KR102416701B1 - Composition for detection of radiation, visualization material for detection of radiation using the same, and method for detection of radiation using the same - Google Patents

Abstract

The present invention provides a composition for sensing radiation comprising a thiophene-based compound in which a dicyanomethylene group is introduced as a terminal functional group; A visualization material for radiation detection using the same and a radiation detection method using the same.

Description

A composition for detecting radiation, a visualization material for detecting radiation using the same, and a method for detecting radiation using the same

The present invention relates to a radiation detection composition, a visualization material for radiation detection using the same, and a radiation detection method using the same.

Due to the leakage of radioactive materials from nuclear-related facilities, natural ecosystems including humans have become insecure from radioactive contamination and radiation damage, and a huge loss of resources for recovery is inevitable as in the case of the Fukushima nuclear power plant accident in Japan. Exposure to radiation especially increases the risk of heart disease or cancer, and even if it is a low-dose leaked radiation, if it cannot be detected in advance, you may face continuous exposure and eventually exposure to radiation exceeding the permissible value. There is a problem in making this happen.

Due to the colorless, tasteless, and odorless nature of radiation, it is impossible to intuitively detect leaked radiation. In the past, a person directly detected the leaked radiation using a radiation detector, and there has been a risk due to radiation exposure.

Therefore, the film-type radiation dosimeter that was developed to solve this risk and is currently on the market judges whether the radiation product (sterilization, etc.) There is a problem that it is impossible to do.

US 4918317 A (1990.04.17)

An object of the present invention is to provide a composition for detecting radiation including a thiophene-based compound in which a dicyanomethylene group is introduced as a terminal functional group as an organic dye for detecting leaked radiation (especially, radiation leaked at a low dose).

However, the technical problem to be achieved by the present invention is not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

The present invention provides a composition for sensing radiation comprising a thiophene-based compound in which a dicyanomethylene group is introduced as a terminal functional group.

According to one embodiment of the present invention, there is provided a material for sensing radiation using the composition for sensing radiation.

According to another embodiment of the present invention, there is provided a radiation detection method using the composition for radiation detection.

The composition for detecting radiation according to the present invention is characterized in that it includes a thiophene-based compound in which a dicyanomethylene group is introduced as a terminal functional group, and the dicyanomethylene group introduced to have a resonance structure in the thiophene-based compound is exposed to radiation. Accordingly, the bandgap energy is greatly increased while reducing both the maximum absorbance wavelength and the onset absorbance wavelength, so even if the radiation leaks at a low dose, there is an advantage that the color change can be easily detected with the naked eye.

According to the present invention, by reducing radiation risk, it is expected that public safety and quality of life can be improved, and a new market related to visualization materials for radiation detection can be created.

1 is a schematic diagram showing a change in bandgap energy according to radiation exposure of a composition for sensing radiation according to an embodiment of the present invention.
2(a) to (d) are graphs showing changes in optical properties according to radiation exposure of radiation sensing compositions according to Examples 1 and 2 and Comparative Examples 1 and 2;
3 is a graph showing the change in visualization according to the radiation exposure of the radiation sensing composition according to Example 1.
4 (a) and (b) are graphs showing changes in optical properties according to exposure to sunlight for one week of the radiation sensing compositions according to Examples 1 and 2;

The conventionally developed film-type radiation dosimeter only detects a high dose and it is impossible to detect the leaked radiation at a low dose. A composition for sensing radiation was prepared by introducing a group as a terminal functional group, and it was confirmed that it could specifically react to radiation leaked at a low dose while having a stable structure, and completed the present invention.

As used herein, "radiation" is a concept that includes all alpha rays, electrons, gamma rays, X-rays, and neutrons emitted when one atomic nucleus changes into another atomic nucleus. Dangerous.

The energy of the radiation may be expressed in gray (Gy), and 1 Gy means when 1 J of radiation energy per 1 kg of living body is absorbed. In this case, Gy can be viewed as a physical unit in which only the magnitudes of mass and energy are displayed without considering the type of radiation.

"Energy of radiation" in the present specification may be a low dose, preferably 0.1 Gy to 100 Gy, more preferably 0.1 Gy to 10 Gy (* Assume that gamma rays or X-rays are exposed to the whole body of the human body during radiation In terms of conversion, it may be 1 Sv to 10 Sv). The composition for sensing radiation according to the present invention may specifically respond to such low-dose radiation.

Hereinafter, the present invention will be described in detail.

The present invention provides a composition for sensing radiation comprising a thiophene-based compound in which a dicyanomethylene group is introduced as a terminal functional group.

를 포함할 수 있다. 이러한 경우, 보다 안정적인 공명 구조를 가질 수 있는 이점이 있다. The thiophene-based compound may include one or more thiophenes as a main backbone, preferably four or more thiophenes, and more preferably,

may include In this case, there is an advantage that can have a more stable resonance structure.

를 포함할 수 있다. 이러한 말단 작용기는 저선량으로 누출된 방사선에도 특이적으로 반응할 수 이점이 있고, 이들은 단순 시아노기에 비해 연장된 공명 구조로 인해, 저선량으로 누출된 방사선에도 월등히 특이적으로 반응할 수 있는 이점이 있다. In addition, the thiophene-based compound includes at least one dicyanomethylene group as a terminal functional group, preferably, may include at least two dicyanomethylene groups, more preferably, at least two dicyanomethylene groups.

may include These terminal functional groups have the advantage of being able to react specifically to radiation leaked at low doses, and they have the advantage of being able to react significantly specifically to radiation leaked at low doses due to their extended resonance structure compared to simple cyano groups. .

Specifically, the thiophene-based compound may be represented by the following Chemical Formula 1:

[Formula 1]

,

,

In Formula 1, R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and each independently hydrogen; C1~ C20 alkyl group; C1~ C20 Alkyl group substituted or unsubstituted C6~ C20 aryl group; Or a C3~ C20 heteroaryl group unsubstituted or substituted with a C1~ C20 alkyl group.

More specifically, the thiophene-based compound may be prepared by first reacting a compound represented by the following Chemical Formula 2 with dimethylformaldehyde; And it may be prepared including the step of reacting the primary reaction product with a compound represented by the following formula (3):

[Formula 2]

,

,

[Formula 3]

,

,

In Formula 2, R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and each independently hydrogen; C1~ C20 alkyl group; C1~ C20 Alkyl group substituted or unsubstituted C6~ C20 aryl group; Or a C3~ C20 heteroaryl group unsubstituted or substituted with a C1~ C20 alkyl group.

At this time, the first reaction is by reacting the compound represented by Formula 2 with n-butyllithium at a temperature of -80°C to -50°C, and then reacting it with dimethylformaldehyde at a temperature of -80°C to 30°C. can be performed. Thereafter, the secondary reaction may be performed by reacting the primary reaction product with chloroform and the compound represented by Formula 3 in the presence of pyridine at a temperature of 50°C to 80°C.

In the thiophene-based compound, both a maximum absorbance wavelength and an onset absorbance wavelength may decrease after exposure to radiation. Specifically, the thiophene-based compound may have an initial absorbance wavelength of 650 nm to 750 nm before exposure to radiation, and an initial absorbance wavelength of 500 nm to 600 nm after exposure to radiation.

In addition, the band gap energy of the thiophene-based compound may increase after exposure to radiation. Specifically, the thiophene-based compound may have a bandgap energy of 1.50 eV to 1.80 eV before exposure to radiation, and a bandgap energy of 2.00 eV to 2.30 eV after exposure to radiation. Accordingly, there is an advantage in that the color change can be easily detected with the naked eye even with radiation leaked at a low dose.

In addition, the present invention provides a visualization material for sensing radiation using the composition.

The visualization material for sensing radiation according to the present invention uses a composition for sensing radiation including a thiophene-based compound in which a dicyanomethylene group is introduced as a terminal functional group. do it with

The visualization material for sensing radiation is for detecting whether or not radiation is exposed through a color change of the material, and may be variously used as a special card, a special sticker, a special paint, a sensor material, and the like.

In addition, the present invention provides a radiation sensing method using the composition.

The radiation detection method according to the present invention uses a radiation detection composition including a thiophene-based compound in which a dicyanomethylene group is introduced as a terminal functional group. do it with

As described above, the composition for sensing radiation according to the present invention is characterized in that it includes a thiophene-based compound in which a dicyanomethylene group is introduced as a terminal functional group. The anomethylene group greatly increases the bandgap energy while reducing both the maximum absorbance wavelength and the onset absorbance wavelength according to radiation exposure, and there is an advantage that the color change can be easily detected with the naked eye even with low dose leaked radiation.

According to the present invention, by reducing radiation risk, it is expected that public safety and quality of life can be improved, and a new market related to visualization materials for radiation detection can be created.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and the contents of the present invention are not limited by the following examples.

[Example]

Example 1

Compound (1) was prepared according to the following formula:

.

.

In this case, compound (1) is 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2 ,3-d;2',3'-d']-s-indaceno[1-2b;5,6-b']dithiophene, the structure of which is as follows:

.

.

The results of confirming the change in optical properties of compound (1) at room temperature according to exposure to 1 Gy gamma rays are shown in Table 1 and FIG. 2(a).

λ _{abs max} /nm λ _{abs onset} /nm Optical band gap/eV Before gamma irradiation (0 Gy) 451 712 1.74 After gamma irradiation (1 Gy) 420 574 2.16

As shown in Table 1 and Figure 2 (a), in the case of compound (1), it is confirmed that both the maximum absorbance wavelength (λ _{abs max} ) and the starting absorbance wavelength (λ _{abs onset} ) after 1 Gy gamma irradiation are reduced, It is confirmed that the bandgap energy significantly increases to about 0.42 eV after irradiation with 1 Gy gamma rays.

In addition, the result of confirming the visualization change according to 1 Gy gamma-ray exposure of compound (1) at room temperature is shown in FIG. 3 .

As shown in FIG. 3 , as a result of visually observing compound (1), it was black before gamma-ray exposure, but yellow after 1 Gy gamma-ray exposure, confirming that it has a distinct color change.

On the other hand, the result of confirming the optical characteristic change according to the exposure to sunlight for one week at room temperature of compound (1) is shown in Figure 4 (a).

As shown in Figure 4(a), in the case of compound (1), it is confirmed that there is no change in the maximum absorbance wavelength (λ _{abs max} ) and the onset absorbance wavelength (λ _{abs onset} ) even after exposure to sunlight for one week, It can be seen that there is no reaction to light rays such as infrared rays, visible rays and ultraviolet rays that make up sunlight.

Example 2

대신

를 출발 물질로 하되, 실시예 1과 동일한 방법으로 화합물 (2)를 제조하였다.

instead

was used as a starting material, but compound (2) was prepared in the same manner as in Example 1.

In this case, compound (2) is 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(hexyl)-dithieno[2,3 -d;2',3'-d']-s-indaceno[1-2b;5,6-b']dithiophene, the structure of which is as follows:

.

.

The results of confirming the optical properties change according to exposure to 1 Gy gamma rays of compound (2) are shown in Table 2 and FIG. 2(b).

λ _{abs max} /nm λ _{abs onset} /nm Optical band gap/eV Before gamma irradiation (0 Gy) 600 712 1.74 After gamma irradiation (1 Gy) 485 588 2.10

As shown in Table 2 and FIG. 2(b), in the case of compound (2), it has the same main skeleton and terminal functional groups as those of compound (1). Similarly, the maximum absorbance wavelength (λ _{abs max} ) after irradiation with 1 Gy gamma rays and the onset absorbance wavelength (λ _{abs onset} ) are all confirmed to decrease, and it is confirmed that the bandgap energy is significantly increased to about 0.36 eV after 1 Gy gamma irradiation. Therefore, it is expected to have a distinct color change after exposure to 1 Gy gamma rays.

On the other hand, the result of confirming the optical characteristic change of compound (2) at room temperature according to exposure to sunlight for one week is shown in FIG. 4(b).

As shown in FIG. 4(b), in the case of compound (2), the maximum absorbance wavelength (λ _{abs max} ) and the onset absorbance wavelength (λ _{abs onset} ) slightly shifted even after exposure to sunlight for one week, but only a very insignificant level confirmed to be Therefore, it can be seen that there is almost no reaction to light rays such as infrared rays, visible rays, and ultraviolet rays constituting sunlight, and the color change cannot be detected with the naked eye.

Comparative Example 1

Compound (3) having the following structure was prepared:

.

.

The results of confirming the optical properties change according to exposure to 1 Gy gamma rays of compound (3) are shown in Table 3 and FIG. 2(c).

λ _{abs max} /nm λ _{abs onset} /nm Optical band gap/eV Before gamma irradiation (0 Gy) 383 423 2.93 After gamma irradiation (1 Gy) 383 423 2.93

As shown in Table 3 and Figure 2(b), in the case of compound (3), although it is a compound having a resonance structure, the maximum absorbance wavelength (λ _{abs max} ) and the starting absorbance wavelength (λ _{abs onset} ) after irradiation with 1 Gy gamma rays and , it is confirmed that there is no change in the bandgap energy. Therefore, no color change will be observed with the naked eye after exposure to 1 Gy gamma rays.

As such, in the case of compound (3), unless it reacts to gamma rays having high energy, it will not react to light rays such as infrared rays, visible rays and ultraviolet rays having lower energy.

Comparative Example 2

Compound (4) having the following structure was prepared:

.

.

The results of confirming the optical properties change according to exposure to 1 Gy gamma rays of compound (4) are shown in Table 4 and FIG. 2(d).

λ _{abs max} /nm λ _{abs onset} /nm Optical band gap/eV Before gamma irradiation (0 Gy) 435 520 2.38 After gamma irradiation (1 Gy) 444 526 2.35

As shown in Table 4 and FIG. 2(b), in the case of compound (4), although it is a thiophene-based compound having a resonance structure, the maximum absorbance wavelength (λ _{abs max} ) and the starting absorbance wavelength (λ _abs ) after irradiation with 1 Gy gamma rays _onset ) and the bandgap energy change level are confirmed to be only insignificant. Therefore, no color change will be observed with the naked eye after exposure to 1 Gy gamma rays.

As such, in the case of compound (4), unless it reacts to gamma rays having high energy, it will not react to light rays such as infrared rays, visible rays and ultraviolet rays having lower energy.

The description of the present invention described above is for illustration, and those of ordinary skill in the art to which the present invention pertains can understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

Claims (10)

A dicyanomethylene group comprising a thiophene-based compound introduced as a terminal functional group
A composition for sensing radiation.
According to claim 1,
The thiophene-based compound is a composition for sensing radiation, characterized in that represented by the following formula (1):
[Formula 1]

,
In Formula 1, R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and each independently hydrogen; C1~ C20 alkyl group; C1~ C20 Alkyl group substituted or unsubstituted C6~ C20 aryl group; Or a C3~ C20 heteroaryl group unsubstituted or substituted with a C1~ C20 alkyl group.
According to claim 1,
The thiophene-based compound may be prepared by first reacting a compound represented by the following Chemical Formula 2 with dimethylformaldehyde; and a second reaction of the first reaction product with a compound represented by the following formula (3), characterized in that it is prepared, comprising:
[Formula 2]

,
[Formula 3]

,
In Formula 2, R ₁ , R ₂ , R ₃ and R ₄ are the same or different, and each independently hydrogen; C1~ C20 alkyl group; C1~ C20 Alkyl group substituted or unsubstituted C6~ C20 aryl group; Or a C3~ C20 heteroaryl group unsubstituted or substituted with a C1~ C20 alkyl group.
The method of claim 1,
The thiophene-based compound is characterized in that both the maximum absorbance wavelength and the onset absorbance wavelength decrease after exposure to radiation, a composition for sensing radiation.
The method of claim 1,
The thiophene-based compound has an onset absorbance wavelength of 650 nm to 750 nm before exposure to radiation, and an onset absorbance wavelength of 500 nm to 600 nm after exposure to radiation, the composition for sensing radiation.
According to claim 1,
The thiophene-based compound is a composition for sensing radiation, characterized in that the bandgap energy increases after exposure to radiation.
According to claim 1,
The thiophene-based compound has a bandgap energy of 1.50 eV to 1.80 eV before exposure to radiation, and a bandgap energy of 2.00 eV to 2.30 eV after exposure to radiation, a composition for sensing radiation.
According to claim 1,
The energy of the radiation is 0.1 Gy to 100 Gy, characterized in that the radiation sensing composition.
A visualization material for sensing radiation using the composition according to any one of claims 1 to 8.
A method for detecting radiation using the composition according to any one of claims 1 to 8.

Images