JPH0224261B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a terminal acetylene compound having a phenyl ketone skeleton connected by an ether bond. This terminal acetylene compound is useful as a structural material with excellent heat resistance, a matrix resin for carbon fiber composite materials, and a resin for powder coatings. [Prior art] Regarding the terminal acetylene compound linked by an ether bond, see Journal of Polymer Science Part B Polymer Letters, Vol. 8
97 pages, 1970 (ASHay, DABolon, KR
Leimer, RFClark, Journal of Polymer
Science Part B Polymer Letters) and Izvestia Academy New York S. S.
S. R. Celia Kemichi Esq. 10th
Volume 1905 Page 1964 (AMSladkov, VV
Korshak, and AGMakhsumov.Izvestiia
Akademii Nauk SSSR Seria
(Khimicheskaia) et al. [Problems to be Solved by the Invention] However, the aliphatic terminal acetylene compound linked by an ether bond has poor heat resistance and undergoes a decomposition reaction before the curing reaction, making it impossible to obtain a useful cured product. [Means for Solving the Problems] The present inventor synthesized and studied a terminal acetylene compound connected by an ether bond with excellent thermal stability, and found that the terminal acetylene compound represented by the following formula The present inventors have discovered that the above can be fully achieved, and have completed the present invention. (In the formula, R is -CH ₂ -,

【formula】

〔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 using a simultaneous thermogravimetric analysis/differential thermal analysis measuring device TG/DTA20 (manufactured by Seiko Electronics Co., Ltd.) in helium at a heating rate of 10° C./min. In addition, nuclear magnetic resonance spectra (NMR) measurements are performed using a high-resolution NMR-PMX60SI (manufactured by JEOL Ltd.)
The measurement was carried out using dimethyl sulfoxide- _d6 solvent and tetramethylsilane as an internal standard substance. (Production Example of Compound (a)) Example 1 200 ml of anisole and 51.0 g of aluminum chloride (anhydrous) were placed in a four-necked flask equipped with a condenser, a thermometer, a stirring device, and a dropping device, and stirred while cooling. Next, a solution of 35.2 g of isophthaloyl chloride dissolved in 200 ml of anisole was added dropwise from a dropping device over a period of 1 hour. After the dropwise addition, the mixture was allowed to react at room temperature for 5 hours with stirring. After the reaction is complete, reduce the reaction solution to 1.5
of water and stirred. The deposited precipitate was separated, washed with water, methanol, and dried. The yield is
The amount was 43.5g (yield = 72.6%). this compound
10.0g, acetic acid 300ml and hydrobromic acid 50ml in a cooling tube,
The mixture was placed in a four-necked flask equipped with a thermometer and a stirrer and boiled for 10 hours. After the reaction was completed, the reaction solution was poured into water from Step 2, and the precipitated crystals were separated, washed with water, and dried to obtain 6.8 g of the compound of the following formula (yield: 73.9%). Example 2 The same operation as in Example 1 was performed except that terephthalic acid chloride was used in place of isophthalic acid chloride, and 7.1 g of the compound of the following formula (yield = 77.2%) was obtained. Example 1 26.2 g of the compound obtained by the method of Production Example 1, 22.0 g of propargyl bromide, 70.0 g of potassium carbonate (anhydrous), and 300 ml of acetone were placed in a four-necked flask equipped with a cooling tube, a stirring device, and a thermometer. Boiled for 10 hours while stirring. After the reaction, the potassium carbonate was removed and the acetone in the reaction solution was evaporated. The residue was washed with methanol and dried to give 21.1 g of cream-colored crystals (yield = 64.9
%) was obtained. The NMR spectrum (Figure 1) of this compound shows that it has the following formula:
It was confirmed to be 3'-bis(4-propargyloxyphenylcarbonyl)benzene. The melting point was 126.7°C. Example 2 The same procedure as in Example 1 was carried out, except that 12.0 g of the compound obtained by the method of Production Example 2, 10.0 g of propargyl bromide, 50.0 g of potassium carbonate (anhydrous) and 200 ml of acetone were used, and 11.5 g of cream-colored crystals were obtained. g (yield =
77.4%). The NMR spectrum (Figure 2) of this compound confirmed that it was 4,4'-bis(4-propargyloxyphenylcarbonyl)benzene represented by the following formula. The melting point was 168.0. 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 is 400
It was warm at ℃. Application Example 2 The compound of Example 2 was subjected to a curing reaction at 200°C for 10 hours. The weight loss temperature of the obtained cured product is 390
It was warm at ℃. Comparative example 1 Bisphenol A 20.0g, propargyl bromide 21.0g,
The same operation as in Example 1 was performed using 60.0 g of potassium carbonate and 300 ml of acetone to obtain a compound represented by the following formula.
24.7g (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 The same operation as in Example 1 was performed using 50.0 g of p,p'-dihydroxydiphenyl, 64.0 g of propargyl bromide, 100 g of potassium carbonate, and 500 ml of acetone to obtain 66.9 g of the compound represented by the following formula (yield = 94.2%). ) was obtained. 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 drawings]

FIG. 1 and FIG. 2 are diagrams showing NMR spectra of the compounds obtained in Example 1 and Example 2 of the present invention, respectively.

Claims (1)

[Claims] 1. General formula (In the formula, R is -CH ₂ -, [Formula] [Formula].) A terminal acetylene compound having a phenyl ketone skeleton connected by an ether bond.