CN115850916B - Wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material and preparation method thereof - Google Patents
Wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material and a preparation method thereof, and belongs to the technical field of composite materials. The neutron shielding composite material comprises trifunctional epoxy resin, tetrafunctional epoxy resin, aliphatic acid anhydride, aromatic dianhydride, phthalic anhydride, a thermal neutron absorber, a toughening agent, a dispersing agent, a defoaming agent, a thixotropic agent and an accelerator. The neutron shielding composite material has high thermal deformation temperature (215 ℃) under load, low heat conductivity coefficient (0.25 w/(m.k)) at the high and low temperature (200 ℃) and good heat insulation performance, can work at high temperature for a long time, can be machined according to requirements, has excellent neutron shielding performance, can be widely applied to neutron radiation shielding occasions of a reactor, is prepared by adopting a casting process, is simple to mold, has no organic solvent and harmful substances in production, has high production safety coefficient, and has no environmental pollution.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a wide-temperature-range (room temperature-200 ℃) low-heat-conduction high-temperature-resistant neutron shielding composite material and a preparation method thereof.
Background
The practice and research to date has shown that none of the "universal materials" is applicable to all nuclear radiation shielding protection applications. The ideal shielding and protecting material is designed into a multilayer sandwich structure, namely, the inner layer and the outer layer are made of heavy materials such as lead, iron and the like, so as to shield gamma rays, and the middle layer is made of light materials with more hydrogen so as to shield neutrons. The light material used as the middle layer is required to have good mechanical properties, and meanwhile, the light material is required to resist high temperature and low heat conduction, so that the light material can not fail or fail slowly under the limit working condition, and more time is obtained for subsequent emergency treatment.
The polymer composite material has the characteristics of light weight, strong designability, wide adjustable range of performance, easy processing and forming and the like, has been applied to a considerable extent in the field of radiation protection, and particularly has strict requirements on shielding efficiency of unit mass (volume). However, the heat resistance of the polymer material is not high, and the problem to be solved in the application of the polymer material in the radiation protection field is always needed. The patent CN202110196713.X adopts high-temperature nylon and polyether-ether-ketone special engineering plastics as a matrix, the use temperature of the prepared neutron/gamma radiation shielding material is 180-300 ℃, but the special engineering plastics are high in price, high in molding temperature and pressure, and high in equipment requirement, and are difficult to apply on a large scale. In the patent CN106317787B, pyromellitic dianhydride is used as a curing agent to prepare a shielding composite material with epoxy resin as a matrix, but acetone is used to dissolve pyromellitic dianhydride in the preparation process, and a large amount of acetone solvent is involved in the preparation process, which is not beneficial to production safety and environmental protection. The patent CN202210403354.5 uses epoxy resin/aromatic amine as a matrix to prepare a light high-temperature-resistant neutron shielding composite material, the preparation process also involves the use of a large amount of solvents, and meanwhile, the material has higher heat conductivity coefficient (room temperature-0.25 w/(m.k)) and still has insufficient thermal deformation temperature under load (> 200 ℃).
In view of this, it is desirable to develop a high temperature resistant neutron shielding composite that has a low thermal conductivity over a wide temperature range.
Disclosure of Invention
One of the purposes of the invention is to provide a wide-temperature-range low-heat-conduction high-temperature-resistance neutron shielding composite material, which has high load thermal deformation temperature (> 215 ℃) and low heat conduction coefficient (< 0.25 w/(m.k)) at the two ends of high temperature and low temperature (room temperature-200 ℃), has good heat insulation performance, can work at high temperature for a long time, can be machined according to requirements, has excellent neutron shielding performance, and can be widely applied to neutron radiation shielding occasions of a reactor.
The second purpose of the invention is to provide a preparation method of the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material, which adopts a casting process to prepare the composite material, has the advantages of simple molding, no organic solvent in production, no harmful substances, high production safety coefficient, no environmental pollution concern and easy machining.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows.
A wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material comprises trifunctional epoxy resin, tetrafunctional epoxy resin, aliphatic acid anhydride, aromatic dianhydride, phthalic anhydride, a thermal neutron absorber, a toughening agent, a dispersing agent, a defoaming agent, a thixotropic agent and an accelerator;
The mass ratio of the trifunctional epoxy resin to the tetrafunctional epoxy resin is 1.0:1.0-5.0:1.0;
The dosage of the toughening agent is 5-40% of the total weight of the trifunctional epoxy resin and the tetrafunctional epoxy resin;
the equivalent ratio of the anhydride groups of the alicyclic anhydride, the phthalic anhydride and the aromatic dianhydride is 1.0:0.06-0.10:0.10-0.20;
the equivalent ratio of epoxy groups contained in the trifunctional epoxy resin, the tetrafunctional epoxy resin and the toughening agent to anhydride groups contained in the alicyclic anhydride, the phthalic anhydride and the aromatic dianhydride is 1.0:0.8-1.0;
the dosage of the thermal neutron absorber is 2% -10% of the total weight of the formula;
the consumption of the dispersing agent is 1.0-5.0% of the weight of the thermal neutron absorber;
the dosage of the defoamer is 0.01-0.5% of the total weight of the formula;
the dosage of the thixotropic agent is 0.5-2.0% of the total weight of the formula;
the usage amount of the accelerator is 0.1-2.0% of the total weight of the aliphatic acid anhydride, the aromatic dianhydride and the phthalic anhydride.
Preferably, the trifunctional epoxy resin is one or a mixture of two of triglycidyl para-aminophenol, tris (4-hydroxyphenyl) methane triglycidyl ether.
Preferably, the tetrafunctional epoxy resin is one or a mixture of two of 4, 4-diaminodiphenylmethane tetraglycidyl amine, 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane.
Preferably, the alicyclic anhydride is one or a mixture of more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and methyl nadic anhydride.
Preferably, the aromatic dianhydride is a mixture of one or more of ethylene glycol bis (trimellitic anhydride ester), 4' -oxydiphthalic anhydride, 3', 4' -benzophenone tetracarboxylic dianhydride.
Preferably, the thermal neutron absorber is boron carbide with the particle size of 5-100 mu m.
Preferably, the toughening agent is a nano core-shell structure modified epoxy resin.
Preferably, the dispersant is a solventless carboxylate copolymer; more preferably, the dispersant is a mixture of one or more of HX4010, HX4013, HX 4015.
Preferably, the defoamer is a polysiloxane-based polymer; more preferably, the defoamer is a mixture of one or more of HX2080, HX2085, HX 2086.
Preferably, the thixotropic agent is a hydrophobic fumed silica; more preferably, the thixotropic agent is one or a mixture of two of HB-139 and HB-620.
Preferably, the accelerator is one or a mixture of two of imidazole compounds and tertiary amine compounds; more preferably, the promoter is one or more of 1-benzyl-2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol.
The preparation method of the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material comprises the following steps:
Step one, proportioning trifunctional epoxy resin, tetrafunctional epoxy resin, aliphatic acid anhydride, aromatic dianhydride, phthalic anhydride, thermal neutron absorber, flexibilizer, dispersant, defoamer, thixotropic agent and accelerator;
Adding the trifunctional epoxy resin, the tetrafunctional epoxy resin and the toughening agent into a reaction vessel, and uniformly mixing to obtain a mixture 1;
Adding alicyclic anhydride and aromatic dianhydride into another reaction container, stirring until the aromatic dianhydride is completely dissolved, adding phthalic anhydride, and stirring until the phthalic anhydride is completely dissolved to obtain a mixture 2;
Step four, adding the mixture 2 obtained in the step three into the mixture 1 obtained in the step two, and uniformly stirring and mixing to obtain a mixture 3;
sequentially adding a dispersing agent, a defoaming agent, a thermal neutron absorber, a thixotropic agent and an accelerator into the mixture 3 in the fourth step under continuous stirring, and uniformly mixing to obtain a mixture 7;
And step six, pouring the mixture 7 obtained in the step five into a mold, cooling to room temperature after solidification and molding, and demolding to obtain the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material.
Preferably, the method further comprises a step seven of machining the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material obtained in the step six.
Preferably, in the second step, the mixing condition is: stirring for 20-30 min at 80-90 ℃ and rotating speed of 300-500 rpm.
Preferably, the process of the third step is as follows: adding alicyclic anhydride and aromatic dianhydride into another reaction container, stirring at 130-150 ℃ and rotating speed of 300-500 rpm, completely dissolving aromatic dianhydride, and cooling to 90-100 ℃; and then adding phthalic anhydride, and continuing stirring at the rotating speed of 300-500 rpm until the phthalic anhydride is completely dissolved, thus obtaining a mixture 2.
Preferably, in the fourth step, the stirring and mixing conditions are as follows: stirring at 80-90 deg.c and 300-500 rpm for 20-30 min.
Preferably, the fifth step comprises the following steps: firstly, adding a dispersing agent and a defoaming agent into the mixture 3 obtained in the step four, and uniformly stirring and mixing to obtain a mixture 4; then adding a thermal neutron absorber into the mixture 4, and stirring and mixing uniformly to obtain a mixture 5; adding the thixotropic agent into the mixture 5, and stirring and mixing uniformly to obtain a mixture 6; and finally adding the accelerator into the mixture 6, and stirring and mixing uniformly to obtain a mixture 7.
More preferably, the dispersant and the defoamer are added into the mixture 3 obtained in the step four, and stirred for 5 to 10 minutes at the temperature of 80 to 90 ℃ and the rotating speed of 1000 to 1500rpm to obtain a mixture 4; then adding a thermal neutron absorber into the mixture 4, and stirring for 5-10 min at the temperature of 80-90 ℃ and the rotating speed of 1000-1500 rpm to obtain a mixture 5; adding a thixotropic agent into the mixture 5, stirring for 15-20 min at 65-75 ℃ and a rotating speed of 1000-1500 rpm, and stirring and defoaming for 1.0-1.5 h at 65-75 ℃ and a rotating speed of 100-300 rpm and minus 0.1MPa to obtain a mixture 6; finally, adding the accelerator into the mixture 6, stirring and defoaming for 10-20 min at 65-75 ℃ and the rotating speed of 300-500 rpm and minus 0.1MPa to obtain a mixture 7.
Preferably, in the sixth step, the curing molding condition is: 90-100 ℃/3-4h+140-150 ℃/2-3h+190-200 ℃/6-7 h, and the temperature rising rate in the temperature rising stage is 3-6 ℃/min.
Compared with the prior art, the invention has the beneficial effects that:
The wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material has excellent high-temperature resistance (load heat deformation temperature is greater than 215 ℃), excellent neutron shielding performance and very low heat conduction coefficient (< 0.25 w/(m.k)) in a wider temperature range (room temperature-200 ℃).
The wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material is prepared by adopting a casting process, is simple to mold, has no organic solvent or harmful substances in production, has high production safety coefficient, and has no environmental pollution concern; the profiled elements can be produced during casting or by subsequent machining, depending on the requirements of use.
The wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material is widely used for shielding and protecting isotope radioactive sources, nuclear power stations, accelerators and radiation laboratories, and is particularly suitable for neutron radiation protection of small-sized mobile nuclear reactors.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below, but it is to be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
The invention relates to a wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material which comprises trifunctional epoxy resin, tetrafunctional epoxy resin, aliphatic acid anhydride, aromatic dianhydride, phthalic anhydride, a thermal neutron absorber, a toughening agent, a dispersing agent, a defoaming agent, a thixotropic agent and an accelerator.
In the above embodiments, the trifunctional epoxy resin is preferably one or a mixture of two of triglycidyl para-aminophenol, tris (4-hydroxyphenyl) methane triglycidyl ether. The trifunctional epoxy resin has good heat resistance. The tetrafunctional epoxy resin is preferably one or two of 4, 4-diaminodiphenyl methane tetraglycidyl amine and 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, and has high crosslinking density and good heat resistance. The mass ratio of the trifunctional epoxy resin to the tetrafunctional epoxy resin is 1.0:1.0-5.0:1.0, and the mass ratio can ensure that the composite material has proper crosslinking density, thereby having good heat resistance, and simultaneously ensuring that the composite material has lower brittleness and processability.
In the technical scheme, the toughening agent is nano core-shell structure modified epoxy resin, and has the characteristics of improving the impact strength of the material and not affecting the thermal performance of the material, such as MX-153, MX-154 and MX-267.
In the technical scheme, the alicyclic anhydride is one or a mixture of more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and methyl nadic anhydride, and has the characteristics of small viscosity, good process operability and better heat resistance.
In the technical scheme, the phthalic anhydride has the characteristics of low price, good heat resistance and easy dissolution in alicyclic anhydride.
In the technical scheme, the aromatic dianhydride is one or a mixture of more of ethylene glycol bis (trimellitic anhydride ester), 4' -oxydiphthalic anhydride and 3,3', 4' -benzophenone tetracarboxylic dianhydride, and has the characteristics of good heat resistance and strong toughness.
In the technical scheme, the equivalent ratio of the anhydride groups of the alicyclic anhydride, the phthalic anhydride and the aromatic dianhydride is 1.0:0.06-0.10:0.10-0.20, and the equivalent ratio can ensure the manufacturability of the castable and the heat resistance of the cured composite material.
In the technical scheme, the thermal neutron absorber is boron carbide with the particle size of 5-100 mu m, and the dosage of the boron carbide is 2-10% of the total weight of the formula.
In the technical scheme, the dispersing agent, the defoaming agent, the thixotropic agent and the accelerator are all auxiliary agents. The dispersant is preferably a solvent-free carboxylate copolymer suitable for oily systems, such as HX4010, HX4013, HX4015. The defoamer is preferably a polysiloxane-based polymer, such as HX2080, HX2085, HX2086. The thixotropic agent is preferably a hydrophobic fumed silica, such as HB-139, HB-620. The accelerator is preferably imidazole compound, tertiary amine compound such as 1-benzyl-2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, benzyl dimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol.
The neutron shielding composite material is a compound of a condensate of epoxy resin and anhydride and other components, the epoxy resin and anhydride react essentially to react between epoxy groups and anhydride groups in a molecular structure, namely active groups, and the proportion of each active group is determined by determining the proportion of each active group, so that the proportion of other components is further determined, and the proportion relation of each component is as follows: the equivalent ratio of epoxy groups contained in the trifunctional epoxy resin, the tetrafunctional epoxy resin and the toughening agent to the anhydride groups contained in the alicyclic anhydride, the phthalic anhydride and the aromatic dianhydride is 1.0:0.8-1.0, the toughening agent is 5-40% of the total mass of the trifunctional epoxy resin and the tetrafunctional epoxy resin, the thermal neutron absorber is 2-10% of the total weight of the formula, the dispersing agent is 1.0-5.0% of the thermal neutron absorber, the defoaming agent is 0.01-0.5% of the total weight of the formula, the thixotropic agent is 0.5-2.0% of the total weight of the formula, and the accelerator is aliphatic acid anhydride, 0.1-2.0% of the total mass of the phthalic anhydride and the aromatic dianhydride.
The preparation method of the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material comprises the following steps:
Step one, proportioning trifunctional epoxy resin, tetrafunctional epoxy resin, aliphatic acid anhydride, aromatic dianhydride, phthalic anhydride, thermal neutron absorber, flexibilizer, dispersant, defoamer, thixotropic agent and accelerator;
Adding the trifunctional epoxy resin, the tetrafunctional epoxy resin and the toughening agent into a reaction vessel (usually a stirring kettle), and stirring for 20-30min at 80-90 ℃ and 300-500r/min to obtain a mixture 1;
Adding alicyclic anhydride and aromatic dianhydride into another reaction container (usually a stirring kettle), stirring at 130-150 ℃ under the condition of 300-500r/min until the aromatic dianhydride is completely dissolved (the material becomes light brown transparent liquid), cooling to 90-100 ℃, adding phthalic anhydride, and continuing stirring under the condition of 300-500r/min until the phthalic anhydride is completely dissolved (the material becomes light brown transparent liquid), so as to obtain a mixture 2;
Step four, transferring the mixture 2 prepared in the step three into the mixture 1 prepared in the step two, and stirring for 20-30min at 80-90 ℃ under the condition of 300-500r/min to obtain a mixture 3;
Step five, adding a dispersing agent and a defoaming agent into the mixture 3 in the step four, and stirring for 5-10min at 80-90 ℃ under the condition of 1000-1500r/min to obtain a mixture 4;
Step six, adding a thermal neutron absorber into the mixture 4 in the step five, and stirring for 5-10min at 80-90 ℃ under the condition of 1000-1500r/min to obtain a mixture 5;
step seven, adding a thixotropic agent into the mixture 5 in the step six under the conditions of 65-75 ℃ and 1000-1500r/min, continuously stirring for 15-20min after the thixotropic agent is added, cooling to 65-75 ℃, stirring at 100-300r/min, and defoaming for 1.0-1.5h under the condition of minus 0.1MPa to obtain a mixture 6;
Step eight, adding an accelerator into the mixture 6 in the step seven, stirring and defoaming for 10-20min under the condition of-0.1 MPa at 65-75 ℃ and 300-500r/min to obtain a mixture 7;
Step nine, pouring the mixture 7 obtained in the step eight into a mold, solidifying and forming, cooling to room temperature along with a furnace, and demolding to obtain the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material;
And step ten, machining the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material prepared in the step nine according to requirements.
In the technical scheme, the curing molding conditions are preferably 90-100 ℃/3-4h+140-150 ℃/2-3h+190-200 ℃/6-7h, and the heating rate in the heating stage is 3-6 ℃/min.
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art unless otherwise indicated. In order to enable those skilled in the art to better understand the technical solutions of the present invention, the present invention will be described in further detail with reference to examples.
In the following examples, various processes and methods, which are not described in detail, are conventional methods well known in the art. Materials, reagents, devices, instruments, equipment and the like used in the examples described below are commercially available unless otherwise specified.
The invention is further illustrated below with reference to examples.
Example 1
The wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material consists of 100 parts by weight of triglycidyl para-aminophenol, 20 parts by weight of 4, 4-diaminodiphenylmethane tetraglycidyl amine, 20 parts by weight of a toughening agent (MX-154), 152.6 parts by weight of methylnadic anhydride (MNA), 17.6 parts by weight of ethylene glycol bis (trimellitic anhydride ester) (TME), 7.6 parts by weight of Phthalic Anhydride (PA), 0.178 parts by weight of 1-benzyl-2-ethylimidazole (1B 2 EZ), 13.43 parts by weight of boron carbide, 0.67 parts by weight of a dispersing agent (HX 4010), 0.34 parts by weight of a defoaming agent (HX 2080) and 3.36 parts by weight of a thixotropic agent (HB 620).
The preparation method of the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material comprises the following steps:
Step one, proportioning trifunctional epoxy resin, tetrafunctional epoxy resin, aliphatic acid anhydride, aromatic dianhydride, phthalic anhydride, thermal neutron absorber, flexibilizer, dispersant, defoamer, thixotropic agent and accelerator;
Step two, adding triglycidyl para-aminophenol, 4-diaminodiphenylmethane tetraglycidyl amine and a toughening agent MX-154 into a stirring kettle, and stirring for 30min at 80 ℃ and 300r/min to obtain a mixture 1;
Step three, adding methyl nadic anhydride and ethylene glycol bis (trimellitic anhydride ester) into another stirring kettle, stirring at 130 ℃ and 300r/min until the ethylene glycol bis (trimellitic anhydride ester) is completely dissolved, cooling to 90 ℃, adding phthalic anhydride, and continuing stirring at 300r/min until the phthalic anhydride is completely dissolved to obtain a mixture 2;
step four, adding the mixture 2 in the step three into the mixture 1 in the step two, and stirring for 30min at 80 ℃ and 300r/min to obtain a mixture 3;
Step five, adding a dispersing agent HX4010 and a defoaming agent HX2080 into the mixture 3, and stirring for 10min at 80 ℃ and 1000r/min to obtain a mixture 4;
Step six, adding boron carbide into the mixture 4, and stirring for 10min at 80 ℃ and 1000r/min to obtain a mixture 5;
Step seven, adding a thixotropic agent HB620 into the mixture 5 at the temperature of 65 ℃ and under the condition of 1000r/min, continuously stirring for 20min after the thixotropic agent is added, cooling to the temperature of 65 ℃, and defoaming for 1.5h under the condition of-0.1 MPa under the stirring of 100r/min to obtain a mixture 6;
step eight, adding 1-benzyl-2-ethylimidazole into the mixture 6, stirring at 65 ℃ and 300r/min under the condition of minus 0.1MPa, and defoaming for 20min to obtain a mixture 7;
Step nine, pouring the mixture 7 into a preheated mold for curing and forming, and curing the mixture: 90 ℃/4h+140 ℃/3h+190 ℃/7h, the heating rate in the heating stage is 3 ℃/min, and after solidification, cooling to room temperature along with the furnace, and demoulding to obtain the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material.
Example 2
The wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material consists of 50 parts by weight of tris (4-hydroxyphenyl) methane triglycidyl ether, 50 parts by weight of 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, 5 parts by weight of toughening agent (MX-153), 95.8 parts by weight of methyl hexahydrophthalic anhydride (MeHHPA), 18.37 parts by weight of 3,3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 5.06 parts by weight of Phthalic Anhydride (PA), 1.19 parts by weight of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), 4.64 parts by weight of boron carbide, 0.046 parts by weight of dispersing agent (HX 4013), 0.69 parts by weight of defoamer (HX 2085) and 1.16 parts by weight of thixotropic agent (HB 139).
The preparation method of the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material comprises the following steps:
Step one, proportioning trifunctional epoxy resin, tetrafunctional epoxy resin, aliphatic acid anhydride, aromatic dianhydride, phthalic anhydride, thermal neutron absorber, flexibilizer, dispersant, defoamer, thixotropic agent and accelerator;
step two, adding tri (4-hydroxyphenyl) methane triglycidyl ether, 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane and a toughening agent MX-153 into a stirring kettle, and stirring for 20min at 80 ℃ and 300r/min to obtain a mixture 1;
Step three, methyl hexahydrophthalic anhydride and 3,3', 4' -benzophenone tetracarboxylic dianhydride are added into another stirring kettle, stirring is carried out under the condition of 150 ℃ and 300r/min until the 3,3', 4' -benzophenone tetracarboxylic dianhydride is completely dissolved, cooling is carried out to 90 ℃, phthalic anhydride is added, and stirring is continued under the condition of 300r/min until the phthalic anhydride is completely dissolved, thus obtaining a mixture 2;
step four, adding the mixture 2 in the step three into the mixture 1 in the step two, and stirring for 30min at 80 ℃ and 300r/min to obtain a mixture 3;
Step five, adding a dispersing agent HX4013 and a defoaming agent HX2085 into the mixture 3, and stirring for 10min at 80 ℃ and 1000r/min to obtain a mixture 4;
Step six, adding boron carbide into the mixture 4, and stirring for 10min at 80 ℃ and 1000r/min to obtain a mixture 5;
step seven, adding a thixotropic agent HB139 into the mixture 5 at the temperature of 65 ℃ and under the condition of 1000r/min, continuously stirring for 20min after the thixotropic agent is added, cooling to the temperature of 65 ℃, and defoaming for 1.5h under the condition of-0.1 MPa under the stirring of 100r/min to obtain a mixture 6;
Step eight, adding 2,4, 6-tris (dimethylaminomethyl) phenol into the mixture 6, stirring at 65 ℃ and 300r/min under the condition of minus 0.1MPa, and defoaming for 20min to obtain a mixture 7;
Step nine, pouring the mixture 7 into a preheated mold for curing and forming, and curing the mixture: 100 ℃/3h+150 ℃/2h+190 ℃/7h, the heating rate in the heating stage is 3 ℃/min, and after solidification, cooling to room temperature along with the furnace, and demoulding to obtain the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material.
Example 3
The wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material consists of 75 parts by weight of triglycidyl para-aminophenol, 25 parts by weight of 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, 40 parts by weight of a toughening agent (MX-267), 84.37 parts by weight of methylnadic anhydride (MNA), 78.68 parts by weight of methyltetrahydrophthalic anhydride (MeTHPA), 24.65 parts by weight of 4,4' -oxydiphthalic anhydride (ODPA), 14.03 parts by weight of Phthalic Anhydride (PA), 4.03 parts by weight of Benzyl Dimethylamine (BDMA), 39.6 parts by weight of boron carbide, 0.79 parts by weight of a dispersing agent (HX 4015), 1.98 parts by weight of a defoaming agent (HX 2086) and 7.92 parts by weight of a thixotropic agent (HB 139).
The preparation method of the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material comprises the following steps:
Step one, proportioning trifunctional epoxy resin, tetrafunctional epoxy resin, aliphatic acid anhydride, aromatic dianhydride, phthalic anhydride, thermal neutron absorber, flexibilizer, dispersant, defoamer, thixotropic agent and accelerator;
step two, adding triglycidyl para-aminophenol, 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane and a toughening agent MX-267 into a stirring kettle, and stirring for 20min at 90 ℃ and 500r/min to obtain a mixture 1;
Adding methyl nadic anhydride, methyl tetrahydrophthalic anhydride and 4,4 '-oxydiphthalic anhydride into another stirring kettle, stirring at 140 ℃ under the condition of 500r/min until the 4,4' -oxydiphthalic anhydride is completely dissolved, cooling to 95 ℃, adding phthalic anhydride, and continuing stirring under the condition of 500r/min until the phthalic anhydride is completely dissolved to obtain a mixture 2;
Step four, adding the mixture 2 in the step three into the mixture 1 in the step two, and stirring for 20min at 90 ℃ under the condition of 500r/min to obtain a mixture 3;
Step five, adding a dispersing agent HX4015 and a defoaming agent HX2086 into the mixture 3, and stirring for 10min at 80 ℃ and 1000r/min to obtain a mixture 4;
adding boron carbide into the mixture 4, and stirring for 5min at 90 ℃ under 1500r/min to obtain a mixture 5;
step seven, adding a thixotropic agent HB139 into the mixture 5 at the temperature of 75 ℃ under the condition of 1500r/min, continuously stirring for 15min after the thixotropic agent is added, then cooling to the temperature of 75 ℃, and defoaming for 1h under the condition of-0.1 MPa under the stirring of 300r/min to obtain a mixture 6;
step eight, adding benzyl dimethylamine BDMA into the mixture 6, stirring at 75 ℃ and 500r/min under the condition of minus 0.1MPa, and defoaming for 10min to obtain a mixture 7;
step nine, pouring the mixture 7 into a preheated mold for curing and forming, and curing the mixture: 100 ℃/3h+150 ℃/2h+200 ℃/6h, the heating rate in the heating stage is 6 ℃/min, and after solidification, cooling to room temperature along with the furnace, and demoulding to obtain the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material.
The performance of the wide temperature range low thermal conductivity high temperature resistant neutron shielding composite material prepared in example 1-example 3 was tested, and the test results are shown in table 1.
TABLE 1 Performance of the broad temperature Domain Low thermal conductivity high temperature resistant neutron shielding composite obtained in example 1-example 3
As can be seen from Table 1, the neutron shielding composite material of the present invention has a low thermal conductivity (< 0.25 w/(m.k)) over a wide temperature range (room temperature to 200 ℃ C.), and has an excellent heat insulation function; the neutron shielding composite material has the thermal deformation temperature exceeding 215 ℃ (Vicat softening point test: 200 ℃ needle penetration depth <0.1 mm), which shows that the neutron shielding composite material can stably work for a long time under the condition of 200 ℃; the neutron shielding composite material has good fast neutron and thermal neutron shielding effect, and is a shielding material especially suitable for neutron radiation protection of small-sized mobile nuclear reactors.
It is apparent that the above embodiments are merely examples for the sake of clarity of illustration and are not limiting of the invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material is characterized by comprising trifunctional epoxy resin, tetrafunctional epoxy resin, alicyclic anhydride, aromatic dianhydride, phthalic anhydride, a thermal neutron absorber, a toughening agent, a dispersing agent, a defoaming agent, a thixotropic agent and an accelerator;
The mass ratio of the trifunctional epoxy resin to the tetrafunctional epoxy resin is 1.0:1.0-5.0:1.0;
The dosage of the toughening agent is 5-40% of the total weight of the trifunctional epoxy resin and the tetrafunctional epoxy resin, and the toughening agent is nano core-shell structure modified epoxy resin;
the equivalent ratio of the anhydride groups of the alicyclic anhydride, the phthalic anhydride and the aromatic dianhydride is 1.0:0.06-0.10:0.10-0.20;
the equivalent ratio of epoxy groups contained in the trifunctional epoxy resin, the tetrafunctional epoxy resin and the toughening agent to anhydride groups contained in the alicyclic anhydride, the phthalic anhydride and the aromatic dianhydride is 1.0:0.8-1.0;
the dosage of the thermal neutron absorber is 2% -10% of the total weight of the formula;
the consumption of the dispersing agent is 1.0-5.0% of the weight of the thermal neutron absorber;
the dosage of the defoamer is 0.01-0.5% of the total weight of the formula;
the dosage of the thixotropic agent is 0.5-2.0% of the total weight of the formula;
the usage amount of the accelerator is 0.1-2.0% of the total weight of the aliphatic acid anhydride, the aromatic dianhydride and the phthalic anhydride.
2. The broad temperature range low thermal conductivity high temperature resistant neutron shielding composite of claim 1, wherein the trifunctional epoxy resin is one or a mixture of two of triglycidyl para-aminophenol, tris (4-hydroxyphenyl) methane triglycidyl ether;
The tetrafunctional epoxy resin is one or two of 4, 4-diaminodiphenyl methane tetraglycidyl amine and 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane;
the alicyclic anhydride is one or a mixture of more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and methyl nadic anhydride;
the aromatic dianhydride is one or a mixture of more than one of ethylene glycol bis (trimellitic anhydride ester), 4' -oxydiphthalic anhydride and 3,3', 4' -benzophenone tetracarboxylic dianhydride;
the thermal neutron absorber is boron carbide with the particle size of 5-100 mu m;
the dispersing agent is a solvent-free carboxylate copolymer;
the defoaming agent is polysiloxane polymer;
The thixotropic agent is hydrophobic fumed silica;
the accelerator is one or a mixture of two of imidazole compounds and tertiary amine compounds.
3. The broad temperature range low thermal conductivity high temperature resistant neutron shielding composite of claim 2, wherein the dispersant is a mixture of one or more of HX4010, HX4013, HX 4015;
the defoamer is one or a mixture of a plurality of HX2080, HX2085 and HX 2086;
the thixotropic agent is one or a mixture of two of HB-139 and HB-620;
The promoter is one or more of 1-benzyl-2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, benzyl dimethylamine and 2,4, 6-tris (dimethylaminomethyl) phenol.
4. A method for preparing the wide temperature range low thermal conductivity high temperature resistant neutron shielding composite material according to any one of claims 1-3, comprising the following steps:
step one, proportioning trifunctional epoxy resin, tetrafunctional epoxy resin, alicyclic anhydride, aromatic dianhydride, phthalic anhydride, thermal neutron absorber, toughening agent, dispersing agent, defoaming agent, thixotropic agent and accelerator;
Adding the trifunctional epoxy resin, the tetrafunctional epoxy resin and the toughening agent into a reaction vessel, and uniformly mixing to obtain a mixture 1;
Adding alicyclic anhydride and aromatic dianhydride into another reaction container, stirring until the aromatic dianhydride is completely dissolved, adding phthalic anhydride, and stirring until the phthalic anhydride is completely dissolved to obtain a mixture 2;
Step four, adding the mixture 2 obtained in the step three into the mixture 1 obtained in the step two, and uniformly stirring and mixing to obtain a mixture 3;
sequentially adding a dispersing agent, a defoaming agent, a thermal neutron absorber, a thixotropic agent and an accelerator into the mixture 3 in the fourth step under continuous stirring, and uniformly mixing to obtain a mixture 7;
and step six, pouring the mixture 7 obtained in the step five into a mold, solidifying and molding, cooling to room temperature, and demolding to obtain the neutron shielding composite material.
5. The method for preparing the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material according to claim 4, further comprising a step seven of machining the neutron shielding composite material obtained in the step six.
6. The method for preparing the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material according to claim 4, wherein the method comprises the steps of,
In the second step, the conditions for uniform mixing are as follows: stirring for 20-30 min at 80-90 ℃ and rotating speed of 300-500 rpm;
in the fourth step, the conditions of stirring and mixing uniformly are as follows: stirring at 80-90 deg.c and 300-500 rpm for 20-30 min.
7. The method for preparing the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material according to claim 4, wherein the method comprises the steps of,
The process of the third step is as follows: adding alicyclic anhydride and aromatic dianhydride into another reaction container, stirring at 130-150 ℃ and rotating speed of 300-500 rpm, completely dissolving aromatic dianhydride, and cooling to 90-100 ℃; and then adding phthalic anhydride, and continuing stirring at the rotating speed of 300-500 rpm until the phthalic anhydride is completely dissolved, thus obtaining a mixture 2.
8. The method for preparing the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material according to claim 4, wherein the fifth step comprises the following steps: firstly, adding a dispersing agent and a defoaming agent into the mixture 3 obtained in the step four, and uniformly stirring and mixing to obtain a mixture 4; then adding a thermal neutron absorber into the mixture 4, and stirring and mixing uniformly to obtain a mixture 5; adding the thixotropic agent into the mixture 5, and stirring and mixing uniformly to obtain a mixture 6; and finally adding the accelerator into the mixture 6, and stirring and mixing uniformly to obtain a mixture 7.
9. The method for preparing the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material according to claim 8, wherein a dispersing agent and a defoaming agent are added into the mixture 3 obtained in the step four, and the mixture is stirred for 5 to 10 minutes at the temperature of 80 to 90 ℃ and the rotating speed of 1000 to 1500rpm to obtain a mixture 4; then adding a thermal neutron absorber into the mixture 4, and stirring for 5-10 min at the temperature of 80-90 ℃ and the rotating speed of 1000-1500 rpm to obtain a mixture 5; adding a thixotropic agent into the mixture 5, stirring for 15-20 min at 65-75 ℃ and a rotating speed of 1000-1500 rpm, and stirring and defoaming for 1.0-1.5 h at 65-75 ℃ and a rotating speed of 100-300 rpm and minus 0.1MPa to obtain a mixture 6; finally, adding the accelerator into the mixture 6, stirring and defoaming for 10-20 min at 65-75 ℃ and the rotating speed of 300-500 rpm and minus 0.1MPa to obtain a mixture 7.
10. The method for preparing the wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material according to claim 4, wherein in the sixth step, the curing and molding conditions are as follows: 90-100 ℃/3-4h+140-150 ℃/2-3h+190-200 ℃/6-7 h, and the temperature rising rate in the temperature rising stage is 3-6 ℃/min.
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|---|---|---|---|---|
| CN104710727A (en) * | 2015-03-27 | 2015-06-17 | 中国科学院长春应用化学研究所 | Epoxy resin based neutron and gamma ray shielding composite material, as well as preparation method and application thereof |
| CN104744894A (en) * | 2015-03-27 | 2015-07-01 | 中国科学院长春应用化学研究所 | Epoxy resin based neutron-shielding composite material and preparation method thereof |
| CN106317784A (en) * | 2016-09-13 | 2017-01-11 | 北京市射线应用研究中心 | Multifunctional epoxy resin radical radiation protective compound material and preparation method thereof |
| CN114806082A (en) * | 2022-04-18 | 2022-07-29 | 中国科学院长春应用化学研究所 | Light high-temperature-resistant heat-insulating neutron shielding composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710727A (en) * | 2015-03-27 | 2015-06-17 | 中国科学院长春应用化学研究所 | Epoxy resin based neutron and gamma ray shielding composite material, as well as preparation method and application thereof |
| CN104744894A (en) * | 2015-03-27 | 2015-07-01 | 中国科学院长春应用化学研究所 | Epoxy resin based neutron-shielding composite material and preparation method thereof |
| CN106317784A (en) * | 2016-09-13 | 2017-01-11 | 北京市射线应用研究中心 | Multifunctional epoxy resin radical radiation protective compound material and preparation method thereof |
| CN114806082A (en) * | 2022-04-18 | 2022-07-29 | 中国科学院长春应用化学研究所 | Light high-temperature-resistant heat-insulating neutron shielding composite material and preparation method thereof |
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