JPH04103579A - Tetracarboxylic acid dianhydride - Google Patents

Abstract

NEW MATERIAL:A tetracarboxylic acid dianhydride shown by formula I ((n) is 1-3 integer). EXAMPLE:Bis (3-phthalic anhydride)-2, 5-furyl. USE:A raw material for heat-resistant resin such as polyimide. PREPARATION:For example, a 3-halo-o-xylene shown by formula II (X is I or Br) is reacted with metal magnesium in diethyl ether and treated with a solution of a 2,5-dihalo-furyl in diethyl ether under chilling for 2 hours to give a 2,5-bis(3-o-xylino)furyl shown by formula TV. Then, this compound is oxidized with potassium permanganate in pyridine and water and the reaction product is isolated and heat-treated at 200 deg.C under reduced pressure to give a tetracarboxylic dianhydride shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel acid dianhydride useful as a raw material for heat-resistant resins such as polyimide.

[Conventional technology]

Polyimide has excellent heat resistance among various organic polymers, so it is widely used in fields ranging from space and aviation to electronic communications. Particularly recently, it has been desired not only to have excellent heat resistance but also to have various performances depending on the application.

For example, base films for flexible printed circuit boards, carrier tapes for TAB (tape automated bonding), and resins for laminates are desired to have a low coefficient of thermal expansion, a low dielectric constant, and low hygroscopicity. However, a polyimide that satisfactorily satisfies these properties has not yet been obtained.

In order to obtain such a polyimide, it is necessary to make the polyimide main chain as rigid as possible to exhibit low thermal expansion. When polyimide is synthesized using pyromellitic acid, which has the most rigid structure in existence, low thermal expansion can be easily achieved, but the polarization of the imide group is large (
Therefore, low hygroscopicity cannot be achieved.Furthermore, it is possible to introduce fluorine to lower the dielectric constant, but this is expected to increase the structural cost and reduce the reactivity of the acid anhydride. It is undesirable.

[Problem that the invention seeks to solve]

The present invention has low thermal expansion, low dielectric constant, and low moisture absorption (water resistance).
The purpose of the present invention is to provide a novel acid dianhydride useful for synthesizing polyimides having excellent properties such as.

[Means for solving problems]

The present inventors have arrived at the present invention as a result of intensive research to solve the above problems.

That is, although the chemical structural formula (1) can be obtained in the present invention, it has been found that because the polarization of the imide group is relatively large, it is not possible to exhibit a low dielectric constant and low hygroscopicity.

Therefore, the present inventors used a tetracarboxylic dianhydride represented by the following chemical structural formula C11) (where n=an integer of 1 to 3) as content.

The present invention will be explained in detail below.

The present inventors conducted various molecular designs for tetracarboxylic dianhydride and evaluated the results. As a result, the heat resistance of the synthesized polyimide decreases with aliphatic, and the main chain is bent, resulting in low thermal expansion. In addition, when polyimide is synthesized using pyromellitic acid, which has the most rigid structure among existing acid anhydrides, the -R- group, which exhibits low thermal expansion, has heat resistance. If polyimide is synthesized using a polyimide with the expected rigid structure, it will not only be possible to achieve low thermal expansion, but also because the molecular weight of the acid anhydride will increase, the imide, which is the polar part of polyimide, will be synthesized. The proportion of rings is small, resulting in a low dielectric constant,
We believe that low hygroscopicity can be achieved, and as a result of intensive study, we found that the following structure is suitable for introducing into the -R~ group of the chemical structure CI[) (where n is an integer of 1 to 3) and came to invent a novel tetracarboxylic dianhydride represented by the above chemical structural formula (1).

As raw materials for constructing the tetracarboxylic dianhydride represented by the above chemical structural formula [1], the following chemical structural formula [
IV) (where n = an integer of 1 to 3) The compound of formula (IV) can be synthesized by reacting with metallic magnesium or metallic lithium, and then reacting with (where X is 1 or Br, and n is an integer of 1 to 3).

In addition, the following reaction formula (VI) (where X is Br or I, n is an integer of 1 to 3, M
can be obtained by the method shown in (metallic magnesium or metallic lithium).

That is, 3-bromo-0-xylene or 3-iodo-〇 (where X is Br or I, n is an integer from 1 to 3, and the catalyst is palladium or an alloy of palladium and mercury) in ether or an aprotic solvent. or a mixture of palladium chloride and mercuric chloride) with 3-bromo-0-xylene or 3-iodo-〇-xylene (where X is Br or I, n is an integer of 1 to 3) to metal palladium, an alloy of palladium and mercury, palladium chloride, or a mixture of palladium chloride and mercury chloride as a catalyst, by oxidative coupling with hydrogen peroxide to form the formula (
TV) can be synthesized.

Next, bis0-xylinofuryl represented by formula (IV),
The oxidation and dehydration reactions of bisO-xylinobifuryl and bisO-xylinobifuryl to the tetracarboxylic dianhydride represented by formula (I) can be carried out by conventional oxidation and dehydration ring closure techniques. For example, potassium permanganate method,
Oxidation of a methyl group by a nitric acid method, etc., and acid anhydride conversion method, such as an acetic anhydride method or a heat dehydration method, can be employed. Alternatively, it is also possible to directly convert the acid anhydride by air oxidation using vanadium pentoxide as a catalyst.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples.

Example 1 Synthesis of 25-bis(3-o-xylino)furyl 3-iodo-〇-quinrene 51°Ig(
22o-01), metal magnesium ribbon 5゜5 g
(225 m*ol) and 500 g of diethyl ether were added. The mixture was stirred at room temperature under a nitrogen atmosphere for 3 hours, then the reaction vessel was cooled with ice and the 25-short-
2.76 g (100 s*ol) of Furil was dissolved in 300 g of diethyl ether, added to the above mixed solution, stirred for 2 hours under water cooling, and then stirred under reflux for 1 hour. After the reaction,
Diethyl ether was distilled off, and the remaining solid content was purified by vacuum distillation using a glass tube oven to obtain 2.5-
Bis(3-0-xylino)furyl was synthesized.

This is the molecular ion peak (m/
e-276) matched the molecular weight of the target component, and as shown below, the measured value and calculated value in elemental analysis almost matched, so it was confirmed to be the target compound.

Elemental analysis calculated value: C: 86.92 H: 1.29 Measured value: c: s6. ao H Near, 40 Example 2 Synthesis of 2.5-bis(3-o-xylino)furyl 51°1 g of 3-iodo-〇-xylene was placed in an Erlenmeyer flask.
(220s*ol), 28% hydrogen peroxide solution 55.0g
(450m5ol), P d Clzo,
9 g (5 mmol), 2.5-short-
Frill 32.0g (10(1+s.

1), 400 g of methanol was added. This mixture was stirred under heating under reflux for 8 hours. After filtering this mixture to remove the metal catalyst, the filtrate was distilled off and the resulting solid content was purified by distillation under reduced pressure using a glass tube oven.
5-bis(3-xylino)furyl was synthesized.

The results of mass spectrometry and elemental analysis were also consistent with Example 1. Example 3 Synthesis of bis(3-phthalic anhydride 12.5-furyl) 2.5-bis(3-o-xylino)furyl 17. 1 g (62+u+ol), pyridine 55
0m = Add 200a1 of distilled water and heat to 100°C,
Potassium permanganate 48.9 g (310+mol
) was added little by little and stirred for 3 hours. After the reaction, the solution was filtered, and the solvent of the filtrate was distilled off to obtain a solid content.

Next, the solid content was dissolved in 6% sodium hydroxide aqueous solution 700%
After heating to 100"C, 58.8 g of potassium permanganate was slowly added and the reaction was carried out with stirring for 2 hours. After the reaction, ethanol was added to decompose the excess potassium permanganate. After cooling the filtrate, hydrochloric acid was added to precipitate the product. After drying this precipitate, it was heat-treated at I Torr and 200°C, and finally purified by sublimation to obtain the target bis. (3-phthalic anhydride) 2,5-furyl was obtained.

This is the molecular ion beak (m/
e-360) corresponds to the molecular weight of the target component, and as shown below, the measured value and the calculated value in elemental analysis almost matched, so it was confirmed that it was the target compound.

Elemental analysis calculated value: C: 66.68 H: 2.24 Measured value: C: 66.80 H: 2.20 Example 4 Synthesis of bis5.5'-((3-orthoxylino)-2-furyl) 51゜1 g of 3-iodo-〇-xylene in an Erlenmeyer flask
(220s+mol), metal magnesium ribbon 5
．． 5g (225■■O1), diethyl ether 400
g was added. The mixture was stirred for 3 hours at room temperature under nitrogen atmosphere, then the reaction vessel was cooled with ice, 384 g (100 mmol) of 55'-short-2,2'-furyl was dissolved in 300 g of diethyl ether, and the above mixture was dissolved in 300 g of diethyl ether. After the reaction, the mixture was stirred for 2 hours under ice cooling, and then stirred under reflux for 1 hour. After the reaction, diethyl ether was distilled off, and the remaining solid content was purified by distillation under reduced pressure using a glass tube oven. Bis55'-((3-orthoxolino)-2-furyl) was synthesized.

This is the molecular ion beak (m/
e=342) was consistent with the molecular weight of the target component, and as shown below, the measured value and calculated value in elemental analysis almost matched, so it was confirmed that it was the target compound.

Elemental analysis calculated value: C: 84.18 H: 6.4B Measured value: C: 84.22 H: 6.40 Example 5 Bis5.5'-[(3-phthalic anhydride)-2
Synthesis of 21.2 g (62 vw of bis5.5'-I(3-orthoxylino)-2-furyl) in 30 flasks.

1) Add pyridine 55 (ld), distilled water 200 d!, heat to 100°C, and add 48°9 g of potassium permanganate.
(31 (1 wsol) was added little by little and stirred for 3 hours. After the reaction, the solution was filtered, and the solvent of the filtrate was distilled off to obtain a solid content.

Next, the solid content was dissolved in 6% sodium hydroxide aqueous solution 750
After heating to 100"C, 60g of potassium permanganate was slowly added and the reaction was carried out with stirring for 2 hours. After the reaction, ethanol was added to decompose the excess potassium permanganate, and the mixture was filtered. After cooling the filtrate,
Hydrochloric acid was added to precipitate the product. After drying this precipitate, it was heat-treated at 1 Torr and 200°C, and finally purified by sublimation to obtain the target product, bis5.5'-((3-phthalic anhydride)-2-furyl). .

This is the molecular ion beak (m/
e=426) was consistent with the molecular weight of the target component, and as shown below, the measured value and the calculated value in elemental analysis almost matched, so it was confirmed that it was the target compound.

Elemental analysis durability value: C: 67.61 H: 2.36 Measured value: C: 67.70 H: 2.50 Example 6 Bis2.5'-(3-ortho-xylino)-5°2'
: 3-
Iodo-〇-xylene 51゜1 g (220+u+o
l), metal magnesium ribbon 5゜5g (225s+
Steel O1) and diethyl ether were added. The mixture was stirred at room temperature under a nitrogen atmosphere for 3 hours, then the reaction vessel was cooled with ice and 25'-short-5.2':5',
2'-Turfrill 4 5.2 g (100mm
ol) in 300 g of diethyl ether, added to the above mixture, stirred for 2 hours under water cooling, and then stirred under reflux for 1 hour.
Time went.

After the reaction, diethyl ether was distilled off, and the remaining solid content was purified by vacuum distillation using a glass tube oven.
Bis2.5'-(3-orthoxylino)-5.2'
:5',2'-terfuryl was synthesized.

This is the molecular ion beak (m/
e = 409) corresponds to the molecular weight of the target component, and as shown below, the measured value and calculated value in elemental analysis almost matched, so it was confirmed that it was the target compound.

Elemental analysis calculated value: C: 82.32 H: 5.92 Measured value: C: 82.40 H: 6.02 Example 7 Bis 2.5” (3-phthalic anhydride)-5,2
Bis2.5'-(3-orthoxylino)-5,2' in a 3-day flask.
: 5', 2'-turfril 25, 4 g (62 m
mol), pyridine 550jli! , distilled water 200d
48.9 g (310 ms+ol) of potassium permanganate was added little by little and stirred for 3 hours. After the reaction, the solution was filtered, and the solvent of the filtrate was distilled off to obtain the solid content. Ta.

Next, the solid content was dissolved in 6% sodium hydroxide aqueous solution 750
After heating to 100° C., 60 g of potassium permanganate was slowly added and the reaction was carried out with stirring for 2 hours. After the reaction, ethanol was added to decompose excess potassium permanganate, and the mixture was filtered. After cooling the filtrate, hydrochloric acid was added to precipitate the product. After drying this precipitate, it was heat-treated at ITorr and 200°C, and finally purified by sublimation to obtain the target bis2.5#-(3-phthalic anhydride)-5,2':5', 2'-terfryl was obtained.

This is the molecular ion beak (m/
e=492) was consistent with the molecular weight of the target component, and as shown below, the measured value and the calculated value in elemental analysis almost matched, so it was confirmed that it was the target compound.

Elemental analysis calculated value: C: 6B, 30 H: 2.46 Measured value: C: 6B, 25 H: 2.5030 21.6 g of loose phenylenediamine (200 m
), 360 g of dimethylref-1 remamide (hereinafter abbreviated as DMF) was taken, and while stirring, 68.5 g of bis(3-phthalene-quanhydride)-2,5-furyl synthesized in Example 3 (190 Mon. ol) was gradually added and stirred for 30 minutes. Next, 10m.

8% by weight of l bis(3-phthalic anhydride)-2
, 5-furyl in DMF was gradually added to obtain a polyamic acid solution.

After mixing acetic anhydride in excess of the theoretical amount and a catalytic amount of tertiary amine with a polyamic acid solution, it was cast onto a glass plate, dried at about 80°C for about 90 seconds, and then a polyamic acid coating was formed. Peel it off from the glass plate, fix the coating to the support frame,
Thereafter, it was heated at about 100° C. for about 90 seconds and then stretched. Next, heating was carried out at about 250°C for about 30 seconds, at about 300°C for about 30 seconds, at about 400°C for about 30 seconds, and at about 450°C for about 2 minutes to obtain a polyimide copolymer film of about 25 microns.

Table 1 shows the physical properties of the polyimide copolymer film obtained.

Comparative Reference Example Production of polyimide copolymer membrane 26.0 diaminodiphenyl ether was added to 30 flasks.
g (130 gmol) and 200 g of DMF, and while stirring, add 27.0 g of pyromellitic dianhydride.
(124 mmol) was gradually added, then 7 of 6-Ol
A polyamic acid solution was obtained by gradually adding a DMF solution of pyromellitic dianhydride in weight percent.

Then, a polyimide copolymer film was obtained in the same manner as in the reference example.

Table 1 shows the physical properties of the polyimide copolymer film obtained.

Table 1 (1) Thermal Mechanical An
Thermal expansion coefficient from 100 to 200°C measured by lysis (2) Measured by ASTM D-150 (3) AS
Measured by TM D-570 [Function/Effect] According to the soft soil, the present invention provides a tetracarboxylic dianhydride for providing a polyimide with low thermal expansion, low dielectric constant, and low hygroscopicity. .

Claims (1)

[Claims] 1. Chemical structural formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼〔I〕 (However, n = an integer from 1 to 3) Tetracarboxylic dianhydride represented by