CN115926074A - Preparation method of lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler - Google Patents
Preparation method of lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler Download PDFInfo
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Abstract
The application provides a preparation method of lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler, which comprises the following steps: preparing hydroxylated boron nitride powder by ball milling boric acid and boron nitride, dispersing the hydroxylated boron nitride powder in an ethanol solution, and adding gamma-mercaptopropyl triethoxysilane to obtain mercapto boron nitride; then adding lead acrylate and an initiator to initiate reaction to obtain lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler; according to the composite material, the boron nitride inorganic filler with the neutron shielding function and the lead acrylate organic filler with the gamma ray shielding function are chemically bonded, so that the interface compatibility between the inorganic filler, the organic filler and a polymer matrix is improved, the dispersion uniformity and the functional filler content of the radiation shielding function filler in the composite material are effectively improved, the radiation shielding performance and the comprehensive mechanical performance of the composite material are improved, and the composite material has a wide application prospect in the field of nuclear radiation protection.
Description
Technical Field
The invention relates to the field of nuclear radiation protection, in particular to a preparation method of lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler.
Background
The nuclear science technology is widely applied to various fields such as national defense, energy, industry, medical treatment and the like, brings great economic and social benefits, and increases the chance of contacting various radiations. The development of radiation protection materials to effectively reduce the harm of radiation to human bodies, equipment and the environment has become an important component of military and civil radiation protection work. Relatively low-price concrete, lead products and the like are widely applied to the protection field of fixed nuclear reactors, accelerators and the like, and play an important role all the time. However, for the occasions with special requirements on weight and volume, such as mobile nuclear power plants, nuclear waste transport and storage containers, space vehicles and the like, the application of the traditional protective materials is limited, and a novel light and efficient radiation protective material is urgently needed.
The polymer-based composite material using the micro powder with the radiation shielding function as the filler has become the research and development direction of novel radiation-proof materials due to the advantages of small density, easy processing and the like. The radiation shielding effect of the polymer-based radiation protection material is closely related to the type, content, dispersibility and the like of the functional filler. The radiation protection effect of the material can be improved by increasing the content of the radiation shielding functional particles, but the mechanical property and the fatigue property of the base material are often influenced when the content of the functional particles is too high, so that the improvement space of the radiation protection effect is limited. Meanwhile, after the micro-nano particles are introduced into a polymer system, a multiphase interface can be generated, including different types such as an organic-organic interface, an inorganic-inorganic interface, an organic-inorganic interface and the like, so that the radiation protection effect and the comprehensive performance are greatly influenced (More C V, alsayed Z, badawi M S, et al, environ Chem Lett, 2021, 19.
The protection mechanism difference of neutrons and gamma rays is large, and for the protection requirement of a mixed radiation field, a plurality of radiation shielding functional elements need to be introduced through optimized design. The natural abundance of isotope B-10 is 19.8%, and the isotope B-10 has a large thermal neutron capture cross section, and boron nitride, boron carbide and the like are widely applied to the neutron shielding field. Lead has a high atomic number and has a good shielding effect on gamma rays. By adopting the traditional physical blending method, the inorganic filler containing boron and the inorganic filler containing lead can be simultaneously introduced into the polymer matrix, and the problem of the interface between the inorganic filler and the polymer matrix needs to be concerned. Chinese patent CN 113072752A discloses a rubber composite material with excellent nuclear protection and flexibility and a preparation method thereof, wherein particles with neutron and gamma ray radiation protection function are introduced into a polymer matrix after being surface modified by a coupling agent, so that the composite material has radiation protection performance and comprehensive use performance; the method can improve the interface between the inorganic filler and the polymer matrix to a certain extent by performing surface modification on the inorganic functional filler, but still has great limitations. The mechanical property and the service behavior of the composite material are influenced due to the poor interface between the inorganic filler and the organic polymer matrix, so that the content of functional elements and the dispersion uniformity are limited, and the radiation shielding property of the composite material is restricted to be improved. Therefore, how to improve the protection performance of the radiation protection material to the mixed radiation field is still a technical problem to be solved in the field.
Disclosure of Invention
In order to meet the protection requirement of a mixed radiation field (neutron and gamma ray radiation), the application provides a preparation method of a lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler, the boron nitride inorganic filler with a neutron shielding function and the lead acrylate organic filler with a gamma ray shielding function are chemically bonded, the interface compatibility between the boron nitride inorganic filler and the lead acrylate organic filler as well as a polymer matrix is improved, the dispersion uniformity and the functional filler content of the radiation shielding functional filler in a composite material are effectively improved, and the radiation shielding performance and the comprehensive mechanical performance of the composite material are improved; the filler simultaneously introduces two radiation shielding functional elements of boron and lead, improves the dispersion uniformity among different functional elements, realizes the balanced protection of a neutron and gamma-ray mixed radiation field, and can improve the mechanical property by introducing the boron nitride nanosheet.
Specifically, the above object is achieved by the following technical solutions:
a preparation method of lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler comprises the following specific steps:
(a) Uniformly mixing boric acid and boron nitride to obtain a ball-milled sample, putting the ball-milled sample into a planetary ball-milling tank, adding grinding balls, preferably selecting the rotation speed of 350 rpm, carrying out ball milling for about 24 hours, and finishing ball milling when the transverse size of the boron nitride in the ball-milled sample is about 100 nm to obtain a ball-milled material; washing the ball-milled material with deionized water, performing suction filtration, repeating the steps until the eluate is neutral, and drying the solid obtained by suction filtration in a forced air drying oven at 80 ℃ to obtain hydroxylated boron nitride powder; in this step, the mass ratio of the grinding balls to the ball-milled sample is preferably 9.
(b) Dispersing the hydroxylated boron nitride powder obtained in the step (a) in an ethanol water solution, performing ultrasonic treatment (450W, 1 h) to uniformly disperse the powder, adding a stirrer, transferring the obtained product to an oil bath pot, adding gamma-mercaptopropyltriethoxysilane, adjusting the pH to 3 by using dilute hydrochloric acid (or acetic acid), continuously stirring and reacting for 24h at the rotation speed of 50 rpm and 30 ℃, washing the product by using deionized water, and drying the product in an oven at 80 ℃ to obtain the mercaptoboron nitride powder for later use; in the step, the volume percentage of the ethanol aqueous solution is preferably 95%, the mass-to-volume ratio of the hydroxylated boron nitride to the ethanol aqueous solution is preferably 1.
(c) Adding absolute ethyl alcohol and acrylic acid into a three-neck flask, putting the three-neck flask into an oil bath kettle preheated to 65 ℃, starting stirring, slowly adding lead oxide powder, heating to 70 ℃, heating and refluxing until the lead oxide is completely dissolved, filtering while the solution is hot, cooling and crystallizing filtrate, performing suction filtration, washing precipitate with deionized water, putting the obtained white solid into an air-blowing drying oven, and drying at 80 ℃ to obtain lead acrylate powder for later use; the volume ratio of the absolute ethyl alcohol and the acrylic acid added in the step is preferably 95;
(d) Dispersing the sulfhydrylation boron nitride prepared in the step (b) and the lead acrylate prepared in the step (c) in absolute ethyl alcohol, transferring a dispersion liquid into a three-neck flask, magnetically stirring and uniformly mixing at the rotating speed of 120rpm, adding an initiator, thermally initiating or photo-initiating a thiol-ene click reaction under the protection of nitrogen, washing a precipitate with hot ethanol, and then placing the precipitate into a forced air drying box to dry at 80 ℃ to obtain the lead acrylate-boron nitride organic-inorganic hybridization radiation shielding functional filler; in the step, the initiator comprises a photoinitiator and a thermal initiator; when a photoinitiator is used, the photoinitiation conditions are preferably magnetic stirring at room temperature while irradiating for 18 h with a portable ultraviolet lamp of 32W and 365 nm; when a thermal initiator is used, the reaction is preferably carried out in a constant-temperature oil bath while magnetically stirring, the reaction temperature is 60 ℃, and the reaction time is 12-24 hours.
Preferably, in the preparation method of the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler, the mass ratio of boric acid to boron nitride in the step (a) is 4.
Preferably, in the preparation method of the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler, the grinding balls used in the step (a) have diameters of 15 mm, 12 mm, 10 mm and 5 mm respectively; the mass ratio of the four grinding balls is preferably 3.
Preferably, in the preparation method of the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler, the silane coupling agent used in the step (b) is gamma-mercaptopropyltriethoxysilane, and the addition amount of the gamma-mercaptopropyltriethoxysilane is 10 wt% of the hydroxylated boron nitride in the dispersion liquid.
Preferably, in the preparation method of the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler, in the step (c), the mass ratio of acrylic acid to lead oxide is 1.5.
Preferably, in the preparation method of the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler, in the step (d), the mass ratio of the mercapto boron nitride to the lead acrylate is 1:1.4.
preferably, in the preparation method of the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler, the photoinitiator used in the step (d) is 2, 2-dimethoxy-2-phenylacetophenone (DMPA), and the thermal initiator is 2, 2-Azobisisobutyronitrile (AIBN); the mass ratio of the initiator to the lead acrylate is 3:1 to 35:1.
the boron nitride inorganic filler with the neutron shielding function and the lead acrylate organic filler with the gamma ray shielding function are chemically bonded but not physically blended, and compared with the existing preparation method, the preparation method has the advantages that: through organic-inorganic hybridization, the interface compatibility among the inorganic filler, the organic filler and the polymer matrix can be improved, the dispersion uniformity and the content of the functional filler of the radiation shielding functional filler in the composite material are effectively improved, and the radiation shielding performance and the comprehensive mechanical performance of the composite material are improved; through organic-inorganic hybridization, a plurality of radiation shielding functional elements can be introduced, the dispersion uniformity among different functional elements is improved, and the balanced protection of a mixed radiation field is realized; the preparation process is simple, adjustable and controllable, the effect is obvious, the dependence on processing equipment is low, the implementation is easy, and the preparation method has wide application prospect in the field of nuclear radiation protection.
Drawings
FIG. 1 is a schematic diagram of the preparation principle of lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler.
FIG. 2 is an infrared spectrum of boron nitride, lead acrylate and lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler prepared in the examples.
FIG. 3 is an elemental distribution diagram of lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler prepared in example 1.
Detailed Description
The present invention will be further described below with reference to examples, in which the starting materials, reagents, instruments and the like are commercially available.
Example 1 preparation method of lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler
(a) Uniformly mixing 20 g of boric acid and 5 g of boron nitride to obtain a ball-milled sample; putting a ball-milled sample into a planetary ball-milling tank, adding grinding balls at the rotation speed of 350 rpm, and finishing ball milling when the transverse size of boron nitride is about 100 nm after ball milling for 24 hours to obtain a ball-milled material; washing the ball-milling material by adopting deionization, and then carrying out suction filtration; washing and filtering for several times until the washing liquid is neutral, and drying the solid obtained by filtering in a forced air drying oven at 80 ℃ to obtain hydroxylated boron nitride powder;
in the embodiment, the mass ratio of the used grinding ball to the ball-milled sample is 9, and the diameters of the grinding balls are 15 mm, 12 mm, 10 mm and 5 mm respectively; the four grinding ball mass ratios are 3.
(b) Dispersing 20 g of hydroxylated boron nitride powder in 200 mL of 95vol% ethanol aqueous solution, and performing ultrasonic treatment (450W, 1 h) to uniformly disperse the hydroxylated boron nitride powder; adding a stirrer, transferring the mixture into an oil bath, adding 2 g of gamma-mercaptopropyltriethoxysilane, adjusting the pH value to 3 by using 0.1 mol/L dilute hydrochloric acid, stirring the mixture for reaction for 24 hours at the rotating speed of 50 rpm at the temperature of 30 ℃, washing the mixture by using deionized water, and drying the washed mixture in an oven at the temperature of 80 ℃ to obtain sulfhydrylation boron nitride powder for later use;
(c) Adding 95 mL of absolute ethyl alcohol and 14 mL of acrylic acid into a three-neck flask, putting the three-neck flask into an oil bath kettle preheated to 65 ℃, starting stirring, slowly adding 22 g of lead oxide powder, heating to 70 ℃, heating and refluxing until the lead oxide is completely dissolved, filtering while hot, cooling and crystallizing filtrate, carrying out suction filtration, taking precipitate for washing, putting the obtained white solid into a forced air drying oven, and drying at 80 ℃ to obtain lead acrylate powder; standby;
(d) Dispersing 0.25 g of the boron nitride hydrosulfide prepared in the step (c) and 3.5 g of the lead acrylate prepared in the step (c) in 75 mL of absolute ethyl alcohol, transferring the dispersion into a three-neck flask, uniformly mixing by magnetic stirring (120 rpm), adding 0.1 g of an initiator AIBN, heating in a constant-temperature oil bath under the protection of nitrogen and magnetic stirring, wherein the reaction temperature is 60 ℃, the reaction time is 12 hours, washing the precipitate with hot ethanol, and drying in a forced air drying oven at 80 ℃ to obtain the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler.
The lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler prepared in the embodiment is used for modifying a silicone rubber composite material (sy 34-3, anhuiming Yisi industry Co., ltd.). The filler content is 40 phr, and the thermal neutron shielding performance is tested by an Am-Be neutron source (moderation) and a He-3 detector, and the gamma ray shielding performance is tested by a Ba-133 source and a NaI detector.
The test result of the shielding performance of the mixed radiation field shows that after the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler is modified, the thermal neutron shielding performance of the silicon rubber-based composite material is improved by 14 percent, and the gamma ray shielding performance is improved by 8 percent.
Example 2
(a) Uniformly mixing 20 g of boric acid and 5 g of boron nitride, putting the mixture into a planetary ball milling tank, adding grinding balls, wherein the mass ratio of the grinding balls to a sample is 9;
(b) Dispersing 20 g of hydroxylated boron nitride powder in 200 mL of 95vol% ethanol solution, performing ultrasonic treatment (450W, 1 h) to uniformly disperse the hydroxylated boron nitride powder, adding a stirrer, transferring the solution into an oil bath pot, adding 2 g of gamma-mercaptopropyltriethoxysilane, adjusting the pH to be =3 by using 0.1 mol/L dilute hydrochloric acid, performing stirring reaction for 24h at the rotation speed of 30 ℃ and 50 rpm, washing the solution by using deionized water, and drying the solution in an oven at the temperature of 80 ℃ to obtain the mercaptoborazonide powder;
(c) Adding 95 mL of absolute ethyl alcohol and 14 mL of acrylic acid into a three-neck flask, putting the three-neck flask into an oil bath kettle preheated to 65 ℃, starting stirring, slowly adding 22 g of lead oxide powder, heating to 70 ℃, heating and refluxing until the lead oxide is completely dissolved, filtering while hot, cooling and crystallizing filtrate, carrying out suction filtration, taking precipitate for washing, and putting the obtained white solid into a forced air drying oven to dry at 80 ℃ to obtain the lead acrylate powder.
(d) Dispersing 0.25 g of sulfhydrylation boron nitride and 3.5 g of lead acrylate in 75 mL of absolute ethyl alcohol, transferring the dispersion liquid into a three-neck flask, stirring and mixing uniformly by magnetic force at the rotating speed of 120rpm, adding 0.4 g of initiator AIBN, heating in a constant-temperature oil bath under the protection of nitrogen and magnetic stirring, controlling the reaction temperature at 60 ℃ and the reaction time at 12 h, washing the precipitate by hot ethanol, and drying in an air-blast drying oven at 80 ℃ to obtain the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler.
The result of the test of the shielding performance of the mixed radiation field (the test method is the same as that of the example 1) shows that the thermal neutron shielding performance of the silicon rubber-based composite material is improved by 13 percent and the gamma ray shielding performance is improved by 10 percent after the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler is modified.
Example 3
(a) Uniformly mixing 20 g of boric acid and 5 g of boron nitride, putting the mixture into a planetary ball milling tank, adding grinding balls, wherein the mass ratio of the grinding balls to a sample is 9;
(b) Dispersing 20 g of hydroxylated boron nitride powder in 200 mL of 95vol% ethanol solution, performing ultrasonic treatment (450W, 1 h) to uniformly disperse the hydroxylated boron nitride powder, adding a stirrer, transferring the mixture into an oil bath pot, adding 2 g of gamma-mercaptopropyltriethoxysilane, adjusting the pH =3 by using 0.1 mol/L dilute hydrochloric acid, performing stirring reaction for 24h at the rotation speed of 30 ℃ and 50 rpm, washing the mixture by using deionized water, and drying the mixture in an oven at the temperature of 80 ℃ to obtain the mercaptoborazonide powder;
(c) Adding 95 mL of absolute ethyl alcohol and 14 mL of acrylic acid into a three-neck flask, putting the three-neck flask into an oil bath kettle preheated to 65 ℃, starting stirring, slowly adding 22 g of lead oxide powder, heating to 70 ℃, heating and refluxing until the lead oxide is completely dissolved, filtering while the mixture is hot, cooling and crystallizing the filtrate, carrying out suction filtration, taking the precipitate for washing, and putting the obtained white solid into a forced air drying oven to dry at 80 ℃ to obtain lead acrylate powder;
(d) Dispersing 0.25 g of sulfhydrylation boron nitride and 3.5 g of lead acrylate in 75 mL of absolute ethyl alcohol, transferring the dispersion into a three-neck flask, uniformly mixing by magnetic stirring, adding 0.4 g of AIBN (initiator), heating by using nitrogen as protective atmosphere and a constant-temperature oil bath at the rotation speed of 120rpm under the condition of magnetic stirring, wherein the reaction temperature is 60 ℃, the reaction time is 24 hours, washing the precipitate by hot ethanol, and drying in a forced air drying oven at 80 ℃ to obtain the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler.
The result of the test of the shielding performance of the mixed radiation field (the test method is the same as that of the example 1) shows that the thermal neutron shielding performance of the silicon rubber-based composite material is improved by 15 percent and the gamma ray shielding performance of the silicon rubber-based composite material is improved by 14 percent after the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler is modified.
Example 4
(a) Uniformly mixing 20 g of boric acid and 5 g of boron nitride, putting the mixture into a planetary ball milling tank, adding grinding balls, wherein the mass ratio of the grinding balls to a sample is 9;
(b) Dispersing 20 g of hydroxylated boron nitride powder in 200 mL of 95vol% ethanol solution, performing ultrasonic treatment (450W, 1 h) to uniformly disperse the hydroxylated boron nitride powder, adding a stirrer, transferring the solution into an oil bath pot, adding 2 g of gamma-mercaptopropyltriethoxysilane, adjusting the pH to be =3 by using 0.1 mol/L dilute hydrochloric acid, continuously stirring the solution at the temperature of 30 ℃ and the rotating speed of 50 rpm for reaction for 24h, washing the solution by using deionized water, and drying the solution in an oven at the temperature of 80 ℃ to obtain the mercaptoborazoned boron nitride powder;
(c) Adding 95 mL of absolute ethyl alcohol and 14 mL of acrylic acid into a three-neck flask, putting the three-neck flask into an oil bath kettle preheated to 65 ℃, starting stirring, slowly adding 22 g of lead oxide powder, heating to 70 ℃, heating and refluxing until the lead oxide is completely dissolved, filtering while hot, cooling and crystallizing filtrate, carrying out suction filtration, taking precipitate for washing, putting the obtained white solid into a forced air drying oven, and drying at 80 ℃ to obtain lead acrylate powder;
(d) Dispersing 0.25 g of mercapto boron nitride and 3.5 g of lead acrylate in 75 mL of absolute ethanol, transferring the dispersion into a three-neck flask, uniformly mixing by magnetic stirring, adding 1.2 g of initiator DMPA, magnetically stirring at room temperature and 120rpm under the protection of nitrogen, simultaneously irradiating for 18 h by using a portable ultraviolet lamp with the wavelength of 32W and 365 nm, washing the precipitate by hot ethanol, and drying in a forced air drying oven at the temperature of 80 ℃ to obtain the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler.
The result of the test of the shielding performance of the mixed radiation field (the test method is the same as that of the example 1) shows that the thermal neutron shielding performance of the silicon rubber-based composite material is improved by 16 percent and the gamma ray shielding performance is improved by 18 percent after the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler is modified.
FIG. 2 is an infrared spectrum of lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler prepared in examples 1-4. Comparing the IR spectra of examples 1, 2, 3, 4 and lead acrylate, it can be seen that the FTIR curves for examples 1, 2, 3, 4 are 1637cm -1 The absorption peaks of unsaturated carbon-carbon double bonds (C = C) in the lead acrylate disappear or the relative intensity is reduced, and the absorption peak is 1418 cm -1 And 1541 cm -1 Still in the form of an acrylate (COO) - ) Has a characteristic peak of symmetric and antisymmetric stretching vibration at 1374 cm -1 And 812 cm -1 Characteristic absorption peaks appear nearby and respectively correspond to an in-plane stretching vibration peak of B-N and an out-of-plane bending vibration peak of B-N-B, and therefore the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler is successfully prepared in examples 1, 2, 3 and 4.
The efficiency of the bonding hybridization is related to the preparation conditions. Comparing example 1 with example 2, the FTIR curve of example 1 is 1637cm -1 Processing propyleneThe absorption peak of unsaturated carbon-carbon double bond (C = C) in the lead acrylate only shows a relative strength reduction, and a small amount of lead acrylate still exists, which indicates that the boron nitride and the lead acrylate are not completely bonded. Compared with examples 2 and 3, the reaction time in example 2 is relatively short, and the FTIR curve of example 2 has more peaks and relatively weak intensity of characteristic peaks. Comparing example 3 with example 4, it can be seen that both thermal initiation and photo initiation can successfully prepare the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler.
FIG. 3 is an elemental distribution diagram of lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler prepared in example 1. In FIG. 3, A is the SEM detection result, B is the Pb-MA distribution result, and C is the N-KA distribution result, it can be seen that the lead acrylate and the boron nitride are effectively hybridized, and the lead element from the lead acrylate and the nitrogen element from the boron nitride are uniformly distributed in the hybrid filler.
The above examples show that the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler can be successfully prepared by grafting hydroxyl on the surface of boron nitride by adopting a boric acid-assisted ball milling process, carrying out sulfhydrylation modification on the boron nitride by using a silane coupling agent, and reacting the boron nitride containing a sulfydryl group with lead acrylate having a double bond structure by using a thiol-ene click reaction principle, wherein the preparation mechanism is shown in fig. 1. The boron nitride inorganic filler with the neutron shielding function and the lead acrylate organic filler with the gamma ray shielding function are chemically bonded, so that the interface compatibility between the inorganic filler and the organic filler and between the inorganic filler and a polymer matrix can be improved, the dispersion uniformity and the functional filler content of the filler with the radiation shielding function in the composite material can be effectively improved, various radiation shielding functional elements can be introduced, the dispersion uniformity of different functional elements can be improved, and the improvement of the radiation shielding performance and the comprehensive mechanical performance of the composite material and the balanced protection of a mixed radiation field can be realized. The preparation process is simple, adjustable and controllable, has obvious effect, is easy to realize, and has wide application prospect in the field of nuclear radiation protection.
The above embodiments are not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention do not depart from the content of the technical solution of the present invention, and all fall within the scope of the technical solution of the present invention.
Claims (9)
1. A preparation method of lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler is characterized by comprising the following specific steps:
(a) Mixing boric acid and boron nitride according to a mass ratio of 4; then washing with deionized water, carrying out suction filtration until the eluate is neutral, and drying the solid obtained by suction filtration to obtain hydroxylated boron nitride;
(b) Dispersing hydroxylated boron nitride in an ethanol water solution, performing ultrasonic dispersion, adding gamma-mercaptopropyltriethoxysilane, adjusting the pH to 3, stirring at 30 ℃ for reaction for 24 hours, washing, and drying to obtain mercaptolated boron nitride;
(c) Dispersing sulfhydrylation boron nitride and lead acrylate in absolute ethyl alcohol, adding an initiator, reacting in a nitrogen atmosphere, washing and drying a precipitate obtained by the reaction, and thus obtaining the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler;
the initiator used includes photoinitiators and thermal initiators; when a photoinitiator is used, the reaction conditions are: irradiating for 18 h by an ultraviolet lamp with the wavelength of 32W and 365 nm at room temperature; when a thermal initiator is used, the reaction conditions are: 60. heating to react at the temperature of 12-24 h.
2. The preparation method of the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler according to claim 1, wherein in the step (a), the mass ratio of the grinding balls to the ball-milled samples is 9.
3. The preparation method of the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler according to claim 1, wherein the addition amount of the gamma-mercaptopropyltriethoxysilane in the step (b) is 10% of the mass of the hydroxylated boron nitride.
4. The method for preparing the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler according to claim 1, wherein the volume concentration of the ethanol aqueous solution in the step (b) is 95%.
5. The method for preparing the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler according to claim 1, wherein the lead acrylate in the step (c) is obtained by the following method: uniformly mixing absolute ethyl alcohol and acrylic acid, stirring at 65 ℃, adding lead oxide, heating to 70 ℃, heating and refluxing until the lead oxide is completely dissolved, filtering, cooling and crystallizing filtrate, and filtering, taking precipitate, washing and drying to obtain the lead acrylate; the mass ratio of the added acrylic acid to the added lead oxide is 1.5.
6. The preparation method of the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler according to claim 1, wherein the mass ratio of the mercapto boron nitride added in the step (c) to the lead acrylate is 1:1.4.
7. the method for preparing the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler according to claim 1, wherein in the step (c), the mass ratio of the added initiator to the lead acrylate is 3:1 to 35:1.
8. the method for preparing the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler according to claim 1, wherein in the step (c), the photoinitiator is 2, 2-dimethoxy-2-phenylacetophenone, and the thermal initiator is 2, 2-azobisisobutyronitrile.
9. The preparation method of the lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler according to claim 2, wherein the grinding balls used in step (a) have diameters of 15 mm, 12 mm, 10 mm and 5 mm, and the mass ratio of the grinding balls is 3.
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