KR20240033582A - Semiconducting polymer-based organic sintillating polymer for nuclear radiation detection and plastic scintillator using the same - Google Patents

Abstract

The present invention relates to a semiconductor polymer-based plastic scintillator, which induces efficient energy transfer under radiation exposure by covalently binding a photosensitive agent capable of detecting radiation to a semiconductor polymer, and emits visible light photons so that a photomultiplier tube can detect them. It is about radiation detection.

Description

Semiconducting polymer-based organic sintillating polymer for nuclear radiation detection and plastic scintillator using the same}

The present invention relates to a semiconductor polymer-based plastic scintillator, which induces efficient energy transfer under radiation exposure by covalently binding a photosensitive agent capable of detecting radiation to a semiconductor polymer, and emits visible light photons so that a photomultiplier tube can detect them. It is about radiation detection.

Recently, green energy has been receiving great attention as an alternative energy source due to the increase in carbon emissions, greenhouse effect, and ocean acidification. These environmental problems are increasing due to the high dependence on fossil fuels for energy, and hydro, wind and solar power still have to meet specific geographical requirements and are affected by climate. Therefore, nuclear energy generation is emerging as an essential power source of energy, and the need for an alternative energy source is increasing due to the depletion of fossil fuels in a rapidly developing modern society. However, nuclear power generation has a major disadvantage, as there is a high risk of radiation leakage, so effective radioactivity monitoring technology is considered as important as nuclear power generation.

Nuclear reactions emit high-energy α-, β-, and γ-rays and neutron rays, and scintillators that monitor these rays produce single high-energy photons that can be detected by a low-energy photomultiplier (PMT). It can be converted into photons. Because scintillator is inexpensive and easy to manufacture, it is widely used in X-ray and gamma-ray detection. The requirements for an ideal scintillator are as follows. (1) contain high energy decay and high atomic number to increase photoelectron generation, (2) exhibit high light yield characteristics, (3) short fluorescence photon lifetime, and (4) low cost to facilitate mass production. Should be. However, elements with high atomic numbers are mainly composed of inorganic oxides, which reduces the scintillator's processability and stability against moisture and oxidation.

Currently known radiation detection scintillators include (1) single crystal, (2) liquid, and (3) plastic scintillator. Single crystal scintillator contains high-purity germanium and NaI, but it is expensive to manufacture in large quantities due to the disadvantage of difficult crystal growth. Easy to pick up and break. Liquid scintillator is a flammable oil and is very sensitive to oxygen, making it difficult to handle, transport, and store. Plastic scintillator is continuously being developed due to its wide range of material selection, despite its relatively low detection efficiency due to the disadvantages mentioned above.

Commercially available plastic scintillators are made of a matrix such as polystyrene, polyvinyltoluene, poly(methyl methacrylate), or polysiloxane, with a radiation sensitizer such as 2,5-diphenyloxazole (PPO) or 1,4-bis(5-phenyloxazol). -2-yl) It is manufactured by mixing benzene (POPOP). Additionally, for optimal scintillation performance, the emission wavelength can be adjusted to the visible light range by adding a wavelength shifter. However, excessively doped fluorescent dopant can act as a plasticizer within the matrix and deteriorate the thermal and mechanical properties of the plastic scintillator. To overcome these limitations, examples of copolymerization of radiation sensitizer derivatives with crosslinking agents or monomers as matrix polymers have been reported, but numerous formulations are required to determine the appropriate content ratio between wavelength shift agents to induce energy transfer to wavelengths in the visible light region. Because it is necessary, it acts as a limitation in mass production. Therefore, there is a need to develop new dopants with high light yield and short fluorescence photon lifetime. Recently, there have been cases of applying quantum dots or perovskites as dopants in plastic scintillator, but quantum dots have a problem of agglomeration due to poor dispersibility within the matrix, and perovskites are not practical due to their poor stability against moisture, light, and heat. There are limits. Most importantly, these dopants contain heavy metals and halogen elements, so there is a risk of secondary environmental pollution during the process of disposing of the scintillator after radiation monitoring.

[Prior Art Document 1] Korean Patent Application No. 10-2019-0117368 Scintillator composition and scintillator using the same

[Prior Art Document 2] Korean Patent Application No. 10-2015-0109351 Zeolite scintillator and manufacturing method thereof

[Prior Art Document 3] J. Nie, C. Li, S. Zhou, J. Huang, X. Ouyang, Q. Xu, High Photoluminescence Quantum Yield Perovskite/Polymer Nanocomposites for High Contrast X-ray Imaging, ACS Appl. Mater. Interfaces 2021, 13, 45, 54348-54353

The present invention seeks to solve the problems of dispersion stability and aggregation, which are problems with existing plastic scintillator, and manufactures a scintillator from a semiconductor polymer in which the radiation sensitizer is covalently linked without the need for two or more dopants, thereby creating a gap between the radiation sensitizer and the wavelength shift agent. It improves radiation detection efficiency by facilitating energy transfer. Additionally, to address concerns about secondary environmental pollution during the process of disposing of the scintillator after radiation monitoring, a plastic scintillator made up of all organic materials is provided.

Semiconductor polymers have an excellent ability to harvest light because they can be adjusted to have a wide absorption wavelength by selecting various monomers. Unlike general fluorescent dyes, it not only has unique energy transfer characteristics within and between molecules of semiconductor polymers, but also, unlike the inorganic plastic scintillator mentioned above, all components are composed of organic components. Therefore, there is no concern about environmental pollution due to secondary waste, and since it is the same polymer and has good compatibility with matrix polymers, the agglomeration problem can also be solved.

Therefore, the present invention has developed an eco-friendly organic-based scintillator that solves the dopant aggregation problem of plastic scintillator and improves energy transfer between a radiation sensitizer and a wavelength shift agent. It does not require two or more dopants and can detect radiation with only one semiconductor polymer. You can.

According to one aspect of the present invention, an organic scintillation polymer comprising a first repeating unit represented by the following formula (1) is provided:

[Formula 1]

In Formula 1 above,

R ₁ is a radiation sensitizer, R ₂ is an alkyl group having 3 to 10 carbon atoms, and * indicates a connecting portion.

According to another aspect of the present invention, a composition for a scintillator containing the organic flash polymer is provided.

According to another aspect of the present invention, a plastic scintillator containing the organic scintillator polymer is provided.

The semiconductor polymer-based plastic scintillator of the present invention has excellent dispersion stability and does not aggregate dopants, so it has high transmittance and excellent optical properties. By manufacturing a semiconductor polymer to which a radiation sensitizer is covalently linked into a scintillator, it can be used as a radiation sensitizer and a wavelength shift agent. Radiation detection efficiency can be improved by facilitating energy transfer between devices.

1 is a flow chart of the manufacturing method of the semiconductor polymer-based plastic scintillator of the present invention;
Figure 2 is a schematic diagram of the semiconductor polymer-based plastic scintillator manufacturing method of the present invention;
Figure 3 is a configuration diagram of a manufacturing device that detects radiation with the scintillator of the present invention;
Figure 4 is an energy spectrum measured under Sr-90 radiation exposure according to the content of the plastic scintillator of the present invention;
Figure 5 is an energy spectrum measured under Sr-90 radiation exposure according to the type of plastic scintillator of the present invention;
Figure 6 is an energy spectrum measured under C-14 radiation exposure according to the content of the plastic scintillator of the present invention;
Figure 7 is an energy spectrum measured under C-14 radiation exposure according to the type of plastic scintillator of the present invention.

Hereinafter, the present invention will be described in detail.

The terms used in this specification are merely used to describe specific embodiments and are not intended to limit the present invention, and unless otherwise defined, are generally understood by those skilled in the art to which the present invention pertains. It has the same meaning as becoming.

Throughout the specification, when a part is said to “include”, “contain”, or “have” a certain component, this means that it may further include other components, unless specifically defined otherwise.

According to one aspect of the present invention, an organic flash polymer comprising a first repeating unit represented by the following formula (1) is provided:

[Formula 1]

In Formula 1, R ₁ is a radiation sensitizer, R ₂ is an alkyl group having 3 to 10 carbon atoms, and * represents a connecting portion.

The R ₁ may be any radiation sensitizer used for scintillator use and is not particularly limited. For example, R ₁ is 2,5-diphenyloxazole (PPO), para terphenyl (PT), 4-bis (2-methylstyryl) benzene (4-bis (2-Methylstyryl) benzene)(bis-MSB), P-terphenyl, 1,4-bis[5-phenyloxazol-2-yl]benzene (POPOP), anthracene, stilbene, Tolan, 2-(4-biphenylyl)-5-phenyl-oxazole (BPO), 2-phenyl-5-(4-biphenylyl)-1,3,4-oxadiazole (PBD) ), 2-(1-naphthyl)-5-phenyloxazole (α-NPO), 1,4-di-(4-methyl-5-phenyl-2-oxazolyl)-benzene (dimethyl-POPOP), It may be any one selected from the group consisting of 1,4-bis-(2-methylstyryl)benzene (bis-MSB).

According to one embodiment of the present invention, R ₁ may be 2,5-diphenyloxazole (PPO) or 1,4-bis[5-phenyloxazol-2-yl]benzene (POPOP). Specifically, R ₁ is represented by the formula 2,5-diphenyloxazole (PPO) or the formula represented by It may be 1,4-bis(5-phenyloxazol-2-yl)benzene (POPOP) represented by .

In this specification, an alkyl group having 3 to 10 carbon atoms refers to a straight-chain or branched alkyl group having 3 to 10 carbon atoms. The alkyl group having 3 to 10 carbon atoms may preferably be an alkyl group having 5 to 9 carbon atoms, and preferably the alkyl group is a straight-chain alkyl group. Examples of the alkyl group include n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, and n-hexyl.

According to one embodiment of the present invention, the organic flash polymer may further include, in addition to the first repeating unit represented by Formula 1, at least one second repeating unit selected from the group consisting of Formulas 2a to 2d below: You can:

[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

In Formula 2a, R ₃ may be an alkyl group having 3 to 10 carbon atoms, preferably an alkyl group having 5 to 9 carbon atoms, and preferably the alkyl group is a straight-chain alkyl group. In Formulas 2a to 2d, * indicates a connection portion.

According to one embodiment of the present invention, the amount of the first repeating unit and the amount of the second repeating unit can be appropriately adjusted depending on the purpose. For example, the amount of the first repeating unit can be adjusted depending on the amount of the desired radiation sensitizer, and the amount of the second repeating unit can be adjusted to the desired fluorescence wavelength so that the photomultiplier tube emits detectable visible light photons. The number of first repeating units and the number of second repeating units may be in a ratio of 2:8 to 8:2.

According to one embodiment of the present invention, the first repeating unit may be represented by the following formula (3):

[Formula 3]

In Formula 3, R ₁ may be any radiation sensitizer used for scintillator, and according to one embodiment of the present invention, R ₁ is 2,5-diphenyloxazole (PPO) or 1,4- It may be bis[5-phenyloxazol-2-yl]benzene (POPOP), specifically (2,5-diphenyloxazole, PPO) or It may be (1,4-bis(5-phenyloxazol-2-yl)benzene, POPOP). In Formula 3, * indicates a connection part.

According to one embodiment of the present invention, the organic flash polymer may include at least one repeating unit selected from the group consisting of the following formulas 4 to 7.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In Formulas 4 to 7,

R ₄ may be any radiation sensitizer used for scintillator, and according to one embodiment of the present invention, R ₁ is 2,5-diphenyloxazole (PPO) or 1,4-bis[5-phenyl It may be oxazol-2-yl] benzene (POPOP), specifically (2,5-diphenyloxazole, PPO) or It may be (1,4-bis(5-phenyloxazol-2-yl)benzene, POPOP).

In Formulas 4 to 7, R ₅ and R ₆ are each independently an alkyl group having 3 to 10 carbon atoms, preferably an alkyl group having 5 to 9 carbon atoms, and preferably the alkyl group is a straight-chain alkyl group.

In Formulas 4 to 7, m ₁ to m ₄ and n ₁ to n ₄ are each independently a rational number of 1 to 15, and may be, for example, a rational number of 1 to 12, 2 to 8, or 3 to 7. Additionally, in Formulas 4 to 7, m ₁ +n ₁ , m ₂ +n ₂ , m ₃ +n ₃ , m ₄ +n ₄ , and m ₅ +n ₅ are each independently rational numbers of 5 to 30, e.g. For example, it may be a rational number of 5 to 20, 6 to 15, or 7 to 12.

According to one aspect of the present invention, a composition for a scintillator containing the above-described organic flash polymer is provided.

The composition for a scintillator can be used to manufacture a scintillator by mixing it with a matrix polymer such as polystyrene, polyvinyltoluene, poly(methyl methacrylate), polyacrylate, or polysiloxane. Alternatively, the composition for a scintillator may further contain a polymerization monomer for a matrix polymer. The polymerization monomer for the matrix polymer may be at least one polymerization monomer for the matrix polymer selected from the group consisting of polystyrene, polyvinyltoluene, poly(methyl methacrylate), polyacrylate, and polysiloxane.

Additionally, the composition for a scintillator may additionally contain a polymerization initiator. The type of the polymerization initiator is not limited, and for example, highly reactive azo compounds, diazo compounds, etc. may be used as the polymerization initiator, preferably azobisisobutyronitrile ( azobis (isobutyronitrile), AIBN).

The organic flash polymer according to the present invention is manufactured into a plastic scintillator by incorporating it into a matrix polymer such as polystyrene, polyvinyltoluene, poly(methyl methacrylate), or polysiloxane, and is used by polishing to the diameter of the photomultiplier tube, Photons are detected under radiation exposure.

Accordingly, according to another aspect of the present invention, a plastic scintillator containing the above-described organic flash polymer is provided. The scintillator may be used to detect radiation, specifically Sr-89, Sr-90, or C-14 radiation sources.

In addition, the manufacturing process of a scintillator containing the organic flash polymer of the present invention includes a first step (S100) of synthesizing a semiconductor polymer; A second step (S200) of synthesizing an organic flash polymer containing the first repeating unit of Chemical Formula 1 by covalently bonding a radiation sensitizer; It may consist of mixing the second-stage organic flash polymer with the matrix plastic polymer (S300), and the flow chart for the manufacturing method is shown in [Figure 1].

In the first step (S100), the semiconductor polymer has a fluorene unit (a fluorene unit that is the basis of the first repeating unit of Formula 1) and a different unit (a polymer unit that is the basis of the second repeating unit of Formulas 2a to 2d) ) is synthesized by Suzuki coupling reaction, but is not limited to this and can be manufactured through various synthetic routes. In order to emit a desired visible light wavelength, the polymer for the second repeating unit can be synthesized using known monomers, and is not limited to Formulas 2a to 2d. Additionally, the amount of radiation sensitizer to be introduced can be determined by adjusting the ratio of the semiconductor polymer for the first repeating unit.

In the second step (S200), an organic flash polymer can be synthesized by covalently bonding a radioactive photosensitizer to the semiconductor polymer. Specifically, the radioactive photosensitizer may react with the halogen of the semiconductor polymer for the first repeating unit (e.g., Br in Preparation Example 1) through a nucleophilic substitution reaction, but is not limited to this, and may be introduced into the side chain of the semiconductor polymer. Any organic chemical synthesis method available can be applied. In addition, in the examples, PPO was introduced as a radiation sensitizer, but the present invention is not limited thereto, and any of the known radiation sensitizers may be introduced.

The plastic scintillator containing the first repeating unit of Formula 1 or an organic flash polymer containing the first repeating unit and the second repeating unit is a matrix such as polystyrene, polyvinyltoluene, poly(methyl methacrylate), polysiloxane, etc. It can be used by dissolving it in a polymer solution and then solidifying it, or it can be used through a crosslinking reaction such as photopolymerization or thermal polymerization in the presence of an initiator with the monomers of these matrix polymers. The matrix polymer used in the scintillator may be any known polymer used in the relevant field, but it is appropriate that it does not absorb visible light. The manufacturing process of the plastic scintillator is shown in [Figure 2].

To detect radiation, a plastic scintillator is brought into contact with a photomultiplier tube using optical grease, a radiation source is placed on the scintillator, a dark environment is created, and equilibrium is maintained for 1 hour. The photomultiplier tube, pre-amplifier, amplifier, and power supply were connected, and the output data was collected as a spectrum using measurement software on a PC. Unless otherwise specified, the measurement time (live time) is set to 600 seconds, but is not limited to this. The manufacturing device for radiation detection is shown in [Figure 3].

Hereinafter, the present invention will be described in more detail with reference to examples to aid understanding of the present invention. However, the following examples are provided only to make the present invention easier to understand, and the content of the present invention is not limited by the following examples.

[Preparation Example 1]: Synthesis of semiconductor polymer (S100)

[Formula aa]

Production Example 1-1 : (CP1) (m=5, n=5)

To prepare the semiconductor polymer of the formula aa, 2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene (0.36 g, 0.5 mmol), 1,4-benzenediboronic acid bis were added to a three-necked round flask. (pinacol) ester (0.33 g, 1 mmol), 9,9-dioctyl-2,7-dibromofluorene (0.27 g, 0.5 mmol), and the catalyst tetrakis(triphenylphosphine)palladium (0.05 mmol) were added to a three-necked round flask and refluxed. The device was installed and purged with argon gas. After adding 12 mL of toluene from which moisture was removed and dissolving the catalyst and reactants, 3 mL of K ₂ CO ₃ (2 M) aqueous solution was added and stirred at 90 ^o C for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate a solid, and the precipitate was filtered. The obtained solid was purified by Soxhlet with methanol and acetone and then dried to obtain CP1. ¹ H NMR (300 MHz, CDCl ₃ ): δ _ppm = 7.815-7.486 (m, 10H), 3.295-3.274 (m, 2H), 2.084-2.006 (m, 4H), 1.668-1.553 (m, 2H), 1.253-1.108 (m, 16H), 0.815-0.793 (m, 5H).

Production Example 1-2 : (CP2) (m=7, n=3)

To prepare the semiconductor polymer of the above formula, 2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene (0.7 mmol), 1,4-benzenediboronic acid bis(pinacol) ester was added to a three-necked round flask. (1 mmol), 9,9-dioctyl-2,7-dibromofluorene (0.3 mmol), and the catalyst tetrakis(triphenylphosphine)palladium (0.05 mmol) were placed in a three-necked round flask, equipped with a reflux, and purged with argon gas. After adding 12 mL of toluene from which moisture was removed and dissolving the catalyst and reactants, 3 mL of K ₂ CO ₃ (2 M) aqueous solution was added and stirred at 90 ^o C for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate a solid, and the precipitate was filtered. The obtained solid was Soxhlet-purified with methanol and acetone and then dried to obtain CP2. ¹ H NMR (300 MHz, CDCl ₃ ): δ _ppm =7.817-7.594 (m, 10H), 3.392-9.275 (m, 2.8H), 2.075 (m, 4H), 1.682-1.616 (m, 2.8H), 1.255-1.109 (m, 14.4H), 0.813 (m, 7H).

Preparation Example 1-3 : (CP3) (m=10, n=0)

To prepare the semiconductor polymer of the above formula, 9,9-Dioctyl-2,7-dibromofluorene (1 mmol), 1,4-benzenediboronic acid bis(pinacol) ester (1 mmol) and the catalyst tetrakis (1 mmol) were added to a three-necked round flask. Triphenylphosphine) palladium (0.05 mmol) was placed in a three-necked round flask, equipped with a reflux device, and purged with argon gas. After adding 12 mL of toluene from which moisture was removed and dissolving the catalyst and reactants, 3 mL of K ₂ CO ₃ (2 M) aqueous solution was added and stirred at 90 ^o C for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate a solid, and the precipitate was filtered. The obtained solid was purified by Soxhlet with methanol and acetone and then dried to obtain CP3. ¹ H NMR (300 MHz, CDCl ₃ ): δ _ppm =7.820-7.481 (m, 10H), 3.319-3.275 (m, 4H), 2.079-2.031 (m, 4H), 1.681-1.660 (m, 4H), 1.229-0.689 (m, 12H).

[Formula ab]

Production Example 1-4 : (CP4) (m=5, n=5)

To prepare the semiconductor polymer of the formula ab, 2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene (0.36 g, 0.5 mmol), 1,4-benzenediboronic acid bis were added to a three-necked round flask. (pinacol) ester (0.33 g, 1 mmol), 4,7-dibromobenzo[c]-1,2,5-thiadiazole (0.15 g, 0.5 mmol) and the catalyst tetrakis(triphenylphosphine)palladium (0.05 mmol) It was placed in a round flask, equipped with a reflux device, and purged with argon gas. After adding 12 mL of toluene from which moisture was removed and dissolving the catalyst and reactants, 3 mL of K ₂ CO ₃ (2 M) aqueous solution was added and stirred at 90 ^o C for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate a solid, and the precipitate was filtered. The obtained solid was purified by Soxhlet with methanol and acetone and then dried to obtain CP4. ¹ H NMR (300 MHz, CDCl ₃ ): δ _ppm = 8.34-8.01 (m, 3H) 7.825-7.446 (m, 5H), 3.47-3.32 (m, 2H), 2.05-1.025 (m, 10H).

Preparation Example 1-5 : (CP5) (m=7, n=3)

To prepare the semiconductor polymer of the formula ab above, 2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene (0.7 mmol), 1,4-benzenediboronic acid bis(pinacol) was added to a three-necked round flask. Add ester (1 mmol), 4,7-dibromobenzo[c]-1,2,5-thiadiazole (0.088g, 0.3 mmol), and the catalyst tetrakis(triphenylphosphine)palladium (0.05 mmol) into a three-necked round flask and reflux. It was installed and purged with argon gas. After adding 12 mL of toluene from which moisture was removed and dissolving the catalyst and reactants, 3 mL of K ₂ CO ₃ (2 M) aqueous solution was added and stirred at 90 ^o C for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate a solid, and the precipitate was filtered. The obtained solid was purified by Soxhlet with methanol and acetone and then dried to obtain CP5. ¹ H NMR (300 MHz, CDCl ₃ ): δ _ppm =8.24-8.03 (m, 1.8 H), 7.802-7.472 (m, 7H), 3.41-3.25 (m, 2.8H), 2.075-0.813 (m, 16.8) H).

[Chemical formula ac]

Production Example 1-6 : (CP6) (m=5, n=5)

To prepare the semiconductor polymer of the formula ac, 2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene (0.36 g, 0.5 mmol), 1,4-benzenediboronic acid bis were added to a three-necked round flask. (pinacol) ester (0.33 g, 1 mmol), 4,7-bis(5-bromothiophen-2-yl)benzo[c][1,2,5]thiadiazole (0.15 g, 0.5 mmol) and the catalyst tetrakis( Triphenylphosphine) palladium (0.05 mmol) was placed in a three-necked round flask, equipped with a reflux device, and purged with argon gas. After adding 12 mL of toluene from which moisture was removed and dissolving the catalyst and reactants, 3 mL of K ₂ CO ₃ (2 M) aqueous solution was added and stirred at 90 ^o C for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate a solid, and the precipitate was filtered. The obtained solid was purified by Soxhlet with methanol and acetone and then dried to obtain CP6. ¹ H NMR (300 MHz, CDCl ₃ ): δ _ppm = 8.17-7.86 (m, 5H), 7.7-7.52 (m, 5H), 3.295-3.274 (m, 2H), 2.084-1.983 (m, 4H), 0.832-0.793 (m, 6H).

Preparation Example 1-7 : (CP7) (m=7, n=3)

To prepare the semiconductor polymer of the formula ac, 2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene (0.7 mmol), 1,4-benzenediboronic acid bis(pinacol) were added to a three-necked round flask. Add ester (1 mmol), 4,7-dibromobenzo[c]-1,2,5-thiadiazole (0.14g, 0.3 mmol), and the catalyst tetrakis(triphenylphosphine)palladium (0.05 mmol) into a three-necked round flask and reflux. It was installed and purged with argon gas. After adding 12 mL of toluene from which moisture was removed and dissolving the catalyst and reactants, 3 mL of K ₂ CO ₃ (2 M) aqueous solution was added and stirred at 90 ^o C for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate a solid, and the precipitate was filtered. The obtained solid was purified by Soxhlet with methanol and acetone and then dried to obtain CP7. ¹ H NMR (300 MHz, CDCl ₃ ): δ _ppm =8.24-8.02 (m, 3H), 7.71-7.42 (m, 7H), 3.392-2.85 (m, 2.8H), 2.42-2.075 (m, 2.8H) ), 1.682-0.816 (m, 11.2H).

[Chemical formula ad]

Production Example 1-8 : (CP8) (m=5, n=5)

To prepare the semiconductor polymer of the formula ad, 2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene (0.36 g, 0.5 mmol), 1,4-benzenediboronic acid bis were added to a three-necked round flask. (pinacol) ester (0.33 g, 1 mmol) 5,8-dibromoquinoxaline (0.14 g, 0.5 mmol) and the catalyst tetrakis(triphenylphosphine)palladium (0.05 mmol) were placed in a three-necked round flask, equipped with a reflux device, and purged with argon gas. After adding 12 mL of toluene from which moisture was removed and dissolving the catalyst and reactants, 3 mL of K ₂ CO ₃ (2 M) aqueous solution was added and stirred for 48 hours at 90 ^o C. After reaction, cooled to room temperature and dissolved in methanol. The solid was poured to precipitate and the precipitate was filtered. The obtained solid was Soxhlet-purified with methanol and acetone and dried to obtain CP8. ¹ H NMR (300 MHz, CDCl ₃ ): δ _ppm = 8.17-7.83 (m, 4H ), 7.72-7.53 (m, 5H), 3.45-3.16 (m, 2H), 2.074-2.02 (m, 2H), 1.672-0.762 (m, 8H).

Production Example 1-9 : (CP9) (m=7, n=3)

To prepare the semiconductor polymer of the above formula ad, 2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene (0.7 mmol), 1,4-benzenediboronic acid bis(pinacol) was added to a three-necked round flask. Ester (1 mmol), 5,8-dibromoquinoxaline (0.08 g, 0.3 mmol), and the catalyst tetrakis(triphenylphosphine)palladium (0.05 mmol) were placed in a three-necked round flask, equipped with a reflux device, and purged with argon gas. After adding 12 mL of toluene from which moisture was removed and dissolving the catalyst and reactants, 3 mL of K ₂ CO ₃ (2 M) aqueous solution was added and stirred at 90 ^o C for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate a solid, and the precipitate was filtered. The obtained solid was purified by Soxhlet with methanol and acetone and then dried to obtain CP9. ¹ H NMR (300 MHz, CDCl ₃ ): δ _ppm =8.07-7.86 (2.4H), 7.57-7.24 (m, 7H), 3.24-2.98 (m, 2.8H), 2.062 (m, 2.8H), 1.72 -0.902 (m, 11.2H).

[Preparation Example 2]: Introduction of photosensitizer to semiconductor polymer (S200)

The process of introducing a photosensitizer into a semiconductor polymer was performed by reacting the polymer synthesized in Preparation Example 1 with an excess of 3-(5-Phenyloxazol-2-yl)phenol and can be represented by the chemical formula Aa.

[Formula Aa]

Preparation Example 2-1: (CP1-PPO)

CP1 (0.55 mmol) of Preparation Example 1-1 and 4 equivalents of K ₂ CO ₃ were placed in a three-necked round flask, equipped with a reflux device, and purged with argon gas. After adding THF and dissolving CP1, 4 equivalents of PPO compared to CP1 were dissolved in a small amount of DMF and added dropwise to the CP1 solution. The reaction was carried out at 80°C for 48 hours. After completion of the reaction, it was cooled to room temperature, the mixture was concentrated, precipitated in acetone, and the precipitate was filtered. The precipitate was dissolved in chloroform, extracted with water to remove K ₂ CO ₃ , and the organic layer was dehydrated with MgSO ₄ . The organic layer was concentrated and precipitated in acetone, and the precipitate was filtered to obtain a gray solid (hereinafter referred to as CP1-PPO). ^1H NMR (300 MHz, CDCl ₃ ) δ _ppm : 7.820-7.481 (m, 19H), 6.908-6.827 (m, 1H) 3.881 (m, 2H), 2.173 (m, 4H), 1.622 (m, 2H) , 1.254-1.108 (m, 16H), 0.881-0.801 (m, 5H).

Preparation Example 2-2: (CP2-PPO)

CP2 (0.18 mmol) of Preparation Example 1-2 and 4 equivalents of K ₂ CO ₃ were placed in a three-necked round flask, equipped with a reflux device, and purged with argon gas. After adding THF and dissolving CP2, 4 equivalents of PPO compared to CP2 were dissolved in a small amount of DMF and added dropwise to the CP2 solution. The reaction was carried out at 80°C for 48 hours. After completion of the reaction, it was cooled to room temperature, the mixture was concentrated, precipitated in acetone, and the precipitate was filtered. The precipitate was dissolved in chloroform, extracted with water to remove K ₂ CO ₃ , and the organic layer was dehydrated with MgSO ₄ . The organic layer was concentrated and precipitated in acetone, and the precipitate was filtered to obtain a gray solid (hereinafter referred to as CP2-PPO). ¹ H NMR (300 MHz, CDCl ₃ ) δ _ppm : 7.785-7.570 (m, 21.6H), 6.918-6.788 (m, 1.4H) 4.065-3.742 (m, 2.8H), 2.036 (m, 4H), 1.591 (m, 2.8H), 1.254-1.102 (m, 14.4H), 0.879-0.805 (m, 7H).

Preparation Example 2-3: (CP3-PPO)

CP3 (0.6 mmol) of Preparation Example 1-3 and 4 equivalents of K ₂ CO ₃ were placed in a three-necked round flask, equipped with a reflux device, and purged with argon gas. After adding THF and dissolving CP3, 4 equivalents of PPO compared to CP3 were dissolved in a small amount of DMF and added dropwise to the CP3 solution. The reaction was carried out at 80°C for 48 hours. After completion of the reaction, it was cooled to room temperature, the mixture was concentrated, precipitated in acetone, and the precipitate was filtered. The precipitate was dissolved in chloroform, extracted with water to remove K ₂ CO ₃ , and the organic layer was dehydrated with MgSO ₄ . The organic layer was concentrated and precipitated in acetone, and the precipitate was filtered to obtain a gray solid (hereinafter referred to as CP3-PPO). ^1H NMR (300 MHz, CDCl ₃ ) δ _ppm : 7.774-7.495 (m, 10H), 6.894-6.730 (m, 2H), 3.880 (m, 4H), 2.139-2.081 (m, 4H), 1.568 (m) , 4H), 0.875-0.741 (m, 12H).

[Formula Ab]

Preparation Example 2-4: (CP4-PPO)

CP4 (0.5 mmol) of Preparation Example 1-4 and 4 equivalents of K ₂ CO ₃ were placed in a three-necked round flask, equipped with a reflux device, and purged with argon gas. After adding THF and dissolving CP4, 4 equivalents of PPO compared to CP4 was dissolved in a small amount of DMF and added dropwise to the CP4 solution. The reaction was carried out at 80°C for 48 hours. After completion of the reaction, it was cooled to room temperature, the mixture was concentrated, precipitated in acetone, and the precipitate was filtered. The precipitate was dissolved in chloroform, extracted with water to remove K ₂ CO ₃ , and the organic layer was dehydrated with MgSO ₄ . The organic layer was concentrated and precipitated in acetone, and the precipitate was filtered to obtain a gray solid (hereinafter referred to as CP4-PPO). ^1H NMR (300 MHz, CDCl ₃ ) δ _ppm : 8.17-7.98 (m, 3H), 7.720-7.381 (m, 19H), 6.808-6.727 (m, 1H), 3.47-3.32 (m, 2H), 2.05 -1.025 (m, 10H).

Preparation Example 2-5: (CP5-PPO)

CP5 (0.2 mmol) of Preparation Example 1-5 and 4 equivalents of K ₂ CO ₃ were placed in a three-necked round flask, equipped with a reflux device, and purged with argon gas. After adding THF and dissolving CP5, 4 equivalents of PPO compared to CP5 were dissolved in a small amount of DMF and added dropwise to the CP5 solution. The reaction was carried out at 80°C for 48 hours. After completion of the reaction, it was cooled to room temperature, the mixture was concentrated, precipitated in acetone, and the precipitate was filtered. The precipitate was dissolved in chloroform, extracted with water to remove K ₂ CO ₃ , and the organic layer was dehydrated with MgSO ₄ . The organic layer was concentrated and precipitated in acetone, and the precipitate was filtered to obtain a gray solid (hereinafter referred to as CP5-PPO). ^1H NMR (300 MHz, CDCl ₃ ) δ _ppm : 8.24-8.03 (m, 1.8 H), 7.685-7.470 (m, 21.6H), 6.718-6.688 (m, 1.4H), 3.41-3.25 (m, 2.8) H), 2.075-0.813 (m, 16.8H).

[Formula Ac]

Preparation Example 2-6: (CP6-PPO)

CP6 (0.4 mmol) of Preparation Example 1-6 and 4 equivalents of K ₂ CO ₃ were placed in a three-necked round flask, equipped with a reflux device, and purged with argon gas. After adding THF and dissolving CP6, 4 equivalents of PPO compared to CP6 were dissolved in a small amount of DMF and added dropwise to the CP6 solution. The reaction was carried out at 80°C for 48 hours. After completion of the reaction, it was cooled to room temperature, the mixture was concentrated, precipitated in acetone, and the precipitate was filtered. The precipitate was dissolved in chloroform, extracted with water to remove K ₂ CO ₃ , and the organic layer was dehydrated with MgSO ₄ . The organic layer was concentrated and precipitated in acetone, and the precipitate was filtered to obtain a gray solid (hereinafter referred to as CP6-PPO). ^1H NMR (300 MHz, CDCl ₃ ) δ _ppm : 8.17-7.86 (m, 5H), 7.830-7.491 (m, 19H), 6.918-6.847 (m, 1H), 3.305-3.284 (m, 2H), 2.084 -1.983 (m, 4H), 0.832-0.793 (m, 6H).

Preparation Example 2-7: (CP7-PPO)

CP7 (0.33 mmol) of Preparation Example 1-7 and 4 equivalents of K ₂ CO ₃ were placed in a three-necked round flask, equipped with a reflux device, and purged with argon gas. After adding THF and dissolving CP7, 4 equivalents of PPO compared to CP7 were dissolved in a small amount of DMF and added dropwise to the CP7 solution. The reaction was carried out at 80°C for 48 hours. After completion of the reaction, it was cooled to room temperature, the mixture was concentrated, precipitated in acetone, and the precipitate was filtered. The precipitate was dissolved in chloroform, extracted with water to remove K ₂ CO ₃ , and the organic layer was dehydrated with MgSO ₄ . The organic layer was concentrated and precipitated in acetone, and the precipitate was filtered to obtain a gray solid (hereinafter referred to as CP7-PPO). ^1H NMR (300 MHz, CDCl ₃ ) δ _ppm : 8.24-8.02 (m, 3H), 7.784-7.549 (m, 21.6H), 6.917-6.787 (m, 1.4H), 3.392-2.85 (m, 2.8H) ), 2.42-2.075 (m, 2.8H), 1.682-0.816 (m, 11.2H).

[Chemical formula Ad]

Preparation Example 2-8: (CP8-PPO)

CP8 (0.6 mmol) of Preparation Example 1-8 and 4 equivalents of K ₂ CO ₃ were placed in a three-necked round flask, equipped with a reflux device, and purged with argon gas. After adding THF and dissolving CP8, 4 equivalents of PPO compared to CP8 was dissolved in a small amount of DMF and added dropwise to the CP8 solution. The reaction was carried out at 80°C for 48 hours. After completion of the reaction, it was cooled to room temperature, the mixture was concentrated, precipitated in acetone, and the precipitate was filtered. The precipitate was dissolved in chloroform, extracted with water to remove K ₂ CO ₃ , and the organic layer was dehydrated with MgSO ₄ . The organic layer was concentrated and precipitated in acetone, and the precipitate was filtered to obtain a gray solid (hereinafter referred to as CP8-PPO). ^1H NMR (300 MHz, CDCl ₃ ) δ _ppm : 8.17-7.83 (m, 4H), 7.620-7.281 (m, 19H), 6.708-6.627 (m, 1H), 3.45-3.16 (m, 2H), 2.074 -2.02 (m, 2H), 1.672-0.762 (m, 8H).

Preparation Example 2-9: (CP9-PPO)

CP9 (0.4 mmol) of Preparation Example 1-9 and 4 equivalents of K ₂ CO ₃ were placed in a three-necked round flask, equipped with a reflux device, and purged with argon gas. After adding THF and dissolving CP9, 4 equivalents of PPO compared to CP9 was dissolved in a small amount of DMF and added dropwise to the CP9 solution. The reaction was carried out at 80°C for 48 hours. After completion of the reaction, it was cooled to room temperature, the mixture was concentrated, precipitated in acetone, and the precipitate was filtered. The precipitate was dissolved in chloroform, extracted with water to remove K ₂ CO ₃ , and the organic layer was dehydrated with MgSO ₄ . The organic layer was concentrated and precipitated in acetone, and the precipitate was filtered to obtain a gray solid (hereinafter referred to as CP9-PPO). ¹ H NMR (300 MHz, CDCl ₃ ) δ _ppm : 8.07-7.86 (2.4H), 7.57-7.24 (m, 7H), 7.675-7.46 (m, 21.6H), 6.898-6.578 (m, 1.4H), 3.24-2.98 (m, 2.8H), 2.062 (m, 2.8H), 1.72-0.902 (m, 11.2H).

Preparation Example 3: Preparation of a plastic scintillator containing a semiconductor polymer to which a radiation sensitizer is covalently bonded (S300)

The plastic scintillator was made by dissolving the initiator AIBN and CP1-PPO to CP3-PPO prepared in Preparation Example 2 in vinyltoluene and heat-polymerizing it in a sealed Petri dish at 40°C for 72 hours. After cooling to room temperature, the polymerized plastic scintillator was separated from the Petri dish and cut to fit the diameter (2 inches) of the photomultiplier tube. In order to check the radiation detection effect according to the content, the content was manufactured by increasing the content from 0 to 1 wt%, and the plastic scintillator according to the type and content of the semiconductor polymer is shown in [Table 1] below.

semiconductor polymer Content (wt%) Manufacturing Example 3-1 CP1-PPO 0.05 Manufacturing Example 3-2 CP1-PPO 0.1 Manufacturing Example 3-3 CP2-PPO 0.05 Manufacturing Example 3-4 CP2-PPO 0.1 Manufacturing Example 3-5 CP3-PPO 0.05 Manufacturing Example 3-6 CP3-PPO 0.1 Manufacturing Example 3-7 CP4-PPO 0.05 Manufacturing Example 3-8 CP4-PPO 0.1 Manufacturing Example 3-9 CP5-PPO 0.05 Manufacturing Example 3-10 CP5-PPO 0.1 Manufacturing Example 3-11 CP6-PPO 0.05 Manufacturing Example 3-12 CP6-PPO 0.1 Manufacturing Example 3-13 CP7-PPO 0.05 Manufacturing Example 3-14 CP7-PPO 0.1 Manufacturing Example 3-15 CP8-PPO 0.05 Manufacturing Example 3-16 CP8-PPO 0.1 Manufacturing Example 3-17 CP9-PPO 0.05 Manufacturing Example 3-18 CP9-PPO 0.1

[Comparative manufacturing example]

[Comparative Manufacturing Example 1] Manufacturing of plastic scintillator without semiconductor polymer

AIBN, an initiator, was dissolved in vinyltoluene and thermally polymerized in a sealed Petri dish at 40°C for 72 hours. After cooling to room temperature, the polymerized plastic scintillator was separated from the Petri dish and cut to fit the diameter (2 inches) of the photomultiplier tube.

[Comparative Manufacturing Example 2] Manufacturing of a plastic scintillator containing only a photosensitizer

0.1 wt% of PPO and AIBN, an initiator, were dissolved in vinyltoluene and thermally polymerized in a sealed Petri dish at 40°C for 72 hours. After cooling to room temperature, the polymerized plastic scintillator was separated from the Petri dish and cut to fit the diameter (2 inches) of the photomultiplier tube.

[Comparative Preparation Example 3] Preparation of a plastic scintillator containing a semiconductor polymer without the introduction of a photoresist

Any one of the semiconductor polymers CP1 to CP9 prepared in Preparation Example 1 (0.1 wt%) and the initiator AIBN were dissolved in vinyltoluene and thermally polymerized in a sealed Petri dish at 40°C for 72 hours. After cooling to room temperature, the polymerized plastic scintillator was separated from the Petri dish and cut to fit the diameter (2 inches) of the photomultiplier tube. Plastic scintillators manufactured from semiconductor polymers CP1 to CP9 are used in Comparative Preparation Examples 3-1 to 3-9.

[Comparative Manufacturing Example 4] Manufacturing of a plastic scintillator mixed with a photosensitive agent and a semiconductor polymer

Comparative Preparation Example 4-1 : Dissolve the semiconductor polymers CP1 (0.1 wt%) and PPO (0.05 wt%) prepared in Preparation Example 1 and the initiator AIBN in vinyltoluene and thermally polymerize them in a sealed Petri dish at 40°C for 72 hours. did. After cooling to room temperature, the polymerized plastic scintillator was separated from the Petri dish and cut to fit the diameter (2 inches) of the photomultiplier tube.

Comparative Preparation Example 4-2 : Dissolve the semiconductor polymers CP2 (0.1 wt%) and PPO (0.07 wt%) prepared in Preparation Example 1 and the initiator AIBN in vinyltoluene and thermally polymerize them in a sealed Petri dish at 40°C for 72 hours. did. After cooling to room temperature, the polymerized plastic scintillator was separated from the Petri dish and cut to fit the diameter (2 inches) of the photomultiplier tube.

Comparative Preparation Example 4-3 : Dissolve the semiconductor polymers CP3 (0.1 wt%) and PPO (0.1 wt%) prepared in Preparation Example 1 and the initiator AIBN in vinyltoluene and thermally polymerize them in a sealed Petri dish at 40°C for 72 hours. did. After cooling to room temperature, the polymerized plastic scintillator was separated from the Petri dish and cut to fit the diameter (2 inches) of the photomultiplier tube.

Comparative Preparation Example 4-4 : Semiconductor polymers CP4 (0.1 wt%) and PPO (0.1 wt%) prepared in Preparation Example 1 and AIBN, an initiator, were dissolved in vinyltoluene and thermally polymerized in a sealed Petri dish at 40°C for 72 hours. did. After cooling to room temperature, the polymerized plastic scintillator was separated from the Petri dish and cut to fit the diameter (2 inches) of the photomultiplier tube.

Comparative Preparation Example 4-5 : Semiconductor polymers CP5 (0.1 wt%) and PPO (0.1 wt%) prepared in Preparation Example 1 and AIBN, an initiator, were dissolved in vinyltoluene and thermally polymerized in a sealed Petri dish at 40°C for 72 hours. did. After cooling to room temperature, the polymerized plastic scintillator was separated from the Petri dish and cut to fit the diameter (2 inches) of the photomultiplier tube.

Comparative Preparation Example 4-6 : Semiconductor polymers CP6 (0.1 wt%) and PPO (0.1 wt%) prepared in Preparation Example 1 and AIBN, an initiator, were dissolved in vinyltoluene and thermally polymerized in a sealed Petri dish at 40°C for 72 hours. did. After cooling to room temperature, the polymerized plastic scintillator was separated from the Petri dish and cut to fit the diameter (2 inches) of the photomultiplier tube.

Comparative Preparation Example 4-7 : Semiconductor polymers CP7 (0.1 wt%) and PPO (0.1 wt%) prepared in Preparation Example 1 and AIBN, an initiator, were dissolved in vinyltoluene and thermally polymerized in a sealed Petri dish at 40°C for 72 hours. did. After cooling to room temperature, the polymerized plastic scintillator was separated from the Petri dish and cut to fit the diameter (2 inches) of the photomultiplier tube.

Comparative Preparation Example 4-8 : Semiconductor polymers CP8 (0.1 wt%) and PPO (0.1 wt%) prepared in Preparation Example 1 and AIBN, an initiator, were dissolved in vinyltoluene and thermally polymerized in a sealed Petri dish at 40°C for 72 hours. did. After cooling to room temperature, the polymerized plastic scintillator was separated from the Petri dish and cut to fit the diameter (2 inches) of the photomultiplier tube.

Comparative Preparation Example 4-9 : Semiconductor polymers CP9 (0.1 wt%) and PPO (0.1 wt%) prepared in Preparation Example 1 and the initiator AIBN were dissolved in vinyltoluene and thermally polymerized in a sealed Petri dish at 40°C for 72 hours. did. After cooling to room temperature, the polymerized plastic scintillator was separated from the Petri dish and cut to fit the diameter (2 inches) of the photomultiplier tube.

Comparative manufacturing examples used in the present invention are shown in [Table 2] below.

Photosensitizer type Comparative Manufacturing Example 1 - Comparative Manufacturing Example 2 PPO Comparative Manufacturing Example 3-1 CP1 Comparative Manufacturing Example 3-2 CP2 Comparative Manufacturing Example 3-3 CP3 Comparative Manufacturing Example 3-4 CP4 Comparative Manufacturing Example 3-5 CP5 Comparative Manufacturing Example 3-6 CP6 Comparative Manufacturing Example 3-7 CP7 Comparative Manufacturing Example 3-8 CP8 Comparative Manufacturing Example 3-9 CP9 Comparative Manufacturing Example 4-1 CP1 + PPO Comparative Manufacturing Example 4-2 CP2 + PPO Comparative Manufacturing Example 4-3 CP3 + PPO Comparative Manufacturing Example 4-4 CP4 + PPO Comparative Manufacturing Example 4-5 CP5 + PPO Comparative Manufacturing Example 4-6 CP6 + PPO Comparative Manufacturing Example 4-7 CP7 + PPO Comparative Manufacturing Example 4-8 CP8 + PPO Comparative Manufacturing Example 4-9 CP9 + PPO

[Example]

[Example 1]: Sr-90 radiation source detection experiment

The Sr-90 radiation source detection experiment was performed using the device configuration shown in Figure 3, and [Figure 4] shows Comparative Preparation Example 1 (Example 1) at 0 wt% to compare the energy spectrum according to the content of the semiconductor polymer to which the radiation sensitizer is bound. This is the energy spectrum measured using Example 1-1), Preparation Example 3-3 (Example 1-4) at 0.05 wt%, and Preparation Example 3-4 (Example 1-5) at 0.1 wt%. As the content of the semiconductor polymer to which the radiation sensitizer is combined increases, the number of detected photons increases. Through this energy spectrum, the detection efficiency of the plastic scintillator of the comparative and manufacturing examples was calculated using the equation below.

[Equation 1]

Intrinsic efficiency refers to efficiency considering the angle at which radiation spreads. Since the radiation source measured in the example used a Sr-90 or C-14 beta source, it is effective to follow intrinsic efficiency. Absolute efficiency and solid angle are as follows. It can be obtained using Equations 2 and 3.

[Equation 2]

Net counting rate refers to the area of the spectrum obtained by measuring with a radioactivity meter divided by the measurement time, and radioactivity refers to the radioactivity (unit: Bq) at the time of measurement considering the half-life of the radiation source.

[Equation 3]

d is the diameter of the photomultiplier tube, and a is the distance between the radiation source and the photomultiplier tube.

The detection efficiency results of the plastic scintillator according to the present invention are shown in [Table 3] below.

Example Scintillator type Detection efficiency (%) Example 1-1 Comparative Manufacturing Example 1 15.5 Example 1-2 Manufacturing Example 3-1 32.40 Example 1-3 Manufacturing Example 3-2 45.32 Example 1-4 Manufacturing Example 3-3 40.64 Examples 1-5 Manufacturing Example 3-4 50.1 Example 1-6 Manufacturing Example 3-5 41.2 Example 1-7 Manufacturing Example 3-6 48.9 Examples 1-8 Manufacturing Example 3-7 39.3 Example 1-9 Manufacturing Example 3-8 41.5 Examples 1-10 Manufacturing Example 3-9 38.6 Example 1-11 Manufacturing Example 3-10 40.3 Examples 1-12 Manufacturing Example 3-11 37.6 Example 1-13 Manufacturing Example 3-12 41.5 Example 1-14 Manufacturing Example 3-13 40.1 Example 1-15 Manufacturing Example 3-14 44.2 Example 1-16 Manufacturing Example 3-15 41.3 Example 1-17 Manufacturing Example 3-16 43.9 Example 1-18 Manufacturing Example 3-17 38.2 Example 1-19 Manufacturing Example 3-18 40.4

As shown in the results in Table 3, it can be seen that the detection efficiency increases as the content of the semiconductor polymer containing the radiation sensitizer increases, and the efficiency is calculated to be more than 3 times higher than that of Comparative Preparation Example 1.

[Comparative Example 1] Sr-90 radiation source detection experiment

In order to compare the performance of the semiconductor polymer combined with the radiation sensitizer of the present invention, Figure 5 shows Comparative Preparation Example 1 (Comparative Example 1-1) and Comparative Preparation Example 2 (Comparative Example 1), which is a plastic scintillator containing only the radiation sensitizer. Example 1-2), Preparation Example 3-4 (Comparative Example 1-21), which is a plastic scintillator made from a semiconductor polymer to which a radiation sensitizer is bound, a plastic scintillator made from a semiconductor polymer to which a radiation sensitizer is not bound. Measurements using Comparative Preparation Example 3-2 (Comparative Example 1-4) and Comparative Preparation Example 4-2 (Comparative Example 1-13), which is a plastic scintillator in which a semiconductor polymer and a photosensitive agent are mixed without a radiation sensitizer. An energy spectrum is shown. The content was fixed at 0.1 wt%. As shown in [Table 4], it can be seen that the plastic scintillator manufactured in Preparation Example 3-4 (Comparative Example 1-21) of the present invention detects the most photons compared to the Comparative Example at the same content. , the detection efficiency was also calculated to be the highest at 50.5%. In addition, it can be seen that the plastic scintillator manufactured in Preparation Examples 3-10, 3-14, and 3-18 of the present invention also shows equivalent performance.

Comparative Example Scintillator type Detection efficiency (%) Comparative Example 1-1 Comparative Manufacturing Example 1 15.5 Comparative Example 1-2 Comparative Manufacturing Example 2 17.5 Comparative Example 1-3 Comparative Manufacturing Example 3-1 18.7 Comparative Example 1-4 Comparative Manufacturing Example 3-2 20.62 Comparative Examples 1-5 Comparative Manufacturing Example 3-3 19.34 Comparative Example 1-6 Comparative Manufacturing Example 3-4 18.2 Comparative Example 1-7 Comparative Manufacturing Example 3-5 15.3 Comparative Examples 1-8 Comparative Manufacturing Example 3-6 11.3 Comparative Example 1-9 Comparative Manufacturing Example 3-7 16.2 Comparative Examples 1-10 Comparative Manufacturing Example 3-8 20.1 Comparative Example 1-11 Comparative Manufacturing Example 3-9 25.6 Comparative Examples 1-12 Comparative Manufacturing Example 4-1 33 Comparative Examples 1-13 Comparative Manufacturing Example 4-2 35 Comparative Examples 1-14 Comparative Manufacturing Example 4-3 30.3 Comparative Examples 1-15 Comparative Manufacturing Example 4-4 28.2 Comparative Example 1-16 Comparative Manufacturing Example 4-5 24.5 Comparative Example 1-17 Comparative Manufacturing Example 4-6 33.2 Comparative Example 1-18 Comparative Manufacturing Example 4-7 24 Comparative Example 1-19 Comparative Manufacturing Example 4-8 19.9 Comparative Examples 1-20 Comparative Manufacturing Example 4-9 21.3 Comparative Example 1-21 Manufacturing Example 3-4 50.5 Comparative Example 1-22 Manufacturing Example 3-10 40.3 Comparative Example 1-23 Manufacturing Example 3-14 40.1 Comparative Example 1-24 Manufacturing Example 3-18 38.2

[Example 2]: C-14 radiation source detection experiment

The C-14 radiation source detection experiment was performed using the device configuration shown in [FIG. 3], and in order to compare the energy spectrum according to the content of the semiconductor polymer to which the radiation sensitizer was bound, Comparative Preparation Example 1 (Example 2) with 0 wt% and Preparation Example 3-3 (Example 2-4) with 0.05 wt% and Preparation Example 3-4 (Example 2-5) with 0.1 wt% were used. The energy spectrum according to the experiment is shown in [Figure 6], and it can be seen that the number of detected photons increases as the content of the semiconductor polymer combined with the radiation sensitizer increases. The detection efficiency of the plastic scintillator manufactured in the manufacturing example of the present invention is shown in [Table 5] below, and the C-14 radiation source was calculated to have a low detection efficiency because it has less energy than Sr-90. However, as it shows a higher detection efficiency compared to the comparative production example, it is judged to have the ability to detect the C-14 radiation source.

Example Scintillator type Detection efficiency (%) Example 2-1 Comparative Manufacturing Example 1 ^7.71 Example 2-2 Manufacturing Example 3-1 0.026 Example 2-3 Manufacturing Example 3-2 0.032 Example 2-4 Manufacturing Example 3-3 0.049 Example 2-5 Manufacturing Example 3-4 0.056 Example 2-6 Manufacturing Example 3-5 0.044 Example 2-7 Manufacturing Example 3-6 0.052 Example 2-8 Manufacturing Example 3-7 0.022 Example 2-9 Manufacturing Example 3-8 0.042 Example 2-10 Manufacturing Example 3-9 0.032 Example 2-11 Manufacturing Example 3-10 0.051 Example 2-12 Manufacturing Example 3-11 0.028 Example 2-13 Manufacturing Example 3-12 0.044 Example 2-14 Manufacturing Example 3-13 0.038 Example 2-15 Manufacturing Example 3-14 0.048 Example 2-16 Manufacturing Example 3-15 0.031 Example 2-17 Manufacturing Example 3-16 0.041 Example 2-18 Manufacturing Example 3-17 0.044 Example 2-19 Manufacturing Example 3-18 0.047

[Comparative Example 2]: C-14 radiation source detection experiment

In order to compare the performance of the semiconductor polymer combined with the radiation sensitizer of the present invention, Figure 7 shows Comparative Preparation Example 1 (Comparative Example 2-1) and Comparative Preparation Example 2 (Comparative Example 2), which is a plastic scintillator containing only the radiation sensitizer. Example 2-2), Preparation Example 3-4 (Comparative Example 2-21), which is a plastic scintillator made from a semiconductor polymer to which a radiation sensitizer is bound, a plastic scintillator made from a semiconductor polymer to which a radiation sensitizer is not bound. Measured using Preparation Example 3-2 (Comparative Example 2-4) and Comparative Preparation Example 4-2 (Comparative Example 2-13), which is a plastic scintillator in which a semiconductor polymer and a photosensitizer are mixed without a radiation sensitizer. The energy spectrum is shown. The content was fixed at 0.1 wt%. As shown in [Table 6], it can be seen that the plastic scintillator manufactured in Preparation Example 3-4 (Comparative Example 2-21) of the present invention detects the most photons compared to the Comparative Example at the same content. , the detection efficiency was calculated to be the highest at 0.056%, and it can be seen that the plastic scintillator manufactured in Preparation Examples 3-10, 3-14, and 3-18 of the present invention also shows equivalent performance.

Comparative Example Scintillator type Detection efficiency (%) Comparative Example 2-1 Comparative Manufacturing Example 1 ^7.71 Comparative Example 2-2 Comparative Manufacturing Example 2 0.03 Comparative Example 2-3 Comparative Manufacturing Example 3-1 0.019 Comparative Example 2-4 Comparative Manufacturing Example 3-2 0.025 Comparative Example 2-5 Comparative Manufacturing Example 3-3 0.016 Comparative Example 2-6 Comparative Manufacturing Example 3-4 0.023 Comparative Example 2-7 Comparative Manufacturing Example 3-5 0.032 Comparative Example 2-8 Comparative Manufacturing Example 3-6 0.027 Comparative Example 2-9 Comparative Manufacturing Example 3-7 0.03 Comparative Example 2-10 Comparative Manufacturing Example 3-8 0.015 Comparative Example 2-11 Comparative Manufacturing Example 3-9 0.028 Comparative Example 2-12 Comparative Manufacturing Example 4-1 0.032 Comparative Example 2-13 Comparative Manufacturing Example 4-2 0.035 Comparative Example 2-14 Comparative Manufacturing Example 4-3 0.017 Comparative Example 2-15 Comparative Manufacturing Example 4-4 0.028 Comparative Example 2-16 Comparative Manufacturing Example 4-5 0.031 Comparative Example 2-17 Comparative Manufacturing Example 4-6 0.025 Comparative Example 2-18 Comparative Manufacturing Example 4-7 0.023 Comparative Example 2-19 Comparative Manufacturing Example 4-8 0.017 Comparative Example 2-20 Comparative Manufacturing Example 4-9 0.033 Comparative Example 2-21 Manufacturing Example 3-4 0.056 Comparative Example 2-22 Manufacturing Example 3-10 0.051 Comparative Example 2-23 Manufacturing Example 3-14 0.048 Comparative Example 2-24 Manufacturing Example 3-18 0.047

The present invention has been described with reference to the embodiments shown in the drawings, but these are merely exemplary, and those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom. Therefore, the true technical protection scope of the present invention should be determined by the technical spirit of the attached patent claims.

Claims (11)

Organic flash polymer comprising a first repeating unit represented by the following formula (1):
[Formula 1]

In Formula 1 above,
R ₁ is a radiation sensitizer,
R ₂ is an alkyl group having 3 to 10 carbon atoms,
* indicates connection. According to paragraph 1,
The R ₁ is 2,5-diphenyloxazole (PPO) or 1,4-bis (5-phenyloxazol-2-yl) benzene (POPOP), an organic flash polymer. According to paragraph 1,
An organic flash polymer further comprising at least one second repeating unit selected from the group consisting of the following formulas 2a to 2d:
[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

In Formula 2a, R ₃ is an alkyl group having 3 to 10 carbon atoms.
In Formulas 2a to 2d, * indicates a connection portion. According to paragraph 1,
The first repeating unit is an organic flash polymer represented by the following formula (3):
[Formula 3]

In Formula 3 above,
R ₁ is (2,5-diphenyloxazole, PPO) or (1,4-bis(5-phenyloxazol-2-yl)benzene, POPOP),
* indicates connection. According to paragraph 3,
An organic flash polymer comprising at least one repeating unit selected from the group consisting of the following formulas 4 to 7:
[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In Formulas 4 to 7,
R ₄ is 2,5-diphenyloxazole (PPO) or 1,4-bis (5-phenyloxazol-2-yl) benzene (POPOP),
R ₅ and R ₆ are each independently an alkyl group having 3 to 10 carbon atoms,
m ₁ to m ₄ and n ₁ to n ₄ are each independently a rational number of 1 to 15,
m ₁ +n ₁ , m ₂ +n ₂ , m ₃ +n ₃ , m ₄ +n ₄ , and m ₅ +n ₅ are each independently rational numbers of 5 to 30. A composition for a scintillator containing the polymer according to any one of claims 1 to 5. According to clause 6,
A composition for a scintillator further containing a polymerization monomer for a matrix polymer. In clause 7,
The composition for a scintillator, wherein the polymerization monomer for the matrix polymer is at least one polymerization monomer for the matrix polymer selected from the group consisting of polystyrene, polyvinyltoluene, poly(methyl methacrylate), polyacrylate, and polysiloxane. According to clause 6,
A composition for a scintillator further containing an azo-based or diazo-based polymerization initiator. A plastic scintillator comprising the polymer according to any one of claims 1 to 5. According to clause 10,
Plastic scintillator used to detect Sr-89, Sr-90, or C-14 radiation sources.