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CN119799053A - A shielding putty material for high radiation areas and preparation method thereof - Google Patents

A shielding putty material for high radiation areas and preparation method thereof Download PDF

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Publication number
CN119799053A
CN119799053A CN202411855499.4A CN202411855499A CN119799053A CN 119799053 A CN119799053 A CN 119799053A CN 202411855499 A CN202411855499 A CN 202411855499A CN 119799053 A CN119799053 A CN 119799053A
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China
Prior art keywords
shielding
flame retardant
epoxy resin
putty material
agent
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CN202411855499.4A
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Chinese (zh)
Inventor
王炳衡
张于胜
田英男
祖愿
王晓霞
彭雄厚
米爱军
李欢
陈宗欢
吴金平
高桂玲
邱林
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China Nuclear Power Engineering Co Ltd
Xian Rare Metal Materials Research Institute Co Ltd
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China Nuclear Power Engineering Co Ltd
Xian Rare Metal Materials Research Institute Co Ltd
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Priority to CN202411855499.4A priority Critical patent/CN119799053A/en
Publication of CN119799053A publication Critical patent/CN119799053A/en
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Abstract

本发明公开一种高辐射区用屏蔽腻子材料及其制备方法，按重量百分比计，该材料的组成包括：屏蔽剂72wt％～86wt％，固化剂1wt％～3.2wt％，三元复配阻燃剂3.4wt％～9.5wt％，分散剂0.1wt％～0.15wt％，消泡剂0.02％wt～0.07wt％，液体阻燃剂1.8wt％～3.5wt％，余量为树脂基体，且所述树脂基体包括海因环氧树脂和双酚A型环氧树脂。本发明中三元复配阻燃剂参与环氧树脂的固化反应，液体阻燃剂起到协同阻燃及调节腻子粘度的作用，加入高填充表面改性的屏蔽剂后，可以使本发明屏蔽腻子材料具有良好的阻燃、高粘接、耐高温、高屏蔽性能、施工方便等特点，综合性能优异，可广泛应用于中、高辐射水平的设备、管道和辐射热点屏蔽，以及屏蔽结构缝隙及孔洞的填补。

The invention discloses a shielding putty material for high radiation area and a preparation method thereof. The material comprises, by weight percentage, 72wt% to 86wt% of a shielding agent, 1wt% to 3.2wt% of a curing agent, 3.4wt% to 9.5wt% of a ternary compound flame retardant, 0.1wt% to 0.15wt% of a dispersant, 0.02wt% to 0.07wt% of a defoaming agent, 1.8wt% to 3.5wt% of a liquid flame retardant, and the remainder is a resin matrix, and the resin matrix comprises a hyaluronic acid epoxy resin and a bisphenol A type epoxy resin. In the invention, the ternary compound flame retardant participates in the curing reaction of the epoxy resin, the liquid flame retardant plays a role of synergistic flame retardancy and adjusting the viscosity of the putty, and after adding a high-filling surface-modified shielding agent, the shielding putty material of the invention can have the characteristics of good flame retardancy, high adhesion, high temperature resistance, high shielding performance, convenient construction, etc., and has excellent comprehensive performance, and can be widely used in equipment, pipelines and radiation hotspot shielding with medium and high radiation levels, as well as filling of gaps and holes in shielding structures.

Description

Shielding putty material for high-radiation area and preparation method thereof
Technical Field
The invention belongs to the technical field of nuclear radiation protection, and particularly relates to a shielding putty material for a high-radiation area and a preparation method thereof.
Background
With the rapid development of nuclear power, nuclear energy is widely applied in various fields such as national defense, industry, medical treatment, ships and the like, and becomes one of indispensable energy sources. Because alpha, beta, gamma, X-rays, neutrons and the like generated by nuclear radiation have a threat to the health of human bodies, the problems of nuclear radiation safety, nuclear waste radioactive pollution, nuclear diffusion and the like are widely concerned, and the performance requirements on the nuclear shielding materials are also higher and higher.
Aiming at the radiation problems of equipment, pipelines and radiation hot spots with medium and high radiation levels and gaps and holes of a shielding structure, a material with a shielding effect is required to play a role in repairing, and the shielding performance equivalent to that of a shielding body material is required to be provided, so that the protective performance of a shielding system can be effectively improved, and higher requirements are put on a shielding putty material. According to the complexity of the field working condition, the viscosity of the putty needs to be flexibly adjusted, and meanwhile, the shielding putty needs to maintain good flame retardant property.
At present, the existing shielding putty material mainly comprises the following steps of (1) taking epoxy resin as a matrix in the CN113372752A, taking aluminum hydroxide as a flame retardant, taking alicyclic amine as a curing agent, adding shielding filler to obtain high-temperature-resistant, high-adhesion and flame-retardant shielding putty, wherein the problem that the flame retardant efficiency of single-component aluminum hydroxide is low, the addition amount of the flame retardant is large, the viscosity of the shielding putty is obviously increased, the addition amount of the shielding filler is limited and the like is difficult to meet the requirements of a medium-high radiation area on neutron and photon shielding performance is solved, and (2) the CN113416443A obtains the shielding putty with adjustable viscosity by adding an active diluent, has good shielding and adhesion strength, but the flame retardance of the shielding putty is not ensured due to the fact that the active diluent belongs to alkyl glycidyl ether, and the epoxy resin is taken as the matrix, the problem of cost is solved, the flame retardant is modified by adopting the additive flame retardant, and the compatibility of the flame retardant and the resin matrix is poor, and the mechanical performance is obviously reduced.
In view of the above, it is necessary to develop a shielding putty material applied to a high-emissivity region, convenient to construct and excellent in comprehensive properties and a preparation method thereof.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the shielding putty material for the high-radiation area and the preparation method thereof, wherein the ternary compound flame retardant participates in the curing reaction of epoxy resin, the liquid flame retardant plays roles of synergetic flame retardance and putty viscosity adjustment, and after the high-filling surface modified shielding agent is added, the shielding putty material has the characteristics of good flame retardance, high adhesion, high temperature resistance, high shielding performance, convenient construction and the like, has excellent comprehensive performance, and can be widely applied to shielding equipment, pipelines and radiation hot spots with medium and high radiation levels and filling gaps and holes of a shielding structure.
The technical scheme for solving the technical problems is as follows:
according to one aspect of the invention, a shielding putty material for a high radiation area comprises the following raw materials in percentage by weight:
72-86 wt% of shielding agent, 1-3.2 wt% of curing agent, 3.4-9.5 wt% of ternary compound flame retardant, 0.1-0.15 wt% of dispersing agent, 0.02-0.07 wt% of defoaming agent, 1.8-3.5 wt% of liquid flame retardant and the balance of resin matrix, wherein the resin matrix comprises hydantoin epoxy resin and bisphenol A epoxy resin.
Optionally, the hydantoin epoxy resin comprises one or more of the formulas (1) - (3), and is specifically as follows:
Wherein x, y and z are integers.
Optionally, the bisphenol a type epoxy resin includes one or more of the formulas (4) - (5), specifically as follows:
wherein m and n are integers.
Optionally, the hydantoin epoxy resin is:
Wherein the epoxy value is between 0.52 and 0.74.
Optionally, the bisphenol a type epoxy resin is:
Wherein the epoxy value is between 0.48 and 0.54.
Optionally, the mass ratio of the hydantoin epoxy resin to the bisphenol A epoxy resin is 4:1-15:1.
Optionally, the mass ratio of the hydantoin epoxy resin to the bisphenol A epoxy resin is 5:1-12:1.
Optionally, the ternary compound flame retardant is a mixture of melamine grafted modified ammonium polyphosphate of formula (6), melamine cyanurate of formula (7) and triazine char-forming agent of formula (8), and the ternary compound flame retardant is specifically as follows:
Optionally, the melamine grafted modified ammonium polyphosphate, melamine cyanurate and triazine char forming agent in the ternary compound flame retardant have a mass ratio of 4:1:2-5:1:5.
Optionally, the curing agent is an alicyclic amine curing agent.
Optionally, the alicyclic amine curing agent is isophorone diamine.
Optionally, the shielding agent is one or a mixture of a plurality of neutron shielding agents and photon shielding agents.
Optionally, the shielding agent is one or a mixture of a plurality of boron carbide, hydroxy iron powder and tungsten powder, and the particle size of the shielding agent is 2-5 mu m.
Optionally, the dispersing agent is one or a mixture of more of gamma-aminopropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane and gamma-glycidoxypropyl trimethoxysilane.
Optionally, the defoamer is a silicon-based defoamer.
Optionally, the liquid flame retardant is an organic phosphorus flame retardant.
According to another aspect of the present invention, there is provided a method for preparing a shielding putty material for a high radiation area, comprising:
Step S1, respectively weighing hydantoin epoxy resin, bisphenol A epoxy resin, a curing agent, a ternary compound flame retardant, a shielding agent, a dispersing agent, a defoaming agent and a liquid flame retardant according to the weight percentages;
S2, adding hydantoin epoxy resin, bisphenol A epoxy resin and ternary compound flame retardant into a container, and uniformly mixing to obtain a first mixture;
s3, adding a shielding agent, a dispersing agent, a defoaming agent and a liquid flame retardant into the first mixture, and uniformly mixing to obtain a second mixture;
And S4, adding a curing agent into the second mixture, and stirring in vacuum to obtain the shielding putty material for the high-radiation area.
Optionally, in the step S2, the uniform mixing condition is that stirring is carried out for 20-30 min under the conditions of 23-30 ℃ and the rotating speed of 500-700 rpm.
Optionally, in the step S3, the uniform mixing condition is that stirring is carried out for 20-30 min under the conditions of 23-30 ℃ and the rotating speed of 30-70 rpm.
Optionally, in the step S4, stirring is performed for 10-20 min under the conditions of 23-30 ℃ and the rotation speed of 30-50 rpm and the vacuum degree of less than or equal to 0.098 MPa.
The beneficial effects are that:
According to the shielding putty material for the high-radiation area and the preparation method thereof, the resin matrix is obtained by compounding the low-viscosity, high-adhesion and nonflammable hydantoin epoxy resin and the heat-resistant bisphenol A epoxy resin, and the resin matrix is subjected to flame retardant modification by introducing a ternary compound high-efficiency flame retardant with low addition amount and the liquid flame retardant, so that the shielding putty material has good flame retardant property. In addition, the liquid flame retardant has a wetting effect on the system, so that after the high-filling shielding filler is added, the shielding putty material has the characteristics of excellent adhesive property, high shielding property, convenience in construction and the like, and has at least the following advantages compared with the prior art:
(1) Unlike traditional hydroxide flame retardant and binary compound phosphorus-nitrogen flame retardant, the ternary compound flame retardant adopted by the invention can melt flame-retardant polymer first when a system is heated, and melamine grafted modified ammonium polyphosphate is heated first to decompose acid with strong dehydration effect. With the rise of temperature, the generated acid can be subjected to esterification reaction with macromolecular triazine char forming agent to be dehydrated, the generated water can be gasified at high temperature, meanwhile, high-purity melamine cyanurate can also generate ammonia (NH 3) and carbon dioxide (CO 2) when heated, and the overflow of water vapor, NH 3 and CO 2 can expand the heated and melted polymer and dilute air and combustible materials around the combustion reaction. The macromolecular triazine charring agent is carbonized to form an expanded carbon layer under the dehydration action of acid generated by melamine grafted modified ammonium polyphosphate, and the continuous compact expanded carbon layer can serve as a physical barrier for heat transfer and mass transfer, and free radicals contained in the macromolecular triazine charring agent can form gaseous free radical reaction in the thermal degradation process of the resin, so that the macromolecular triazine charring agent is favorable for terminating a free radical reaction chain in thermal cracking of epoxy resin and slowing down the thermal degradation of the epoxy resin. The polymer is flame-retarded from two aspects of gas phase and condensed phase in the whole process, so that the shielding putty material has good flame-retardant performance, the oxygen index is more than 32, and the V0 grade is achieved by vertical combustion.
(2) The traditional ammonium polyphosphate is added into resin through physical mixing, so that the problems of poor compatibility and obvious reduction of mechanical properties exist between the traditional ammonium polyphosphate and a resin matrix. The melamine grafted modified ammonium polyphosphate has good compatibility with epoxy resin, and simultaneously, the grafted side group and the other two flame retardants both contain amine groups, so that the melamine grafted modified ammonium polyphosphate can participate in the curing reaction of the epoxy resin, and the crosslinking density of a cured product is improved, so that the material has good mechanical properties.
(3) According to the shielding putty material, the added liquid flame retardant can play a role in carrying out flame retardant modification by cooperating with the ternary compound flame retardant, and can adjust the viscosity of a system, so that the wettability between the resin and the bonding base material is increased while the processability of the system is increased, and the bonding strength of the shielding putty material is further improved.
(4) The surface of the hydroxyl iron powder used in the shielding putty material has active groups, and the shielding agent modified by the dispersing agent has good interface compatibility with epoxy resin, has no obvious aggregation, and is favorable for preparing the shielding putty material with uniform density.
Drawings
FIG. 1 is a schematic diagram of a preparation method of a shielding putty material for a high radiation area in an embodiment of the invention;
FIG. 2 is a scanning electron microscope image of the shielding putty material in preparation example 1 of the present invention
FIG. 3 is a graph showing the tensile property, bending property, vicat softening point, oxygen index, vertical burning and the like of the shielding putty material for high radiation area in preparation example 1 of the present invention;
FIG. 4 is a test sample of the shielding property of the shielding putty material for high emissivity region in preparation example 1 of the present invention;
FIG. 5 is a sample of the high emissivity region shielding putty material of preparation example 1 of the present invention after vertical burn performance;
FIG. 6 is a graph showing the results of testing the vertical burning properties of the shielding putty material for high emissivity region in preparation example 1 of the present invention.
FIG. 7 is a graph showing the results of limiting oxygen index performance test of the shielding putty material for high emissivity region in preparation example 1 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, a clear and complete description of the technical solutions of the present invention will be provided below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The method aims at solving the problems that in the prior art, the flame retardant efficiency of aluminum hydroxide with a single component is low, the addition amount of a flame retardant is large, the viscosity of the shielding putty is obviously increased, the addition amount of a shielding filler is limited, and the like, and the requirements of a medium-high radiation area on neutron and photon shielding performance are difficult to meet, or the flame retardance of the shielding putty cannot be ensured due to the adoption of an active diluent which belongs to alkyl glycidyl ether, or the problems that the compatibility of the flame retardant and a resin matrix is poor, the mechanical performance is obviously reduced, and the like are solved. The invention provides a shielding putty material for a high-radiation area, which comprises the following raw materials in percentage by weight
The material composition comprises:
72-86 wt% of shielding agent, 1-3.2 wt% of curing agent, 3.4-9.5 wt% of ternary compound flame retardant, 0.1-0.15 wt% of dispersing agent, 0.02-0.07 wt% of defoaming agent, 1.8-3.5 wt% of liquid flame retardant and the balance of resin matrix, wherein the matrix comprises hydantoin epoxy resin and bisphenol A epoxy resin.
Correspondingly, the invention also provides a preparation method of the shielding putty material for the high-radiation area, which comprises the following steps:
Step S1, respectively weighing hydantoin epoxy resin, bisphenol A epoxy resin, a curing agent, a ternary compound flame retardant, a shielding agent, a dispersing agent, a defoaming agent and a liquid flame retardant according to the weight percentages;
S2, adding hydantoin epoxy resin, bisphenol A epoxy resin and ternary compound flame retardant into a container, and uniformly mixing to obtain a first mixture;
s3, adding a shielding agent, a dispersing agent, a defoaming agent and a liquid flame retardant into the first mixture, and uniformly mixing to obtain a second mixture;
And S4, adding a curing agent into the second mixture, and stirring in vacuum to obtain the shielding putty material for the high-radiation area.
Example 1
As shown in fig. 1, the embodiment discloses a shielding putty material for a high radiation area, which comprises the following raw materials in percentage by weight:
72-86 wt% of shielding agent, 1-3.2 wt% of curing agent, 3.4-9.5 wt% of ternary compound flame retardant, 0.1-0.15 wt% of dispersing agent, 0.02-0.07 wt% of defoaming agent, 1.8-3.5 wt% of liquid flame retardant and the balance of resin matrix, wherein the matrix comprises hydantoin epoxy resin and bisphenol A epoxy resin.
In some embodiments, the hydantoin epoxy resin comprises one or more of formulas (1) - (3).
Specifically, the formulas (1) to (3) are respectively shown below:
Wherein x, y and z are integers.
In some embodiments, the bisphenol a type epoxy resin includes one or more of formulas (4) - (5).
Specifically, the formulas (4) to (5) are respectively shown below:
Wherein m and n are integers.
In some more preferred embodiments, the hydantoin epoxy resin has a structural formula (1) and an epoxy value of 0.52 to 0.74.
In some more preferred embodiments, the bisphenol a type epoxy resin has a structural formula of formula (4), and the epoxy value is between 0.48 and 0.54.
In some embodiments, the mass ratio of the hydantoin epoxy resin to the bisphenol a epoxy resin is 4:1-15:1, which can ensure that the hydantoin epoxy resin can sufficiently reduce the viscosity of the bisphenol a epoxy resin.
In some more preferred embodiments, the mass ratio of the hydantoin epoxy resin to the bisphenol a epoxy resin is 5:1-12:1, so that the cured product has good heat resistance while the low viscosity of the system is ensured.
In some embodiments, the ternary compound flame retardant is a mixture of melamine grafted modified ammonium polyphosphate, melamine cyanurate and triazine char forming agent, and has synergistic effect of condensed phase flame retardance and gas phase flame retardance, so that the flame retardance of the material can be improved. In addition, the resin can also participate in the curing reaction of the resin, and exist in a system in a chemical bonding mode, so that the crosslinking density is improved, and the good mechanical property is maintained.
Specifically, the melamine grafted modified ammonium polyphosphate, melamine cyanurate and triazine char forming agent are respectively shown in the formula (6), the formula (7) and the formula (8).
In some more preferred embodiments, the melamine grafted modified ammonium polyphosphate, melamine cyanurate and triazine char forming agent in the ternary compound flame retardant have a mass ratio of 4:1:2-5:1:5, so that the ternary compound flame retardant has a good flame retardant synergistic effect.
In some embodiments, the curing agent is a cycloaliphatic amine curing agent.
In some more preferred embodiments, the alicyclic amine curing agent is isophorone diamine curing agent, which has the characteristics of high hydrogen content, high strength after curing, convenient operation and room temperature curing, and the dosage in the method is 1-3.2 wt% of the total weight of the formula, and the proportion can ensure the operability of the material and the strength of the material after curing.
In some embodiments, the shielding agent is a neutron shielding agent, a mixture of one or more of photon shielding agents.
In some more specific embodiments, the shielding agent is a mixture of one or more of boron carbide, hydroxy iron powder and tungsten powder, for example, single tungsten powder and a compound mixture of hydroxy iron powder and boron carbide, and the particle size of the compound mixture is 2-5 μm, so that neutrons and gamma rays can be shielded.
In some embodiments, the dispersant is a mixture of one or more of gamma-aminopropyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane.
In some embodiments, the defoamer is a silicon-based defoamer.
In some embodiments, the liquid flame retardant is an organic phosphorus based flame retardant.
The shielding putty material for the high radiation area of the embodiment is characterized in that a resin matrix is obtained by compounding low-viscosity, high-adhesion and nonflammable hydantoin epoxy resin and heat-resistant bisphenol A epoxy resin, and the resin matrix is subjected to flame retardant modification by introducing a low-addition amount ternary compound high-efficiency flame retardant and a liquid flame retardant, so that the shielding putty material has good flame retardant property, and in addition, the liquid flame retardant has a wetting effect on a system, so that the shielding putty material is endowed with the characteristics of excellent adhesive property, high shielding property, convenient construction and the like after the high-filling shielding agent is added, and has the following advantages compared with the prior art:
(1) Unlike traditional hydroxide flame retardant and binary compound phosphorus-nitrogen flame retardant, the ternary compound flame retardant adopted in the embodiment can melt flame retardant polymer first when the system is heated, and melamine grafted modified ammonium polyphosphate is heated first to decompose acid with strong dehydration effect. With the rise of temperature, the generated acid can be subjected to esterification reaction with macromolecular triazine char forming agent to be dehydrated, the generated water can be gasified at high temperature, meanwhile, high-purity melamine cyanurate can also generate ammonia (NH 3) and carbon dioxide (CO 2) when heated, and the overflow of water vapor, NH 3 and CO 2 can expand the heated and melted polymer and dilute air and combustible materials around the combustion reaction. The macromolecular triazine charring agent is carbonized to form an expanded carbon layer under the dehydration action of acid generated by melamine grafted modified ammonium polyphosphate, and the continuous compact expanded carbon layer can serve as a physical barrier for heat transfer and mass transfer, and free radicals contained in the macromolecular triazine charring agent can form gaseous free radical reaction in the thermal degradation process of the resin, so that the macromolecular triazine charring agent is favorable for terminating a free radical reaction chain in thermal cracking of epoxy resin and slowing down the thermal degradation of the epoxy resin. The polymer is flame-retarded from two aspects of gas phase and condensed phase in the whole process, so that the shielding putty material has good flame-retardant performance, the oxygen index is more than 32, and the V0 grade is achieved by vertical combustion.
(2) The traditional ammonium polyphosphate is added into resin through physical mixing, so that the problems of poor compatibility and obvious reduction of mechanical properties exist between the traditional ammonium polyphosphate and a resin matrix. The melamine grafted modified ammonium polyphosphate adopted in the embodiment has good compatibility with epoxy resin, and simultaneously, the grafted side group and the other two flame retardants both contain amine groups, so that the melamine grafted modified ammonium polyphosphate can participate in the curing reaction of the epoxy resin, and the crosslinking density of a cured product is improved, so that the material has good mechanical properties. Wherein the mechanism of the curing reaction is as follows:
(3) According to the shielding putty material, the added liquid flame retardant plays a role in carrying out flame retardant modification by cooperating with the ternary compound flame retardant on one hand, and on the other hand, the viscosity of a system can be adjusted, the processability of the system is improved, the wettability between resin and an adhesive substrate is improved, and the adhesive strength of the shielding putty material is further improved.
(4) The shielding putty material of the embodiment has active groups on the surface of the used hydroxyl iron, and the shielding agent modified by the dispersing agent has good interface compatibility with epoxy resin, has no obvious aggregation and is beneficial to preparing the shielding putty material with uniform density.
Example 2
The embodiment discloses a preparation method of a shielding putty material for a high-radiation area, which comprises the following steps:
Step S1, respectively weighing hydantoin resin, bisphenol A epoxy resin, a curing agent, a ternary compound flame retardant, a shielding agent, a dispersing agent, a defoaming agent and a liquid flame retardant according to the weight percentage in the embodiment 1;
S2, adding hydantoin resin, bisphenol A epoxy resin and ternary compound flame retardant into a container, and uniformly mixing to obtain a first mixture;
s3, adding a shielding agent, a dispersing agent, a defoaming agent and a liquid flame retardant into the first mixture, and uniformly mixing to obtain a second mixture;
And S4, adding a curing agent into the second mixture, and carrying out vacuum stirring, so that the phenolic aldehyde and the curing agent are subjected to curing reaction to obtain the shielding putty material with the three-dimensional network structure for the high radiation area.
In some embodiments, the uniform mixing condition in the step S2 is that stirring is carried out for 20-30 min under the conditions of 23-30 ℃ and the rotating speed of 500-700 rpm;
In some embodiments, the uniform mixing in the step S3 is carried out under the conditions of 23-30 ℃ and 30-70 rpm of rotation speed for 20-30 min.
In some embodiments, the vacuum stirring condition in the step S4 is that stirring is carried out for 10-20 min under the conditions of 23-30 ℃, the rotating speed of 30-50 rpm and the vacuum degree of less than or equal to 0.098MPa, and the construction can be carried out according to different working conditions.
According to the preparation method of the shielding putty material for the high-radiation area, the matrix resin is obtained by compounding the low-viscosity, high-adhesion and nonflammable hydantoin epoxy resin and the heat-resistant bisphenol A epoxy resin, the treated high-filling shielding agent is uniformly dispersed in the matrix, and the liquid flame retardant and the ternary compound flame retardant in the system are used for synergistic flame retardance. In addition, the amino group contained in the ternary compound flame retardant participates in the curing reaction of the epoxy resin, and exists in a system in a chemical bond combination mode, and the prepared shielding putty material has the characteristics of good flame retardance, high adhesion, high temperature resistance, high shielding performance, convenient construction and the like, and several groups of specific preparation are provided below, and the preparation method of the shielding putty material for the high-radiation area in the embodiment is described in detail as follows:
preparation example 1
Step S1, respectively weighing 10 weight percent of hydantoin epoxy resin (hydantoin epoxy resin in a formula (1), an epoxy value of 0.70-0.74), 2 weight percent of bisphenol A epoxy resin (model E51, an epoxy value of 0.48-0.54), 3.2 weight percent of isophorone diamine hardener, 9.5 weight percent of ternary compound flame retardant (melamine grafted modified ammonium polyphosphate: melamine cyanurate: macromolecular char forming agent mass ratio of 5:1:5), 71 weight percent of hydroxyl iron powder, 1 weight percent of boron carbide powder, 0.15 weight percent of dispersant (gamma-aminopropyl triethoxysilane), 0.02 weight percent of defoamer (silicon defoamer, model HS-028), 3.5 weight percent of liquid flame retardant (organophosphorus flame retardant, model CRP-002);
S2, adding the hydantoin epoxy resin of the formula (1), E51 and the ternary compound flame retardant into a container, and stirring for 25 minutes at 25 ℃ and 600rpm to obtain a first mixture;
S3, adding hydroxy iron powder, boron carbide powder, gamma-aminopropyl triethoxysilane, a silicon defoamer HS-028 and an organic phosphorus liquid flame retardant CRP-002 into the first mixture, and stirring for 30min at 25 ℃ and a rotating speed of 70rpm to obtain a second mixture;
and S4, adding isophorone diamine curing agent into the second mixture, and stirring for 10min under the conditions of 23 ℃ and 30rpm of rotation speed and vacuum degree of less than or equal to 0.098MPa to obtain the shielding putty material for the high-radiation area.
Fig. 2 is a scanning electron microscope image of the material prepared in this preparation example, and it can be seen that the shielding agent is uniformly dispersed and well combined with the resin matrix interface.
FIG. 3 is a graph showing test samples for tensile properties, bending properties, vicat softening point, oxygen index, vertical combustion, etc. prepared in this preparation example;
FIG. 4 shows a test piece for shielding property of 11cm in diameter and 2cm in thickness prepared in this preparation example.
FIG. 5 is a sample of the vertical burning properties of the material prepared in this preparation example, and the test data is shown in FIG. 6, with the vertical burning grade at V0.
FIG. 7 shows the results of limiting oxygen index property detection of the materials prepared in this preparation example. The oxygen index was 35.91%.
Preparation example 2
Step S1, respectively weighing 8 weight percent of hydantoin epoxy resin (hydantoin epoxy resin in a formula (1), an epoxy value of 0.70-0.74), 1 weight percent of bisphenol A epoxy resin (model E44, an epoxy value of 0.41-0.47), 1.8 weight percent of isophorone diamine hardener, 3.4 weight percent of ternary compound flame retardant (melamine grafted modified ammonium polyphosphate: melamine cyanurate: macromolecular char forming agent mass ratio of 4:1:2), 84 weight percent of tungsten powder, 0.1 weight percent of dispersing agent (gamma-methacryloxypropyl trimethoxysilane), 0.02 weight percent of antifoaming agent (silicon antifoaming agent, model HS-018), 1.8 weight percent of liquid flame retardant (organophosphorus flame retardant, model CRP-002);
S2, adding the hydantoin epoxy resin of the formula (1), E44 and the ternary compound flame retardant into a container, and stirring for 30 minutes at the temperature of 30 ℃ and the rotating speed of 700rpm to obtain a first mixture;
step S3, adding tungsten powder, gamma-methacryloxypropyl trimethoxy silane, a silicon defoamer HS-018 and an organic phosphorus flame retardant CRP-001 into the first mixture, and stirring for 25min at 30 ℃ and a rotating speed of 55rpm to obtain a second mixture;
And S4, adding isophorone diamine curing agent into the second mixture, and stirring for 20min under the conditions of 30 ℃ and 50rpm of rotation speed and vacuum degree of less than or equal to 0.098MPa to obtain the shielding putty material for the high-radiation area.
Preparation example 3
Step S1, respectively weighing 6wt% of hydantoin epoxy resin (hydantoin epoxy resin in a formula (2), epoxy value of 0.52-0.55), 0.5wt% of bisphenol A epoxy resin (model: E51, epoxy value of 0.48-0.54), 1wt% of isophorone diamine hardener, 5wt% of ternary compound flame retardant (melamine grafted modified ammonium polyphosphate: melamine cyanurate: macromolecular char forming agent mass ratio of 4:1:4), 81wt% of tungsten powder, 3wt% of hydroxy iron powder, 2wt% of boron carbide, 0.13wt% of dispersant (gamma-glycidyl ether oxypropyl trimethoxysilane), 0.07wt% of silicon defoamer (model: HS-027), 2.0wt% of organophosphorus liquid flame retardant (dimethyl methylphosphonate);
S2, adding the hydantoin epoxy resin of the formula (2), E51 and the ternary compound flame retardant into a container, and stirring for 20min at 23 ℃ and 500rpm to obtain a first mixture;
Step S3, adding tungsten powder, hydroxy iron powder, boron carbide, gamma-glycidol ether oxygen propyl trimethoxy silane, a silicon defoamer HS-027 and methyl dimethyl phosphonate into the mixture 1 in the step two, and stirring for 20min at 23 ℃ and 30rpm to obtain a second mixture;
And S4, adding isophorone diamine curing agent into the mixture 2 in the third step, and stirring for 15min under the conditions of 25 ℃ and 40rpm of rotation speed and vacuum degree of less than or equal to 0.098MPa to obtain the shielding putty material for the high radiation area.
Preparation example 4
S1, respectively weighing 8wt% of hydantoin epoxy resin (hydantoin epoxy resin shown in a formula (3) with an epoxy value of 0.70-0.74), 2wt% of bisphenol A epoxy resin (1 wt% of E51, 0.48-0.54 of epoxy value, 1wt% of E44 and 0.41-0.47 of epoxy value), 2.4wt% of isophorone diamine curing agent, 9wt% of ternary compound flame retardant (melamine grafted modified ammonium polyphosphate: melamine cyanurate: macromolecular char forming agent with a mass ratio of 4:1:3), 76wt% of tungsten powder, 0.12wt% of dispersing agent (0.06 wt% of gamma-glycidyl ether oxypropyl trimethoxysilane; 0.06wt% of gamma-aminopropyl triethoxysilane), 0.05wt% of silicon-based defoamer (model: HS-027) and 2.5wt% of organic phosphorus-based liquid flame retardant (dimethyl methylphosphonate);
s2, adding hydantoin epoxy resin of the formula (3), E51, E44 and ternary compound flame retardant into a container, and stirring for 20min at 23 ℃ and 500rpm to obtain a first mixture;
step S3, adding tungsten powder, gamma-glycidol ether oxypropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, a silicon defoamer HS-027 and dimethyl methylphosphonate into the mixture 1 in the step two, and stirring for 20min at 23 ℃ and a rotating speed of 30rpm to obtain a second mixture;
And S4, adding isophorone diamine curing agent into the mixture 2 in the third step, and stirring for 15min under the conditions of 25 ℃ and 40rpm of rotation speed and vacuum degree of less than or equal to 0.098MPa to obtain the shielding putty material for the high radiation area.
Preparation example 5
Step S1, respectively weighing 15wt% of hydantoin epoxy resin (5 wt% of hydantoin epoxy resin of formula (1), epoxy value of 0.70-0.74; 5wt% of hydantoin epoxy resin of formula (2), epoxy value of 0.52-0.55; 5wt% of hydantoin epoxy resin of formula (3), epoxy value of 0.70-0.74), 1wt% of bisphenol A epoxy resin (model: E44, epoxy value of 0.41-0.47), 2.5wt% of isophorone diamine hardener, 6wt% of ternary compound flame retardant (melamine grafted modified ammonium polyphosphate: melamine cyanurate: mass ratio of macromolecular char forming agent is 5:1:4), 70wt% of tungsten powder, 3wt% of hydroxy iron powder, 2wt% of boron carbide, 0.14wt% of dispersing agent (gamma-aminopropyl triethoxysilane), 0.04wt% of silicon defoamer (model: HS-027), 2.5wt% of organophosphorus liquid flame retardant (methylphosphonate);
Step S2, adding the hydantoin epoxy resin of the formula (1), the hydantoin epoxy resin of the formula (2), the hydantoin epoxy resin of the formula (3), E44 and the ternary compound flame retardant into a container, and stirring for 20min at 23 ℃ and the rotating speed of 500rpm to obtain a first mixture;
Step S3, adding tungsten powder, hydroxy iron powder, boron carbide, gamma-glycidol ether oxypropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, a silicon defoamer HS-027 and dimethyl methylphosphonate into the mixture 1 in the step two, and stirring for 20min at 23 ℃ and a rotating speed of 30rpm to obtain a second mixture;
And S4, adding isophorone diamine curing agent into the mixture 2 in the third step, and stirring for 15min under the conditions of 25 ℃ and 40rpm of rotation speed and vacuum degree of less than or equal to 0.098MPa to obtain the shielding putty material for the high radiation area.
Comparative example 1
The difference compared to preparation example 1 is that 12wt% of the flame retardant in this comparative example is all aluminum hydroxide flame retardant.
The aluminum hydroxide in the formula has low flame retardant efficiency, oxygen index of 25.2%, vertical combustion stepless, obvious increase of system viscosity after adding the aluminum hydroxide, difficult material molding, 15.7MPa of tensile strength, 26.8MPa of bending strength and lower mechanical property.
Comparative example 2
Compared with preparation example 1, the comparison example is characterized in that the mass ratio of melamine grafted modified ammonium polyphosphate to melamine cyanurate in 9.5wt% of the compound flame retardant is changed to 5:1.
In the formula, a macromolecular char forming agent is not added, the synergistic flame retardant effect of melamine grafted modified ammonium polyphosphate and melamine cyanurate is insufficient, the vertical combustion reaches V0, and the oxygen index is 28.3%.
Comparative example 3
Compared with preparation example 1, the preparation method is characterized in that the mass ratio of melamine grafted modified ammonium polyphosphate to melamine cyanurate to macromolecular char forming agent in the ternary compound flame retardant of 9.5wt% is 5:1:4, so that the addition amount of macromolecular char forming agent is reduced.
In the formula, the addition amount of the macromolecular char forming agent is insufficient, the vertical combustion is of V0 grade, and the oxygen index is 31.5%.
Comparative example 4
Compared with preparation example 1, the formulation composition of the comparative example is changed into 19.4wt% of polyethylene, 1.48wt% of boron carbide and 79% of lead powder which are commonly used in the prior art.
In the formula, the hydrogen content is high, the neutron shielding coefficient is high (2.29), but the material cannot be bonded, and the mechanical property, the Vicat softening point and the flame retardant property (oxygen index 21.4% and vertical burning grade is stepless) are all lower than those of preparation example 1.
Comparative example 5
Compared with preparation example 2, the comparative example is characterized in that 3.4 weight percent of ternary compound flame retardant is changed into melamine grafted modified ammonium polyphosphate.
In the formula, the melamine grafted modified ammonium polyphosphate has good compatibility with resin, excellent mechanical property and V0 grade vertical burning, but the flame retardant effect is insufficient, and the oxygen index is 30.8 percent (< 32%).
Comparative example 6
The difference compared with preparation example 2 is that the organic phosphorus liquid flame retardant is changed to 4.0wt%.
In the formula, the oxygen index reaches 32%, but the addition amount of the organic phosphorus liquid flame retardant is excessive, so that the mechanical property of the material is obviously reduced, and the tensile strength is 16.2MPa.
And (3) testing the product effect:
The properties of the high emissivity region shielding putty materials prepared in preparation examples 1 to 5 and the materials prepared in comparative examples 1 to 6 were tested, the comparative examples are the same as the test standards according to the preparation examples, and the test results are shown in tables 1 and 2.
Table 1 test results of preparation examples
Table 2 comparative test results
As can be seen from Table 1, the Vicat softening points of the shielding putty materials prepared in preparation examples 1-5 are above 200 ℃, the linear expansion coefficients are below 1X 10 -4K-1, the bonding strength is above 10MPa, which indicates that the shielding putty material has good thermal properties, good bonding strength and is favorable for repairing and bonding working conditions, in addition, the material combustion grades of the shielding putty materials prepared in preparation examples 1-5 reach V0 level due to the combined action of the ternary compound flame retardant and the liquid flame retardant, the oxygen index is above 32%, and the shielding putty material has good fireproof flame retardant property and greatly improves the use safety of the material. The ternary compound flame retardant participates in the resin curing reaction, and the material has good mechanical properties, and the 2cm shielding putty material has excellent radiation shielding effect, so that the ternary compound flame retardant can be widely applied to shielding equipment, pipelines and radiation hot spots with medium and high radiation levels and filling gaps and holes of shielding structures.
As can be seen from tables 1 and 2, the oxygen index was <32 when the single-function flame retardant, the binary flame retardant, and the char-forming agent were added in the same amount. The system processability is poor, the addition amount of the liquid flame retardant is excessive, the unmodified flame retardant is added, and the like, so that the mechanical property of the material is reduced, and the tensile strength is less than 20MPa.
It is to be understood that the above embodiments are merely illustrative of the application of the principles of the present invention, but not in limitation thereof. Various modifications and improvements may be made by those skilled in the art without departing from the spirit and substance of the invention, and are also considered to be within the scope of the invention.

Claims (20)

1.一种高辐射区用屏蔽腻子材料，其特征在于，按重量百分比计，其原料组成包括：1. A shielding putty material for high radiation areas, characterized in that, by weight percentage, its raw material composition includes: 屏蔽剂72wt％～86wt％，固化剂1wt％～3.2wt％，三元复配阻燃剂3.4wt％～9.5wt％，分散剂0.1wt％～0.15wt％，消泡剂0.02％wt～0.07wt％，液体阻燃剂1.8wt％～3.5wt％，余量为树脂基体，且所述树脂基体包括海因环氧树脂和双酚A型环氧树脂。The invention comprises 72wt% to 86wt% of shielding agent, 1wt% to 3.2wt% of curing agent, 3.4wt% to 9.5wt% of ternary composite flame retardant, 0.1wt% to 0.15wt% of dispersant, 0.02%wt to 0.07wt% of defoaming agent, 1.8wt% to 3.5wt% of liquid flame retardant, and the balance is resin matrix, and the resin matrix comprises hyaluronic acid epoxy resin and bisphenol A epoxy resin. 2.根据权利要求1所述的高辐射区用屏蔽腻子材料，其特征在于，所述海因环氧树脂包括式(1)-式(3)中的一种或多种，2. The shielding putty material for high radiation areas according to claim 1, characterized in that the hydantoin epoxy resin comprises one or more of formula (1) to formula (3), 其中，x、y、z均为整数。Among them, x, y, and z are all integers. 3.根据权利要求1所述的高辐射区用屏蔽腻子材料，其特征在于，所述双酚A型环氧树脂包括式(4)-式(5)中的一种或多种，3. The shielding putty material for high radiation areas according to claim 1, characterized in that the bisphenol A type epoxy resin comprises one or more of formula (4) to formula (5), 其中，m、n均为整数。Wherein, m and n are both integers. 4.根据权利要求1所述的高辐射区用屏蔽腻子材料，其特征在于，所述海因环氧树脂为：4. The shielding putty material for high radiation areas according to claim 1, characterized in that the hydantoin epoxy resin is: 其中，环氧值在0.52～0.74之间。Among them, the epoxy value is between 0.52 and 0.74. 5.根据权利要求1所述的高辐射区用屏蔽腻子材料，其特征在于，所述双酚A型环氧树脂为：5. The shielding putty material for high radiation areas according to claim 1, characterized in that the bisphenol A type epoxy resin is: 其中，环氧值在0.48～0.54之间。Among them, the epoxy value is between 0.48 and 0.54. 6.根据权利要求1所述的高辐射区用屏蔽腻子材料，其特征在于，所述海因环氧树脂与所述双酚A型环氧树脂的质量比例为4：1～15：1。6 . The shielding putty material for high radiation areas according to claim 1 , characterized in that the mass ratio of the hydantoin epoxy resin to the bisphenol A epoxy resin is 4:1 to 15:1. 7.根据权利要求1所述的高辐射区用屏蔽腻子材料，其特征在于，所述海因环氧树脂与所述双酚A环氧树脂的质量比例为5：1～12：1。7. The shielding putty material for high radiation areas according to claim 1, characterized in that the mass ratio of the hydantoin epoxy resin to the bisphenol A epoxy resin is 5:1 to 12:1. 8.根据权利要求1所述的高辐射区用屏蔽腻子材料，其特征在于，所述三元复配阻燃剂为式(6)密胺接枝改性聚磷酸铵、式(7)三聚氰胺氰尿酸盐、式(8)三嗪类成炭剂的混合物，8. The shielding putty material for high radiation areas according to claim 1, characterized in that the ternary composite flame retardant is a mixture of melamine grafted modified ammonium polyphosphate of formula (6), melamine cyanurate of formula (7), and triazine carbonizing agent of formula (8), 9.根据权利要求8所述的高辐射区用屏蔽腻子材料，其特征在于，所述三元复配阻燃剂中密胺接枝改性聚磷酸铵：三聚氰胺氰尿酸盐：三嗪类成炭剂质量比例为4：1：2～5：1：5。9. The shielding putty material for high radiation areas according to claim 8, characterized in that the mass ratio of melamine grafted modified ammonium polyphosphate: melamine cyanurate: triazine carbonizing agent in the ternary composite flame retardant is 4:1:2 to 5:1:5. 10.根据权利要求1所述的高辐射区用屏蔽腻子材料，其特征在于，所述固化剂为脂环胺类固化剂。10 . The shielding putty material for high radiation areas according to claim 1 , wherein the curing agent is an alicyclic amine curing agent. 11.根据权利要求10所述的高辐射区用屏蔽腻子材料，其特征在于，所述脂环胺类固化剂为异佛尔酮二胺。11. The shielding putty material for high radiation areas according to claim 10, characterized in that the alicyclic amine curing agent is isophoronediamine. 12.根据权利要求1所述的高辐射区用屏蔽腻子材料，其特征在于，所述屏蔽剂为中子屏蔽剂、光子屏蔽剂中的一种或多种的混合物。12 . The shielding putty material for high radiation areas according to claim 1 , wherein the shielding agent is a mixture of one or more of a neutron shielding agent and a photon shielding agent. 13.根据权利要求12所述的高辐射区用屏蔽腻子材料，其特征在于，所述屏蔽剂为碳化硼、羟基铁粉、钨粉中的一种或多种的混合物，其粒径为2～5μm。13. The shielding putty material for high radiation areas according to claim 12, characterized in that the shielding agent is a mixture of one or more of boron carbide, hydroxy iron powder, and tungsten powder, and its particle size is 2 to 5 μm. 14.根据权利要求1所述的高辐射区用屏蔽腻子材料，其特征在于，所述分散剂为γ-氨丙基三乙氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷中的一种或多种的混合物。14. The shielding putty material for high radiation areas according to claim 1, characterized in that the dispersant is a mixture of one or more of γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-glycidyloxypropyltrimethoxysilane. 15.根据权利要求1所述的高辐射区用屏蔽腻子材料，其特征在于，所述消泡剂为硅系消泡剂。15. The shielding putty material for high radiation areas according to claim 1, characterized in that the defoaming agent is a silicon-based defoaming agent. 16.根据权利要求1所述的高辐射区用屏蔽腻子材料，其特征在于，所述液体阻燃剂为有机磷系阻燃剂。16. The shielding putty material for high radiation areas according to claim 1, characterized in that the liquid flame retardant is an organic phosphorus flame retardant. 17.一种高辐射区用屏蔽腻子材料的制备方法，其特征在于，包括：17. A method for preparing a shielding putty material for high radiation areas, characterized by comprising: 步骤S1，按照权利要求1-16任一项所述的重量百分比分别称取海因环氧树脂、双酚A型环氧树脂、固化剂、三元复配阻燃剂、屏蔽剂、分散剂、消泡剂、液体阻燃剂；Step S1, weighing hydantoin epoxy resin, bisphenol A epoxy resin, curing agent, ternary composite flame retardant, shielding agent, dispersant, defoaming agent, and liquid flame retardant respectively according to the weight percentages described in any one of claims 1 to 16; 步骤S2，将海因环氧树脂、双酚A型环氧树脂、三元复配阻燃剂加入到容器中，经混合均匀后，得到第一混合物；Step S2, adding hydantoin epoxy resin, bisphenol A epoxy resin, and ternary composite flame retardant into a container, and mixing them evenly to obtain a first mixture; 步骤S3，将屏蔽剂、分散剂、消泡剂、液体阻燃剂加入到第一混合物中，经混合均匀后，得到第二混合物；Step S3, adding the shielding agent, dispersant, defoaming agent, and liquid flame retardant to the first mixture, and mixing them evenly to obtain a second mixture; 步骤S4，将固化剂加入第二混合物中，经过真空搅拌后，得到高辐射区用屏蔽腻子材料。Step S4, adding the curing agent into the second mixture, and after vacuum stirring, obtaining a shielding putty material for high radiation areas. 18.根据权利要求17所述的高辐射区用屏蔽腻子材料，其特征在于，在所述步骤S2中，混合均匀的条件为：23～30℃、转速500～700rpm条件下搅拌20～30min。18. The shielding putty material for high radiation areas according to claim 17, characterized in that, in the step S2, the conditions for uniform mixing are: stirring at 23-30°C and a rotation speed of 500-700 rpm for 20-30 minutes. 19.根据权利要求17所述的高辐射区用屏蔽腻子材料，其特征在于，在所述步骤S3中，混合均匀的条件为：23～30℃、转速30～70rpm条件下搅拌20～30min。19. The shielding putty material for high radiation areas according to claim 17, characterized in that, in the step S3, the mixing conditions are: stirring for 20 to 30 minutes at 23 to 30°C and a rotation speed of 30 to 70 rpm. 20.根据权利要求17所述的高辐射区用屏蔽腻子材料，其特征在于，在所述步骤S4中，真空搅拌的条件为：23～30℃、转速30～50rpm、真空度≤0.098MPa条件下搅拌10～20min。20. The shielding putty material for high radiation areas according to claim 17, characterized in that, in the step S4, the vacuum stirring conditions are: stirring for 10 to 20 minutes at 23 to 30°C, a rotation speed of 30 to 50 rpm, and a vacuum degree of ≤0.098 MPa.
CN202411855499.4A 2024-12-16 2024-12-16 A shielding putty material for high radiation areas and preparation method thereof Pending CN119799053A (en)

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