Modified solid polyalkylaluminoxane and catalyst for olefin oligomerization reaction

Patent metadata

Field	Value
Publication number	US-10124326-B2
Application number	US-201515515390-A
Country	US
Kind code	B2
Filing date	Sep 24, 2015
Priority date	Sep 30, 2014
Publication date	Nov 13, 2018
Grant date	Nov 13, 2018

Abstract

A modified solid polyalkylaluminoxane is provided, which is capable of providing α-olefin suppressing adhesion of any polymer produced as a by-product onto the reactor wall and the stirrer, and which is capable of providing a highly active olefin oligomerization reaction catalyst. An olefin oligomerization reaction catalyst containing the modified solid polyalkylaluminoxane is also provided. The modified solid polyalkylaluminoxane for olefin oligomerization reactions contains structural units represented by general formula (a) and structural units represented by general formula (b), whose median diameter is equal to or larger than 0.1 μm and equal to or smaller than 50 μm,

in which R′ in the general formula (a) represents an alkyl group having 1 to 20 carbon atoms, and R″ in the general formula (b) represents a halogenated alkoxy group having 1 to 20 carbon atoms or a halogenated aryloxy group having 6 to 20 carbon atoms.

First claim

The invention claimed is:

1. A modified solid polyalkylaluminoxane for olefin oligomerization reactions, the modified polyalkylaluminoxane having a median diameter of 0.1 μm to 50 μm and comprising
structural units represented by the following general formula (a), and
structural units represented by the following general formula (b),

in which R′ in the general formula (a) represents an alkyl group having 1 to 20 carbon atoms; and R″ in the general formula (b) represents a halogenated alkoxy group having 1 to 20 carbon atoms or a halogenated aryloxy group having 6 to 20 carbon atoms.

2. The modified solid polyalkylaluminoxane of claim 1 , wherein
R″ in the general formula (b) is a halogenated aryloxy group having 6 to 20 carbon atoms.

3. The modified solid polyalkylaluminoxane of claim 2 , wherein
the halogenated aryloxy group having 6 to 20 carbon atoms is a pentafluorophenoxy group.

4. The modified solid polyalkylaluminoxane of claim 1 , wherein
the ratio (m/(m+n)) of the number (m) of the structural units represented by the general formula (b) to the total of the number (n) of the structural units represented by the general formula (a) and the number (m) of the structural units represented by the general formula (b) is 0.05 to 0.5.

5. An olefin oligomerization reaction catalyst comprising
the modified solid polyalkylaluminoxane of claim 1 and
at least one complex selected from the following group of transition metal complexes,
wherein the group of transition metal complexes is a group consisting of transition metal complexes represented by the following general formula (2-1), transition metal complexes represented by the following general formula (2-2), transition metal complexes represented by the following general formula (2-3), transition metal complexes represented by the following general formula (2-4), and transition metal complexes represented by the following general formula (2-5),

in which
M 1 in each of the general formula (2-1), the general formula (2-2), and the general formula (2-3) represents a transition metal atom of Group 4 of the periodic table of the elements;
X 1 , X 2 , X 3 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 in each of the general formula (2-1), the general formula (2-2), and the general formula (2-3), R 12 , R 13 , R 14 , R 15 , and R 16 in each of the general formula (2-2) and the general formula (2-3), and R 17 , R 18 , R 19 , R 20 , and R 21 in the general formula (2-3) each independently represent a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a substituted hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, a substituted hydrocarbyloxy group having 1 to 20 carbon atoms, a substituted silyl group, or a disubstituted amino group;
when two selected from R 1 , R 2 , R 3 , and R 4 each are a hydrocarbyl group having 1 to 20 carbon atoms, a substituted hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, or a substituted hydrocarbyloxy group having 1 to 20 carbon atoms, the two selected from R 1 , R 2 , R 3 , and R 4 are optionally bonded to each other at a site thereof formed by removing a hydrogen atom from the substituent group;
when two selected from R 5 , R 6 , R 7 , R 8 , and R 9 each are a hydrocarbyl group having 1 to 20 carbon atoms, a substituted hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, or a substituted hydrocarbyloxy group having 1 to 20 carbon atoms, the two selected from R 5 , R 6 , R 7 , R 8 , and R 9 are optionally bonded to each other at a site thereof formed by removing a hydrogen atom from the substituent group;
when two selected from R 12 , R 13 , R 14 , R 15 , and R 16 each are a hydrocarbyl group having 1 to 20 carbon atoms, a substituted hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, or a substituted hydrocarbyloxy group having 1 to 20 carbon atoms, the two selected from R 12 , R 13 , R 14 , R 15 , and R 16 are optionally bonded to each other at a site thereof formed by removing a hydrogen atom from the substituent group;
when two selected from R 17 , R 18 , R 19 , R 20 , and R 21 each are a hydrocarbyl group having 1 to 20 carbon atoms, a substituted hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, or a substituted hydrocarbyloxy group having 1 to 20 carbon atoms, the two selected from R 17 , R 18 , R 19 , R 20 , and R 21 are optionally bonded to each other at a site thereof formed by removing a hydrogen atom from the substituent group;
R 10 in the general formula (2-1) and R 11 in the general formula (2-1) and the general formula (2-2) each independently represent a hydrocarbyloxy group having 1 to 20 carbon atoms, a substituted hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, a substituted hydrocarbyloxy group having 1 to 20 carbon atoms, a substituted silyl group, or a disubstituted amino group; and
R 10 and R 11 may be bonded to each other at a site thereof formed by removing a hydrogen atom from the substituent group,

in which
M 2 in the general formula (2-4) represents a transition metal atom of Group 4 of the periodic table of the elements;
A 21 represents an oxygen atom, a nitrogen atom, a phosphorus atom, or a sulfur atom Z 1 represents a group linking A 21 and N to each other, and the smallest number of the bonds linking A 21 and N to each other is 4 to 6, and the bond linking A 21 and Z 1 to each other may be a double bond;
R 24 , R 25 , R 26 , R 27 , R 28 , X 4 , X 5 , and X 6 each independently represent a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a substituted hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, a substituted hydrocarbyloxy group having 1 to 20 carbon atoms, a substituted silyl group, or a disubstituted amino group;
when two selected from R 24 , R 25 , R 26 , R 27 , and R 28 each are a hydrocarbyl group having 1 to 20 carbon atoms, a substituted hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, or a substituted hydrocarbyloxy group having 1 to 20 carbon atoms, the two selected from R 24 , R 25 , R 26 , R 27 , and R 28 are optionally bonded to each other at a site thereof formed by removing a hydrogen atom from the substituent group;
R 29 represents a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a substituted hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbylidene group having 1 to 20 carbon atoms, or a substituted hydrocarbylidene group having 1 to 20 carbon atoms, the bond linking R 29 and A 21 to each other may be a double bond, and R 29 may be bonded to Z 1 ,

in which
M 2 in the general formula (2-5) represents a transition metal atom of Group 4 of the periodic table of the elements;
A 22 represents a nitrogen atom or a phosphorus atom, and Z 2 represents a group linking A 22 and N to each other and the smallest number of the bonds linking A 22 and N to each other is 4 to 6;
R 24 , R 25 , R 26 , R 27 , R 28 , X 4 , X 5 , and X 6 each independently represent a hydrogen atom, a halogen atom, a hydrocarbyl group having

Assignees

• Sumitomo Chemical Co

Inventors

• Sogoh Kenji
• Kashiwame Yohei
• Hino Takahiro

Classifications

• B01J31/1616

  Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts (catalysts comprising molecular sieves B01J29/00) · CPC title

• C07F5/068

  preparation of alum(in)oxanes · CPC title

• C07C2/30

  containing metal-to-carbon bond; Metal hydrides · CPC title

• B01J31/143 Primary

  of aluminium · CPC title

• C08F4/02

  Carriers therefor · CPC title