JPH1180348A - Novel polyaryleneamine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound that is excellent in heat resistance, processability and productivity and is useful as a material for a variety of resins. SOLUTION: The recurring units of formula I [R<1> -R<5> are each H, a 1-20C (thio) alkyl, a 1-20C alkoxy, cyano] are incorporated to obtain the objective compound, preferably with a weight-average molecular weight of 1,000-1,000,000 calculated as polystyrene. This compound is obtained by reaction of (A) an aniline derivative as 3-toluidine with (B) a 4,4'-dihalogenodiphenyl ether as 4,4'-dibromodiphenyl ether in the presence of (C) a catalyst comprising a palladium compound as [tris(dibenzylidene acetone)dipalladium (0)] and a phosphine as tri-tert.-butylphosphine and of (D) a base as sodium tert.-butoxide, preferably in an inert gas atmosphere at about 20-250 deg.C for several minutes to 20 hours.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyaryleneamine, and more particularly, to heat resistance,
The present invention relates to a polyaryleneamine which is useful as a material for various resin applications because of its excellent workability and productivity.

[0002]

2. Description of the Related Art Conventionally, general-purpose resins such as polyethylene, polyvinyl chloride, and polystyrene; thermosetting resins such as epoxy resins and phenol resins;
Engineering plastics such as polypropylene, polyamide and modified polyphenylene ether have been used.

In recent years, super-engineering plastics such as polyphenylene sulfide, polyphenylene sulfide ketone, polyimide, polyetherimide, and liquid crystal polymer have attracted attention as resins having excellent heat resistance.

[0004]

The above-mentioned general-purpose resins and engineering plastics are relatively easy to handle, but have low heat resistance, and are suitable for applications requiring heat resistance such as the electric / electronic field and the automobile field. It hasn't been.

For this reason, resins having excellent heat resistance, such as thermosetting resins and super engineering plastics, are used for these applications.

[0006] However, thermosetting resins have excellent heat resistance, but they take a long time to process and form products, are inferior in product workability, and are difficult to perform molding again once they are commercialized. have.

Therefore, super engineering plastics which have excellent heat resistance even if they are thermoplastic have attracted attention. However, these super engineering plastics commonly require a very special reaction solvent during the production thereof. In addition, there is a problem that the productivity of the resin itself is extremely low because a high reaction temperature is required.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a novel polyaryleneamine which is useful as a resin material because of its excellent heat resistance and productivity.

[0009]

Means for Solving the Problems The present inventors have made intensive studies on the above problems and as a result, have found that a specific polyarylamine has excellent heat resistance and productivity, and have completed the present invention.

That is, the present invention is a polyaryleneamine comprising a repeating unit represented by the following general formula (1).

[0011]

Embedded image

(Wherein R ^{1 to} R ⁵ are each independently
Hydrogen atom, alkyl group having 1 to 20 carbon atoms, 1 to 2 carbon atoms
A thioalkyl group of 0, an alkoxy group having 1 to 20 carbon atoms,
Represents a fluorine, carbonyl, carboxyl, sulfonyl, sulfoxyl, nitro or cyano group. The polyaryleneamine of the present invention is composed of a repeating unit represented by the above general formula (1), in which diphenyl ether residues and residues of an aniline derivative are alternately bonded. Examples of the residue of the aniline derivative include 3-toluidine, aniline, 3-fluoroaniline, 4-fluoroaniline, 2-toluidine, 4-toluidine, 2-anisidine, 3-anisidine, 4-anisidine, and 3-ethylaniline. , 4-ethylaniline, 2,
4-dimethoxyaniline, 2,5-dimethoxyaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,4,6-trimethylaniline, 4-cyanoaniline, 4-aminomethylbenzoate, 4-nitroaniline , 3,4-difluoroaniline, 3,4,5-trifluoroaniline, 2,3,4,5-tetrafluoroaniline, 2,3,4,5,6-pentafluoroaniline and the like. Among them, polyaryleneamine, which is particularly excellent in heat resistance, has an aniline residue,
-Toluidine residues and 4-fluoroaniline residues are preferred.

The polyaryleneamine of the present invention has a high melting point, and among them, those having a melting point of 245 ° C. or more are particularly useful as a heat-resistant resin.

The weight average molecular weight of the polyarylamine of the present invention is not particularly limited as long as it is called a polymer, but it is excellent in mechanical properties and the like. It is preferably 5,000, and in particular, because of excellent processing characteristics,
It is preferably from 00 to 50,000.

The polyaryleneamine of the present invention may be produced by any method, and is not particularly limited. An example of a production method which can be easily produced is shown below.

That is, a novel polyaryleneamine can be easily produced by reacting 4,4'-dihalogenodiphenyl ether and an aniline derivative with a catalyst comprising a palladium compound and phosphine in the presence of a base.

The anilines used in the above production method include, for example, 3-toluidine, aniline, 3-aniline,
Fluoroaniline, 4-fluoroaniline, 2-toluidine, 4-toluidine, 2-anisidine, 3-anisidine, 4-anisidine, 3-ethylaniline, 4-ethylaniline, 2,4-dimethoxyaniline, 2,5-dimethoxy Aniline, 2,3-dimethylaniline, 2,4-
Dimethylaniline, 2,4,6-trimethylaniline,
4-cyanoaniline, 4-aminomethylbenzoate,
4-nitroaniline, 3,4-difluoroaniline,
3,4,5-trifluoroaniline, 2,3,4,5-
Examples include tetrafluoroaniline, 2,3,4,5,6-pentafluoroaniline and the like.

4,4 'used in the above-mentioned production method
-As dihalogenodiphenyl ether, for example,
4,4'-dichlorodiphenyl ether, 4,4'-dibromodiphenyl ether, 4,4'-diiododiphenyl ether, 4-chloro-4'-bromodiphenyl ether, 4-chloro-4'-iododiphenyl ether, 4-bromo-4 '-Iododiphenyl ether and the like.

In the above production method, aniline and 4,4
The amount of 4′-dihalogenodiphenyl ether used is in the range of aniline / 4,4′-dihalogenodiphenyl ether (molar ratio) = 0.5 to 1.5, and particularly high-molecular-weight polyaryleneamine is obtained. 0.9
It is preferably in the range of ~ 1.1.

The palladium compound used as a catalyst component in the above-mentioned production method is not particularly limited, and for example, sodium hexachloropalladium (IV) tetrahydrate, hexachloropalladium (IV)
Tetravalent palladium compounds such as potassium citrate; palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, palladium acetylacetonate (II),
Dichlorobis (benzonitrile) palladium (II),
Dichlorobis (acetonitrile) palladium (II),
Dichlorobis (triphenylphosphine) palladium (II), dichlorotetraamminepalladium (I
I), divalent palladium compounds such as dichloro (cycloocta-1,5-diene) palladium (II) and palladium trifluoroacetate (II); tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) Zero-valent palladium compounds such as dipalladium chloroform complex (0) and tetrakis (triphenylphosphine) palladium (0) can be mentioned.

The amount of the palladium compound used in the above production method is not particularly limited,
Halogen atom 1 of 4'-dihalogenodiphenyl ether
0.00001 to 20.20 per mol of palladium.
It is preferably in the range of 0 mol%, and the reaction proceeds if palladium is within the above range. Since an expensive palladium compound is used, it is particularly preferable that the amount is 0.001 to 5.0 mol% in terms of palladium per 1 mol of a halogen atom of the raw material 4,4'-dihalogenodiphenyl ether.

The phosphine used as a catalyst component in the above-mentioned production method is not particularly limited, but for example, triethylphosphine, tricyclohexylphosphine, triisopropylphosphine, tri-n
Trialkylphosphines such as -butylphosphine, triisobutylphosphine, tri-sec-butylphosphine, tri-tert-butylphosphine; triphenylphosphine, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri ( p-tolyl) phosphine, BINAP, trimesityl phosphine, diphenylphosphinoethane, diphenylphosphinopropane,
Aryl phosphines such as diphenylphosphinoferrocene can be mentioned, and tritertiary butyl phosphine is particularly preferred because of having high reaction activity.

In the above production method, the phosphine may be used in an amount of 0.01 to 10000 times the mol of the palladium compound. Since expensive phosphine is used, it is more preferably in the range of 0.1 to 10 moles per mole of the palladium compound.

In the above production method, when a palladium compound and phosphine are used as the catalyst components, when both are added to the reaction system as a combined catalyst, the addition method may be either a single addition to the reaction system or a preparation in the form of a complex in advance. May be added.

The base used in the above production method may be selected from, for example, carbonates such as sodium carbonate and potassium carbonate, inorganic bases such as alkali metal alkoxides, and organic bases such as tertiary amines. Although not limited thereto, more preferably, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium-tert-butoxide, sodium-tert-butoxide, potassium-tert
An alkali metal alkoxide such as butoxide,
These may be added to the reaction field as they are, or may be prepared in situ from an alkali metal, an alkali metal hydride or an alkali metal hydroxide and an alcohol and supplied to the reaction field.

In the above-mentioned production method, the amount of the base used is not particularly limited, but 4,4'-
It is preferable to use 0.5 mole or more per 1 mole of halogen atom of dihalogenodiphenyl ether. The amount of the base does not change even if it is added in a large excess, but it is more preferably in the range of 1.0 to 5 moles because the post-treatment operation after the completion of the reaction becomes complicated.

In the above production method, the reaction is usually preferably carried out in an inert solvent. Such an inert solvent is not particularly limited as long as it is a solvent that does not significantly inhibit the present reaction.
Aromatic hydrocarbon solvents such as toluene and xylene; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; acetonitrile, dimethylformamide, dimethylsulfoxide, hexamethylphosphottriamide and the like; among these, benzene, toluene, Aromatic hydrocarbon solvents such as xylene are particularly preferred.

In the above production method, the reaction is preferably carried out under normal pressure and in an atmosphere of an inert gas such as nitrogen or argon. However, the reaction can be carried out even under a pressurized condition.

In the above production method, the reaction conditions include:
For example, the reaction temperature may be selected from the range of 20 ° C. to 250 ° C., more preferably 50 ° C. to 150 ° C., and the reaction time may be selected from the range of several minutes to 20 hours.

The polyaryleneamine of the present invention can be used alone as a resin material. However, various fillers such as glass fiber, carbon fiber, talc, calcium carbonate, mica, etc .; various pigments; It can also be used by mixing with a stabilizer or the like.

General-purpose resins such as polyethylene, polyvinyl chloride and polystyrene; engineering plastics such as polypropylene, polyamide and modified polyphenylene ether; super-engineering plastics such as polyphenylene sulfide, polyphenylene sulfide ketone, polyimide, polyetherimide, liquid crystal polymer, etc. It can also be used as an alloy blend.

[0032]

The polyaryleneamine of the present invention is extremely useful as a resin material because of its excellent heat resistance and productivity.

[0033]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

Example 1 In a 200 ml four-necked flask equipped with a cooling tube and a thermometer, 2.14 g (0.02 mol) of 3-toluidine was added at room temperature.
l), 4,4'-dibromodiphenyl ether 6.56
g (0.02 mol), 4.61 g of sodium tert-butoxide (1.2 equivalents to bromine atom) and o
-80 ml of xylene were charged. To this mixture were added 103.5 mg (0.5 mol%) of tris (dibenzylideneacetone) dipalladium and 0.2 ml of tritertiarybutylphosphine (4 equivalents based on the palladium compound) under a nitrogen atmosphere. Thereafter, the temperature was raised to 120 ° C. in a nitrogen atmosphere, and the reaction was performed for 3 hours while heating and stirring at 120 ° C. After the completion of the reaction, 60 ml of water was added and washed with water, then separated into oil and water by a separating funnel, and the organic phase was concentrated under reduced pressure to obtain an orange solution. This solution was dropped into a solution of THF: methanol = 1: 5 to precipitate a white powder. This white powder was collected by filtration and dried under reduced pressure to give 4.20.
g of a white powder was obtained. The melting point of this polymer is 249.4
° C (measured by TG / DTA220, manufactured by Seiko Denshi).

This polyaryleneamine is converted to a THF-based GP
As a result of analysis with C (manufactured by Tosoh, HLC8120), the average molecular weight was 19,600 in terms of polystyrene.
Further, this polyaryleneamine was analyzed by NMR (manufactured by JEOL Ltd., GSX-400) and IR (manufactured by Shimadzu Corporation, DR-400).
1 and 2 show the results of elemental analysis (CHN CORDER MT-5 manufactured by Yanaco).
Table 1 shows the results.

[0036]

[Table 1]

Example 2 2.22 g (0.02 m) of 4-fluoroaniline was placed in a 200 ml four-necked flask equipped with a cooling tube and a thermometer at room temperature.
ol), 4,4'-dibromodiphenyl ether 6.5
6 g (0.02 mol), 4.61 g (1.2 equivalents to bromine atom) of sodium tert-butoxide and 80 ml of o-xylene were charged. To this mixture were added 103.5 mg (0.5 mol%) of tris (dibenzylideneacetone) dipalladium and 0.2 ml of tritertiarybutylphosphine (4 equivalents based on the palladium compound) under a nitrogen atmosphere. Thereafter, the temperature is increased to 120 ° C. in a nitrogen atmosphere, and the mixture is heated and stirred at 120 ° C. for 3 hours.
A time reaction was performed. After the completion of the reaction, 60 ml of water was added and washed with water, then separated into oil and water by a separating funnel, and the organic phase was concentrated under reduced pressure to obtain an orange solution. This solution was dropped into a solution of THF: methanol = 1: 5 to precipitate a white powder. This white powder was collected by filtration and dried under reduced pressure to 4.4.
5 g of a white powder was obtained. The melting point of this polymer is 252.
9 ° C. (measured by TG / DTA220, manufactured by Seiko Denshi).

The polyaryleneamine was converted to a THF-based GP.
As a result of analysis by C (manufactured by Tosoh, HLC8120), the average molecular weight was 19,800 in terms of polystyrene.
The polyaryleneamine was analyzed by NMR (JNM-SX270, manufactured by JEOL Ltd.) and IR (Shimadzu Corporation, D
R-8000), the results of elemental analysis (CHN CORDER MT, manufactured by Yanaco) are shown in FIGS.
Table 2 shows the results.

[0039]

[Table 2]

Example 3 1.86 g (0.02 mol) of aniline was added to a 200 ml four-necked flask equipped with a cooling tube and a thermometer at room temperature.
6.56 g of 4'-dibromodiphenyl ether (0.0
2 mol), sodium tert-butoxide 4.6
1 g (1.2 equivalents based on bromine atoms) and 80 ml of o-xylene were charged. Tris (dibenzylideneacetone) dipalladium 103.5 was added to this mixture under a nitrogen atmosphere.
mg (0.5 mol%) and 0.2 ml of tritertiarybutylphosphine (4 equivalents to the palladium compound) were added. Thereafter, the temperature is set to 120 ° C. in a nitrogen atmosphere
The reaction was carried out for 3 hours while heating and stirring at 120 ° C. After the completion of the reaction, after adding 60 ml of water and washing with water,
The solid was collected by filtration. The solid was washed with 30 ml each of water, THF and methanol. After washing, drying under reduced pressure.
05 g of a white powder was obtained. The melting point of this polymer is 25
9.4 ° C. (TG / DTA22 manufactured by Seiko Instruments Inc.)
0).

This polymer was subjected to IR (DR, manufactured by Shimadzu Corporation)
FIG. 3 shows the result of elemental analysis (y
Table 3 shows the results of measurement by CHN CORDER MT-5 manufactured by Anaco.

[0042]

[Table 3]

[Brief description of the drawings]

FIG. 1 shows the N of the polyaryleneamine obtained in Example 1.
It is an MR chart.

FIG. 2 shows the I of the polyaryleneamine obtained in Example 1.
It is an R chart.

FIG. 3 shows the N of the polyaryleneamine obtained in Example 2.
It is an MR chart.

FIG. 4 shows I of the polyaryleneamine obtained in Example 2.
It is an R chart.

FIG. 5 shows I of the polyaryleneamine obtained in Example 3.
It is an R chart.

Claims (6)

[Claims] 1. A polyaryleneamine comprising a repeating unit represented by the following general formula (1). Embedded image (Wherein, R ^{1 to} R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a thioalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, fluorine, and a carbonyl group. , A carboxyl group, a sulfonyl group, a sulfoxyl group, a nitro group, and a cyano group.) 2. The polyaryleneamine according to claim 1, comprising a repeating unit represented by the following general formula (2). Embedded image 3. The polyaryleneamine according to claim 1, comprising a repeating unit represented by the following general formula (3). Embedded image 4. The polyaryleneamine according to claim 1, comprising a repeating unit represented by the following general formula (4). Embedded image 5. The polyaryleneamine according to claim 1, wherein the weight average molecular weight is in the range of 1,000 to 1,000,000 in terms of polystyrene. 6. The polyaryleneamine according to claim 1, wherein the weight average molecular weight is in the range of 5,000 to 50,000 in terms of polystyrene.