CN111286033B - Grafted polysilane scintillator and preparation method thereof - Google Patents

Grafted polysilane scintillator and preparation method thereof Download PDF

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CN111286033B
CN111286033B CN202010086384.9A CN202010086384A CN111286033B CN 111286033 B CN111286033 B CN 111286033B CN 202010086384 A CN202010086384 A CN 202010086384A CN 111286033 B CN111286033 B CN 111286033B
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scintillator
scintillation
backbone
polysilane
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CN111286033A (en
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浦文婧
芦伟
宋佑新
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Hefei Gaite Environmental Protection Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/16—Measuring radiation intensity
    • G01T1/20—Measuring radiation intensity with scintillation detectors
    • G01T1/202—Measuring radiation intensity with scintillation detectors the detector being a crystal
    • G01T1/2023—Selection of materials

Abstract

The invention relates to a grafted polysilane scintillator and a preparation method thereof, belonging to the technical field of advanced nuclear technology application and environmental protection. The polysilane scintillator prepared by taking the Polymethylsilane (PMS) and the reagent containing the scintillation group as raw materials and grafting the reactant containing the scintillation group onto a Polymethylsilane (PMS) molecular chain has the advantages of both an organic crystal scintillator and a plastic scintillator, and has stronger degradation resistance and stronger environmental adaptability under the conditions of high temperature and radiation.

Description

Grafted polysilane scintillator and preparation method thereof
Technical Field
The invention relates to a grafted polysilane scintillator and a preparation method thereof, belonging to the field of advanced nuclear technology application and environmental protection research.
Background
Tritium, as a radioactive isotope of hydrogen, is mainly derived from nuclear facilities such as heavy water reactors, fusion reactors, tritium process research facilities, fuel post-processing plants and the like, and the most important application thereof is fusion reaction with deuterium. However, tritium environmental monitoring is becoming increasingly important because tritium is radioactive and is very easily absorbed by organisms, which can be harmful to human health if leaked into the environment. Tritium contamination needs to be monitored on surfaces such as instruments, floors, walls, and work clothes in factories where tritium is produced, operated, and stored, and in experimental facilities.
Tritium undergoes mainly beta decay, and the content of tritium can be detected by detecting decay electrons. At present, a tritium measuring instrument mainly comprises a counter, an amplifier, a signal acquisition module, a main module, peripheral equipment and the like. The counter detects beta rays emitted by tritium, converts the beta rays into electric signals, amplifies the electric signals through the amplifier, and obtains the content of the tritium after counting, storage and processing through the main module. The detectability and sensitivity of the counter depends on the scintillator properties therein. Scintillators are materials capable of emitting light after absorbing high-energy particles or rays, and play an important role in the field of radiation detection. Because the average energy of decay electrons emitted by tritium is only 5.7keV, the half-life period is 12.43 years, and the number of unit decay electrons is low, a windowless or thin-window counter with high sensitivity is needed for directly measuring tritium, and a scintillator in the counter is required to have low excitation energy, wide energy spectrum range, high luminous efficiency, high stability and easy processing into various shapes.
The plastic scintillators with widely used polystyrene and methyl polystyrene as substrates have good radiation resistance, high transparency, good light transmission performance and high mechanical strength, but have the problems of durability and environmental adaptability. Such as: peroxide generated in the thermal oxidation process absorbs light emitted by the scintillator; cracks are generated due to mechanical degradation caused by chemical stress, thereby deteriorating light transmission properties; the reduction in scintillator molecular weight leads to surface and internal defects, yellowing, dullness, cracking, and the like. Therefore, there is an urgent need to develop a new polymer scintillator system, which has a higher environmental adaptability and an improved degradation resistance under high temperature and radiation conditions, while having a higher luminous efficiency.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a grafted polysilane scintillator and a method for preparing the same, which are used to solve the technical problems of poor durability and environmental applicability of the existing plastic scintillators.
The invention aims to be realized by the following technical scheme:
in a first aspect, the present invention discloses a grafted polysilane scintillator, wherein the scintillator has a chemical structure represented by formula i:
Figure BDA0002382196560000021
wherein L is1The graft substitution rate x is 0-0.8, L2The graft substitution rate y is 0 to 0.16, and the degree of polymerization n is 18 to 23.
A first scintillating group L1The matrix of the (C) is 2-3 oxazole rings or benzene rings connected by single bonds,
second scintillation group L2The parent of (a) is 4-5 oxazole rings or benzene rings connected by single bonds.
Further, the main chain of the grafted silane type scintillator is formed by connecting Si-Si single bonds, and each chain link is provided with a methyl (-CH)3) And one hydrogen (-H); a portion of the hydrogens (-H) on the grafted polysilane scintillator can be replaced by the first scintillator group L1And/or a second scintillation group L2And (4) graft substitution.
The first scintillating group L1The precursor of (A) being directly linked to the Si-Si backbone or via the-O-, carbonyl group, -CH2-CH2-linked to a Si-Si backbone; the second scintillator L2The precursor of (A) being directly linked to the Si-Si backbone or via the-O-, carbonyl group, -CH2-CH2-linked to a Si-Si backbone.
Preferably, the first scintillating group L1Is prepared from a parent body of
Figure BDA0002382196560000031
Figure BDA0002382196560000032
One or more of the above;
second scintillation group L2Is prepared from a parent body of
Figure BDA0002382196560000033
Figure BDA0002382196560000034
One or more of them.
In particular, the first scintillating group L1Is prepared from a parent body of
Figure BDA0002382196560000035
When attached to the Si-Si backbone directly or through the-O-, carbonyl, -CH2-CH2The products attached to the Si-Si backbone are respectively:
Figure BDA0002382196560000036
the first scintillating group L1Is prepared from a parent body of
Figure BDA0002382196560000037
When attached to the Si-Si backbone directly or through the-O-, carbonyl, -CH2-CH2The products attached to the Si-Si backbone are respectively:
Figure BDA0002382196560000038
Figure BDA0002382196560000041
the first scintillating group L1Is prepared from a parent body of
Figure BDA0002382196560000042
When attached to the Si-Si backbone directly or through the-O-, carbonyl, -CH2-CH2The products attached to the Si-Si backbone are respectively:
Figure BDA0002382196560000043
Figure BDA0002382196560000044
the first scintillating group L1Is prepared from a parent body of
Figure BDA0002382196560000045
When attached to the Si-Si backbone directly or through the-O-, carbonyl, -CH2-CH2The products attached to the Si-Si backbone are respectively:
Figure BDA0002382196560000046
Figure BDA0002382196560000047
the first scintillating group L1Is prepared from a parent body of
Figure BDA0002382196560000048
When attached to the Si-Si backbone directly or through the-O-, carbonyl, -CH2-CH2The products attached to the Si-Si backbone are respectively:
Figure BDA0002382196560000049
Figure BDA00023821965600000410
in particular, a second scintillation group L2Is prepared from a parent body of
Figure BDA00023821965600000411
When it is attached directly to the Si-Si backbone or through the-O-, carbonyl, -CH2-CH2The products attached to the Si-Si backbone are respectively:
Figure BDA0002382196560000051
the second scintillation group L2Is prepared from a parent body of
Figure BDA0002382196560000052
When it is attached directly to the Si-Si backbone or through the-O-, carbonyl, -CH2-CH2The products attached to the Si-Si backbone are respectively:
Figure BDA0002382196560000053
in a second aspect, the present invention provides a method for preparing the scintillator according to the first aspect, comprising the steps of:
s1, drying the raw material Polymethylsilane (PMS) and a reagent containing a scintillation group;
s2, grafting the reactant containing the scintillation group to a polymethyl silane (PMS) molecular chain through a Si-H nucleophilic substitution reaction or an addition reaction;
s3, adopting a solvent settling-dissolving method for 2-5 times in the product purification process.
In particular, the scintillation group is divided into a first scintillation group L1And a second scintillation group L2A first scintillating group L1Is prepared from a parent body of
Figure BDA0002382196560000054
Figure BDA0002382196560000055
One or more of the above;
second scintillation group L2Is prepared from a parent body of
Figure BDA0002382196560000056
Figure BDA0002382196560000061
One or more of, a scintillating group L1And L2Are each directly linked to the Si-Si backbone or via-O-, carbonyl, -CH2-CH2-linked to a Si-Si backbone.
Further, the scintillation group L1And L2The chemical structure of the direct connection of the parent body and the Si-Si main chain is obtained by adopting the nucleophilic substitution reaction of a corresponding Grignard reagent and Si-H;
the scintillation group L1And L2The precursor of (A) being linked to the Si-Si main chain via a carbonyl groupThe structure is obtained by nucleophilic substitution of corresponding acyl chloride and Si-H;
the scintillation group L1And L2The structure of the precursor and the Si-Si main chain which are connected through oxygen atoms is obtained by nucleophilic substitution reaction of-OH and Si-H under the catalysis of chloroplatinic acid;
the scintillation group L1And L2The precursor of (A) and the Si-Si main chain are connected through an ethylene group-CH2-CH2-the linked structure is obtained by hydrosilylation of a vinyl group.
Further, in the step S3, the product purification process adopts a multiple solvent dissolution-sedimentation method, the crude product is completely dissolved in the solvent, and then the sedimentation agent is added to the solvent solution containing the crude product to obtain a purified precipitated product;
and washing the precipitate product with absolute ethyl alcohol, and performing multiple dissolving-settling-washing processes to obtain the purified grafted polysilane.
Preferably, the solvent is a nonpolar solvent, and comprises one or more of n-hexane, toluene or tetrahydrofuran.
Preferably, the settling agent is a strong polar solvent, and comprises one or more of methanol, dimethyl sulfoxide or acetonitrile.
Advantageous effects
Compared with the prior art, the invention has the following beneficial effects:
(1) the main chain of the polysilane is completely composed of Si-Si, and Si atoms are connected with each other by sigma bonds. Because the radius of the Si atom is large and an empty 3d orbit exists, when the main chain electron is excited, the main chain electron is easy to jump to the 3d orbit, and the electron on the main chain electron can be widely delocalized along the Si-Si main chain of the molecule, so that the sigma conjugate effect similar to the large pi conjugate effect is obtained, and the organic scintillator has unique optical and electrical properties and can be used as a novel organic scintillator. Firstly, polysilane has a light-emitting mechanism superior to that of an organic crystal scintillator, the energy level difference of Si-Si bonds sigma → sigma is slightly larger than that of pi → pi, the average energy of beta rays released by tritium decay is 1.5-4.5 times of that of pi → pi transition, so that the electronic energy level difference of sigma → sigma transition is more matched, and in addition, the polysilane material has short light-emitting relaxation time, basically does not generate phosphorescence and is favorable for counting optical quanta. Secondly, polysilanes have excellent mechanical and processing properties similar to plastic scintillators. The polysilane is a linear long-chain polymer and has excellent flexibility and ductility, and some polysilanes also have good solubility and film-forming property and excellent processability. In addition, the polysilane has excellent acid resistance, alkali resistance, corrosion resistance and oxidation resistance, the polysilane without active groups has good chemical stability, high temperature resistance and radiation resistance, and the general polysilane can be decomposed at 400 ℃, so that the polysilane can be made into materials with various shapes and volumes and is also suitable for various application occasions and conditions. The modified polysilane is used as a scintillator material, and can provide effective tritium detection technical support for the operation of future fusion demonstration reactors and commercial reactors.
(2) The invention adopts modified polysilane as the scintillator material, utilizes the delocalization characteristic of a polymer chain to enable the luminescence waveband of the material to be adjustable, simplifies the inherent states of a liquid scintillator and a common polystyrene-based plastic scintillator with multiple components (a first scintillator and a second scintillator), changes the forbidden bandwidth of the scintillator by adjusting the types and the number of substituents on a Si-Si main chain, enables the scintillator to be adapted to a tritium beta decay energy spectrum, and improves the luminescence efficiency.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 shows the preparation of the grafted polysilane scintillator PPO-PMS provided in example 11H-NMR spectrum;
FIG. 2 is a diagram of an ultraviolet absorption spectrum of the grafted polysilane scintillator PPO-PMS provided in example 1;
FIG. 3 is a graph showing the change of infrared spectrum of the grafted polysilane scintillator PPO-PMS provided in example 1;
FIG. 4 is a plot of the Si-H content of the grafted polysilane scintillator PPO-PMS provided in example 1 as a function of time;
FIG. 5 is an electron fluorescence spectrum of the grafted polysilane scintillator PPO-PMS provided in example 1;
FIG. 6 shows the grafted polysilane scintillator POPOPOP-PMS provided in example 21H-NMR spectrum;
FIG. 7 is a graph of the UV absorption spectrum of the grafted polysilane scintillator POPOPOP-PMS provided in example 2;
FIG. 8 is a graph of the infrared absorption spectrum of the grafted polysilane scintillator POPOPOP-PMS provided in example 2 as a function of exposure time;
FIG. 9 is a fluorescence spectrum of the grafted polysilane scintillator POPOPOP-PMS provided in example 2;
FIG. 10 is a comparison photograph of the natural light and fluorescence of the grafted polysilane scintillator film provided in example 2.
Detailed Description
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and together with the description, serve to explain the principles of the invention and not to limit the scope of the invention.
Example 1
A grafted polysilane scintillator PPO-PMS, the chemical structural formula of the scintillator is represented by formula I:
Figure BDA0002382196560000091
wherein L is1Has the structural formula
Figure BDA0002382196560000092
The graft substitution rate x is 0.32, L2The graft substitution rate y of (a) is 0, and the degree of polymerization n is 18 to 23.
The preparation method of the grafted polysilane scintillator PPO-PMS comprises the following steps:
s1, drying the raw materials of Polymethylsilane (PMS) and p-phenylphenol;
specifically, Polymethylsilane (PMS) and p-phenylphenol are used as raw materials, and a sodium reflux method is adopted in a toluene solvent for drying the PMS; the solvent anhydrous tetrahydrofuran is prepared by adopting a sodium reflux method; synthetic reagents and other solvents used
Figure BDA0002382196560000093
Drying the molecular sieve to obtain residual water<20ppm。
S2, grafting p-phenylphenol to a Polymethylsilane (PMS) molecular chain through a Si-H nucleophilic substitution reaction;
specifically, under the anhydrous and anaerobic conditions, p-phenylphenol and PMS are subjected to nucleophilic substitution reaction of-OH and Si-H in a tetrahydrofuran solvent under the catalysis of chloroplatinic acid to prepare a crude PPO-PMS product.
S3, the product purification process adopts a solvent sedimentation-dissolution method for multiple times, and the process is repeated for 3 times.
The method comprises the following substeps:
s31, dissolving the crude product in a mixed nonpolar solution composed of n-hexane and toluene according to the volume ratio of 1: 1; s32, dropwise adding a polar solvent (namely settling agent) methanol into the nonpolar solution of the crude product, so that the solubility of the grafted polysilane is reduced and the grafted polysilane is settled; and S33, washing the precipitate with absolute ethyl alcohol, and then performing the dissolving-settling-washing process again to finally obtain the purified grafted polysilane scintillator PPO-PMS.
S4, performance detection
And respectively performing nuclear magnetism characterization, infrared spectrum, ultraviolet spectrum, fluorescence spectrum, molecular weight determination and antioxidant infrared analysis and test on the synthesized grafted polysilane scintillator PPO-PMS.
(1) Nuclear magnetic characterization of grafted polysilane scintillator PPO-PMS
Method for grafting polysilane scintillator PPO-PMS1The H-NMR spectrum is shown in FIG. 1, which shows that the scintillation group has been successfully attached to the Si-Si long chain: wherein 0 to 0.9ppm is attributed to Si-CH3A proton peak of 3.3 to 3.6ppm is attributed to the polysilane main chainAnd Si-H far away from the scintillation group is moved to a low field under the influence of the conjugated charge absorption effect, so that the proton peak of ArO-Si-H appears at 4.8ppm, and the peak of 7.4-8.0 ppm is the proton peak on the biphenyl ring.
(2) Ultraviolet absorption spectrum of grafted polysilane scintillator PPO-PMS
The ultraviolet absorption spectrum of PPO-PMS is shown in FIG. 2, and it can be seen from the figure that the ultraviolet absorption spectrum shows two peaks, wherein the absorption peak caused by the sigma-sigma transition of electrons near 220nm represents the conjugated ultraviolet absorption of the Si-Si main chain, and the peak of the high wave band is near 260nm, is the absorption peak caused by the pi-sigma (pi-sigma) transition of electrons represents the conjugated ultraviolet absorption of the side group and the main chain.
(3) Infrared spectral change of PPO-PMS (Poly-p-phenylene oxide-Poly-siloxane) grafted polysilane scintillator and Si-H content-time condition
The scintillator oxidation resistance was evaluated by the amount of change in infrared spectrum with the exposure time in air. FIG. 3 is an infrared spectrum of PPO-PMS taken in an air atmosphere for 42 hours, and it can be observed that the Si-H bond is 2160cm at 0 hour-1And 2100cm-1There are also obvious splitting peaks corresponding to Si-H (2160 cm) adjacent to p-phenylphenoxy substituent-1) And Si-H (2100 cm) remote from the bulky substituent-1). 2100cm with large selection variation-1Peaks were compared to 1250cm in the spectrum-1Wherein represents Si-CH3The peak height of the standard peak is defined as a reference peak, and 2100cm in a spectrogram at 0h is defined after the spectrogram is normalized-1The peak height was 100%, and a curve showing the change of Si-H content in PPO-PMS with oxidation time was obtained, as shown in FIG. 4. As can be seen from FIG. 4, the (Si-H)% change amplitude of PPO-PMS is about 20%, which indicates that PPO-PMS shows higher protection capability to Si-H bond and has stronger oxidation resistance due to more obvious side steric hindrance effect.
(4) Electronic fluorescence spectrum of grafted polysilane scintillator PPO-PMS
And (3) dissolving the purified grafted polysilane scintillator PPO-PMS in tetrahydrofuran, preparing a polymer film on a glass substrate by adopting a spin-coating method, and testing the solubility and the film-forming property. The fluorescence intensity and efficiency of the material were evaluated using electron irradiation with an average kinetic energy of 5.7KeV to simulate the actual environment of beta decay.
The electron fluorescence spectrum of the PPO-PMS scintillator is shown in FIG. 5. Compared with the conventional liquid flash, the PPO-PMS has obvious red shift, improves the fluorescence emission intensity by nearly 3 orders of magnitude and has the fluorescence efficiency of more than 90 percent. The method is favorable for absorbing 5.7keV electron energy generated by tritium decay, efficiently converts the electron energy into fluorescence photons, and improves the sensitivity of the scintillation counter.
Example 2
A grafted polysilane scintillator POPOPOP-PMS, wherein POPOPOP scintillation groups are directly connected with a Si-Si main chain, and the chemical structural formula of the scintillator is represented by a formula I:
Figure BDA0002382196560000111
wherein L is1The graft substitution rate x of (A) is 0, L2Has the structural formula
Figure BDA0002382196560000112
The graft substitution rate y is 0.12, and the polymerization degree n is 18-23. The specific synthetic process is as follows:
s1 preparation of raw materials
Polymethyl silane (PMS) and 1- (5-phenyl-2-oxazolyl) -4- (5- (4-bromophenyl) -2-oxazolyl) benzene are used as raw materials; drying PMS in toluene solvent by sodium reflux method; the solvent anhydrous tetrahydrofuran is prepared by adopting a sodium reflux method; synthetic reagents and other solvents used
Figure BDA0002382196560000123
Drying the molecular sieve to obtain residual water<20ppm。
S2 grafting reaction
The chemical structure of the direct connection of the scintillation group and the Si-Si main chain is obtained by adopting the nucleophilic substitution reaction of a corresponding Grignard reagent and Si-H. Specifically, under the anhydrous and oxygen-free conditions, 1- (5-phenyl-2-oxazolyl) -4- (5- (4-bromophenyl) -2-oxazolyl) benzene and magnesium powder in a tetrahydrofuran medium generate a Grignard reagent, and the Grignard reagent and Si-H undergo nucleophilic substitution reaction, and the synthesis reaction equation is shown as a formula III.
POPOP-PMS：
Figure BDA0002382196560000121
Figure BDA0002382196560000122
S3 sample purification
The product purification process was repeated 3 times using multiple solvent precipitation-dissolution.
The method comprises the following substeps:
s31, dissolving the crude product in n-hexane in a nonpolar solvent; s32, adding a polar solvent acetonitrile into the nonpolar solution of the crude product to reduce the solubility of the grafted polysilane and cause sedimentation; and S33, washing the precipitate with absolute ethyl alcohol, and then performing the dissolving-settling-washing process again to finally obtain the purified grafted polysilane POPOPOPOPOP-PMS.
S4, performance detection
And performing nuclear magnetism characterization, infrared spectrum, ultraviolet spectrum, fluorescence spectrum, molecular weight determination and antioxidant infrared analysis and test on the synthesized material. The following is the performance detection condition of the grafted polysilane scintillator POPOPOP-PMS:
(1) nuclear magnetic characterization of grafted polysilane scintillator POPOPOP-PMS
The nuclear magnetic spectrum of POPOPOP-PMS is shown in figure 6, and the spectrum shows that POPOPOP groups are successfully connected to a Si-Si main chain: wherein the most representative main chain Si-CH is in the range of 0-0.7 ppm3The proton peaks of the two-dimensional structure are in one-to-one correspondence, and Si-CH in the spectrograms of several products is set3The peak area of the proton peak was 1, and normalization was performed. The position of Si-H shifts due to the effect of conjugation of the scintillation side group, and a peak ascribed to the remaining Si-H appears at 4.6 ppm. And 7.8-8.8 ppm of the scintillation side group has three peaks corresponding to proton peaks on a benzene ring and an oxazole ring on the scintillation side group.
(2) Ultraviolet absorption of grafted polysilane scintillator POPOPOP-PMS
The ultraviolet absorption spectrum of the POPOPOP-PMS scintillator is shown in figure 7, and as can be seen from figure 7, the POPOPOP-PMS has two absorption peaks at 260nm and 360nm, the two absorption peaks are respectively attributed to sigma-delta transition of electrons at a Si-Si main chain and pi-delta transition of a POPOP scintillation group, and the peak at the middle 250-360 nm represents n-sigma-delta or pi-sigma-delta transition of electrons, so that mutual influence of the silicon main chain and a scintillation side group is reflected.
(3) Infrared absorption of grafted polysilane scintillator POPOPOPOP-PMS
The change of the infrared absorption spectrum of the POPOPOP-PMS scintillator along with the exposure time is shown in figure 8, and the oxidation resistance of the POPOPOP-PMS scintillator is evaluated by the change of the infrared spectrum along with the exposure time in the air; 2100-2200 cm in FIG. 8-1The higher the intensity of the corresponding Si-H peak is, the higher the content of Si-H bonds in the product is, the height of the Si-H peak in the spectrogram of 0-42H in the graph of FIG. 8 is not changed, and the Si-H content cannot be reduced along with the increase of the exposure time in the air, which shows that the POPOP-PMS has strong oxidation resistance and high stability in the air.
(4) Fluorescence spectrum and fluorescence photograph of grafted polysilane scintillator POPOPOPOP-PMS
The fluorescence spectrum and efficiency of the material are evaluated by simulating a beta decay actual environment through electron irradiation with the average kinetic energy of 5.7keV, the maximum fluorescence emission wavelength of the POPOPOP grafted polysilane scintillator is 400-470 nm, the fluorescence efficiency is 0.93, and the POPOPOP grafted polysilane scintillator is located in a visible light section, as shown in FIG. 9. The polymer film prepared by spin coating method on the glass substrate has good solubility and film forming property, and shows bright fluorescence under electron irradiation, as shown in FIG. 10.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (7)

1. A grafted polysilane scintillator having the chemical structure represented by formula i:
Figure FDA0003345992480000011
wherein the graft substitution rate x is 0.32, and the graft substitution rate y is 0; or the graft substitution rate x is 0, the graft substitution rate y is 0.12, the polymerization degree n is 18-23,
a first scintillating group L1Is prepared from a parent body of
Figure FDA0003345992480000012
Second scintillation group L2Is prepared from a parent body of
Figure FDA0003345992480000013
The first scintillating group L1The precursor of (A) being directly linked to the Si-Si backbone or via the-O-, carbonyl group, -CH2-CH2-linked to a Si-Si backbone; the second scintillator L2The precursor of (A) being directly linked to the Si-Si backbone or via the-O-, carbonyl group, -CH2-CH2-linked to a Si-Si backbone.
2. A method of preparing the grafted polysilane scintillator of claim 1, comprising the steps of:
s1, drying the raw material polymethylsilane and the reagent containing the scintillation group;
s2, grafting the reactant containing the scintillation group to the molecular chain of the polymethylsilane through Si-H nucleophilic substitution reaction or addition reaction;
s3, adopting a solvent settling-dissolving method for 2-5 times in the product purification process.
3. The method of claim 2, wherein the scintillating group is divided into a first scintillating group L1And a second scintillation group L2A first scintillating group L1Is prepared from a parent body of
Figure FDA0003345992480000021
Second scintillation group L2Is prepared from a parent body of
Figure FDA0003345992480000022
Scintillation group L1And L2Are each directly linked to the Si-Si backbone or via-O-, carbonyl, -CH2-CH2-linked to a Si-Si backbone.
4. The method of claim 3,
the scintillation group L1And L2The chemical structure of the direct connection of the parent body and the Si-Si main chain is obtained by adopting the nucleophilic substitution reaction of a corresponding Grignard reagent and Si-H;
the scintillation group L1And L2The parent body of the silicon-based material is connected with a Si-Si main chain through a carbonyl group, and the structure is obtained by nucleophilic substitution of corresponding acyl chloride and Si-H;
the scintillation group L1And L2The structure of the precursor and the Si-Si main chain which are connected through oxygen atoms is obtained by nucleophilic substitution reaction of-OH and Si-H under the catalysis of chloroplatinic acid;
the scintillation group L1And L2The precursor of (A) and the Si-Si main chain are connected through an ethylene group-CH2-CH2-the linked structure is obtained by hydrosilylation of a vinyl group.
5. The method of any of claims 3-4,
in the step S3, the product purification process adopts a multiple solvent dissolution-precipitation method, the crude product is completely dissolved in the solvent, and then the precipitation agent is added to the solvent solution containing the crude product to obtain a purified precipitation product;
and washing the precipitate product with absolute ethyl alcohol, and performing multiple dissolving-settling-washing processes to obtain the purified grafted polysilane.
6. The method of claim 5, wherein the solvent is a non-polar solvent comprising one or more of n-hexane, toluene, or tetrahydrofuran.
7. The method of claim 6, wherein the settling agent is a strongly polar solvent comprising one or more of methanol, dimethyl sulfoxide, or acetonitrile.
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