JPS6396170A - Terminal acetylene compound linked with ether bond having cyanostilbene skeleton - Google Patents

Abstract

NEW MATERIAL:A terminal acetylene compound linked with ether bonds having a cyanostilbene skeleton, expressed by formula I (R is -CH2-, formula II or III; n is 1 or 2). EXAMPLE:p,p'-Bis(propargyloxy)cyanostilbene. USE:Useful as a matrix resin for structural materials, carbon-fiber composite materials and resin for powder coating materials having improved heat resistance, capable of initiating curing reaction by heating at >=200 deg.C temperature to provide cured articles having excellent heat resistance and further giving diacetylene group-containing polyethers having improved heat resistance by oxidative coupling using a copper catalyst, etc. PREPARATION:For example, as shown in the reaction formulas, a compound expressed by formula IV and a compound expressed by formula V are subjected to condensation reaction and the resultant product is then boiled in a mixed solvent of acetic acid and hydrobromic acid to give a compound expressed by formula VI, which is heated with propargyl bromide in the presence of potassium carbonate in acetone to afford the aimed compound expressed by formula I (n is 1).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a terminal acetylene compound having a cyanostilbene skeleton linked by a nityl bond. The terminal acetylene compound of the present invention is useful as a structural material with excellent heat resistance, a matrix resin for carbon fiber composite materials, and a resin for powder coatings.

[Conventional technology]

As for the terminal acetylene compound connected by an ether linkage, see Journal of Polymer Science Part B Polymer Letters Vol. 8, p. 97, 1970 (
A.S., Hay, D.A., Bol'on, K.R.

Leimer+ R, F, C1ark, Journa
l of Polymer 5ctencePart
B Polymer Letters) and Izvestia Academy New York, Varnish, Varnish, Earl.

Celia Chemicheskei Volume 10 Page 1905
1964 (8, M, 51 adkov,, V, V
,Korshak+and A.G.,Makhsumo
v+ Izvestiia Akademii Nau
kSSSR5eria Khimicheskaia
) etc.

[Problem that the invention seeks to solve]

However, the aforementioned aliphatic terminal acetylene compounds connected by ether bonds have poor heat resistance and undergo a decomposition reaction before the curing reaction, making it impossible to obtain a useful cured product.

[Means for solving problems]

The present inventors synthesized and studied terminal acetylene compounds connected by ether bonds with excellent thermal stability, and found that the terminal acetylene compound represented by the following formula (1) satisfactorily achieves the above object, The present invention has now been completed.

C11°n is an integer from 1 to 2. ) A terminal acetylene compound having a cyanostilbene skeleton connected by an ether bond.

The compound represented by the above formula (1) has the following formulas (a) to (C
), compounds (d) to (f), and (phantom compound) can be synthesized by the following synthesis methods (11 to (6)).

In the general formula (g), R is the same as in the above formula (1), and X represents a halogen atom.

This compound (phantom) can be easily synthesized by substituting the hydroxyl group of propargyl alcohol, 2-methyl-3-butyn-2-ol, and 3-butyn-2-ol with halogen with thionyl halide or the like.

Method for synthesizing the compound represented by the general formula (I) ■A, Synthesis method for a compound where n is 1 (1) Synthesis method (2) 3. Synthesis method for a compound where n is 2 (3) [1] Synthesis method (4) Synthesis method (5) Synthesis method (6) The reactions used above are, for example, halogen substitution reaction of hydroxyl group: New Experimental Chemistry Course Vol. 14 (1), 361
Page, Etherification Reaction: Chemical and Pharmaceutical Bulletin Vol. 11 (8), p. 1042, 19
63 (1, Iwai, J. Ide.

Chemical and Pharmaceutical
al Bulletin), Bulletin Do La
Nsheti Hemic de France, Volume 9, 301
6 pages, 1966 (Bulletin de la 5
Chimique de France
) or New Experimental Chemistry Course, Volume 14 (1), p. 568, Condensation Reaction: Organic Synthesis (OrganicSy
ntheses,) + volume m, page 715 or Journal of American History Society (
J, Am, Chera, Soc, Volume 64, Page 885.

It is disclosed in 1942, Ether Cleavage Reaction: New Experimental Chemistry Course, No. 4S, p. 538, etc.

Specifically, for example, (1) p-anisaldehyde at a ratio of 1 mole to p-methoxyphenylacetonitrile, methanol and ethanol or tetrahydrofuran, 1.4
- A compound obtained by reacting dioxane and N,N-dimethylformamide with a mixed solvent of methanol or ethanol at room temperature in the presence of an alkali catalyst for 3 to 4 hours in a mixed solvent of acetic acid and hydrobromic acid. Boiling for a period of time yields a precursor represented by the following formula [■].

By heating this precursor and propargyl bromide in acetone in the presence of potassium carbonate (anhydrous), the formula (1)
) (n=1) can be obtained.

(2) A compound of the following formula can be obtained by heating p-hydroxybenzaldehyde and propargyl bromide in acetone in the presence of potassium carbonate (anhydrous).

Methanol, ethanol or tetrahydrofuran, ■,4-dioxane, N,N-
The general formula (Il (n-2
) can be obtained.

(3) Methanol and ethanol or tetrahydrofuran, 1,4-
A compound obtained by reacting dioxane and N,N-dimethylbormamide with a mixed solvent of methanol or ethanol at room temperature in the presence of an alkali catalyst for 3 to 4 hours was reacted for 10 hours in a mixed solvent of acetic acid and hydrobromic acid. The mixture is boiled for a period of time to obtain a precursor represented by the following formula (III).

(III) By heating this precursor and propargyl bromide in acetone in the presence of potassium carbonate (anhydrous), the formula (1)
) (n=2) can be obtained.

As the alkali catalyst for the condensation reaction in the above reaction, sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium butyralate, etc. are used.

The terminal acetylene compound of the present invention having a cyanostilbene skeleton and linked by an ether bond synthesized as described above undergoes a curing reaction when heated to a temperature of 200°C or higher, resulting in a cured product with excellent heat resistance. is obtained, and by oxidative coupling using a copper catalyst or the like, a diacetylene group-containing polyether with excellent heat resistance can be obtained.

Furthermore, the compound of the present invention may optionally contain a polymerization initiator,
Plasticizers, organic solvents, reactive diluents, extenders, fillers,
Various additives such as reinforcing agents, pigments, flame retardants, thickeners, and flexibility agents can be blended.

〔Example〕

A more specific explanation will be given below with reference to Examples, but these Examples are merely illustrative and the present invention is not limited by the Examples.

In the examples, the weight loss temperature was measured in helium at a heating rate of 10° C./min using a simultaneous thermogravimetric analysis/differential thermal analysis measuring device TG/DTA 20 (manufactured by Seiko Electronics Industries, Ltd.). Also, measurement of infrared absorption spectrum (IR)
is based on the potassium bromide (KBr) measurement method.

(Precursor production example) Example 1 5 equipped with a thermometer, cooler, dropping device and stirring device
10g of potassium hydroxide in a 00ml four-bottle flask
150m of ethanol! ! Then, 13.9 g of p-anisaldehyde was added and stirred. While stirring, 15.0 g of p-methoxyphenylacetonitrile was added dropwise into the flask from a dropping device over about 0.5 hours, and the mixture was allowed to react at room temperature for 3.0 hours.

After the reaction, the precipitated crystals were separated by cooling with ice, washed with ethanol, and dried to give 21.1 g of a pale green compound (yield: 7.
8%).

Next, 20g of the above pale green compound and 750mj of acetic acid! was placed in 11 four-bottle flasks equipped with the same equipment as above, and 150 mj2 of hydrobromic acid was added dropwise from the dropping equipment.
The mixture was reacted in a boiling state for 10 hours.

After the reaction was completed, the reaction solution was poured into 2.5ml of ion-exchanged water, and the precipitated crystals were separated in a furnace, washed with water, and dried to obtain 10.9g (yield: 61%) of a compound represented by the following formula. The melting point of this crystal was 243°C.

Example 2 1 equipped with thermometer, cooler, dripping device and stirring device
Pour a solution of 10 g of potassium hydroxide completely dissolved in 130 ml of ethanol into a four-bottle flask, and then add p-
10.8 g of methoxyphenylacetonitrile, 4.9 g of terephthalaldehyde.

A solution of 200 ml of 1.4 dioxane was added dropwise at room temperature over 1 hour with stirring. After the reaction was completed for 3 hours at the same temperature, the precipitated crystals were separated, washed with methanol, dried,
11.5 g of a yellow compound was obtained.

Next, 10.0 g of the above compound and 600 mj of acetic acid! was placed in 11 four-bottle flasks equipped with the same equipment as above, and 170 ml of hydrobromic acid was added dropwise from the dropping equipment, and then
The mixture was reacted in a boiling state for 10 hours. After the reaction is complete, separate the filtrate and add 3 I of ion-exchanged water! to separate the precipitates. The precipitate was then dissolved in 1.5 g of a 10% aqueous solution of NaOH and filtered.

After neutralizing the filtrate with hydrochloric acid and filtering the precipitate and washing with water,
After drying, 5.25 g of a compound represented by the following formula was obtained.

Example 3 24.6 g of p-hydroxybenzaldehyde was placed in a fourth If flask equipped with a thermometer, condenser and stirrer.
Propargyl bromide 24.0g, potassium carbonate (anhydrous) 66
．． Add 3g and 300ml of acetone and heat to 60°C while stirring.
After the reaction was completed for 10 hours, the potassium carbonate was separated from the furnace and the acetone was volatilized. The residue was redissolved in methyl isobutyl ketone, and this solution was washed twice with a 10% aqueous sodium carbonate solution and three times with water, then dehydrated with magnesium sulfate (anhydrous), and the methyl isobutyl ketone was evaporated to dryness to form a compound of the following formula. p-benzaldehyde propagyl ether 2
9.2 g was obtained.

Example 1 Precursor production 13.1 g of the compound obtained by the method of Example 1,
Propargyl bromide 13.2 g, potassium carbonate (anhydrous) 6
1.5g and 300mj of acetone! The mixture was placed in a No. 11 flask equipped with a condenser, a thermometer, and a stirrer, and reacted at 60° C. for 10 hours with stirring. After the reaction was completed, the potassium carbonate was separated off and the acetone in the reaction solution was evaporated, followed by recrystallization from methanol and drying to obtain 3.8 g of cream-colored crystals f (yield -79.7%). This compound was analyzed by JR (first
As a result, it was confirmed that it was p,p'-bis(propargyloxy)cyanostilbene represented by the following formula.

The melting point was 133.7°C.

Example 2 Precursor Production 5.0 g of the compound obtained by the method of Example 2, 3.6 g of propargyl bromide, 50 g of potassium carbonate (anhydrous), and 300 ml of acetone were subjected to the same reaction as in Example 1. After evaporating the acetone, it was washed with methanol and dried to obtain 4.8 g of yellow crystals (yield: 79.4%).

An IR analysis (Fig. 2) of this compound confirmed that it was bis(p-propargyloxy-α-cyanostilbene)-p-phenylene represented by the following formula.

Example 3 A solution of 5.0 g of potassium hydroxide completely dissolved in 150 ml of methanol was placed in a 500 ml four-loaf flask equipped with a stirrer, a condenser and a thermometer, and then the solution was prepared in Precursor Preparation Example 3. 4.1 g of the obtained compound was added and stirred to uniformly dissolve. Next, 1.9 g of 1,4-phenylene diacetonitrile was added and reacted at room temperature for 3 hours. The precipitated crystals were separated in a furnace, washed with heated methanol, and dried to yield 3.5 g of yellow crystals. rate = 70.2%). When this compound was subjected to IR analysis (Fig. 3), it was confirmed that it was bis(p-propargyloxy-β-cyanostilbene)-p-phenylene represented by the following formula.

stomach The melting point was 243.2°C.

Application Example 1 The compound of Example 1 was subjected to a curing reaction at 200° C. for 10 hours. The weight loss temperature of the obtained cured product was 350°C.

Application Example 2 The compound of Example 2 was subjected to a curing reaction at 250°C for 3 hours. The weight loss temperature of the obtained cured product was 396°C.

Application Example 3 The compound of Example 3 was subjected to a curing reaction at 250° C. for 3 hours. The weight loss temperature of the obtained cured product was 410°C.

Comparative Example 1 Bisphenol A 20.0g, Propargyl Bromide 21
．． 0g, potassium carbonate 60.0g and acetone 300g
ml and the same operation as in the production example of compound (If) was performed to obtain 24.7 g of the compound represented by the following formula (yield = 92.6%).
) was obtained.

The melting point was 83.6°C.

When this compound was subjected to a curing reaction at 200° C. for 10 hours, a thermal decomposition reaction occurred and carbonization occurred.

Comparative Example 2 Using 50.0 g of p, p-' dihydroxygenyl, 64.0 g of propargyl bromide, 100 g of potassium carbonate, and 500 ml of acetone, the same operation as in the production example of compound (II) was carried out to produce compound 66. represented by the following formula. 9g (yield = 94
．． 2%).

The melting point was 83.4°C.

When this compound was subjected to a curing reaction at 200° C. for 10 hours, a thermal decomposition reaction occurred and carbonization occurred.

[Brief explanation of the drawing]

1 to 3 are diagrams showing infrared absorption spectra of compounds obtained in Examples 1 to 3 of the present invention, respectively.

Claims (1)

[Claims] General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is -CH_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and n is an integer of 1 to 2.) A terminal acetylene compound connected by an ether bond having a cyanostilbene skeleton represented by