JPS62258338A - Novel p-terphenyltetracarboxylic acid or its dianhydride and production thereof - Google Patents

Abstract

NEW MATERIAL:p-Terphenyl-3,4,3'',4''-tetracarboxylic acid expressed by formula I or dianhydride thereof expressed by formula II. USE:A raw material for excellent heat-resistant polyimide resins, curing agent, etc., for epoxy resins, phenolic resins, etc. PREPARATION:A 4-halogoeno-o-xylene is reacted with metallic Mg and converted into Grignard reagent expressed by formula III (X1 is Cl, Br or I) by a conventional method and a p-dihalogenobenzene expressed by formula IV (X2 is same as X1) is subjected to double cross coupling with the above- mentioned compound expressed by formula I in the presence of a nickel metal complex catalyst e.g. dichloro[1,2-bis(diphenylphosphino)ethane]nickel, etc., to afford a compound expressed by formula V, which is then oxidized with a permanganate, nitric acid or air in the liquid phase to provide the compound expressed by formula I. The resultant compound expressed by formula I is then cyclodehydrated while heating or with acetic anhydride or directly oxidized in the vapor phase to give the compound expressed by formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel para-terphenyltetracarboxylic acid or its dianhydride and a method for producing the same.

[Conventional technology]

Conventionally, as aromatic tetracarboxylic acid or its dianhydride, pyromellitic acid or its dianhydride, benzophenone tetracarboxylic dianhydride, etc. have been known.
Known as a raw material for polyimide resin.

Also, as terphenyltetracarboxylic acid.

West German Patent Publication No. 2,100.391, British Patent No. 1,338.932 and US Patent No. 3,891
．． Para-terphenyl-2,3,2",3"-tetracarboxylic acid-2,3:2",3"-dianhydride represented by the formula [■] described in the specification of No. 633 is known. ing.

The tetracarboxylic dianhydride represented by the formula [I] is a compound synthesized by the route shown by the following reaction formula [■].

Sunawachi, 1. An intermediate compound is obtained by a Diels-Alder reaction between 4-bis(α-furano)benzene and two molecules of maleic anhydride, and this is further dehydrated with concentrated sulfuric acid or polyphosphoric acid to obtain a tetracarboxylic dianhydride. Due to the nature of the reaction, the position of the acid anhydride group is 2,
The compound represented by formula [I] is used as a crosslinking agent for epoxy resins or phenol-formaldehyde resins.

In addition, as meta-terphenyltetracarboxylic acid,
It is only reported in French Patent No. 1.556.159 (Chemical Abstracts Vol. 71, 49609k), and its synthesis method is based on the following reaction formula (
1).

(Tetracarboxylic dianhydride) + 802 +HCL
[:II[] Namely, using copper as a catalyst, meta-benzenedisulfonyl chloride and excess phthalic anhydride are reacted under phthalic anhydride reflux conditions while generating sulfur dioxide gas and hydrogen chloride gas. −
It was intended to be terphenyltetracarboxylic dianhydride, and the melting point of the obtained compound was 130 to 165C.

[Problem that the invention seeks to solve]

Conventionally known aromatic tetracarboxylic dianhydrides and diamine compounds, such as diaminodiphenyl ether,
Polyimide resins obtained from diaminodiphenylmethane and the like are known as heat-resistant resins, but with recent advances in technology, even greater heat resistance is desired.

Further, the para-terphenyltetracarboxylic dianhydride represented by the above formula [1] is known as a crosslinking agent for epoxy resins or phenol resins.

However, since the para-terphenyltetracarboxylic dianhydride has acid anhydride groups at the 2, 3-position and the 2//, 3"-position, the polyimide resin synthesized using it as a raw material is It is difficult to increase the molecular weight, and therefore the heat resistance is also insufficient.

In addition, due to the nature of the synthesis reaction, the position of the acid anhydride group in the meta-terphenyltetracarboxylic dianhydride may be unknown, and the resulting compound may have a melting point of 130 to 16
Because it has a wide range of 5C, it is a mixture of various compounds with different positions of acid anhydride groups, and when such tetracarboxylic dianhydride is used as a raw material for polyimide resin, only low molecular weight polyimide resin can be obtained. Heat resistance is insufficient.

In order to solve these problems, the present invention provides novel terphenyltetracarboxylic acids or dianhydrides thereof, as well as methods for producing them.

[Failure to solve the problem]

First invention c. Hala-terphenyl-3,4゜3'',4
″-Tetracarboxylic acid or its dianhydride.

Para-terphenyl-3,4,3",4"-tetracarboxylic acid is a compound represented by the following formula [■].

In addition, this dianhydride para-terphenyl-3,4
, 3", 4〃-tetracarboxylic acid-3゜4:3", 4"
-Dianhydride is a compound represented by the following formula [■].

The novel para-terphenyltetracarboxylic acid or its dianhydride according to the present invention has carboxyl groups or acid anhydride groups at the 3, 4-positions and the 3//, 4//- positions, and is para-terphenyl and has a structure different from that of the conventional para-terphenyltetracarboxylic dianhydride represented by formula [I]. Therefore, when polyamic acid is reacted with a diamine compound and further dehydrated to form a polyimide resin, it becomes a linear preparation with extended molecules, making it possible to provide a polyimide resin with excellent heat resistance.

The second invention relates to a method for producing the compound according to the first invention.

That is, the second invention has 3. 4. 3", 4"
-Tetramethyl-para-terphenyl-3,4,3'', which is characterized by oxidation of para-terphenyl or subsequent further dehydration and ring closure reaction.

The present invention relates to a method for producing 4"-tetracarbo/acid or its dianhydride.

The above 3,4,3'',4''-tetramethyl-para-terphenyl can be obtained by subjecting 4-halogeno-ortho-xylene to a double cross-coupling reaction with the Grignard reagent doparadihalogenobenzene.

The manufacturing method will be explained in detail below.

Para-terphenyltetracarboxylic acid and its dianhydride according to the present invention can be produced by the reaction represented by the following formula [■].

o I[':1 (here, Xt and X2 each independently represent chlorine, bromine, or iodine) That is, after reacting 4-halogeno-ortho-xylene with metallic magnesium according to a conventional method to obtain a Grignard reagent, , Para-dihalogenobenzene and a nickel metal complex catalyst are added to this to form tetramethyl and S-laterphenyl through a double cross-coupling reaction. In the resulting intermediate, terphenyl is converted to para-terphenyl-3,4°3'',4''-tetracarboxylic acid by permanganate, nitric acid, or liquid phase air oxidation, followed by para-terphenyl-3,4°3'',4''-tetracarboxylic acid with heating or acetic anhydride. Terphenyl-3゜4.3″, 4
“-tetracarbo/acid-3,4:3//,4”-dianhydride. Alternatively, the above dianhydride can be directly obtained by gas phase oxidation of 3,4°3tt,4ti-tetramethyl-para-terphenyl.

This method will be explained in more detail.

Examples of 4-halogeno-ortho-xylene include u,4-iodo-ortho-xylene and 4-promo-ortho-xylene.

A method of using 4-halogeno-ortho-xylene as a Grignard reagent is to use 1.0 gram atom or more of metallic magnesium per 1.0 mole of 4-halogeno-ortho-xylene. If the magnesium metal is less than 1.0 gram atom, unreacted 4-halogeno-
Ortho-xylene reacts with Grignard reagent of no-ortho-xylene and 4-halogeno-ortho-xylene,
This is not preferred because tetramethyl-piphenyl is produced.

When preparing a Grignard reagent, the reaction temperature is above Oc and below the solvent flux temperature, and the reaction time is 1 to 10 minutes.
It's time.

When the amount of metallic magnesium used in the reaction exceeds 1.0 gram atom per 1.0 mole of 4-halogeno-ortho-xylene, unreacted metallic magnesium remains, which is removed by filtration. Examples of solvents used at this time include methyl ether and tetrahydrofuran.

Examples of para-dihalogenobenzene include para-dibromobenzene and para-dichlorobenzene. Among these, use of para-dibromobenzene will increase the yield of the double cross coupling reaction.

The amount of para-dihalogenobenzene used is 4-halogenobenzene.
0.5 mol is used per 1.0 mol of the Grignard reagent of orthoky7lene. When the amount is less than 0.5 mol, the Grignard reagent remains after the reaction is completed, and this is hydrolyzed during the next washing with water to form ortho-xylene, which does not interfere with the reaction, but the yield decreases. Moreover, if it exceeds 0.5 mole, it is not preferable because a large amount of poly-para-phenylene by-products will be produced.

Examples of nickel metal complex catalysts include dichlorobis(triphenylphosphine)nickel, cifromopis(triphenylphosphine)nickel, shorthis(triphenylphosphine)nickel, dichloro(1,2-bis(diphenylphosphino)ethane)nickel, dibromo[ :
1.2-bis(diphenylphosphino)ethane]nickel, dichloro[''l, 3-bis(diphenylphosphino)flopantnickel, dibromoll:1.3-bis(diphenylphosphino)flopantnickel, etc. .

The nickel metal complex catalyst has a content of 0.1 to 0.1 to
It is preferable to use 1.0% by weight.

The double cross coupling reaction is preferably carried out at 20 to 60C, and the reaction time is usually 1 to 5 hours. If the reaction temperature is low, the reaction time will only become longer and this is not an essential problem; however, if the reaction temperature is higher than 60C, high-boiling components such as poly-para-phenylene or by-products such as tetramethyl-biphenyl It is easy to live with many living things.

After the reaction is completed, the magnesium salt is removed by washing with water. The intermediate 3,4,3'',4''-tetramethyl-para-terphenyl can be purified by recrystallization using toluene, xylene, etc. as a solvent, if necessary.

Intermediate 3,4,3'',4''-tetramethyl-para-terphenyl is oxidized to produce para-terphenyl 3 according to the invention
．． 4. 3″,4″-tetracarboxylic acid can be obtained.

The case of oxidation using permanganate will be explained next.

As the permanganate, potassium permanganate or the like is used. The solvent used is a mixture of water and pyridine, with a weight ratio of 1.0 of water to 0.5 to 2.0 of pyridine.
It is preferable that 3,4 for 100g of this solution
．． 3″,4″-tetramethyl-para-terphenyl 5
Add ~15 g of potassium permanganate to the mixture and gradually add 12 times the mole of potassium permanganate. If the amount is less than 12 times the mole, the oxidation reaction will not be completed.

The reaction temperature is 50C or higher and the reflux temperature (93C) or lower, and the reaction time is usually 5 to 10 hours. In this reaction, potassium permanganate becomes manganese oxide, which is insoluble in the solvent, and this is removed by filtration. The filtrate contains para-
Since terphenyl-3,4゜3'',4''-tetracarboxylic acid is dissolved as a potassium salt, acid precipitation treatment is performed with concentrated hydrochloric acid, but since pyridine is contained in the filtrate, pyridine is distilled off using a rotary evaporator. After removing it, acid precipitate it.

Add concentrated hydrochloric acid until the pH of the solution reaches 1.
White para-terphenyl-3,4,3''.

4"-tetracarboxylic acid crystals are obtained. At this time, in order to precipitate from an aqueous solution, para-terphenyl-3,4,3"
, 4''-tetracarboxylic acid is a compound having two molecules of water of crystallization.

Para-terphenyl-3,4, thus obtained
A method of heating 3″, 4″-tetracarboxylic acid at 120 to 250 C under a reduced pressure of 5 to 50 body Hg for 1 to 24 hours,
A method of adding 30 to 60 g of acetic anhydride to 1 g of the para-terphenyl-3゜4.3'',4''-tetracarboxylic acid, heating under reflux for 0.5 to 2 hours, followed by hot filtration and recrystallization, etc. Due to the parameter error 3.4.3″, 4
"-tetracarboxylic acid-3,4:3",4"-dianhydride.

Para-terphenyl-3,4,3'' according to the invention.

4''-tetracarboxylic acid or its dianhydride is useful as a raw material for polyimide resins and other resins, and as a curing agent for epoxy resins, phenol resins, and the like.

〔Example〕

Hereinafter, % means electrolytic corrosion %.

Example 1 (1) Manufacture of Grignard medicine ^ A two-four flask equipped with an Aline condenser, a dropping funnel, a thermometer, and a stirring device was sufficiently dried under an argon gas atmosphere, and then 100 mt of tetrahydrofuran was dehydrated with metallic sodium. , magnesium metal 9.72 g
and promo-ortho-xylene (4-promo-ortho-
Xylene 75% and 3-promo-ortho-xylene 25%
% mixture) 10.0 g was added. When the reaction solution started to be taken and the Grignard reagent started to be produced, 64.0 g of the same promo-ortho-kydurene as above was added to the dropping funnel.
A mixed solution of 100 mA of and tetrahydrofuran was added dropwise over 1 hour. During this time, since the reaction was exothermic, the reaction temperature was maintained at 40 C while cooling with a water bath.

Since metallic magnesium remained even after the dropwise addition was completed, the mixture was heated in an oil bath and stirred for 5 hours at a temperature of 40 C to completely react the metallic magnesium and obtain a Grignard reagent.

(2) 3,4.3″,4″-tetramethyl-para-
Preparation of terphenyl Next, 0.37 g of dichloro[1,2-bis(diphenylphosphino)ethane]nickel catalyst (0.5% based on the total amount of promo-ortho-xylene) was added to the flask and added from the dropping funnel. Para-dichlorobenzene 29.4
g (0,200 mol) in 85 mt of tetrahydrofuran
was added dropwise over 1 hour. During this time, the reaction temperature was maintained at 35C.

After the completion of dropping, keep the temperature at 35C +H' for another hour.
Pka completed the double cross coupling reaction.

300 mt of toluene was added to the reaction completed liquid, and 150 m4 of ion-exchanged water was slowly cooled over 1 hour while stirring, and colorless flaky crystals were precipitated. Remove the crystals by filtration,
When dried, 26.8 g was obtained.

The melting point of this crystal is 168-169C, and Figure 1 shows the proton nuclear magnetic resonance (IH-NMR) spectrum and the second
The figure shows the analysis results of carbon nuclear magnetic resonance (13C-NMR) spectrum. In Figure 1, 2.29- and 2.32
Absorption based on the methyl group proton of P and 7.17 to 7.6
The integrated intensity ratio of absorption based on the benzene ring proton of 5P is 180:150 (=12:10) for the former: the latter.
, which is in good agreement with the theoretical value. In Figure 2,
It can be seen that the obtained compound (theoretical carbon 22) has a symmetric structure since only 10 peaks appear. Furthermore, the absorptions 1 to 1 in Figure 2 are in good agreement with the predicted chemical shifts of the benzene ring carbons according to Savitzky's rule for the benzene ring carbons with carbon numbers ■ to ■ of the compound represented by the formula [■]. 8 has appeared.

From the above, the above crystal is 3. 4. It was confirmed to be 3'', 4''-tetramethyl-para-terphenyl.

(3) Para-terphenyl-3,4,3″,4″-
Production of tetracarboxylic acid, then 3. 4. 14.3 g (50 mmol) of 3″,4″-tetramethyl-para-terphenyl, 200 g of pyridine, and 200 g of ion-exchanged water were added to an Aline cooling tube.
Four pieces of 1 with a thermometer and a stirring device were placed in a flask, the inside of the flask was heated to 80C, 110.7 g (700 mmol) of potassium permanganate was gradually added over 3 hours, and then an additional 5 Stirring was continued while maintaining the temperature at 80C for an hour. The precipitate of manganese oxide produced in the reaction was removed by filtration, and the pyridine in the filtrate was distilled off using a rotary evaporator. After acid precipitation with 36% hydrochloric acid, white fine crystals were precipitated. The pH of the solution at this time was 1. After repeating filtration and water washing twice, it was dried under reduced pressure to obtain 6 g of white powdery crystals II.

The melting point of this crystal was 311-313C.

The infrared absorption spectrum of this crystal is shown in FIG.

For 0.4 g of this crystal, 50 mt of methanol and 97
% sulfuric acid was added and refluxed for 8 hours to methyl esterify the above crystals. The results of the IH-NMR spectrum of the obtained methyl ester compound are shown in FIG. In Figure 4, the integrated intensity ratio of the absorption based on the methyl group protons of 3.91F and 3.94P and the absorption based on the benzene term protons of 7.71 to 7.95F is 180:151 (=12 : 10.07) was in good agreement with the theoretical value (methyl esterification of the compound of formula uvj).

Further, the results of elemental analysis of the above crystal were as follows.

Actual value Carbon: 59.67%, Hydrogen: 4.15% Theoretical value Carbon: 65.03%, Hydrogen: 3.47X (However, the theoretical value is the value obtained as a compound of formula [■]) Elemental analysis As a result, since the measured value and the theoretical value were different, the above crystal was subjected to differential calorimetry analysis at a heating rate of 5C/min, and endothermic peaks were found at 1601Z', 230t:'' and 310C.160C and Total 17 at 230C
A weight loss of % by weight was observed. The endothermic peak at 310C is due to the melting point, but at 160tZ' and 2
The endothermic peak at 30C is due to dehydration. If para-terphenyl-3,4,3'',4''-tetracarboxylic acid undergoes dehydration and ring closure due to heating during differential calorimetry analysis and becomes the corresponding acid anhydride, the reduction in liability would be 9%. . From this, it is thought that the obtained crystals contain water of crystallization, and the actual value of the above elemental analysis is the theoretical value of elemental analysis when two molecules of water of crystallization are hydrated in the compound of formula [■] Carbon 5
9.73% and hydrogen 4.10%.

From the above, it was confirmed that the above crystal was para-terphenyl-3,4,3'',4''-tetracarboxylic acid represented by the formula [■] and had two molecules of water of crystallization.

(4) Para-terphenyl-3,4,3″,4″-
Preparation of tetracarboxylic acid-3,4:3'',4''-dianhydride Next, 10.0 g of the above crystals and 400 g of acetic anhydride were placed in a 1 ton square flask, and dissolved by heating under reflux for 30 minutes. When the mixture was filtered and allowed to cool, pale powdery fine crystals were precipitated. It was filtered and dried under reduced pressure to obtain 6.9 g of powdered crystals. This powder crystal infrared absorption spectrum and LH-NMR.

The spectra are shown in FIGS. 5 and 6, respectively.

The melting point of this crystal is 311 to 313°C, and as a result of elemental analysis, it is 71.28% carbon and 2.76% hydrogen, and the theoretical value (compound of formula [v]) is 71.36cX carbon and 2.7% hydrogen.
Good agreement with 72%, para-terphenyl-3,4,3
It was confirmed that it was ",4"-tetracarboxylic acid-3,4:3",4"-dianhydride.

Application Example Para-terphenyl-3°4.3″ obtained in Example 1
, 4″-tetracarboxylic acid-3,4:3′; 4″-dianhydride 10.0 g (27.0 mmol), 4°4′-
5.41 g (27.0 mmol) of diaminodiphenyl ether and 787 g of N-methylpyrrolid as reaction solvent
．． 3 g was charged into a 200 ml three-neck flask equipped with a stirring device, and stirred for 8 hours at a temperature of 25 C under a nitrogen atmosphere to obtain a polyamic acid cloth (non-volatile content: 15% by weight). During the reaction, the maximum viscosity of the polyamic acid cloth was 30 poise (measured at 25C).

The obtained polyamic acid varnish was cast onto a glass plate and heat-treated at 150 tT for 1 hour and 350C for 11 hours in a hot air constant temperature bath to remove one reaction solvent, and the polyamic acid was converted into polyimide by a dehydration reaction to form a thick film. Sa 40
A μm polyimide film was obtained.

This polyimide film was exposed to air at 460C for 3 hours.
The weight loss after standing for 0 minutes was 2.1% by weight, and the weight loss starting temperature according to thermobalance analysis (heating rate 10C/min) was 4.
It was 72C.

Comparative application example Pyromellitic dianhydride 8.0g (36.7 mmol)
,4. 4'-diaminodiphenyl ether 7.3
4 g (36.7 mmol) and 86.9 g of N-methylpyrrolidone were reacted in the same manner as in the application example, and the nonvolatile content was 15
A heavy weight polyamic acid varnish was synthesized.

At this time, the maximum viscosity of the polyamic acid varnish during the reaction is 3.
．． It was OOO poise (measured at 25C).

A polyimide film was obtained from the obtained polyamic acid varnish in the same manner as in the application example, and the heat resistance of this film was measured.The weight loss after being left in air at 460C for 130 minutes was 3.
．． 5% by weight, thermobalance analysis (heating rate 10C/min)
The temperature at which weight loss started was 4607:''.

〔Effect of the invention〕

Para-terphenyl-3,4,3'' according to the invention.

4''-tetracarboxylic acid or its dianhydride is useful as a new compound and as a raw material for polyimide resins and the like.

[Brief explanation of drawings]

Figure 1 shows the intermediate 3,4゜3// in Example 1.
, 4″-tetramethyl-para-terphenyl lH-N
MR spectrum, Figure 2 is the 13C-NMR spectrum of 3,4,3':4''-tetramethyl-para-terphenyl, Figure 3 is para-terphenyl-3,4,3'',4
4 is the IH-NMR spectrum of para-terphenyl-3,4,3'',4''-tetracarboxylic acid tetramethyl ester, and Figure 5 is the infrared absorption spectrum of para-terphenyl-3,4,3'',4''-tetracarboxylic acid. 4,3",4"
-Tetracarboxylic acid-3,4:3'',4''-dianhydride's infrared absorption spectrum and Figure 6 show para-terphenyl-3,4,3'',4〃-tetracarboxylic acid-3,4:
3 shows an IH-NMR spectrum of 3″,4″-dianhydride.

Claims (1)

[Claims] 1. Para-terphenyl-3,4,3'',4''-tetracarboxylic acid or its dianhydride. Para-terphenyl-3,4,3 characterized by oxidizing 2,3,4,3'',4''-tetramethyl-para-terphenyl or further subjecting it to a dehydration ring-closure reaction thereafter.
A method for producing ``,4''-tetracarboxylic acid or its dianhydride. A patent claim in which 3,3,4,3″,4″-tetramethyl-para-terphenyl is obtained by double cross-coupling reaction of a Grignard reagent of 4-halogeno-ortho-xylene and para-dihalogenobenzene. para-terphenyl-3,4,3″,4″ as described in item 2 within the range of
- A method for producing a tetracarboxylic acid or its dianhydride. 4. The method for producing para-terphenyl-3,4,3'',4''-tetracarboxylic acid or its dianhydride according to claim 3, wherein the para-dihalogenobenzene is para-dichlorobenzene.