# US 2014/0194637 A1 · A-olefin oligomer and production method thereof

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- Number: US 2014/0194637 A1
- Document ID: US20140194637A1
- Status: Published application
- Kind: A1
- Application number: 14/238,165
- Filed: 2012-07-31
- Published: 2014-07-10
- Earliest claimed: 2011-08-12
- Assignees: Idemitsu Kosan Co., Ltd.
- Inventors: Minako Tsuji; Takuji Okamoto; Takenori Fujimura; Yutaka Minami
- Web page: https://patentgrep.com/patent/US20140194637A1

## CPC

- C07C 2/34: Metal-hydrocarbon complexes
- B01J 31/143: {of aluminium}
- B01J 31/146: {of boron}
- B01J 31/2295: {Cyclic compounds, e.g. cyclopentadienyls}
- C07C 2/24: with metals
- C07C 2/32: as complexes, e.g. acetyl-acetonates {(complexes of salts of acids of halogen C07C2/20)}
- C07C 11/02: Alkenes
- C07C 11/21: Alkatrienes; Alkatetraenes; Other alkapolyenes
- C07F 7/0803: {Compounds with Si-C or Si-Si linkages}
- C08F 110/14: Monomers containing five or more carbon atoms
- B01J 2231/20: Olefin oligomerisation or telomerisation
- B01J 2531/48: Zirconium
- C07C 2531/14: of aluminium or boron
- C07C 2531/38: of titanium, zirconium or hafnium
- C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

An α-olefin oligomer having the following features (1) to (6), and a method for producing the α-olefin oligomer using a particular double-crosslinked meso complex provide an α-olefin oligomer that contains a smaller amount of a dimer component while having a low viscosity, not in accordance with the Schulz-Flory distribution, and a method for producing the same: (1) a trimer component proportion C3 (% by mass) that is larger than a theoretical value obtained from the S—F distribution, (2) a hexamer component proportion C6 (% by mass) that is smaller than a theoretical value obtained from the S—F distribution, (3) a kinematic viscosity at 100° C. of 20 mm2/s or less, (4) a meso triad fraction [mm] measured by 13C-NMR of 40% by mol of less, (5) from 0.2 to 1.0 of a vinylidene group per one molecule, and (6) an average carbon number of a monomer unit of from 6 to 30, wherein the S—F distribution is calculated based on a chain propagation probability α calculated from a dimer component proportion C2 (% by mass).

## Claims

### Claim 1

An α-olefin oligomer, having:
a trimer component proportion C3 in an amount % by mass that is larger than a theoretical value obtained from a S—F distribution,
a hexamer component proportion C6 in an amount % by mass that is smaller than a theoretical value obtained from the S—F distribution,
a kinematic viscosity at 100° C. of 20 mm2/s or less,
a meso triad fraction [mm] measured by 13C-NMR of 40% by mol or less,
from 0.2 to 1.0 of a vinylidene group per one molecule, and
an average carbon number of a monomer unit of from 6 to 30,
wherein the S—F distribution is calculated based on a chain propagation probability α calculated from a dimer component proportion C2 (% by mass).

### Claim 2

A meso transition metal compound of formula (I):
wherein
M is a metal element of Groups 3 to 10 in the Periodic Table;
X is a σ-bonding ligand, in which when there are plural ligands represented by X, the plural ligands may be the same as or different from each other;
Y is a Lewis base, in which when there are plural Lewis bases represented by Y, the plural Lewis bases may be the same as or different from each other;
A and A′ are each independently a crosslinking group selected from the group consisting of a hydrocarbon group having from 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having from 1 to 20 carbon atoms, a silicon-comprising group, a germanium-comprising group and a tin-comprising group, in which A and A′ are different from each other;
m and n are each an integer of 1 or more, in which m and n are different from each other, and m+n is 3 or more;
q is an integer of from 1 to 5, which is ((valency of M)−2);
r is an integer of from 0 to 3; and
E is a group of formula (II), in which two groups represented by E may be the same as or different from each other:
wherein
R2 is each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to 20 carbon atoms, a halogen-comprising hydrocarbon group having from 1 to 4 carbon atoms, a silicon-comprising group and a hetero atom-comprising group; and
the bonds shown with the wavy line represent bonds to -(A)m- and -(A′)n-.

### Claim 3 (depends on 1)

The α-olefin oligomer according to claim 1, wherein the α-olefin oligomer is obtained by polymerizing an α-olefin with a polymerization catalyst comprising:
(A) a meso transition metal compound of formula (I), and
(B) at least one component selected from the group consisting of (B-1) a compound that is capable of forming an ionic complex through reaction with the transition metal compound as the component (A) or a derivative thereof, and (B-2) aluminoxane:
wherein in formula (I),
M is a metal element of Groups 3 to 10 in the Periodic Table;
X is a σ-bonding ligand, in which when there are plural ligands represented by X, the plural ligands may be the same as or different from each other;
Y is a Lewis base, in which when there are plural Lewis bases represented by Y, the plural Lewis bases may be the same as or different from each other;
A and A′ are each independently a crosslinking group selected from the group consisting of a hydrocarbon group having from 1 to 20 carbon atoms, a halogen-comprising hydrocarbon group having from 1 to 20 carbon atoms, a silicon-comprising group, a germanium-comprising group and a tin-comprising group, in which A and A′ are different from each other;
m and n are each an integer of 1 or more, in which m and n are different from each other, and m+n is 3 or more;
q is an integer of from 1 to 5, which is ((valency of M)−2);
r is an integer of from 0 to 3; and
E is a group of formula (II), in which two groups represented by E may be the same as or different from each other:
wherein in formula (II),
R2 is each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to 20 carbon atoms, a halogen-comprising hydrocarbon group having from 1 to 4 carbon atoms, a silicon-comprising group and a hetero atom-comprising group; and
the bonds shown with the wavy line represent bonds to -(A)m- and -(A′)n-.

### Claim 4

A method for producing an α-olefin oligomer, comprising polymerizing an α-olefin with a polymerization catalyst comprising:
(A) a meso transition metal compound of formula (I), and
(B) at least one component selected from the group consisting of (B-1) a compound that is capable of forming an ionic complex through reaction with the transition metal compound as the component (A) or a derivative thereof, and (B-2) aluminoxane:
wherein in formula (I),
M is a metal element of Groups 3 to 10 in the Periodic Table;
X is a σ-bonding ligand, in which when there are plural ligands represented by X, the plural ligands may be the same as or different from each other;
Y is a Lewis base, in which when there are plural Lewis bases represented by Y, the plural Lewis bases may be the same as or different from each other;
A and A′ are each independently a crosslinking group selected from the group consisting of a hydrocarbon group having from 1 to 20 carbon atoms, a halogen-comprising hydrocarbon group having from 1 to 20 carbon atoms, a silicon-comprising group, a germanium-comprising group and a tin-comprising group, in which A and A′ are different from each other;
m and n are each an integer of 1 or more, in which m and n are different from each other, and m+n is 3 or more;
q is an integer of from 1 to 5, which is ((valency of M)−2);
r is an integer of from 0 to 3; and
E is a group of formula (II), in which two groups represented by E may be the same as or different from each other:
wherein in formula (II),
R2 is each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to 20 carbon atoms, a halogen-comprising hydrocarbon group having from 1 to 4 carbon atoms, a silicon-comprising group and a hetero atom-comprising group; and
the bonds shown with the wavy line represent bonds to -(A)m- and -(A′)n-.

### Claim 5 (depends on 4)

The method according to claim 4, wherein the polymerization catalyst is a catalyst obtained by contacting the meso transition metal compound (A), the component (B) and an organoaluminum compound (C) with each other in advance to polymerizing.

### Claim 6 (depends on 5)

The method according to claim 5, wherein the polymerization catalyst is a catalyst obtained by contacting the meso transition metal compound (A), the component (B), the organoaluminum compound (C) and an α-olefin having from 3 to 18 (D) with each other in advance to polymerizing.

### Claim 7 (depends on 4)

The method according to claim 4, wherein in the formula (I), the crosslinking group -(A)m- is of formula (IV), and the crosslinking group -(A′)n- is of formula (IV′):
wherein in formulae (IV) and (IV′),
B and B′ are each independently a carbon atom, a silicon atom, a germanium atom or a tin atom;
R3 and R4 are each independently a hydrogen atom, an aliphatic hydrocarbon group having from 1 to 20 carbon atoms, an aromatic hydrocarbon group having from 6 to 20 carbon atoms, an oxygen-comprising group having from 1 to 20 carbon atoms, amine-comprising group having from 1 to 20 carbon atoms or a halogen-comprising group having from 1 to 20 carbon atoms; and
m and n are each independently an integer of 1 or more.

### Claim 8 (depends on 4)

The method according to claim 4, wherein the aluminoxane (B-2) is a linear aluminoxane of formula (VII), a cyclic aluminoxane of formula (VIII), or both:
wherein R9 is a hydrocarbon group having from 1 to 20 carbon atoms or a halogen atom, in which groups represented by R9 may be the same or different; and
w is a number of from 2 to 50, which is an average polymerization degree.

### Claim 9 (depends on 4)

The method according to claim 4, wherein the polymerization reaction is performed at a temperature of from 40 to 200° C.

### Claim 10 (depends on 4)

The method according to claim 4, wherein the polymerization reaction is performed under a hydrogen pressure of from an atmospheric pressure to 10 MPa (G).