected from a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group, and a silicon-containing group, form a crosslinked structure via A 1 and A 2 , and may be identical to or different from each other;
X represents a α-bonding ligand, and when a plurality of X's are present, the plurality of X's may be identical to or different from each other, and X may be crosslinked with any other X, E 1 , E 2 or Y;
Y represents a Lewis base, and when a plurality of Y's are present, the plurality of Y's may be identical to or different from each other, and Y may be crosslinked with any other Y, E 1 , E 2 , or X;
A 1 and A 2 each represent a divalent crosslinking group for bonding two ligands, and each represent a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, —O—, —CO—, —S—, —SO 2 —, —Se—, —NR 1 —, —PR 1 —, —P(O)R 1 —, —BR 1 —, or —AlR 1 —, wherein R 1 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20

Assignees

• Idemitsu Kosan Co

Inventors

• Nishida Masayuki
• Samejima Kanako

Classifications

• C08F110/06 Primary

  Propene · CPC title

• C08F2500/17

  Viscosity · CPC title

• C08F10/00

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

• C08F4/645

  Component covered by group C08F4/64 with a metal or compound covered by group C08F4/44, not provided for in a single group of groups C08F4/642 - C08F4/643 {(C08F4/60003 - C08F4/60196 take precedence)} · CPC title

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title