JPS6023383A - Novel tetracarboxylic acid dianhydride and its preparation - Google Patents

Abstract

NEW MATERIAL:The 2, 3, 4, 4a, 4b, 5, 6, 7-octahydrophenanthrene-3, 4, 5, 6-tetracarboxylic acid anhydride of formula. USE:Raw material of polyimide resin and polyester resin, and hardener of epoxy resin, etc. PREPARATION:1mol of p-divinylbenzene is made to react with preferably 1.8- 3.0mol of maleic anhydride in the presence of a polymerization inhibitor (e.g. phenothiazine, 2,6-di-t-butyl-4-methylphenol, etc.), if necessary in an organic solvent such as toluene, preferably at 50-150 deg.C. The weight ratio of the solvent to the raw material is 0.2-10. The p-divinylbenzene is not necessarily the one having high purity, and may be a mixture with m-divinylbenzene.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel tetracarboxylic dianhydride and a method for producing the same.

In order to synthesize a new acid anhydride as a raw material for polyimide resin, the inventors of the present invention have conducted repeated studies focusing on the anti-mold properties of divinylbenzene and maleic anhydride. What is Obtained 1-Heading 1 The present invention has been achieved.

That is, 5 the present invention relates to 2,3.4.4a,4b15.6.7-octahydrophenanthrene to 3.4.5.6-tetracarboxylic dianhydride represented by the structural formula and a method for producing the same. .

This compound can be produced by a simple operation of, for example, dissolving P-divinylbenzene, maleic anhydride, and an inhibitor in an organic solvent and then heating the solution. Not limited to methods.

P-divinylbenzene, which is a raw material used in the present invention, does not necessarily have to be of high purity; for example, a mixture with bar-divinylbenzene can also be used. In such a case, the target tetracarboxylic dianhydride can be easily separated from the by-products.
When divinylbenzene alone is used, the product has a high melting point (approximately 295C) and is extremely difficult to handle because it is insoluble in swamp media, and hardening agents such as epoxy 4fJ resin are difficult to handle. It is also difficult to use it as an intermediate for synthetic products.

The number of maleic anhydride used, which is the other component, is 15 to 4 mol per 1 mol of p-divinylbenceph, preferably [7 < is 1
It is 8 to 30 moles.

Further, the polymerization IA tl agent may be one that completely inhibits the homopolymerization of p-divinylbenzene or the copolymerization of p-divinylbenzene and maleic anhydride. -) tylphenol, 2,6-syncropentyl-4-methylphenol, 2,2'-methylenebis(4-ethyl-6-macyarybutylphenol), 4.47-methylenebis(
2,6-ditertiary-butylphenol) = 4.4'
- Phenolic compounds such as thiobis(6-methyl-6-ternary-butylphenol), phenothiazine compounds such as phenothiazine, benzophenothiazine, acetamidophenothiazine, hydroquinone, benzylhydroquinone, dimenyarybutylhydroxyne, catechol, P-mer Examples include quinone compounds such as nyarybutylcatechol and pyrogallol, and N-nitrosamine compounds such as I9-nitrosodiphenylamine and N-nitron dimethylamine. The amount of such a polymerization inhibitor to be used is appropriately determined depending on the type thereof, reaction temperature, and other conditions.

00 relative to the theoretical amount of tetracarboxylic dianhydride produced
The weight is 1 to 10, preferably 01 to 5. If the amount used is too small, by-products are likely to be produced, and if the amount used is too large, it will be economically disadvantageous.

The organic solvent is preferably one that satisfies all the necessary amounts of p-divinylbenzene, maleic anhydride, and polymerization inhibitor, but is not particularly limited.Specific examples include benzene, toluene, xylene, hexane, Examples include hydrocarbon solvents such as heptane and cyclohexane, chlorine solvents such as carbon tetrachloride, ethane trichloride, and ethane dichloride, ether solvents such as tetrahydrofuran and dioxane, and ketone solvents such as acetone and methyl ethyl ketone. The amount of these solvents used is 02 to 10 times the total amount of p-divinylbenzene and maleic anhydride (overlapping basis)
It is preferable that

In addition, the reaction temperature is 30 to 200 C1, preferably 50 to 1
It is 50C.

The obtained tetracarboxylic dianhydride of the present invention is an adduct of a p-divinylbenzene molecule and two molecules of maleic anhydride, has a melting point of about 223 C, is a white solid, and is suitable for use in, for example, polyimide resin or polyester resin. The present invention will now be described with reference to Examples.

Example Three-necked fume with thermometer, reflux condenser, and stirrer 5, (
92.6% pure p-divinylbenzene 105.4
p (0.75 mol), maleic anhydride 147.1i (1
, 5 mol), 2.5 y-% of phenothiazine, and 2507 gold of toluene were charged, the temperature was raised to 60 C, the mixture was uniformly dissolved, and the mixture was reacted at 105 G for 8 hours. After the completion of graze removal, the precipitated product was separated and recrystallized with acetic anhydride to obtain a white solid. The melting point of this product was 223C. or.

The elemental analysis values were (Measured value Theoretical value o 66.18 66.26 H4,134,52 029, 6929,42), and the O-NMR results were as shown in the table below. □ Therefore, this It was confirmed that the compound was a compound represented by the above structural formula [■].This compound was soluble in acetone and tetrahydrofuran.

Comparative Example A white powder was obtained by carrying out the same reaction as in Example 1, except that crystalline divinylbenzene was used in place of p-divinylbenzene used in Example 1.

This product has a high melting point of 292-294C, so it is difficult to use it as a curing agent for epoxy resins, and it can also be used as a raw material for polyimide resins, which are unsuitable for polar solvents such as dimethylacetamide and dimethylsulfoxide. 2.It is inappropriate and has little usefulness.

Patent applicant: Zeon Corporation 7-

Claims (1)

[Claims] 1, 2. j4,4a,4b,5.6.7-octahydrophenanthrene-5.4.5.6-tetracarboxylic dianhydride. 2. The addition reaction of P-divinylbenzene and maleic anhydride in the presence of an inhibitor is the 1Nj characteristic. 2.5.4.4a, 4b, 5.6,7-octahydrophenanthrene-5 , 4,5,6-Tetracarboxylic dianhydride production method.