Solid polyaluminoxane composition, olefin polymerization catalyst, olefin polymer production method and solid polyaluminoxane composition production method

Patent metadata

Field	Value
Publication number	US-10150823-B2
Application number	US-201715588358-A
Country	US
Kind code	B2
Filing date	May 5, 2017
Priority date	Feb 8, 2013
Publication date	Dec 11, 2018
Grant date	Dec 11, 2018

Abstract

An object of the invention is to provide a solid polyaluminoxane composition suitably used as a cocatalyst and a catalyst carrier in combination with an olefin oligomerization or polymerization catalyst, without the use of solid inorganic carriers such as silica. The solid polyaluminoxane composition of the invention includes a polyalkylaluminoxane and a trialkylaluminum, and has a solubility in n-hexane at 25° C. of less than 0.50 mol % as measured by a specific method (i), a solubility in toluene at 25° C. of less than 1.0 mol % as measured by a specific method (ii), and a 13 mol % or more molar fraction of alkyl groups derived from the trialkylaluminum moieties relative to the total number of moles of alkyl groups derived from the polyalkylaluminoxane moieties and the alkyl groups derived from the trialkylaluminum moieties as measured with respect to tetrahydrofuran-d 8 soluble components by a specific method (iii).

First claim

The invention claimed is:

1. A solid polyaluminoxane composition comprising a polyalkylaluminoxane and a trialkylaluminum,
the composition having a solubility in n-hexane at 25° C. of less than 0.50 mol % as measured by a method (i) described below,
the composition having a solubility in toluene at 25° C. of less than 1.0 mol % as measured by a method (ii) described below,
the molar fraction of alkyl groups of the trialkylaluminum moieties being 13 mol % or more relative to the total number of moles of alkyl groups of the polyalkylaluminoxane moieties and the alkyl groups of the trialkylaluminum moieties as measured with respect to tetrahydrofuran-d 8 soluble components by a method (iii) described below:
[Method (i)]
2 g of the solid polyaluminoxane composition is added to 50 mL of n-hexane held at 25° C.; the mixture is stirred for 2 hours and is filtered to give a filtrate and a residue; and the aluminum concentration in the filtrate is measured by ICP atomic emission spectroscopy (ICP-AES) to determine the solubility as the ratio of aluminum atoms present in the filtrate relative to the amount of aluminum atoms corresponding to 2 g of the solid polyaluminoxane composition;

[Method (ii)]
the solubility is measured in a similar manner to the method (i) except that toluene is used in place of n-hexane;

[Method (iii)]
0.5 mL of tetrahydrofuran (THF)-d 8 (a heavy solvent) is added to 10 mg of the solid polyaluminoxane composition; the mixture is stirred at 25° C. for 2 hours; and the molar fraction is determined by analyzing the THF-d 8 soluble components by 1H-NMR at a measurement temperature of 24° C.

2. The solid polyaluminoxane composition according to claim 1 , wherein the composition has a solubility in tetrahydrofuran at 25° C. of 95 mol % or less as measured by a method (iv) described below:
[Method (iv)]
the solubility is measured in a similar manner to the method (i) except that tetrahydrofuran is used in place of n-hexane.

3. The solid polyaluminoxane composition according to claim 1 , wherein the polyalkylaluminoxane contains a structural unit represented by General Formula (1) below and the trialkylaluminums include trimethylaluminum

4. The solid polyaluminoxane composition according to claim 1 , wherein the polyalkylaluminoxane is polymethylaluminoxane and the trialkylaluminum is trimethylaluminum, and
the molar fraction of methyl groups of the trimethylaluminum moieties is 13 mol % or more relative to the total number of moles of methyl groups of the polymethylaluminoxane moieties and the methyl groups of the trimethylaluminum moieties as measured with respect to tetrahydrofuran-d 8 soluble components by the method (iii).

5. The solid polyaluminoxane composition according to claim 1 , wherein the composition has a specific surface area in the range of 400 to 800 m 2 /g.

6. The solid polyaluminoxane composition according to claim 1 , wherein the composition is particles having a median diameter D50 in the cumulative volume in the range of 0.1 to 100 m.

7. The solid polyaluminoxane composition according to claim 1 , wherein the uniformity represented by the following equation is not more than 0.27,
Uniformity=Σ Xi|D 50− Di|/D 50Σ Xi   (Equation)

wherein Xi is the histogram value of a particle i, D50 is the volume-based median diameter, and Di is the volume-based diameter of the particle i.

8. An olefin polymerization catalyst obtained by bringing the solid polyaluminoxane composition described in claim 1 into contact with a transition metal compound (H) having a transition metal atom selected from Groups 3 to 10 in the periodic table, the transition metal compound being represented by General Formula (8) below:
R 31 R 32 R 33 R 34 M  (8)

in the formula, M is a transition metal atom selected from Groups 3 to 10 in the periodic table, and R 31 , R 32 , R 33 and R 34 are the same as or different from one another and each is a cyclopentadienyl skeleton-containing group, an alkyl, a cycloalkyl, an aryl, an aralkyl, an alkoxy, an aryloxy, a halogen atom, an alkylsilyl, an alkylamide, an alkylimide, —SO 3 R or a hydrogen atom.

9. An olefin polymer production method comprising a step of polymerizing one or more olefins selected from α-olefins having 2 to 20 carbon atoms, cycloolefins having 3 to 20 carbon atoms and diene compounds having 4 to 20 carbon atoms in the presence of the olefin polymerization catalyst described in claim 8 .

Assignees

• Mitsui Chemicals Inc

Inventors

• Tsurugi Kou
• Hanada Shiori
• Shibahara Atsushi
• Kawamura Kazumori
• Nishino Fumiaki
• Harada Yasuyuki
• Yamada Wataru
• Matsumoto Akiko
• Hara Isao
• Nakamura Tatsuya
• Muroto Toshihiro

Classifications

• C08F4/027

  Polymers · CPC title

• C08F4/02

  Carriers therefor · CPC title

• C07F5/068

  preparation of alum(in)oxanes · CPC title

• C08F4/65922 Primary

  containing at least two cyclopentadienyl rings, fused or not · CPC title

• C08F110/02

  Ethene · CPC title