JPH0653819B2 - Film of calixarene and / or calixarene derivative and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a film of calixarene and / or a calixarene derivative.

(Prior Art) Calixarene is a cyclic oligomer formed by condensation of phenol-formaldehyde. The characteristics of calix arene are high melting point, poor solubility in solution,
And the formation of clathrate compounds, which are expected to be adsorbents for uranyl ions in seawater and heavy metal ions in wastewater due to their clathrate ability. It is a compound being studied. In particular, attempts have been made to synthesize derivatives for the purpose of improving the solubility in water.

(Problems to be solved by the invention) However, since the calixarene and / or the calixarene derivative is poorly soluble in an organic solvent, an example of kneading the calixarene in a polymer is found, but the calixarene and / or the calixarene Until now, the arene derivative itself has not been used as a film. Therefore, an object of the present invention is to provide firstly a film of calixarene and / or a calixarene derivative, and secondly to provide a production method thereof.

(Means for Solving the Problems) The present inventor has found that it is possible to form a calixarene and / or a calixarene derivative into a film as a result of an experimental study for achieving the above-mentioned object. Has been completed.

That is, the present invention is a film of calixarene and / or calixarene derivative having a thickness of 100 Å or more. Further, the production method of the present invention comprises the steps of forming a solution containing a calixarene and / or a calixarene derivative as a film on a substrate by a spin coating method, and baking at a temperature of 400 ° C. or lower to remove the residual solvent.

The calixlane and / or calixarene derivative used in the present invention is a cyclic oligomer produced by condensation of phenol and formaldehyde and a derivative thereof, and has a structure represented by the following general formula.

It is known that n is 4,5,6,7,8, and especially n = 4,6 and 8 can be synthesized in a good yield in one step. R is-
_{H, -H 3, -COCH 3,} - (CH 2) nCH 3, -CH 2 Ar, -
_{CH 2 CHCHC 2, -SiCH 3,} -CH 2 COOH , etc. R 'is _{-H, -t-C 4 H 9} , -Br, -SO 3 Na, -CH 2 N
_{H 2, -N = NAr, -CH} 2 Cl, -COAr, NO 2, -C 6 H
₅ COOH = CH _{2 and the} like Unlike cyclodextrins, calixarenes having a benzene ring can be synthesized into various derivatives by utilizing an aromatic substitution reaction.

It has been recently revealed that these calixarene and / or calixarene derivatives have an inclusion function similar to that of cyclodextrins and crown ethers.Synthesis of water-soluble calixarene was studied, and inclusion in an aqueous solution was reported. Has been done. However, to use it as a functional material, it is extremely useful to make it into a film. It was found that these calixarene and / or calixarene derivatives are hardly soluble in organic solvents, but a film having a thickness of 100Å or more can be produced even from a dilute solution. The solvent preferably has a high boiling point and is well compatible with the substrate to be coated.
For example, pyridine is preferable in terms of solubility, but it is not preferable as a solvent for coating glass, quartz, silicon substrates and the like. On the other hand, cyclohexanone and dioxane are examples of preferable solvents. An extremely thin film is not preferable in terms of defects, but 100 Å or more functions as a film. In the manufacturing method of the present invention, the substrate is spin-coated and then baked at a temperature of 400 ° C. or lower.
This is because it is stable up to about 0 ° C. The obtained film has high heat resistance and has extremely high hardness as compared with a general polymer film.

By obtaining such a film, it is possible to handle the calixarene and / or the calixarene derivative, which had been treated as a powder or a solution, in the form of a film, and this film exerts various functions characteristic of the calixarene. It is a base material for.

(Example) Synthesis example 1; 10 g of t-butyl-calix [4] arene p-tert-butylphenol was dissolved in 9.7 g of 37% aqueous formaldehyde solution, and a 3N aqueous sodium hydroxide solution was added.
10 ml was added. This should be done at 50-55 ° C for 45 hours, then 110-120
Heated at ° C for 2 hours. Then, 100 ml of 1N hydrochloric acid was added, and after stirring for 1 hour, the insoluble matter was filtered and dried at 110 ° C. in vacuum for 1 hour. It was dissolved in 70 g of diphenyl ether, heated at 220 ° C. for 2 hours, and extracted with ether acetate to obtain crude crystals.
Recrystallization from chloroform-methanol gave 3.2 g of t-butylcalix [8] arene. The melting point was 344-346 ° C. Confirmation was performed by IR, NMR, and mass spectrum. The same applies hereinafter.

Synthesis Example 2 t-Butyl-calix [8] arene 27.8 g of p-tert-butylphenol was dissolved in 150 ml of xylene, 9 g of paraformaldehyde was added, and 0.4 ml of a 10N aqueous potassium hydroxide solution was added. This was heated under reflux for 4 hours, the precipitate was filtered, and washed with toluene, ether, acetone, and water in this order to obtain a crude crystal. This was recrystallized from chloroform and t-butyl-calix [8] arene was added to 15.5.
g got. The melting point was 411 to 412 ° C.

Synthesis Example 3 t-octyl-calix [8] arene 37.14 g of p-tert-butylphenol was dissolved in 150 ml of xylene, 9 g of paraformaldehyde was dissolved therein, and 0.4 ml of a 10N aqueous potassium hydroxide solution was added. This was heated to reflux for 4 hours. Then, it was extracted with chloroform to obtain crude crystals. Recrystallization from chloroform-methanol gave 7.1 g of t-octyl-calix [8] arene. The melting point was 338-340 ° C.

Synthesis Example 4; calix [6] arene t-butyl-calix [6] arene 10 g and phenol 6.0 g
Was dissolved in toluene, 12.4 g of aluminum chloride was added,
It was stirred at room temperature for 1 hour. Further, 100 ml of cold water was added, and the organic layer was evaporated. It was washed with acetone, methanol, etc. to obtain 3.9 g of calix [6] arene. Melting point 380
It was ~ 381 ° C.

Synthesis Example 5: t-Butyl-calix [8] arene-acetate 2 g of t-butyl-calix [8] arene was dissolved in 100 ml of pyridine, 0.2 ml of acetic anhydride was added, and the mixture was stirred for 30 minutes. The reaction solution was poured into water and the insoluble matter was filtered to obtain crude crystals. This was recrystallized from chloroform to obtain 2.1 g of t-butyl-calix [8] arene acetate.

Example 1 Of the t-butyl-calix [8] arene shown in Synthesis Example 2,
A 0.25 wt% t-butyl-calix [8] arenecycloxanone solution was prepared, passed through a 0.2 μm filter, and then spin-coated to form a film on a silicon substrate. Spin coating was performed at a rotation speed of 300 rpm for 10 seconds, and subsequently, at 800 rpm for 60 seconds. This was baked at 150 ° C. for 30 minutes to obtain a film. The film thickness of the obtained film was 600Å. The Vickers hardness of the surface was 100 or more by a micro hardness meter.

Example 2 The products of Synthesis Examples 1, 3, 4, and 5 were spin-coated in the same manner as in Example 1 to obtain a film thereof.

Example 3 The products of Synthesis Examples 2 and 4 were mixed and spin-coated in the same manner as in Example to obtain a film thereof.

(Effect of the invention) As is clear from the above description, a film of calixarene and / or calixarene derivative is obtained, and high heat resistance by obtaining this film,
Not only can coating of high hardness be performed, but an effective means for using calixarene as a functional material has been obtained.

Claims (4)

[Claims] 1. A film of calixarene and / or calixarene derivative having a thickness of 100Å or more. 2. The film according to claim 1, wherein the film is formed on a substrate. 3. A calixarene and / or calixarene which comprises a step of forming a solution containing a calixarene and / or a calixarene derivative as a film on a substrate by a spin coating method and baking at a temperature of 400 ° C. or lower to remove a residual solvent. Alternatively, a method for producing a film of a calixarene derivative. 4. The method according to claim 3, wherein the solvent is cyclohexanone.