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Method for preparing tetra(fluoroaryl) borate

A fluoroaryl, borate technology, applied in the field of preparing proton ammonium tetraborate, can solve the problem of being sensitive to heat-sensitive vibration, etc., and achieve the effects of reduced heat and vibration sensitivity, high purity, and high yield

Inactive Publication Date: 2011-05-25
ALBEMARLE CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Furthermore, alkali metal tetrakis(fluoroaryl)borates tend to be heat sensitive and shock sensitive when dry

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0049] All operations in this example were carried out in a dry nitrogen atmosphere. N, N-dimethylaniline (N, N-dimethylaniline) (1.90 g, 15.7 mol) was added to about 14.9 g of toluene-wetted, purified potassium tetrakis(pentafluorophenyl) borate solid (70.4 wt % Potassium tetrakis(pentafluorophenyl)borate, 10.5g, 14.6mmol). Next, diethyl ether (88 g) was added to the mixture. The mixture was stirred until potassium tetrakis(pentafluorophenyl)borate was dissolved. While stirring, an aqueous solution of hydrochloric acid (83.5 g, 0.71 wt %; 0.59 g neat, 16.3 mmol) was added over 5 minutes while maintaining the temperature <15°C. With continuous stirring, the temperature was allowed to heat up to 18°C ​​for over 30 minutes. Stirring was then interrupted, the mixture was allowed to remain forming separate aqueous and organic phases, the lower aqueous phase was removed and discarded. As stirring continued, the organic phase was washed with aqueous sodium chloride (42.5 g, 0.25...

Embodiment 2

[0052] All operations in this example were carried out under nitrogen atmosphere. A 10 wt% solution of potassium tetrakis(pentafluorophenyl)borate (13.0 g, 18.2 mmol) in diethyl ether was treated with N,N-dimethylaniline (2.35 g, 19.4 mmol). While stirring, 103.3 g of 0.71 wt% aqueous HCl (0.73 g, 20.1 mmol) were added at 10°C. With continuous stirring, the temperature was allowed to warm slightly to 18°C ​​over 45 minutes. Stirring was then discontinued and the lower aqueous phase was removed by a scrubber. The organic phase was treated with 50.5 g of 1 wt% NaCl in water at 15-18°C, and the mixture was stirred for about 60 minutes. Stirring is then discontinued and the lower aqueous phase can be removed with a scrubber.

[0053] A wet solution comprising N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate was added to the reflux mixture, which was a 3:1 mixture of toluene and Isopar-E, at about 113°C. As the ether and water began to co-condense with the toluene and Is...

Embodiment 3

[0055] Potassium tetrakis(pentafluorophenyl)borate (2.80g, 3mmol), N, N-dimethylaniline (0.382g, 3.15mmol) and Et 2 O (12.0g) in N 2 The atmosphere was simultaneously added to the reactor and stirred to mix together. When at 10-15°C temperature N 2 While stirring under atmosphere for about 15 minutes, an aqueous solution of HCl (1 wt%, 3.3 mmol) was added dropwise to the potassium tetrakis(pentafluorophenyl)borate mixture. The pH of the aqueous layer is about 2-3. The reaction mixture was stirred at 25°C for 2 hours. The mixture is allowed to stand to separate and the aqueous layer can be removed, which has a pH of 2-3. h 2 A solution of O (12 g) and NaCl (0.09 g) was added to the ether layer to rinse the ether solution of dimethylanilinium tetrakis(pentafluorophenyl)borate to remove excess HCl, dimethylaniline chloride, and KCl by-products . The mixture was stirred for half an hour, allowed to stand for half an hour to separate the aqueous and organic layers, and the p...

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Abstract

This invention provides a process for producing a protic ammonium tetrakis(<F>aryl)borate. The process comprises mixing together (a) at least one alkali metal tetrakis(<F>aryl)borate, at least one magnesium tetrakis(<F>aryl)borate, at least one halomagnesium tetrakis(<F>aryl)borate, or a mixture of two or more of the foregoing, (b) at least one amine, and (c) one or more liquid dihydrocarbyl ethers, one or more liquid hydrocarbons, one or more liquid halogenated hydrocarbons, or a mixture of two or more of the foregoing, to form a solution or slurry in a liquid organic medium. At least one protic acid is mixed together with at least a portion of the solution or slurry formed in i), such that a protic ammonium tetrakis(<F>aryl)borate is formed. The amine has the formula R3N, in which each R is independently a hydrocarbyl group containing up to about thirty carbon atoms. Each of the <F>aryl groups is a fluorine-containing aryl group that has bonded directly to an aromatic ring at least two fluorine atoms, or at least two perfluorohydrocarbyl groups, or at least one fluorine atom and at least one perfluorohydrocarbyl group.

Description

technical field [0001] The present invention relates to a method for preparing protic ammonium tetrakis (fluoroaryl) borate by using alkali metal tetrakis (fluoroaryl) borate, bis[tetrakis (fluoroaryl) borate] magnesium and tetrakis (fluoroaryl) borate halide magnesium Methods. Protic ammonium tetrakis(fluoroaryl)borates are used as cocatalysts in metallocene-catalyzed polymerization reactions. Background technique [0002] Methods for preparing protic ammonium tetrakis(fluoroaryl)borates are well known in the art. An example of this is the process disclosed in U.S. Patent No. 6,162,950 in which an alkali metal tetrakis(fluoroaryl)borate is reacted with a simple protic ammonium salt to form a protic ammonium tetrakis(fluoroaryl)borate. Another method for the preparation of protic ammonium tetrakis(fluoroaryl)borates is that disclosed in patent U.S. 6,169,208, in which magnesium bis[tetrakis(fluoroaryl)borate] is reacted with a simple protic ammonium salt to form tetrakis(f...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F5/02
CPCC07F5/027
Inventor 约翰·Y.·李拉吉夫·S.·马瑟
Owner ALBEMARLE CORP