JP2015074721A - Method for producing arylamine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an arylamine compound in which the palladium content and the phosphorus content are 0.1 to 100 ppm, respectively without using an oxidizing agent.SOLUTION: An arylamine compound is separated from a mixture which is obtained by mixing an arylamine compound containing more than 100 ppm of palladium and more than 100 ppm of phosphorus, an inorganic adsorbent and a nitrogen-containing heteroaromatic compound having 3 to 15 carbon atoms.

Description

  The present invention relates to a method for producing an arylamine compound having a Pd content and a P content of 0.1 to 100 ppm, respectively.

  An arylamine compound or the like is used for an organic EL display or the like. The arylamine compound is generally known to be efficiently produced using a reaction catalyst containing a palladium compound and a phosphorus compound. The arylamine compound produced by such a production method usually contains palladium or phosphorus exceeding 100 ppm. When a large amount of palladium (hereinafter also referred to as “Pd”) or phosphorus (hereinafter also referred to as “P”) derived from the reaction catalyst remains in the material for the organic EL display, the emission start voltage of the organic EL display is increased and the light emission is increased. It is known that problems such as a decrease in efficiency and a decrease in stability are likely to occur, and a method for efficiently removing Pd and P has been studied (for example, Patent Document 1).

  However, in the above method, a step of treating the material with an oxidizing agent is essential, and it is necessary to use an oxidizing agent such as hydrogen peroxide or OXONE (hydrogen persulfate reagent comprising hydrogen persulfate). Therefore, in this method, the arylamine compound is oxidized to produce an amine oxide compound. In the field of electronic materials, it is known that a very small amount of impurities has an adverse effect, and therefore, there has been a demand for a treatment method in which an oxide such as amine oxide is not generated. In view of equipment corrosion, work risk, etc., a method using no oxidizing agent has been desired.

International Publication WO 2004/108800 Publication

  The present invention has been made in view of the above-described background art, and its purpose is to reduce the Pd content and the P content without using an oxidizing agent, specifically, 0.1 to 100 ppm each. It is to provide a method for producing an arylamine compound.

  As a result of intensive studies to solve the above problems, the present inventors have found that an arylamine compound containing more than 100 ppm of Pd or more than 100 ppm of P, an inorganic adsorbent, and a nitrogen-containing heteroaromatic having 3 to 15 carbon atoms. By mixing the compounds and then separating the arylamine compound, it was found that an arylamine compound having a Pd content and a P content of 0.1 to 100 ppm was obtained, and the present invention was completed.

  According to the present invention, an arylamine compound having a Pd content and a P content of 0.1 to 100 ppm can be produced without using an oxidizing agent. Therefore, an arylamine compound having a Pd content and a P content of 0.1 to 100 ppm can be produced safely and easily without producing an amine oxide compound.

  Hereinafter, the present invention will be described in detail.

  The present invention relates to a method for producing an arylamine compound having a Pd content and a P content of 0.1 to 100 ppm each, and an arylamine compound and an inorganic adsorbent containing palladium exceeding 100 ppm or phosphorus exceeding 100 ppm And a nitrogen-containing heteroaromatic compound having 3 to 15 carbon atoms, and then the arylamine compound is separated.

  The arylamine compound in the present invention is not particularly limited as long as it is generally known. Among these, the arylamine compound of the present invention is preferably an arylamine polymer in terms of excellent adaptability to the production method.

  The arylamine polymer is not particularly limited as long as it is a generally known substance, but means an arylene group or heteroarylene group and an amino group alternately bonded, and the amino group is a diarylamino group or Represents a triarylamino group.

  The arylamine polymer is preferably represented by the following general formula from the viewpoint of high adaptability to the production method.

（式中、Ａｒ^１は、各々独立して、置換基を有してもよいアリール基又はヘテロアリール基を表わす。Ａｒ^２は、各々独立して、置換基を有してもよいアリーレン基又はヘテロアリーレン基を表わす。ｎは２以上の整数を表す。）
Ａｒ^１で表される置換基を有してもよいアリール基又はヘテロアリール基は、特に限定するものではないが、本製造方法への適応効果が高い点で、置換基を有してもよい炭素数６〜２４のアリール基又は置換基を有してもよい炭素数３〜２４のアリール基であることが好ましい。当該置換基としては、特に限定するものではないが、例えば、フェニル基、トリル基、メトキシフェニル基、ｎ−ブチルフェニル基、ｔ−ブチルフェニル基、トリフルオロメチルフェニル基、フルオロフェニル基、シアノフェニル基、ジフェニリル基、ターフェニル基、ナフチル基、フルオレニル基、６−フェニルヘキシルフェニル基ピリジル基、メチルピリジル基、フェニルピリジル基、カルバゾリル基、チエニル基、ビチエニル基、フリル基、ジベンゾフリル基、ジベンゾチエニル基等が挙げられる。

(In the formula, each Ar ¹ independently represents an aryl group or a heteroaryl group which may have a substituent. Ar ² each independently represents an arylene group which may have a substituent or Represents a heteroarylene group, and n represents an integer of 2 or more.)
The aryl group or heteroaryl group which may have a substituent represented by Ar ¹ is not particularly limited, but may have a substituent in terms of high adaptability to the production method. It is preferable that it is a C3-C24 aryl group which may have a C6-C24 aryl group or a substituent. The substituent is not particularly limited, and examples thereof include a phenyl group, a tolyl group, a methoxyphenyl group, an n-butylphenyl group, a t-butylphenyl group, a trifluoromethylphenyl group, a fluorophenyl group, and a cyanophenyl. Group, diphenylyl group, terphenyl group, naphthyl group, fluorenyl group, 6-phenylhexylphenyl group pyridyl group, methylpyridyl group, phenylpyridyl group, carbazolyl group, thienyl group, bithienyl group, furyl group, dibenzofuryl group, dibenzothienyl group Groups and the like.

The arylene group or heteroarylene group that may have a substituent represented by Ar ² is not particularly limited, but may have a substituent in terms of high adaptability to the production method. A C6-C24 arylene group or a C3-C24 heteroarylene group which may have a substituent is preferable. The substituent is not particularly limited. For example, benzenediyl group, toluenediyl group, methoxybenzenediyl group, n-butylbenzenediyl group, trifluoromethylbenzenediyl group, fluorobenzenediyl group, cyanobenzene Diyl group, diphenyldiyl group, terphenyldiyl group, naphthalenediyl group, fluorenediyl group, pyridinediyl group, methylpyridinediyl group, phenylpyridinediyl group, carbazolediyl group, thiophenediyl group, frangylyl group, dibenzofurandyl group , Dibenzothiophene diyl group, phenylenepyridine diyl group and the like.

  In the present invention, the Pd content and the P content represent the Pd content and the P content in the arylamine compound of the present invention, respectively. The content of the atoms is not particularly limited, but can be quantified by ICP (inductively coupled plasma) analysis.

  In the present invention, an arylamine compound containing palladium exceeding 100 ppm or phosphorus exceeding 100 ppm is produced using a reaction catalyst containing at least a palladium compound and a phosphorus compound in terms of high adaptability to the production method, Preference is given to arylamine compounds containing more than 100 ppm palladium or more than 100 ppm phosphorus.

  Palladium and phosphorus in the present invention are derived from the reaction catalyst used in the synthesis reaction of the arylamine compound of the present application.

  The palladium compound used for the reaction catalyst is not particularly limited. For example, palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, palladium (II) acetylacetonate, dichlorobis ( Benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorotetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II), Divalent palladium compounds such as palladium (II) trifluoroacetate, tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium (0) chloroform complex, tetrakis (tripheny Phosphine) palladium (0), palladium - can be mentioned 0-valent palladium compounds such as carbon.

  The phosphorus compound used for the reaction catalyst is not particularly limited, and examples thereof include alkyl phosphines, aryl phosphines, and oxides thereof. Examples of the alkyl phosphines include triethylphosphine, tricyclohexylphosphine, triisopropylphosphine, tri-n-butylphosphine, triisobutylphosphine, tri-sec-butylphosphine, tri-tert-butylphosphine, and the like. Examples of aryl phosphines include triphenylphosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri (p-tolyl) phosphine, 2,2′-bis (diphenylphosphino) -1, Examples thereof include 1'-binaphthyl (BINAP), trimesityl phosphine, diphenylphosphinoethane, diphenylphosphinopropane, diphenylphosphinoferrocene and the like.

  The inorganic adsorbent used in the present invention is not particularly limited as long as it is a generally known material, and examples thereof include alumina, carbon, silica gel, zeolite, zirconia, magnesia, titania and the like.

  Of these, silica gel is preferred because of its high adaptability to the present production method. The silica gel may be porous or non-porous, may be A-type or B-type, and may be used for medium-low pressure chromatography or HPLC. Of these, silica gel for medium to low pressure chromatography is preferred because of its high adaptability to the present production method.

  The nitrogen-containing heteroaromatic compound having 3 to 15 carbon atoms in the present invention is not particularly limited as long as it is a generally known compound. However, a pyrrolyl group, an imidazolyl group, A nitrogen-containing heteroaromatic compound having 3 to 15 carbon atoms having a pyridyl group, a pyrimidyl group, a benzimidazolyl group, an indolyl group, a quinolyl group, an isoquinolyl group, or a phenanthrolinyl group is preferable.

  A nitrogen-containing heteroaromatic compound having 3 to 15 carbon atoms (or carbon number having a pyrrolyl group, an imidazolyl group, a pyridyl group, a pyrimidyl group, a benzimidazolyl group, an indolyl group, a quinolyl group, an isoquinolyl group, or a phenanthrolinyl group The nitrogen-containing heteroaromatic compound of 3 to 15 is not particularly limited, and examples thereof include pyrrole, 3-methylpyrrole, imidazole, 1-methylimidazole, 2-methylimidazole, pyridine, 2-methylpyridine, 3- Methylpyridine, 4-methylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2,2'-bipyridyl, 4,4'-bipyridyl, pyrimidine, 2-methylpyrimidine, 4-methylpyrimidine, 2-phenylpyrimidine, 4 -Phenylpyrimidine, 2,2'-bipyrimidine, 4,4'- Pyrimidine, benzimidazole, 2-methylbenzimidazole, indole, 2-methylindole, quinoline, 6-methylquinoline, 7-methylquinoline, 8-methylquinoline, isoquinoline, 2-phenylquinoline, isoquinoline, 1-methylisoquinoline, 6 -Methylisoquinoline, 8-methylisoquinoline, 1-phenylisoquinoline, 2,2 ′, 6 ′, 2 ″ -terpyridyl and the like. Of these, pyrrole, pyridine, 2,2'-bipyridyl, or 2,2 ', 6', 2 "-terpyridyl is particularly preferable because of its high adaptability to the present production method. In the present invention, with respect to the nitrogen-containing heteroaromatic compound having 3 to 15 carbon atoms, one compound can be used alone, or two or more compounds can be mixed and used.

  Although it does not specifically limit as an arylamine compound in this invention, An arylamine etc. can be mentioned and any of primary, secondary, or tertiary may be sufficient. Among these, an amine compound having a molecular weight or a weight average molecular weight in the range of 500 to 1,000,000 is more preferable from the viewpoint of high adaptability to the present production method.

  When the arylamine compound containing palladium exceeding 100 ppm or phosphorus exceeding 100 ppm, the inorganic adsorbent, and the nitrogen-containing heteroaromatic compound having 3 to 15 carbon atoms may be mixed in the presence of an organic solvent. The organic solvent is not particularly limited as long as it is a generally known one. For example, an aliphatic hydrocarbon solvent, an alcohol solvent, an aromatic hydrocarbon solvent, an ether solvent, an aprotic polar solvent Specific examples include chloroform, dichloromethane, n-hexane, cyclohexane, octane, methanol, ethanol, isopropanol, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, acetonitrile, dimethylformamide, and the like. Examples thereof include dimethyl sulfoxide.

  The solvent is preferably selected based on the solubility of the arylamine compound of the present invention and the nitrogen-containing heteroaromatic compound having 3 to 15 carbon atoms. Among these, it is preferable to select a solvent that dissolves the arylamine compound of the present invention well. These solvents may be used by mixing two or more kinds of solvents at an arbitrary ratio, but are preferably used alone from the viewpoint of post-treatment and reuse.

  In the arylamine compound of the present invention, in addition to palladium and phosphorus, other compounds such as a solvent, a metal, and a base used for the synthesis reaction of the arylamine compound may be contained.

  The arylamine compound of the present invention is a reaction solution for the Buchwald-Hartwig reaction (hereinafter referred to as “CN bond reaction”), which is one of organic synthesis reactions using a reaction catalyst containing at least a palladium compound and a phosphorus compound. In some cases, the reaction solution after the reaction can be used as it is in the production method of the present invention, or a reaction solution that has been subjected to post-treatment such as extraction, filtration, and distillation. Moreover, you may use what was diluted or concentrated using the solvent used for CN bond reaction, or another solvent.

  In the C—N bonding reaction, the palladium compound used is not particularly limited, and examples thereof include the same compounds as described above.

  In the C—N bonding reaction, the phosphorus-based ligand used is not particularly limited, and examples thereof include the same ones as described above.

  Although it does not specifically limit as an arylamine compound used for this invention, It is preferable that it is a solution with a density | concentration of 0.2 to 40 weight%, and 0.5 to 10 weight from the point of solution viscosity and processing efficiency. It is more preferable that the solution has a concentration of%.

  A method of mixing an arylamine compound containing palladium exceeding 100 ppm or phosphorus exceeding 100 ppm, an inorganic adsorbent, and a nitrogen-containing heteroaromatic compound having 3 to 15 carbon atoms is not particularly limited. Examples include a method of mixing in a container and stirring for a predetermined time to make contact, a column chromatography method, a fixed bed chromatography method, a moving bed chromatography method, and a simulated moving bed chromatography method.

  Although it does not specifically limit as the usage-amount of a C3-C15 nitrogen-containing heteroaromatic compound, It is 1 to 200 times by weight with respect to an arylamine compound, Preferably it is 2 to 100 times by weight. By setting it as 1 weight times or more, high palladium and / or phosphorus removal efficiency is obtained, and it is economically preferable to set it as 200 weight times or less.

  The temperature at which the arylamine compound containing palladium exceeding 100 ppm or phosphorus exceeding 100 ppm, the inorganic adsorbent, and the nitrogen-containing heteroaromatic compound having 3 to 15 carbon atoms is not particularly limited, but is usually -10 to 170 ° C., preferably 0 to 150 ° C.

  The time for mixing the arylamine compound containing 100 ppm of palladium or 100 ppm of phosphorus, the inorganic adsorbent, and the nitrogen-containing heteroaromatic compound having 3 to 15 carbon atoms is not particularly limited. 5 hours, preferably 0.5 to 2 hours.

  In addition, a person skilled in the art is able to separate an arylamine compound from a mixture of an arylamine compound containing more than 100 ppm of palladium or more than 100 ppm of phosphorus, an inorganic adsorbent, and a nitrogen-containing heteroaromatic compound having 3 to 15 carbon atoms. A known method can be used.

  For example, a method for separating the inorganic adsorbent from the mixture is not particularly limited, and examples thereof include a method of filtering using a filter paper, a membrane filter, a glass filter, or the like.

  The method for separating the nitrogen-containing heteroaromatic compound having 3 to 15 carbon atoms from the mixture is not particularly limited, and examples thereof include distillation, concentration to dryness, reprecipitation, and recrystallization. Of these, reprecipitation is preferred because of its high adaptability to the production method.

  The solvent used for reprecipitation is not particularly limited as long as the nitrogen-containing heteroaromatic compound having 3 to 15 carbon atoms can be dissolved. For example, aliphatic hydrocarbon solvents, alcohol solvents, aromatics Group hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, and aprotic solvents. Further, since it may be required to completely remove the residual solvent in the arylamine compound, the solvent to be used is preferably a low boiling point one. Furthermore, taking into account the recovery rate of arylamine compounds, the availability of the solvent, and the economic efficiency, methanol is an alcohol solvent, ethanol is an ester solvent, and ethyl acetate is an ester solvent, and acetone is a particularly preferable solvent. .

  If this manufacturing method is used, palladium or phosphorus can be efficiently removed from the arylamine compound. Therefore, the present invention is useful as a method for removing palladium or phosphorus in arylamine compounds.

  Examples of the present invention are shown below, but the present invention is not construed as being limited to these examples.

Preparation Example 1 Synthesis of Arylamine Polymer (2) Into a 300 mL four-necked round bottom flask equipped with a condenser and a thermometer, 8.12 g (20.0 mmol) of 4,4′-diiodobiphenyl, 4- n-Butylaniline 3.04 g (20.4 mmol), sodium-tert-butoxide 7.69 g (80.0 mmol; 2 mol per iodine atom) and o-xylene 80 mL were charged. To this mixture, 92.0 mg (0.10 mmol; 0.25 mol% with respect to iodine atom) of tris (dibenzylideneacetone) dipalladium prepared in advance in a nitrogen atmosphere and 161.8 mg (0 of tri-tert-butylphosphine) O-xylene (10 mL) was added. Thereafter, the temperature was raised to 120 ° C. in a nitrogen atmosphere, and the mixture was aged for 3 hours while heating and stirring at 120 ° C.

  Thereafter, 0.60 g (4.00 mmol) of 4-n-butylaniline was added, and the reaction was further performed for 3 hours. Next, 2.52 g (16.0 mmol) of bromobenzene was added, and the mixture was aged for 3 hours with heating and stirring at 120 ° C.

  After completion of the reaction, the reaction mixture was cooled to about 80 ° C. and then slowly added to a stirred solution of 90% aqueous acetone (2000 mL). The solid was collected by filtration and washed in the order of acetone, water, and acetone, and then dried under reduced pressure at 100 ° C. for 6 hours under vacuum to obtain 5.71 g of pale yellow powder A.

  The obtained light yellow powder A (5.71 g) was dissolved in chlorobenzene (285.5 g) to prepare a 2.0 weight percent chlorobenzene solution, which was filtered through a glass filter with 57 g of Celite 545. The resulting chlorobenzene solution was concentrated under reduced pressure to 4.0 weight percent and slowly added to a stirred solution of acetone (2000 mL). The solid was collected by filtration and dried under reduced pressure to obtain 5.14 g of pale yellow powder B. (Total yield 86%).

  When the obtained pale yellow powder B was measured by a nuclear magnetic resonance analyzer (Gemini 200 manufactured by Varian) and elemental analysis, it was confirmed to be an arylamine polymer represented by the following general formula (2). The results of elemental analysis are shown in Table 1.

  Moreover, as a result of analyzing the arylamine polymer by GPC (apparatus: HLC-8220GPC; column: TSKgel SuperH3000-TSKgel SuperH2000-TSKgelSuperH1000 (both manufactured by Tosoh Corporation)), the weight average molecular weight was 35,900 in terms of polystyrene. And the number average molecular weight was 21,000 (dispersion degree 1.7).

  Moreover, when the arylamine polymer was wet-decomposed with sulfuric acid and nitric acid and the Pd content was quantified with ICP-AES (ICP emission spectroscopic analyzer, Perkin Elmer, Optima 5300 DV), the weight of the arylamine polymer was determined. And 200 ppm of palladium and 105 ppm of phosphorus.

得られた式（２）で表されるアリールアミンポリマー ４．００ｇをトルエン ３９６ｇに溶解させ、１．０重量％の溶液を調製した。これを溶液Ａとする。

4.00 g of the resulting arylamine polymer represented by the formula (2) was dissolved in 396 g of toluene to prepare a 1.0 wt% solution. This is designated as Solution A.

Example 1
In a 50 mL round bottom flask, at room temperature under a nitrogen atmosphere, 25.0 g of solution A (arylamine polymer content 0.25 g) and 0.25 g of 2,2′-bipyridyl (1.0 times the weight of arylamine polymer) The mixture was stirred for 2 hours with a rotor of φ4 × 10 mm under a nitrogen atmosphere at 100 ° C. The mixture was cooled to room temperature and passed through column chromatography packed with 25 g of silica gel (Wako Pure Chemical Industries, Wako Gel (registered trademark) C-100) (100 times by weight with respect to the arylamine polymer), When the obtained filtrate was slowly added to acetone (200 mL) with stirring, fine crystals were precipitated. Crystals were isolated by filtration using filter paper and dried under reduced pressure to obtain 0.23 g of a light yellow powder of arylamine polymer (recovery rate 92%). The palladium content and phosphorus content were quantified in the same manner as in Preparation Example 1. The results are shown in Table 2.

Example 2
An arylamine polymer was obtained in the same manner as in Example 1 except that 2,2′-bipyridyl in Example 1 was changed to 4,4′-bipyridyl (recovery rate 88%). The palladium content and phosphorus content were quantified in the same manner as in Preparation Example 1. The results are shown in Table 2.

Example 3
An arylamine polymer was obtained in the same manner as in Example 1 except that 2,2′-bipyridyl in Example 1 was changed to 2,2 ′, 6 ′, 2 ″ -terpyridyl (recovery rate 92%). The palladium content and phosphorus content were quantified in the same manner as in Preparation Example 1. The results are shown in Table 2.

Example 4
A 100 mL round-bottom flask was charged with 25.0 g of solution A (arylamine polymer content 0.25 g) and 25.0 g of pyridine (100 weight times with respect to arylamine polymer) at room temperature under nitrogen atmosphere, 100 ° C., nitrogen atmosphere The mixture was stirred for 2 hours with a rotor of φ4 × 10 mm. The mixture was cooled to room temperature and concentrated to dryness with an evaporator. To the residue, 25.0 g of toluene was added and redissolved, and this toluene solution was filled with 25 g of silica gel (Wako Pure Chemical Industries, Ltd., Wakogel (registered trademark) C-100) (100 times the weight of the arylamine polymer). The obtained filtrate was slowly added to acetone (200 mL) with stirring, and fine crystals were precipitated. Crystals were isolated by filtration using filter paper and dried under reduced pressure to obtain 0.21 g of a light yellow powder of arylamine polymer (recovery rate 84%). The palladium content and phosphorus content were quantified in the same manner as in Preparation Example 1. The results are shown in Table 2.

Comparative Example 1
An arylamine polymer was obtained in the same manner as in Example 1 except that charging of 2,2′-bipyridyl of Example 1 (mixing with Solution A) was not performed (recovery rate: 92%). The palladium content and phosphorus content were quantified in the same manner as in Preparation Example 1. The results are shown in Table 2.

調製例２ アリールアミンポリマー（３）の合成
調製例１の４，４’−ジヨードビフェニルを４，４’’−ジヨードターフェニルに変更した以外は、実施例１と同様にしてアリールアミンポリマーの淡黄色粉体Ｃを６．３８ｇ取得した（トータル収率８５％）。ポリスチレン換算で重量平均分子量４０，５００および数平均分子量２５，３００（分散度１．６）であった。得られた淡黄色粉体Ｃを核磁気共鳴分析装置により測定したところ、下記式（３）で表されるアリールアミンポリマーであることが確認された。

Preparation Example 2 Synthesis of Arylamine Polymer (3) Arylamine polymer in the same manner as in Example 1 except that 4,4′-diiodobiphenyl in Preparation Example 1 was changed to 4,4 ″ -diiodoterphenyl. 6.38 g of a pale yellow powder C was obtained (total yield 85%). The weight average molecular weight was 40,500 and the number average molecular weight was 25,300 (dispersity 1.6) in terms of polystyrene. When the obtained pale yellow powder C was measured by a nuclear magnetic resonance analyzer, it was confirmed to be an arylamine polymer represented by the following formula (3).

  Moreover, palladium content and phosphorus content were quantified by the same operation as the adjustment example 1. The results are shown in Table 3.

淡黄色粉体Ｃ ０．２５ｇをトルエン ２４．７５ｇに溶解させ、１．０重量％の溶液を調製した。これを溶液Ｂとする。

0.25 g of pale yellow powder C was dissolved in 24.75 g of toluene to prepare a 1.0 wt% solution. This is designated as Solution B.

Preparation Example 3 Synthesis of Arylamine Polymer (4) Except that the 4,4′-diiodobiphenyl of Preparation Example 1 was changed to 2,7-dibromo-9,9-di-n-octylfluorene, Example 1 Similarly, 7.50 g of light yellow powder E of arylamine polymer was obtained (total yield 70%). The weight average molecular weight was 28,700 and the number average molecular weight was 15,900 (dispersity 1.8) in terms of polystyrene. When the obtained pale yellow powder D was measured with a nuclear magnetic resonance analyzer, it was confirmed to be an arylamine polymer represented by the following formula (4).

  Moreover, palladium content and phosphorus content were quantified by the same operation as the adjustment example 1. The results are shown in Table 3.

淡黄色粉体Ｄ ０．２５ｇをトルエン ２４．７５ｇに溶解させ、１．０重量％の溶液を調製した。これを溶液Ｃとする。

0.25 g of pale yellow powder D was dissolved in 24.75 g of toluene to prepare a 1.0 wt% solution. This is solution C.

Example 5
An arylamine polymer was obtained in the same manner as in Example 1 except that the solution A was changed to the solution B in Example 1 (recovery rate 88%). The palladium content and phosphorus content were quantified in the same manner as in Preparation Example 1. The results are shown in Table 3.

Example 6
In Example 3, an arylamine polymer was obtained in the same manner as in Example 1 except that the solution A was changed to the solution C (recovery rate 92%). The palladium content and phosphorus content were quantified in the same manner as in Preparation Example 1. The results are shown in Table 3.

いずれのアリールアミンポリマーにおいてもＰｄを８０％以上、Ｐを５０％以上の除去率で除去し、Ｐｄ含有量及びＰ含有量が各々０．１〜１００ｐｐｍであるアリールアミン化合物を製造することができた。

Any arylamine polymer can remove Pd at a removal rate of 80% or more and P at a removal rate of 50% or more to produce an arylamine compound having a Pd content and a P content of 0.1 to 100 ppm each. It was.

  The arylamine compound produced by the production method of the present invention can be applied particularly to electronic materials (hole transport materials, light emitting materials, etc. for organic EL devices).

  Since the arylamine compound produced by the production method of the present invention has a remarkably low palladium compound content and / or phosphorus compound content relative to the weight of the arylamine compound, the adverse effect on the organic EL device performance can be kept low. .

Claims (7)

Mixing an arylamine compound containing palladium exceeding 100 ppm or phosphorus exceeding 100 ppm with an inorganic adsorbent and a nitrogen-containing heteroaromatic compound having 3 to 15 carbon atoms, and then separating the arylamine compound from the resulting mixture A method for producing an arylamine compound, characterized in that a palladium content and a phosphorus content are each 0.1 to 100 ppm. An arylamine compound containing palladium exceeding 100 ppm or phosphorus containing more than 100 ppm is produced using a reaction catalyst containing at least a palladium compound and a phosphorus compound, and an arylamine compound containing more than 100 ppm palladium or more than 100 ppm phosphorus The manufacturing method according to claim 1, wherein: The production method according to claim 1 or 2, wherein the produced arylamine compound is an arylamine compound having a palladium content and a phosphorus content of 1 to 50 ppm each. The C3-C15 nitrogen-containing heteroaromatic compound has a pyrrolyl group, an imidazolyl group, a pyridyl group, a pyrimidyl group, a benzimidazolyl group, an indolyl group, a quinolyl group, an isoquinolyl group, or a phenanthrolinyl group. It is a nitrogen-containing heteroaromatic compound of -15, The manufacturing method as described in any one of Claims 1 thru | or 3 characterized by the above-mentioned. The nitrogen-containing heteroaromatic compound having 3 to 15 carbon atoms is pyrrole, pyridine, 2,2'-bipyridyl, or 2,2 ', 6', 2 ''-terpyridyl. 5. The production method according to any one of 4 above. The arylamine compound is represented by the general formula (1)

(In the formula, each Ar ¹ independently represents an aryl group or a heteroaryl group which may have a substituent. Ar ² each independently represents an arylene group which may have a substituent or Represents a heteroarylene group, and n represents an integer of 2 or more.)
The production method according to claim 1, wherein the polymer is an arylamine polymer represented by the formula: The manufacturing method according to any one of claims 1 to 6, wherein the inorganic adsorbent is silica gel.