JPS5939893A - Novel imide compound - Google Patents

Abstract

NEW MATERIAL:An imide compound shown by the formula I (R is -CH2-, -CO-, or -O-; D is group shown by the formula II or formula III; n is 0, or 1). EXAMPLE:An imide compound shown by the formula II containing an oxazinone ring. USE:A raw material for a heat-resistant polymer, and a curing agent for epoxy resins. Providing improved heat resistance. PROCESS:For example, a compound shown by the formula III obtained by reacting aminobenzoic acid with maleic anhydride is treated with acetic anhydride to give a compound shown by the formula IV. This compound is then reacted with thionyl chloride to give a compound shown by the formula V, to which cyclopentadiene is added by a Diels-Alder reaction, the resultant compound is reacted with anthrailic acid to give a compound shown by the formula VI, which is subjected to ring closure through dehydration with acetic anhydride.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel imide compound FC, and more particularly to a novel imide compound containing an oyasazinone ring.

Traditionally, maleic anhydride and 5-norbornene-2 anhydride
, 3-dicarboxylic acid is used, for example, as a raw material for heat-resistant polyimide. For example, 5-/lupol semi-2,3-dicarboxylic anhydride is pyromellitic dianhydride,
Aromatic tetracarboxylic dianhydrides such as penzophene/tetracarboxylic dianhydride and methylene dianiline.

Co-compression with an aromatic diamine such as oxydianiline produces an oligomer containing a full poryl hemi-ring at the end, and heat-polymerization of this produces a heat-resistant polyimide.

However, this method requires 5-norbornene-2,
There is a drawback that the degree of polymerization of the oligomer is limited depending on the age of the 3-dicarboxylic acid.

The present inventors have conducted research aimed at finding a compound that can be self-polymerized by itself and can be bonded to the main chain or end of a polymer, and as a result, has arrived at the present invention.

That is, the present invention is based on the following formula (1) This is a novel tr-imide compound.

Specific examples of the compound represented by the above formula (1) include compounds represented by the royal structural formula.

These imide compounds can be synthesized, for example, through six reaction steps as shown below. An example of its synthesis can be expressed by the reaction formula shown below.

That is, amic acid obtained by reacting ami-7 benzoic acid and maleic anhydride is imidized using n-acid anhydride,
Next, it is reacted with thionyl chloride to form an acid p-ride, and cyclopentadiene is added to the 4 by Deelsfluder reaction, and then it is reacted with anthranilic acid, and the resulting 7-mide acid is dehydrated and ring-closed with acetic anhydride to obtain the desired product. get.

Here, if bisanthranilic acid is used instead of anthranilic acid, a novel imide compound in which n is 1 in the general formula (11) can be obtained.

In the present invention, the compound represented by formula (1) can also be synthesized by a method other than the above method.

Yotsu°C can also be synthesized.

Can you get it?

゛ New results obtained using the above Hr8 method! ! The imitation compound is preferably an organic solvent such as methyl alcohol.

A recrystallizer is prepared using ethyl alcohol, bupyl alcohol, butyl alcohol, dioxane fc, etc.

When the ivr imide compound of the present invention is used, for example, in the production of polyimide, polyquinazolone, or polyimidazoquinazolone, the obtained oligomer or polymer undergoes a crosslinking reaction by heating, which can improve the secondary transition point of the heat-resistant polymer. Even better heat-resistant polymers can be obtained.

In addition, when the new imide compound of the general formula (1) is reacted with, for example, an aromatic polyimide compound, it becomes an aromatic compound containing pear-shaped lumps. It provides an epoxy resin with good heat resistance.

Next, the present invention will be further explained with reference to Examples. In the examples, "parts" means "parts by weight."

Example 1 rn7S/137 parts of benzoic acid and 44 parts of soluble soda
1 part was dissolved in 1000 parts of water, and then acetic acid was added to neutralize the mixture. A solution consisting of 120 parts of maleic anhydride and 120 parts of dioxane was then added dropwise at room temperature, and the mixture was allowed to react with stirring for 2 hours. To this reaction mixture, 125 parts of acetic acid was added and stirred thoroughly, and then the formed crystals were separated, thoroughly washed with water and methanol, and then dried under reduced pressure at 40 to 50°C to obtain 120 parts of the desired product.

After heating and reacting 1000 parts of acetic acid at 80 to 90°C for 1 hour, most of the excess acetic anhydride and the acetic acid produced by the reaction were distilled off at a temperature below 80°C under regional pressure, and the resulting reaction mixture was poured into water. The mixture was added and stirred for 3 hours. Then the reaction mixture was diluted with 1
The mixture was separated and dried under reduced pressure at 40 to 50°C (-1.90 parts of the desired product was obtained. 3.900 parts were heated and refluxed for 2 hours with stirring.

During this period, S02 and HCI occurred frequently. After reaction 7
Excess thionyl chloride is distilled off under subilator vacuum,
Next, 150 parts of toluene was added and dissolved by heating, and to the resulting solution... added xane 300@II, cooled to room temperature, separated the precipitated crystals, dried, and 70 parts of the target product was removed. Obtained.

A portion of the mixture was exposed to a heating bath, then cooled to 20° C., and 29 parts of dicyclopentadiene obtained by thermally decomposing dicyclopentadiene in a conventional manner was added while stirring. At this time, the temperature of the reaction mixture rose to 40°C due to the heat of reaction. At the same time, crystals of objective 1J began to precipitate in the reaction mixture.

The reaction mixture was stirred as it was for 3 hours, then most of the toluene was distilled off under reduced pressure, and the crystals were separated from P to obtain 75 parts of the desired product (melting point: 172-176°C).

10 parts of 75 parts of isatoic anhydride and 220 parts of pyridine
I added this after a minute of mourning. The reaction mixture was then heated to reflux of the pyridine over a period of 1 hour, followed by further heating to reflux for 30 minutes. Thereafter, when the reaction mixture was cooled, crystals were precipitated. The crystals were washed separately with water, dried at 80°C under reduced pressure, and recrystallized by adding 1500 parts of butyl to give 58 parts of the desired product (melting point: 203-207°C). The infrared absorption spectrum of this new imide compound is shown in FIG.

Example 2 137 parts of m-74 benzoic acid was dissolved in a mixed bath agent of 150 parts of dimethylform 1 and 320 parts of xylene by heating at 100°C, and while stirring, anhydrous 5-norporin-2,
164 parts of 3-dicarboxylic acid was added and then heated to 140°C to distill off water produced as a result of the reaction from the reaction system.
Allowed time to react. Thereafter, the reaction mixture was cooled with water, and the precipitated crystals were separated, washed with xylene, and dried to obtain 264 parts of the desired ql/J (melting point: 218-221°C).

500 parts of 100% of the mixture was added and 0.1 part of Bili 2 was added, and the mixture was heated fR+X on a 100°C oil bath for 2 hours. This ml502 and H
Cl1! was generated rapidly, and the raw material carboxylic acid was completely dissolved. After the reaction was completed, thionyl chloride was distilled off under reduced pressure using an aspirator and dried. 200 parts of twittetoluene was added and the reaction product was dissolved by heating, and then 400 parts of hexane was added to precipitate crystals. The precipitated crystals were cooled, separated, dried, and 103 parts of the target product (melting point 172-174°C) was obtained.
) was obtained.

5. Dissolve 5'-methylene bisanthranilic acid 5093 in 2000 parts of an aqueous solution containing 51 parts of potassium carbonate,
A solution of 350 parts of muamide was added dropwise to the mixture under stirring at 5° C. or below.

After the completion of the reaction, the reaction was continued for 60 minutes with stirring, and then hydrochloric acid was added to cause acid precipitation. The precipitated product was separated into 1 portion, washed with water, and dried to obtain 107 parts of the desired product.

1,000 parts of acetic anhydride was added to 100 parts of the acid 7amide obtained in C) above, and the mixture was heated under reflux at 6:00 pm in a four-way air stream. Then, the obtained reaction mixture was subjected to a 7-svinter KMJ under reduced pressure.
li! The mixture was dried, dioxane was added thereto, the mixture was heated and dissolved, and the mixture was again cooled with water. The precipitated crystals were separated from each other and dried to obtain 70 parts of the desired product.

The melting point of the imide compound obtained here is 190~! 95
℃, and as a result of examining the infrared absorption spectrum of this compound, 1765(1)-1 has a characteristic absorption due to oxazinone, and 1710crn-' has a characteristic absorption not due to imide bond (each has a characteristic absorption). It was recognized.

Example 3 75 parts of 7-thranilic acid was dissolved in an aqueous solution consisting of 177 parts of potassium subacid and 4600 parts of water.Synthesized in the same manner as in Example 1 under stirring at 1%.
The mixture was added dropwise at a temperature of 5°C or lower. After the completion of the dropwise addition, the reaction was allowed to proceed for 60 minutes with stirring, and then hydrochloric acid was added for acid precipitation. After washing with water and drying, 380 parts of the desired product was obtained.

3500 parts of acetic anhydride was added to 350 parts of the amic acid obtained in &) above, and the mixture was reacted by heating at 95° C. for 5 hours in an air stream. Crystals precipitated during the reaction. After the reaction was completed, the reaction mixture was cooled to room temperature, and the crystals were separated and dried to obtain 152 parts of the desired product.

The melting point of the obtained new butimide compound a is 268-274°C
Met. In addition, as a result of studying the infrared absorption spectrum of the substance, it was found that 1 762 t,,n-1 has a characteristic absorption that is very characteristic of oxanone, and that 1 725 cm-1 of a maleimide bond has a characteristic absorption that is very characteristic. were recognized respectively.

[Brief explanation of drawings]

Figure 1 is an infrared absorption spectrum. Patent applicant: Director-General of the Agency of Industrial Science and Technology (Amendment) February 7, 1982 Director-General of the Japan Patent Office (1), Application for Approval of Case No. 57-149873 (2) Title of Invention: New Imide Compound (3), Person Making Amendment Case Relationship with Patent applicant: 1-3-1-5 Kasumigaseki, Chiyoda-ku, Tokyo Contents of the amendment (1) Meigetsu 1st Secretary, page 7, line 1, “Refines.” r
$, V I'J. In the present invention, compound U of n-1 (n-00 compound C hereinafter referred to as monooxyamazinone) and n-1 compound U
b (()), Comparing bisoxanone and Nei-Ji, it is found that: ■ Monooyaza 7non sword can be synthesized easily and in high yield; ■ It is easy to purify and it is easy to obtain a product with high 1!'II1 anti. , further corrected to ζ (■Using this compound and curing it, for example, by method 1), the 4+Y compound obtained has characteristics such as high bending strength, so it is preferable.'' (2) Opening/closing 77! Mu'!, 8th line "Can do" [
can. For example, the novel imide compound J of the book JPY 6 Ming is an aromatic polyamine such as metaphenylenediamine. toluylene diamine, 4, 1L'~diami, nonphenylmethane, 4,4'-2ami, nonphenyl ether, l,3-bis(p-7 minophenoxy) penvin, l,3-his(m-7 minophenoxy) ) benzene, 4, +1'-bis<p-7 minophenoxy) diphene; rusulfone, etc. and, if necessary, an aromatic 1-tracarboxylic anhydride such as pyrmellitic anhydride,
A heat-resistant oligomer is obtained by heating and curing the oligomer obtained by reacting with pe/zophenone detracarboxylic anhydride. ” and corrected [F. (3) In the third line from the bottom of page 247, "represents" means "represents." In the present invention, the purity of the target product was measured by dissolving Sanlu in dimethylformamide and using Kluver Meation Chromatography. (Used: Shimadzu LC-3A, Column: zorbnx (PGM-ne'
)8+P8M-10008), temperature: 30'C. Carrier: Dimenalform 7 Mido, Yokoideha K: 2
90n+u) Correct it as J. (4) "120 copies" on page 8, line 9 of Dictionary is corrected to "220 copies (yield: Article 94)." (5) Change “°9o part” in the 2nd row of irises from the bottom of page 4M8 to “9
0 copies (yield: 81 mo)." (M) Correct sr, "I-yo part (yield 72%)" in the same 19 negative line 9, "I-yo part (yield 72%)" (7) "Target product (
(Melting point: 172-176°C)” should be corrected to “Target product (yield: 84%, melting point: 172-176°C).” (8) [Target (melting point 2o
3" should be corrected as "Objective vtJ (yield: 60.7, purity: 98, melting point: 203.''). 93%, melting point.'' (transfer) On page 12, line 7, [゛(melting point 172-174
C) Correct J to "(yield 97cm, melting point 172-174°C)". al) In the 12th line of the same sentence, 18th line, "I got something." is corrected to "I got something (yield: 79 cm)." (b) Correct "dioxane" in lines 5 to 6 of Group K13'P to read "dioxane-ethyl alcohol." ) "I got a promise" on page 13, line 8 of the same book is changed to "I got a promise."
A yield of 73% and a purity of 73% were obtained. ” he corrected. oI 4m1ae4W<InH, correct it as "objective % v J wor I'+ target (yield 89 range)". 01 Same No. 5] In the first line of page 5, the FJ term of 152 parts is corrected to [182 parts of target product (with a purity of 95%). 00 Add the following after line t8 on page 15. "Example 4 46 sounds!i'4-dissolved in 2,000 parts of an aqueous solution containing 52 parts of potassium carbonate using a 7 anthranilic acid solution (100 parts separately synthesized in a 7 anthranilic acid solution) was added to 350 parts of dimethylformamide. The dissolved vinegar solution was added dropwise while stirring at 35°C.
Q tQ React while stirring, then add hydrochloric acid ° [+
′+! Separate the precipitated solids from door to door, submerge them in water, and dry them.
113 parts of the target product (yield: 85 buns) was obtained. Here j′→
Add 1130 parts of hot water to 113 parts of acid amide to 1M,
The mixture was then heated under reflux for 6 hours while being filtered. The resulting reaction mixture was then concentrated to dryness under reduced pressure in an amebylator, dioxane-ethyl alcohol was added and dissolved by heating, then cooled again with water, and the precipitated 1' crystals were separated and dried to give 75 parts. A compound represented by the following formula was obtained. Yield 7o%, purity 98
%Met. Reference Examples 1 and 2 The imide compounds prepared in Examples 1 and 2 were treated with N-
Add 40 parts of methylpyrrolidone and then add 4.5 parts to each solution.
3.96 parts of 4'-diaminodiphenylmethane, respectively
After reacting at 180'C for 3 hours, N-methylpyrrolidone in the resulting oligomer solution was evaporated in a dryer at 200'C open, and the remaining target product was transferred to a molding machine.
After ati rF and T-defoaming treatment at 50 to 290"C, apply at 320°C for 1 hour and pressure 50 at 57/1ffl;
E-mold the disk-shaped lft compound with a thickness of 3n to I+? Ta. C) Post-cure the cured product at 300'C for 6 hours.
, hardness and three-point bending tests (pressure between fulcrums @ 20 m) were conducted. 0 fruit 4 I will dedicate it to the following table.''That's it.

Claims (1)

[Claims] general formula An imide compound represented by