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

Patent metadata

Field	Value
Publication number	US-10870715-B2
Application number	US-201816171192-A
Country	US
Kind code	B2
Filing date	Oct 25, 2018
Priority date	Feb 8, 2013
Publication date	Dec 22, 2020
Grant date	Dec 22, 2020

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-d8 soluble components by a specific method (iii).

First claim

The invention claimed is:

1. A method of producing a solid polyaluminoxane composition, the method comprising:
(1) reacting a polyaluminoxane composition solution (A), which comprises a polyalkylaluminoxane, a trialkylaluminum and a hydrocarbon solvent, with at least one organic compound (B) containing at least one of X, which is a Group 15 element of the Periodic Table, and Y, which is a Group 16 element of the Periodic Table, to form at least one component represented by General Formulae (5′) to (6′) below;

wherein alkyl groups of the trialkylaluminum are selected from alkyl groups having 1 to 20 carbon atoms;
wherein each -T and -Q is independently selected from the alkyl groups of the trialkylaluminum, or a polyaluminoxane group of the polyalkylaluminoxane, and R 13 and R 14 is each independently selected from a hydrocarbon groups having 1 to 50 carbon atoms, and precipitating a solid polyaluminoxane composition by reacting the polyaluminoxane composition solution (A) with the at least one component represented by General Formulae (5′) to (6′).

2. The method according to claim 1 , wherein 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 (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 1 H-NMR at a measurement temperature of 24° C.

3. The method according to claim 1 , wherein the solid polyaluminoxane composition having a solubility in n-hexane at 25° C. of less than 0.50 mol % as measured by a method (i) 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.

4. The method according to claim 1 , wherein the solid polyaluminoxane composition having a solubility in toluene at 25° C. of less than 1.0 mol % as measured by a method (ii) described below,
[Method (ii)]
2 g of the solid polyaluminoxane composition is added to 50 mL of toluene 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.

5. The method according to claim 1 , wherein the solid polyaluminoxane composition has a solubility in tetrahydrofuran at 25° C. of 95 mol % or less as measured by a method (iv) described below:
[Method (iv)]
2 g of the solid polyaluminoxane composition is added to 50 mL of tetrahydrofuran 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.

6. The method according to claim 1 , wherein the uniformity of the solid polyaluminoxane composition represented by the following equation is not more than 0.40,
Uniformity= ΣXi|D 50− Di|/D 50 ΣXi

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.

7. The method according to claim 1 , wherein the precipitation step is performed at 40° C. or above.

8. The method according to 1 , wherein the method comprising a step of thermally aging the precipitate after the precipitation step.

9. The method according to claim 8 , wherein the thermal aging temperature is 65 to 200° C.

10. The method according to claim 1 , wherein the polyaluminoxane composition solution (A) is a partial hydrolysis reaction product of trialkylaluminum.

11. The method according to claim 1 , wherein the molar fraction of alkyl groups of the trialkylaluminum moieties being 16 mol % or more relative to the total number of moles of all the alkyl groups in the polyaluminoxane composition solution (A).

12. The method according to claim 1 , wherein the polyalkylaluminoxane in the polyaluminoxane composition solution (A) includes a polyaluminoxane containing a structural unit represented by General Formula (1) below:

13. The method according to claim 1 , wherein the trialkylaluminums in the polyaluminoxane composition solution (A) include trimethylaluminum.

14. The method according to claim 1 , wherein the polyalkylaluminoxane in the polyaluminoxane composition solution (A) is polymethylaluminoxane and the trialkylaluminum in the polyaluminoxane composition solution (A) is trimethylaluminum.

15. An olefin polymerization catalyst production method, wherein the method comprising bringing the solid polyaluminoxane composition produced by the method 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, R is a monovalent functional group.

16. 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 produced by the method described in claim 15 .

17. The method according to claim 1 , wherein the components represented by general Formulae (5) to (7) are the components represented by General Formula (6) below;
—(R12)Al—YR13 . . .  (6)

in General Formula (6), R12 is a hydrocarbon group having 1 to 20 carbon atoms or is an oxygen atom, Y is oxygen element, and R13 is hydrocarbon groups having 1 to 50 carbon atoms.

18. The method according to claim 17 , wherein the component represented by General Formula (6) is a reaction product of the polyaluminoxane composition solution (A) and at least one oxygen-containing organic compound (C).

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

• C08F4/02

  Carriers therefor · CPC title

• C08F210/16

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

• C08F4/65922 Primary

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

• C08G79/10

  a linkage containing aluminium · CPC title

• C08F10/00 Primary

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