JPS6357557A - Bicyclo(2.2.1)heptane-2,3,5,6-tetracarboxylic acid tetraesters and production thereof - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R1 is H or lower alkyl; R2-R5 are alkyl, cycloalkyl, alkenyl, etc.; the steric structure of alkoxycarbonyl is 2endo, 3endo, 3exo, 6exo, etc.). EXAMPLE:Bicyclo[2.2.1]heptane-2endo, 3endo, 5exo, 6exo-tetracarboxylic acid tetramethyl ester. USE:Useful as a precursor for a tetracarboxylic acid dianhydride. PREPARATION:The compound of formula I can be produced by reacting the compound of formula II (e.g. R1 is H or lower alkyl; R2 and R3 are alkyl, cycloalkyl, alkenyl or aralkyl; the steric structure of alkoxycarbonyl group is 2endo, 3endo, 2exo and 3exo-) with an alcohol and CO2 in the presence of a palladium catalyst and an oxidizing agent (e.g. cupric chloride, ferric chloride, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention provides novel and useful bicyclo[2,2,1]
This invention relates to hebutane-2,3,5,6-tetracarboxylic acid tetraesters and their production method.

``Prior art'' In general, tetracarboxylic acid tetraesters are tetracarginic acid 2, which is a raw material for polyimide bunsou, which has poor heat resistance.
It is an industrially useful compound as an anhydride precursor.

As a method for producing a tetracarboxylic acid ester having a bicyclo ring, for example, A, Flory (A, Flor
ey ) etc. are Herpeti force, Chemica, Acta (Hslv
, Chlm, Acta) Vol. 63, p. 1149 (1
980) discusses heterocyclic compounds. Also,
A. Flory et al., Vol. 58, p. 1488 (197
In 5), bicyclotetracarboxylic acid tetraester is obtained.

``Problems to be solved by the invention'' However, in order to produce this compound, it is necessary to go through a complicated process of as many as 'I/'i steps, and the yield is only 8.
% is very low. Furthermore, the alkoxylic zl? of this compound? Nyl group is 2 exo, 3 endo,
55ndo.

6 Since it has a steric structure of exo-, tetracardic acid dianhydride cannot be obtained from this compound.

"Means for Solving the Problems" The present inventors have conducted intensive research in order to easily obtain tetracarboxylic acid tetraester useful as a precursor of tetracardic acid dianhydride having a bicyclo ring, which is useful as a raw material for polyimide. As a result, it is shown by the following general formula (1),
When bicyclotetracarboxylic acid tetraesters have a steric structure capable of forming an acid anhydride ring and are used as a raw material for polyimide resin, the resulting polyimide resin is
The inventors have discovered that they are solvent soluble and have excellent heat resistance, leading to the completion of the present invention.

That is, the present invention is based on (1) the general formula (wherein R1 is a hydrogen atom or a lower argyl group,
2, R3, R4 and R5 each represent an alkyl group, a cycloalkyl group, an alkenyl group or an aralkyl group, which may be the same or different, and the alkoxycar+p-nyl group is 2 endo , 3 endo , 511X0
.

6 oxo- or 2exo, 3exo, 5o
It has a three-dimensional structure of xo, 6exo-. ) Bicyclo[:2,2.11butane-2,3
, 5,6-tetracarboxylic acid tetraesters, and 2, general formula (wherein R4 is a hydrogen atom or a lower alkyl group, R
2 and R3 may be the same or different, an alkyl group,
Cycloalkyl group, alkenyl group or ara, TI/kyl a wo A, katsualkoxycarbonyl group 2 en
do + 3 endo- or 2 exo, 3 a
It has an xo-steric structure. ) Bicyclo[:2.2.1)hept-5-xno-2.3-dicarboxylic acid diesters represented by , R4 in the formula is a hydrogen atom or a lower alkyl group, R
2, R3, R4 and R5 each represent an alkyl group, a cycloalkyl group, an alkenyl group or an aralkyl group, which may be the same or different, and the alkoxycarbonyl group is 2 endo * 3 endo , 5 exa
+6 exa- or 2exo, 3exo, 5oxo, 6
It has an exo- three-dimensional structure. ) Bicyclo[2,2,1]hegetane-2,3,
The present invention provides a method for producing 5,6-tetracarboxylic acid tetraesters.

Bicyclo (:2) represented by the general formula [■] used in the present invention
．． 2.1) Hept-5-ene-2,3-dicarboxylic acid esters [hereinafter referred to as diesters of general formula (II)]. ], for example, bicyclo(2,2,1] to 7')
Dimethyl-5-ene-2,3-dicarboxylate, bicyclo[:2.2.1:]]hept-5-ene-2,3-dicarboxylate, diethylbicyclo(2,2,1)hept-5-
Diallyl ene-2,3-sicargonate, bicyclo[2,
2,1]hept-5-ene-2,3-dicarboxylic acid dicyclohexyl, bicyclo[:2.2.1]hefto-5-
Diphenyl ene-2,3-dicarboxylate, 1-methyl-
Bicyclo[:2.2.1]hept-5-ene-2,3-
Dimethyl dicarboxylate, 1-methyl-vinculo[2,2
, 1] diethyl hezot-5-ene-2,3-dicarboxylate, 1-methyl-bicyclo[2,2,1]hept-5-
ene-2,3-dicar/@diallyl, 1-methyl-bicyclo(2,2,1]hept-5-ene-2,3-dicarboxylic acid dicyclohexyl, 1-methyl-bicyclo(2
, 2,1) diphenyl hept-5-ene-2,3-dicarboxylate.

As the palladium catalyst used for the tetraesterification of the diesters of the above general formula (If), inorganic acid salts, organic acid salts, supported para-noum, etc. can be used.
Examples include radium radium, radium nitrate, radium sulfate, radium acetate, palladium propionate, palladium carbon, palladium alumina, and 1,000 radium black.
It is preferable to use it in a range of 1 to 0.1 times the mole. In addition, in this reaction, Pd2+ is reduced to Pd', so this is converted into Pd
It is necessary to use a copper compound or an iron compound as an oxidizing agent to convert to d2+.

Specific examples include cupric chloride, cupric nitrate, cupric sulfate, cupric acetate, ferric chloride, ferric nitrate, ferric sulfate, and ferric acetate. The amount used is twice the molar amount of the diester of general formula (It).

Furthermore, since acid is produced as a by-product from the oxidizing agent during the reaction, it can also be removed by adding a base. Such bases include:
Fatty acid salts such as sodium acetate, sodium propionate, and sodium butyrate are preferred.

Examples of alcohols used for tetraesterification include t
haalkyl alcohol, cycloalkyl alcohol,
Alkenyl alcohol, aralkyl alcohol are
Specific examples include methanol, ethanol, butanol, allyl alcohol, cyclohexanol, benzyl alcohol, etc., and these are used individually or in combination of two or more.

These alcohols can be added in an amount greater than the theoretical amount and used as a solvent as they are. Furthermore, hydrocarbon solvents such as n-hexane, cyclohexane, heptane, and pentane can also be used as the solvent.

Furthermore, the -carbon oxide does not need to be of high purity and may be mixed with a gas that is inert to this reaction. Further, the pressure is not particularly limited, but is preferably from normal pressure to 15 kl/cm2.

Is the reaction temperature for tetraesterification constant? The temperature is preferably 1 to 60°C, and if the reaction is carried out at a high temperature, the yield tends to decrease. It is appropriate that the reaction time is about 15 minutes to 24 hours. After the reaction is completed, the bicyclo[2,3,
5,6-tetracarboxylic acid tetraesters are obtained in high yield.

It will be done.

"Effects of the Invention" The tetracarboxylic acid tetraesters of general formula (I) of the present invention are useful as precursors of tetracargenic acid dianhydride, which is a raw material for heat-resistant resins such as polyamic acid or priimide.

In fact, the tetracarbo/acid dianhydrides obtained by hydrolyzing the tetracarboxylic acid tetraesters of the general formula (1) of the present invention and further dehydration closure, diaminosophenylmethane, cyamino diphenyl ether, and phenylene. Aromatic diamines such as cyamine and diaminodiphenylsulfone are combined with dimethylformamide, dimethylacetamide,
Polyimides made by heating polyamic acid obtained by reacting it in a solvent such as N-methylpyrrolidone, or by dehydrating and closing it with an acid anhydride such as propionic anhydride or acetic anhydride are known aromatic polyimides. In terms of its solvent solubility and heat resistance as determined by thermogravimetric analysis, it exhibited a high thermal decomposition onset temperature not found in conventionally known aliphatic polyimides. The polyimide thus obtained can be used as a material for polyimide films used as flexible wiring boards and heat-resistant insulating tapes, and can also be used as a material for electric wire enamel, protective coatings for semiconductors, liquid crystal alignment films, etc.

"Examples" The present invention will be explained in more detail by showing Examples, Application Examples, and Comparative Application Examples below. All parts and weights in the examples are based on weight (excluding tensile elongation).

Example 1 Bicyclo(2,2,1)hept-5-ene-2endO
*3 Endo-dical dimethyl phosphate 2 L, Og
(0,100 mol), cupric chloride 26.9.9 (0,
200 mol), palladium chloride 0.059 (0.0o
028 mol), methanol 158.0. ! ij was placed in a reaction vessel, stirred vigorously while introducing carbon oxide, and allowed to react for 1 hour. Carbon monoxide was then removed from the system.
After the reaction solution was passed through and evaporated, the reaction product was dissolved in chloroform 10
Dissolved in 0M and then washed with water. Further, this chloroform layer was washed with a saturated aqueous solution of hydrogen carbonate, concentrated, and reprecipitated with n-hexane to obtain bicyclo[2,
2,1]hebutane-2endo, 3endo,
5 exo.

6 Tetramethyl exo-tetracarboxylate 31.2g
(yield 95%).

Example 2 Bisik' [:2.2.1:l hept-5-ene-2
endo r3 endo-dicarboxylic acid dimethyl 21
．． 0,! i+ (0,100 mol) instead of bicyclo(2,Z,X)hept-5-ene-2exa, 3
Dimethyl exa-dicarboxylate 21.0g (0,10
Bicyclo(2,2,1)hebutane-211!0,3*xo,
31.5y of tetramethyl 5exo, 6exo-tetracarboxylate (yield: 96 buns) was obtained.

Example 3 Bicyclo[2,2,1]hept-5-ene-2endO
t35ndo-dicarboxylic acid dimethyl 21. OF (0
, 100 mol), l-methylbicyclo l:2
．． 2.1:]]Hepto5-en-2endo, 3
Dimethyl endo-dicarboxylate 22.4.9 (0
, 100 mol) in the same manner as in Example 1,
1-methylbicyclo(2,2,1:l heptane-25
ndo, 3 undo, 5 exa, 66XO
-tetramethyl tetracarboxylate 32.39 (yield 94
%) was obtained.

Example 4 Bicyclo(2,2,1)hept-5-ene-2endo
.

3 Dimethyl endo-dicarboxylate 21.09 (0
, 100 mol), l-methylbicycloC2,
2,1:]]Heptoe5-en-2ego,, 3
22.4 g of dimethyl axo-dicarboxylate (0,10
1-methylbicyclo[2°2-1]hebutane-2exo,
32.5 g (yield 95%) of tetramethyl 3exo, 3exo, 6exo-tetracarboxylate was obtained.

Example 5 Bicyclo[2,2,1]hept-5-ene-2end
o.

3 Endo-dicarboxylic acid dimethyl 21.0 g (0
, 100 mol) of bicyclol: 2.2.1'l
Bicyclo[''2.
2.13 hebutane-2axo, 3exa-dimethyl dicarboxylate-5endo, 6endo-diallyl dicarboxylate 27.49 (yield 72S) was obtained.

Example 6 Bicyclo(2,2,1)hept-5-ene-2endo
.

3 Dimethyl ando-dicarboxylate 21.0 g (0
, 100 mol) was replaced with bicyclo(2,2,1)hept-5-ene-2endo, 3endo-dical dicyclohexyl 34°6.9 (0,100 mol). In the same way as 1, bicyclo(2
,2,1) hebutane-2exo, 3exo-dimethyl dicarboxylate-5endo.

6 endo-dicarboxylic acid dicyclohexyl 40.9
g (yield 88es) was obtained.

Example 7 Bicyclo(2,2,1)hept-5-ene-2endo
.

3endo-dicarboxylic acid dimethyl 21. O,! i+
(0,100 mol) instead of bicyclo(2,2,1
) hept-5-ene-2endo, 3endo-
Bicyclo[2
, 2,13hebutane-2exa, 3exo-dimethyl dicarboxylate-5endor 6ando-dicarboxylic acid diphenyl 40.7 g (yield: 90 g) was obtained.

Example 8 Allyl alcohol 1 instead of methanol 15.8.9
7.4g and benzene 120. ! Bicyclo I:2.2.1]hebutane-2ando, 3endo-dimethyl dicarboxylate-5*xo, 61! 26.6 g (yield: 70 g) of dimethyl IKO-dicarboxylate was obtained.

Example 9 Methanol 158. O,! BicycloC2,2,11butane-2ando, 3endo-dimethyldicarboxylate-5ego, 6exa in the same manner as in Example 1 except that 30.0 g of cyclohexanol and 1201 benzene were used in place of i'. -37.2 g (yield: 80%) of dicyclohexyl dicarboxylate was obtained.

Example 10 Bicyclo I:2.2.1]hebutane-2.ndo, 32.69 (yield: 68%) of dimethyl 3ando-dicarboxylate-5axo, 6*xo-dicarpo/dibenzyl acid was obtained.

The analysis results of the bicyclotetracarboxylic acid tetraesters obtained by purifying the tetracarboxylic acid tetraesters of Examples 1 to 4 by distillation are shown in Tables 1 and 2.

Application example 1 (Application example to acid anhydride) Bicyclo(2,2,1)hebutane obtained in Example 2
2@xo, 3erxo, 5exo, 6ex
Tetramethyl o-tetracarboxylate 32.8 g (0,
100 mol) was added to a solution 40a of potassium hydroxide in water/ethanol (1:1), refluxed for 2 hours, and after removing the ethanol, acidified with hydrochloric acid, and then
After extraction with /It/ ether three times, the mixture was dehydrated with sodium sulfate, and after removing the ether, 150y of acetic anhydride was added and refluxed for 2 hours. The reaction solution was then concentrated to give bicyclo(2,2,1)butane-2exa
, 3exo, 5exo, 6exo ++ 17.2.9 (yield: 73) of tetracarboxylic dianhydride was obtained.

Application example 2 (Application example to polyimide) 4.4'-diaminodiphenyl ether (DDE) 6
0,1 g (0,300 mol) was dissolved in 634 g of cresol, and then in this solution, the bicyclo(2,2,1) obtained in Application Example 1 was added while maintaining the temperature at 20-30°C.
Hebutane-2evo, 3exa, 5exo
, 6 exa-tetracarbo/acid dianhydride 70.
9.9 (0,300 mol) was added little by little to 1 while stirring.
Add over a period of time, and after addition, reduce the temperature to 30-40℃
The reaction was continued for 10 hours, and the reaction was completed to obtain a cresol solution of polyamic acid.

Next, xylene 75j9 was added to this solution, and the temperature was raised to 200'C4 for about 3 hours, and then the temperature was kept at the same temperature for 44 hours.
Holds time. During this time, a total of [859] of water and xylene distilled out was collected. Thereafter, this reaction solution was cooled to room temperature to obtain 782 g of polyimide solution.

Next, this resin solution was cast onto a glass plate and heated to 120°C.
for 30 minutes, then dried at 200℃ for 1 hour to obtain a film thickness of 25μ
A film-like polyimide of m was obtained.

Mechanical strength was evaluated by measuring the tensile strength and tensile elongation of this 4-limide film, and heat resistance was evaluated by measuring the 5% weight dehumidification temperature by thermogravimetric analysis (TGA). However, this polyimide film had excellent mechanical strength and heat resistance.

The measurement method is shown below, and the measurement results are shown in Table 3.

O tensile strength and tensile elongation: Measured in accordance with ASTM D-882-64T.

05chi Weight loss temperature: Thermogravimetric analyzer SSC560 manufactured by Seiko Electronics Co., Ltd.
The temperature at which the sample weight decreased by 5% was measured in air at a temperature increase rate of 10° C./min and a sample amount of 10 to 100 ml.

Comparative application example 1 (same as above) Bisik O(2,2,1) Hebutane-2exo, 3
5-(2,5-dioquinetetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-cycarpic anhydride79. 2 // (0,
A control film polyimide was obtained in the same manner as in Application Example 1 except that 300 mol) was used. Next, mechanical strength and heat resistance were evaluated in the same manner, and both were found to be inferior. The measurement results are shown in Table 3.

Comparative application example 2 (same as above) Bicyclo(2,2,1)hebutane-2exo, 3e
xo.

A control sample was prepared in the same manner as in Application Example 1, except that 78.7 g (0.3 oomol) of methylbicyclooctenetetracarzenic acid dianhydride was used instead of 5.xo, 6 exo-tetracarbo/acid dianhydride. A film-like polyimide was obtained.

Next, mechanical strength and heat resistance were evaluated in the same manner, and both were found to be inferior. The measurement results are shown in Table 3.

Comparative application example 3 (same as above) Bicyclo(2,2,13hebutane-2exo, 3
exo, 5exo, 66XO-tetracarbo/
An attempt was made to obtain a polyimide solution in the same manner as in Application Example 1, except that pyromellitic anhydride 65.4.9, which is an aromatic tetracarboxylic acid anhydride, was used in place of the acid dianhydride. Polyimide produced during the heating of the acid precipitated from the solvent, making it impossible to obtain a polyimide solution.

Application example 3 (Application example to polyamic acid) 4.4'-diaminodiphenylmethane (DDM) 59
．． 4g (0,300 mol) of dimethylacetamide 63
Bicyclo[2,2゜1]hebutane-2exo, 3@X0, 5exo, 6 obtained in Application Example 1 was dissolved in 4I and maintained at a temperature of 20 to 30°C in this solution.
70.9 g of exo-tetracarboxylic dianhydride (0,
300 mol) was added little by little over 1 hour with stirring, and after the addition was completed, the reaction was continued for 6 hours while maintaining the temperature at 30 to 40°C to obtain a dimethylacetamide solution of polyamic acid.

This polyamic acid solution was cast onto a glass plate and heated to 120°C.
for one hour at
A conventional polyimide film was obtained.

When the mechanical strength and heat resistance of this polyimide film were evaluated in the same manner as in Application Example 1, it was found to be excellent in both. The results are shown in Table-3.

・Tsu Table-3

Claims (1)

[Claims] 1. General formula (wherein R_1 is a hydrogen atom or a lower alkyl group,
R_2, R_3, R_4 and R_5 each represent an alkyl group, cycloalkyl group, alkenyl group or aralkyl group, which may be the same or different, and the alkoxycarbonyl group is 2endo, 3endo, 5exo, 6e
xo- or 2exo, 3exo, 5exo, 6exo-
It has a three-dimensional structure. ) Bicyclo[2,2,1]heptane-2,3,
5,6-tetracarboxylic acid tetraesters. 2. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼……(II) (However, R_1 in the formula is a hydrogen atom or a lower alkyl group,
R_2 and R_3 represent an alkyl group, a cycloalkyl group, an alkenyl group, or an aralkyl group, which may be the same or different, and the alkoxycarbonyl group is 2endo
, 3endo-, 2exo, and 3exo-. ) Bicyclo[2,2,1]hept-5-ene-
2,3-dicarboxylic acid diesters with palladium catalyst,
In the presence of an oxidizing agent, it is reacted with alcohol and carbon monoxide, and the general formula ▲ has numerical formulas, chemical formulas, tables, etc. ▼... (I) (However, R_1 in the formula is a hydrogen atom or a lower alkyl group,
R_2, R_3, R_4 and R_5 each represent an alkyl group, cycloalkyl group, alkenyl group or aralkyl group, which may be the same or different, and the alkoxycarbonyl group is 2endo, 3endo, 5exo, 6e
xo- or 2exo, 3exo, 5exo, 6exo-
It has a three-dimensional structure. ) Bicyclo[2,2,1]heptane-2,3,
Method for producing 5,6-tetracarboxylic acid tetraesters.