JPH0567631B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Industrial Application] The present invention relates to a triazine ring polymer having a novel chemical composition and a method for producing the same, and more specifically to optical materials, particularly fluorescent materials, functional materials using semiconductivity, lubricating materials, and heat-resistant materials. The present invention relates to a triazine ring multimer useful as a synthetic polymer and a method for producing the same. [Prior art and problems to be solved] Conventionally, as a polymer having a triazine ring,
Polymers of vinyl-s-triazines [(polymer 38 ,
196 (1989)] and melamine resin, but the former is a one-dimensional (linear) polymer, and the latter is amorphous because it bonds in a three-dimensional disorder. The s-triazine ring is a 6π electron system, and the 6 atoms (3 carbon, 3 nitrogen) form the same plane, so if the π electron system can be expanded two-dimensionally, it will be a very useful material optically and electrically. However, until now, no triazine ring layered polymer that forms a two-dimensional plane has been synthesized. [Means for Solving the Problems] Under the current circumstances, the present inventors have repeatedly studied the synthesis of carbon and nitrogen compounds under various conditions, and have found that carbon and nitrogen compounds such as cyanuric chloride and melamine have been synthesized. It was discovered that a new layered compound consisting of carbon, nitrogen and hydrogen could be synthesized by using a compound containing a triazine ring as a reaction raw material, and this was proposed in Japanese Patent Application No. 173186/1986. This has the general formula C ₃ NxHy (4≦X≦5,
It is a carbon nitride having a layered structure represented by 0≦Y≦4), which is produced by reacting cyanuric chloride and ammonia or cyanuric chloride and melamine at 200 to 400°C,
It is obtained by subsequently performing heat treatment at 400 to 600°C. The present inventors have discovered that the compound obtained as an intermediate in such a reaction exhibits extremely excellent physical properties as a fluorescent material, and has arrived at the present invention. That is, the present invention is based on the general formula (C ₃ N ₃ ) _a (NH) _b (NH ₂ ) _c X _d [where X is Cl, F, CN, NO ₂ , OH, OM
(M represents at least one kind of alkali metal), 2≦a≦10, 1≦b≦10, 0≦c≦
11, 1≦d≦12. ] It is a triazine ring multimer represented by. Those in which X is Cl can be obtained by reacting cyanuric chloride and ammonia or cyanuric chloride and melamine in the range of room temperature to 400°C,
Then, by treatment with water, acid, alkali, hydrocyanic acid, cyanide compound, hydrogen fluoride, metal fluoride, etc.
Compounds in which Cl is completely or partially substituted are obtained. The present invention also provides a phosphor comprising this compound. As mentioned above, the compound of the present invention can be obtained by reacting cyanuric chloride with ammonia or cyanuric chloride with melamine, or by treating this reaction with water, acid, alkali, etc. Let's talk about the conditions. The reaction between cyanuric chloride and ammonia occurs at room temperature ~
It is carried out at a temperature of 400℃. At around room temperature, the main reaction is that one or two of the three chlorines in the molecule of cyanuric chloride are replaced with amino groups, and although some amino groups and chlorine react and condensation occurs due to dehydrochlorination, The extent is slight;
More preferably, the reaction is carried out at a temperature of 100°C or higher.
At around 200°C, amino groups and chlorine react, and condensation due to dehydrochloric acid progresses, and at around 4000°C, condensation due to dehydrochloric acid further progresses. When carrying out the above reaction, the amount of ammonia to cyanuric chloride is preferably 2 mol or more per 1 mol of cyanuric chloride, and 4 mol or more considering the reaction rate.
The ammonia used in the reaction can be of any concentration; 100% concentration can be used, but in order to control the reaction rate, it should be diluted with an inert gas such as nitrogen or argon to a range of up to 30%. You can also do it. Next, the reaction between cyanuric chloride and melamine will be described. Melamine is known to sublimate and decompose at temperatures above 350°C, and since it remains solid up to this temperature, it is necessary to choose a temperature above 154°C, where cyanuric chloride exists as a liquid, in order to substantially proceed with the reaction. be. Therefore, a suitable reaction temperature is 154°C or higher and 350°C or lower. The reaction in this temperature range proceeds in the same way as in the case of cyanuric chloride and ammonia. When carrying out the above reaction, the amount of melamine relative to cyanuric chloride must be such that the ratio of melamine to 1 mol of cyanuric chloride is 1 mol or more. The compound obtained by the above reaction is a polymer having a triazine ring as its basic skeleton, and the degree of polymerization varies depending on the reaction temperature. That is, it is estimated that at a reaction temperature of about 200°C, a mixture of dimers to hexamers is formed, and on average, a tetramer is formed. The structure of a typical tetramer is considered as follows.

[C] In addition to this, it is thought that linear multimer structures and various multimers are included, but all of them have an unsubstituted chlorine atom in the molecule. . Furthermore, it is thought that at a reaction temperature of about 400°C, molecules of approximately octamer size are arranged more orderly than the reaction product at a reaction temperature of 200°C.
This can be inferred from the fact that in the X-ray diffraction diagram shown in Figure 1, the diffraction lines are sharper at a reaction temperature of 400°C than at a reaction temperature of 200°C. Although the reaction mechanism of the present invention is not necessarily clear, at around room temperature one or two of the three chlorines in the molecule of cyanuric chloride are replaced with amino groups, and at around 200°C, amino groups are substituted.
It is thought that Cl reacts and condensation occurs due to dehydrochloric acid to form a tetramer, and at around 400°C, condensation due to dehydrochloric acid further proceeds to form an octamer. The above structure can be determined by the elemental analysis described below,
This estimate was made by integrating the results of X-ray diffraction, IR spectrum, and ESCA spectrum, and we will discuss them one by one. The reaction between cyanuric chloride and ammonia produces ammonium chloride, which is removed by water treatment to separate it from the target product. Through this treatment, unsubstituted chlorine atoms present in the molecule are partially replaced with hydroxyl groups. Further, the raw material cyanuric chloride is removed by acetone treatment. The reaction products thus treated with water and acetone were analyzed.
Table 1 shows the elemental analysis values of compounds obtained by conducting reactions at reaction temperatures of 200°C and 400°C, and when compared with the calculated values for multimers in Table 2, the 200°C reaction produced tetramers; The 400°C reaction product is similar to the calculated value for the octamer. Next, the analysis results by X-ray diffraction method will be described. The X-ray diffraction diagram is shown in Figure 1, and the measurement conditions are: Cu-Kα rays, 30 KV, 20 mA, scanning speed: 1°/min, time constant: 1 sec, full scale:
10Kcps, and the measurement conditions in the enlarged diagram are:
Cu-Kα radiation, 40KV, 30mA, scanning speed: 1°/
min, time constant: 1sec, full scale: 10Kcps. First, for the 200℃ reaction product, 2θ is 26.5 ~
A maximum diffraction line with a peak at 28.0° can be seen. This corresponds to the Fjanderwaals distance d=
3.3Å, which is graphite (3.35
Å), close to the interlayer distance of h-BN (3.33 Å). This is because the 200℃ reaction product consists of several types of multimers.
This is thought to be because the interplanar spacing appears in the direction perpendicular to the layer plane, and the plane direction is disordered. On the other hand, the 400℃ reaction product shows a very complex and sharp diffraction pattern, but this is because the molecular weight of the polymer is relatively uniform and ordered, and the diffraction lines in the three-dimensional direction are It is thought that it is to appear. FIG. 2 shows the IR spectrum of the compound of the present invention. The large band between 1650 and 1250 cm ^-1 is due to the C-N and C=N stretching vibrations of the triazine ring, and also due to the 800 cm -1
~810 cm ^-1 is considered to be due to bending vibration, and this confirms that the triazine ring (a six-membered C ₃ N ₃ ring) remains in the product without being decomposed. In addition, the 200℃ reaction product consists of -NH ₂ absorption at 3333 cm ^-1 and NH 2 absorption at 3143 cm ^-1 , and it is thought that a considerable amount of NH ₂ groups remain at the end, and the 400℃ reaction product It can be seen that the -NH ₂ absorption band decreased in the sample, indicating that polymerization progressed more than at 200°C, and the ratio of NH ₂ groups at the terminals decreased. FIG. 3 shows an ESCA spectrum measured using Mg-Kα radiation. In the starting material cyanuric chloride, both carbon and nitrogen atoms are positively polarized due to the electron-withdrawing Cl group, and C _1S and
The N _1S spectrum has a peak on the high energy side. The N _1S spectrum of the product after the reaction at 200°C and 400°C shifted to 398.5 eV, a spectrum similar to that of melamine. In this case, the half width of the peak is large, and it is thought that the peaks of nitrogen in the triazine ring (low energy side: 398.5 eV) and nitrogen in the NH ₂ group (high energy side: 399.4 eV) overlap. As the reaction temperature increases, the peak on the high energy side decreases. This is the above
It agrees well with the IR spectrum results. The compound obtained by the reaction of cyanuric chloride and ammonia or the reaction of cyanuric chloride and melamine can be treated with water, acid, alkali, hydrocyanic acid, cyanide compound, hydrogen fluoride, metal fluoride, etc. Although the substituted chlorine can be replaced, no major changes in various physical properties such as fluorescence properties are observed compared to those before the replacement. The thermal stability of the compounds of the invention naturally depends on the reaction temperature. That is, the compounds of the present invention are obtained at each reaction temperature, and the reaction proceeds further in a temperature range higher than the reaction temperature. Therefore, from the viewpoint of thermal stability, those obtained by reaction at higher temperatures are superior. A major feature of this compound is that it exhibits fluorescent properties. Figure 4 shows the spectrum when irradiated with light of a wavelength corresponding to the excitation light of a high-pressure mercury lamp.
The excitation light is 365nm ultraviolet light, and the slit width is 1.5nm.
It was measured in The solid line is the compound of the present invention and is the product at a reaction temperature of 200°C. The broken line indicates the compound obtained by further heat-treating the compound of the present invention (reaction temperature: 400°C) at 500°C (Japanese Patent Application No. 173186/1986). Although this heat-treated product has an intensity comparable to that of the well-known calcium halophosphate, the compound of the present invention emits extremely high intensity fluorescence at 407 nm. FIG. 5 shows the relationship between production reaction temperature and relative luminescence intensity. All products produced at reaction temperatures up to 400°C have higher luminescence intensity than those treated at 500°C, and in particular, the reaction products at 200°C have extremely high luminescence intensity (approximately 7.5 times that of those treated at 500°C). It is. Although the reason for the high emission intensity of the 200°C reaction product is not clear, it is thought to be related to the resonance isoelectronic structure of the π electrons of the compound. FIG. 6 shows the relationship between the reaction temperature and the emission peak position of the reaction product when excited with excitation light of 365 nm, with the multimer being on the lower wavelength side. Hereinafter, the present invention will be specifically explained with reference to Examples. Example 1 56 g of cyanuric chloride as a raw material was placed in the center of a device consisting of a quartz glass tube with an inner diameter of 40 mm and a length of 1000 mm, and 50 g of ammonia and nitrogen as a carrier gas were each placed in the center.
cc/min, 100 c.c./min, and after thorough mixing, the mixture was introduced into the tube. The pressure inside the tube was atmospheric pressure. Under the above conditions, the reaction was carried out at room temperature, 200°C, and 400°C until ammonia absorption disappeared, and then the product was taken out and a portion was treated with water and acetone to separate the product. This product was analyzed by the following means. Elemental analysis: Quantitative analysis using normal combustion method Indicated. The reaction at room temperature yielded 8.4 g of 2-chloro-4,
The total amount of 6-diamino-s-triazine and the acetone-soluble compound is mostly 2-amino-4,6-dichloro-s-triazine, with a slight condensation of 27.5
I got g. The reaction at 200°C yielded 24.8 g of a water-insoluble and acetone-insoluble product. This product was a white powder and was stable in air. The reaction at 400°C yielded 42.0 g of a water-insoluble and acetone-insoluble product. This product was a white powder with a slight yellowish tinge and was stable in air. Table 2 shows the theoretical atomic weight % of various triazine ring polymers. Based on the atomic weight % of the products obtained at each reaction temperature, it is estimated that the reaction product at 200℃ is mainly composed of tetramers. did. It was also estimated that the 400°C reaction product was mainly a cyclic octamer.

【table】

[Table] Example 2 Using the same equipment as in Example 1, 1 g of cyanuric chloride
Mix 0.7 g of melamine and place it in the center of the reaction tube.
The reaction was carried out at 200°C for 1 hour under nitrogen flow. As a result, 0.5 g of a white product was obtained. This product was confirmed to be a mixture of some unreacted melamine and a compound almost the same as the 200°C product obtained in Example 1 from the X-ray diffraction pattern and the like. Example 3 Using the reaction product produced in Example 1, a diameter of 10
The sample was filled in a 1.0 mm holder and irradiated with 365 nm light, which is the excitation light of a high-pressure mercury lamp, using a xenon lamp through a quartz glass window with a slit width of 1.5 nm, and its fluorescence spectrum was measured. As a result, the reaction temperature of 200°C emitted extremely high intensity fluorescence at 407 nm. Furthermore, when the reaction temperature was 400°C, strong fluorescence was emitted at a wavelength of 422 nm. Fig. 4 shows the fluorescence spectra of the product obtained at a reaction temperature of 200°C and for reference, the product obtained at a reaction temperature of 400°C and treated at 500°C. [Effects of the Invention] The compound of the present invention is a novel triazine ring polymer, and has excellent properties such as fluorescent properties, lubricating properties, and heat resistance properties.

[Brief explanation of drawings]

FIG. 1 is an X-ray diffraction diagram of the compound of the present invention, and FIG. 2 is a diagram showing the IR spectrum of the compound of the present invention. FIG. 3 is an ESCA spectrum of the compound of the present invention, and FIG. 4 is a spectrum showing fluorescent properties. FIG. 5 shows the relationship between reaction temperature and luminescence intensity, and FIG. 6 shows the relationship between reaction temperature and luminescence peak position.

Claims (1)

[Claims] 1 General formula (C ₃ N ₃ ) _a (NH) _b (NH ₂ ) _c X _d [where X is Cl, F, CN, NO ₂ , OH, OM
(M represents at least one kind of alkali metal), 2≦a≦10, 1≦b≦10, 0≦c≦
11, 1≦d≦12. ] A triazine ring multimer. 2. The method for producing a triazine ring polymer according to claim 1, characterized in that cyanuric chloride and ammonia or cyanuric chloride and melamine are reacted at a temperature ranging from room temperature to 400°C. 3 React cyanuric chloride and ammonia or cyanuric chloride and melamine in the range of room temperature to 400°C,
Next, water, acid, alkali, cyanide, cyanide compound,
2. The method for producing a triazine ring polymer according to claim 1, which comprises treating with hydrogen fluoride or a metal fluoride. 4. A phosphor comprising the triazine ring multimer according to claim 1.