JPS5952172B2 - Method for producing amide-imide compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel amide-imide compound containing a hydroxyl group at its terminal.

Generally, amide-imide resins consisting of amide bonds and imide bonds are linear resins that are excellent in heat resistance, chemical resistance, and mechanical properties.

The present invention provides an amide-imide resin having such excellent properties or a low-molecular-weight amide-imide compound containing an amide bond and an imide bond (hereinafter collectively referred to as an amide-imide compound), which has an isocyanate group, an epoxy group, a carboxyl group,
Reactive with reactive groups contained in other resins or monomers, such as acid anhydride groups.

The present invention relates to a method for producing a novel amide-imide compound to which a high hydroxyl group is added. That is, the present invention provides a molar ratio of 1.15 mol of polyvalent amide to an acid component obtained by replacing part of tricarboxylic anhydride or its derivative or tricarboxylic anhydride with another carboxylic acid or its semiconductor device. The above is added and reacted to produce a product having an aromatic amine group at the end, and then alkylene carbonate is further added and reacted to produce an amidimide compound containing a hydroxyl group at the end. The iricarboxylic acid or its derivative used in the present invention includes trimellitic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 2,3,5-naphthalenetricarboxylic anhydride, 2-(3,4- dicarboxyphenyl)-2-(3
-carboxyphenyl)propane anhydride, 3-, 4-tricarboxybenzophenone anhydride, etc., and derivatives thereof are carboxylic acids or tricarboxylic acids obtained by reacting these acid anhydrides with water or lower alcohols. lower alkyl esters, acid chlorides, phenyl esters, etc. Further, other polycarboxylic acids or derivatives thereof used by partially replacing tricarboxylic acid anhydride or its derivatives include terephthalic acid, isophthalic acid, adipic acid, succinic acid, pyromellitic acid, and benzophenonetetracarboxylic acid. dianhydride, N, N' diphenylmethalin trimellitimide, ゜butanetetracarboxylic acid, 3-
Acids such as carboxyphenyl-N(4-carboxyphenyl)phthalimide or lower alkyl esters thereof,
Such as phenyl ester or acid chloride.

Further, the polyvalent amines used in the present invention include 4, l-diaminodiphenylmethane, metaphenylenediamine, 4,
,1-diamino3,J-dimethyldiphenylmethane,2
, 4-tolylenediamine, 4,4'-diamine 3,
3',5',y-tetramethyldiphenylmethane, 4,
In addition to diamines such as 4'-diaminodiphenyl ketone and 4,4'-diaminodiphenyl ether alone or as a mixture, 3,4,S-triaminodiphenyl sulfone, 3,3'
,4,4'-tetraaminodiphenylmethane, 1,2,
Tri- or tetraamines such as 4,5-tetraaminobenzene and 3,4,S-triaminodiphenylmethane can be used in combination.

However, when using a polyvalent amine with a valence of 3 or higher, if two of the amino groups in the metal are bonded to carbons located adjacent to each other in the aromatic ring, imidazole, which has excellent heat resistance, Although some pyrolone rings are formed, a product having properties similar to those containing only amide bonds and imide bonds as described above can be obtained.

Further, a part of the polyvalent amine may be replaced with a polyhydric alcohol.

In this case, an ester bond is formed in addition to an amide bond and an imide bond, and the heat resistance of the resulting product is slightly lower than that of a product using only polyvalent amines, but its solubility in solvents is Alternatively, the flow characteristics of the resin can be modified. Note that polyhydric alcohols include ethylene glycol,
These include glycerin, 1,4-butanediol, tris(2-hydroxyethyl)isocyanurate, N,N'-dihydroxyethylpyromellitimide, 1,3,6-hexanetriol, bentaerythritol, and the like.

Regarding the amount of polyvalent amine added to the acid component,
It depends on whether the amide-imide compound produced as an intermediate is producing a high molecular weight resin or a raw material for a low molecular weight resin, but in either case, a product containing an aromatic amino group at the end is first produced. In order to achieve this effect, it is necessary to mix the polyvalent amine in a molar ratio of 1.15 times or more with respect to the total acid components, and in the case of resins, it is generally 1.15 to 1.15 times or more.
About 1.4 times, or about 1.5 to 2 times in the case of raw materials for resins. In the case of raw materials for resins, it is better to mix in an excess of 2 times the mole or more, and after reaction and zeification, remove the excess polyvalent amine. Separate,
Although it is possible to react with alkylene carbonate after a certain time, it is also possible to react with alkylene carbonate as it is without separating it, and then separate the reaction product of the polyvalent amine and alkylene carbonate.

The alkylene carbonate used in the present invention is ethylene carbonate or propylene carbonate, and these may be used alone or in combination.

The amount of alkylene carbonate to be added is not particularly limited, but it is preferably at least 1 time, generally 2 to 4 times, in molar ratio to the product having an aromatic amino group at the end.

Note that when alkylene carbonate is used in excess, the excess alkylene can be effectively used as a reaction solvent. The amide-imide compound containing a hydroxyl group at the terminal end is highly reactive with various reactive groups such as isocyanate groups, epoxy groups, carpoxyl groups, and acid anhydride groups. The resinous material can be used to obtain modified resins with excellent properties by using a suitable curing agent.

Conversely, low molecular weight substances can be reacted with epoxy resins, polyurethane resins, etc., polyisocyanates, polyhydric carboxylic acids, acid anhydrides, etc., and used for the synthesis of new heat-resistant resins. For example, the high molecular weight resinous material synthesized by the method of the present invention can be cured by forming an amide-imide urethane resin using polyisocyanate as a crosslinking agent. In addition, low molecular weight resin raw materials easily react with polyhydric carboxylic acids or polyisocyanates, etc.
For example, an amide-imide ester resin can be synthesized by polymerizing with dicarboxylic acid. Next, examples of the present invention will be described.

Example 1 Trimellitic anhydride 1549, 238 g of 4,4'-diaminodiphenylmethane was dissolved in N-methylpyrrolidone 2009
Did you die inside and raise the temperature to 205 degrees Celsius for 5 hours and react? Closed.

When the infrared absorption vector of the obtained product was measured, it was found that the absorption due to the 5-membered ring imide group was about 5.6μ and about 7.25μ, the absorption due to the amide bond was about 6μ, and the absorption was about 2.
．． Absorption attributable to amino groups was observed at 95μ, confirming that the resin was an amide-imide resin with an aromatic amino group at the end. Next, 106 g of ethylene carbonate was added to this resin, and the temperature was raised to 140 to 180° C. over 8 hours to cause a reaction while releasing carbon dioxide gas.

When the infrared absorption vector of the obtained product was measured, in addition to the absorption caused by the above-mentioned amide bond and imide bond, absorption caused by the hydroxyl group occurred at about 2.6μ, indicating that the hydroxyl group was introduced. I confirmed that. Example 2 Trimellitic anhydride 1929, metatolylene diamine 1839 and solvent naphtha 2509 were added to 190
The temperature was raised to .degree. C., and the reaction was continued for 5 hours at this temperature while distilling off water and a portion of naphtha.

After applying the obtained product to a salt plate and drying it, the infrared absorption vector was measured, and it was found to be about 5.6μ and about 7μ.
．． The absorption caused by the imide bond of the 5-membered ring at 25μ was observed, the absorption caused by the amide bond at about 6μ, and the absorption caused by the amino group at about 2.95μ. It was confirmed that it was an oligomer. Next, ethylene carbonate 1069 was added to this resin, the temperature was raised to 180° C. over 3 hours, and the reaction was further carried out at this temperature for 3 hours while distilling carbon dioxide gas.

When the infrared absorption vector of the obtained product was measured, in addition to the absorption caused by the amide and imide bonds mentioned above, there was an absorption caused by the hydroxyl group at about 2.6μ, confirming that the hydroxyl group was introduced. did. Example 3 3,go,4'-monotricarboxybenzophenone anhydride 3
249,4,4'-diaminodiphenyl ether 270
9 and under the same reaction conditions as in Example 1, an amide-imide resin having an amino group at the terminal was obtained.

Next, propylene carbonate 1409 was added to this resin, and a reaction was carried out in the same manner as in Example 1. It was confirmed by infrared spectroscopy that the obtained product contained hydroxyl groups in addition to amide and imide bonds. As is clear from Examples 1 to 3 above, according to the method of the present invention, an amide-imide compound containing a highly reactive hydroxyl group at the terminal can be obtained very easily.

As mentioned above, the amidimide compound containing a hydroxyl group at the end obtained by the method of the present invention is a compound useful as a raw material for obtaining a resin with excellent heat resistance, chemical resistance, and mechanical properties. An example is shown below.

Application Example A paint obtained by adding and dissolving the phenolic adduct 509 of toluylene diisocyanate to 1 kg of a solution obtained by diluting the product obtained in Example 3 with N-methylpyrrolidone to a concentration of 201f6 was used. After applying 8 times to the diameter copper wire, 4
An insulated wire with a coating thickness of 45 μm was obtained by baking at 00° C.

The results of measuring the performance of this insulated wire are as follows.

Dielectric breakdown voltage 13kV Abrasion resistance (700g) 80 times heat resistance No cracking (heated at 230℃ for 1 hour after wrapping around a 2Q diameter rod) Chemical resistance Pencil hardness 4H (at room temperature in benzene and alcohol As detailed above, the method of the present invention can obtain an amide-imide compound containing a highly reactive hydroxyl group at the terminal by an extremely simple method, and this compound has heat resistance,
It is useful as a raw material for obtaining resins with excellent chemical resistance and mechanical properties, and its practical value is extremely great.

Claims (1)

[Claims] 1 The molar ratio of polyvalent amine to tricarboxylic acid anhydride or its derivative, or an acid component obtained by substituting a part of tricarboxylic acid anhydride with another carboxylic acid or its derivative, is 1.
A method for producing an amidimide compound containing a hydroxyl group at the terminal, which comprises adding 15 moles or more, reacting to produce a product having an aromatic amino group at the terminal, and further reacting by adding alkylene carbonate thereto. .