CN110437607A - A kind of Medical anti-radiation material and preparation method thereof - Google Patents
A kind of Medical anti-radiation material and preparation method thereof Download PDFInfo
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
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Abstract
The invention discloses a kind of Medical anti-radiation materials, it is characterized in that, each raw material of following parts by weight is made: ethenyl blocking condensation polymer 30-50 parts polyamide-based, 10-20 parts of ultra high molecular weight polyethylene fiber, Bi-Pr-Y-O5-10 parts, graphene oxide cladding metal powder 20-30 parts, 1-3 parts of initiator, 1-3 parts of coupling agent containing selenium.The invention also discloses the preparation methods of the Medical anti-radiation material.Medical anti-radiation material radiation-proof effect disclosed by the invention is significant, big to bremsstrahlung slip, pollution-free, and mechanical mechanics property and weatherability are good.
Description
Technical field
The present invention relates to medical material tech fields more particularly to a kind of Medical anti-radiation material and preparation method thereof.
Background technique
As science and technology steps into modernization, nuclear energy is widely applied in various aspects such as production, scientific research, medical treatment, with
People's daily life is also closely bound up.In medical test and treatment technology, inspection and treatment to certain malignant diseases can
Improve the diagnosis rate and treatment rate of disease using the use to radioactive instrument, these instruments, but they can generate it is various
The radiation of ray, these rays can generate harm to normal tissue, can increase malignant tumour, leukaemia, degenerative neurological system
The disease incidence for a variety of diseases such as disease, cardiovascular disease, reproductive system lesion of uniting can cause biological cell mutation, hematopoiesis function
The diseases such as energy missing, cancer.Therefore, radiation proof material causes the extensive concern of people.
Traditional radiation proof material mainly uses stereotype, flint glass, concrete, heavy metallic oxide and height hydrogeneous organic
Compound etc. separates the work and life environment of ray radiation source and people, to protect injury of the ray to human body.But this
A little density of material are big, and price, corrosion resistance, shielding property need to be further increased.Exactly under this form, radiation protection
Composite material enters the sight of people, and this kind of material has lesser density, lower cost, higher shielding property and
As " star " in current radiation proof material.However, Composite anti-radiation material in the prior art contains lead or lead mostly
Low-melting alloy, either lead or leaded low-melting alloy are made of heavy metal element, in radiative process,
Electrons generate a large amount of bremsstrahlung in heavy metal layer, and (bremsstrahlung, also known as brake radiation, refers to charged particle and atom
Or atomic nucleus slows down when colliding the radiation of sending suddenly), and the photon that bremsstrahlung generates is that do not had in treatment plan
It fully takes into account, pollution will necessarily have an impact radiotherapy result, and meeting normal tissue damages, and existing skill
This material in art is also more or less there is poor processability, production and processing difficulty, and product radiation resistance obtained is not
The problems such as ideal.
United States Patent (USP) US20040029998A1 discloses a kind of radiation proof material, is greater than 4 using thermoplastic resin and specific gravity
Non-lead, cadmium heavy metal be prepared for a kind of radiation proof material for substituting lead, this material facilitates sizing, and has and prevent well
Efficacy of irradiation.Although above-mentioned patent successfully provides a kind of can substituting lead and anti-with good radiation proof function
Radiative material, but for the pollution problem of bremsstrahlung, there is no very good solution measures.
Therefore, it is significant to develop a kind of radiation-proof effect, big to bremsstrahlung slip, pollution-free, production and processing is convenient, machine
Tool mechanical property and the good Medical anti-radiation material of weatherability accord with the demands of the market, before having extensive market value and application
Scape.
Summary of the invention
In order to overcome the defects of the prior art, the present invention provides a kind of Medical anti-radiation material and preparation method thereof, should
Preparation method simple process, easy to operate, preparation efficiency and finished product rate are high, practical；The medical anti-spoke being prepared
It is significant to penetrate material radiation-proof effect, big to bremsstrahlung slip, pollution-free, mechanical mechanics property and weatherability are good.
To achieve the above object of the invention, the technical solution adopted by the present invention is that, a kind of Medical anti-radiation material, following weight
Each raw material of part is made: ethenyl blocking condensation polymer 30-50 parts polyamide-based, ultra high molecular weight polyethylene fiber 10-20 containing selenium
Part, 5-10 parts of Bi-Pr-Y-O, graphene oxide coat metal powder 20-30 parts, 1-3 parts of initiator, 1-3 parts of coupling agent.
Further, the preparation method of the ethenyl blocking polyamide-based condensation polymer containing selenium includes the following steps: 2,
2'- seleno dibenzoic acid, 2,5- thiophene dicarboxylic acid, 4,4'- diaminobenzene anilid, catalyst are dissolved in shape in high boiling solvent
It is added in reaction kettle at solution, then by solution, with air in nitrogen or inert gas replacement kettle, 100-110 DEG C of reaction under normal pressure
3-5 hours, after be warming up to 230-250 DEG C, carried out polycondensation reaction 18-24 hours at 100-300Pa, after be cooled to room temperature, adjust
To normal pressure, then addition 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline and 4- ethylene aniline into reaction system, in 25-
Be stirred to react at 35 DEG C 1-2 hours, after settle out in water, then successively use ethanol washing, ethenyl blocking obtained after dry containing selenium
Polyamide-based condensation polymer.
Preferably, 2, the 2'- seleno dibenzoic acid, 2,5- thiophene dicarboxylic acid, 4,4'- diaminobenzene anilid, urge
The ratio between agent, high boiling solvent, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline, amount of substance of 4- ethylene aniline are
0.3:0.7:1:(0.3-0.6):(6-10):0.1:0.05。
Preferably, the catalyst is selected from least one of Thiophosphonate, phosphorous acid, thio-phosphamide.
Preferably, the high boiling solvent is in dimethyl sulfoxide, n,N-Dimethylformamide, N-Methyl pyrrolidone
It is at least one；The inert gas is selected from one of helium, neon, argon gas.
Further, the preparation method of the Bi-Pr-Y-O includes the following steps: bismuth chloride, praseodymium nitrate, yttrium chloride
It is added to the water to form solution, is then spray-dried solution, obtain the granular precursor being uniformly mixed on molecular level；
Granular precursor is placed in 650-800 DEG C of Muffle furnace and calcines 8-10h, after be cooled to room temperature, cross 100-300 mesh mesh, obtain
Bi-Pr-Y-O。
Preferably, the bismuth chloride, praseodymium nitrate, yttrium chloride, water mass ratio be 1:0.1:0.1:(20-40).
Further, the preparation method of the graphene oxide cladding metal powder, includes the following steps: metal powder point
Dissipate in ethyl alcohol, after silane coupling agent KH560 is added thereto, be stirred to react at 60-80 DEG C 2-4 hours, after add oxygen
Graphite alkene and basic catalyst are stirred to react 8-10 hours at 70-80 DEG C, rear to take out, dry after being eluted with water, and are obtained
Graphene oxide coats metal powder.
Preferably, the quality of the metal powder, ethyl alcohol, silane coupling agent KH560, graphene oxide, basic catalyst
Than being 1:(3-5): 0.1:(2-3): (0.3-0.5).
Preferably, the metal powder includes at least a kind of heavy metal powder and a kind of light metal powder；The heavy metal
Powder is selected from least one of copper, chromium, nickel, bismuth, zinc, cobalt, tungsten, barium；The light metal powder is in aluminium, strontium, barium, magnesium
It is one or more.
Preferably, the basic catalyst is selected from least one of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate.
Preferably, the initiator is selected from least one of azodiisobutyronitrile, azobisisoheptonitrile；The coupling agent
Selected from least one of Silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570.
Further, the preparation method of the Medical anti-radiation material includes the following steps: by weight to mix each raw material
Close uniformly, after add twin-screw extrude extrusion molding, obtain Medical anti-radiation material.
Preferably, the extrusion temperature in the area the extrusion molding double screw extruder extrusion molding Shi Ge are as follows: the first area 180-
190 DEG C, 192-198 DEG C of the secondth area, 200-210 DEG C of third area, the 4th 212-220 DEG C of area, the 5th 225-230 DEG C of area, die head temperature
Degree is 220-230 DEG C.
The beneficial effects of adopting the technical scheme are that
(1) Medical anti-radiation material provided by the invention, preparation method simple process is easy to operate, preparation efficiency and production
Product high yield rate, it is practical, it is suitble to large-scale production, application value with higher.
(2) Medical anti-radiation material provided by the invention overcomes more than conventional medical radiation proof material or lacks existing add
Work performance is poor, production and processing is difficult, and product radiation resistance obtained is undesirable, counts to the photon that bremsstrahlung generates in treatment
It is not fully taken into account in drawing, pollution will necessarily have an impact radiotherapy result, and meeting normal tissue damages
Technical problem, the Medical anti-radiation material radiation-proof effect being prepared is significant, big to bremsstrahlung slip, pollution-free, machine
Tool mechanical property and weatherability are good.
(3) Medical anti-radiation material provided by the invention, several component ethylene base sealing ends contain the polyamide-based condensation polymer of selenium, surpass
High molecular weight polyethylene fiber, Bi-Pr-Y-O, graphene oxide cladding metal powder all have radiation protection ability, act synergistically,
So that radiation-proof effect is more preferably；Substrate ethenyl blocking contains in the polyamide-based condensation polymer of selenium and contains selenium, supra polymer on strand
Weight polyethylene fiber is hydrogen-rich structure, Bi-Pr-Y-O is the bismuth metal alloy oxide of rare earth metal doping, graphene oxide packet
It is strong to cover the constituent structure radiation protection ability such as metal powder, is free of lead, cadmium, environmental pollution can be effectively reduced, while can reduce to adding
The health hazards of worker person, it is more environmentally friendly.
(4) Medical anti-radiation material provided by the invention, during the preparation process, under the action of initiator, vinyl envelope
End polyamide-based condensation polymer containing selenium is grafted with ultra high molecular weight polyethylene fiber, so that each ingredient becomes organic whole, is mentioned
The comprehensive performance of high material；The introducing of benzoyl amine structure on material molecule chain, thiophene-structure can assign material excellent synthesis
While performance, moreover it is possible to be conducive to improve the shielding property of material；Graphene oxide coats metal powder, can effective protection gold
Belong to powder, prevents its oxidation corrosion, meanwhile, the introducing of graphene-structured can further improve shielding property.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, and make features described above of the invention,
Purpose and advantage are more clear understandable, and the present invention will be further explained with reference to the examples below.Embodiment is only used for
It is bright the present invention rather than limit the scope of the invention.
Present invention raw material as used in the following examples is commercially available.
Embodiment 1
Each raw material of a kind of Medical anti-radiation material, following parts by weight is made: ethenyl blocking polyamide-based polycondensation containing selenium
30 parts of object, 10 parts of ultra high molecular weight polyethylene fiber, 5 parts of Bi-Pr-Y-O, graphene oxide coat 20 parts of metal powder, azo
1 part of bis-isobutyronitrile, 1 part of Silane coupling agent KH550.
The preparation method of the ethenyl blocking polyamide-based condensation polymer containing selenium includes the following steps: 2,2'- seleno two
Benzoic acid, 2,5- thiophene dicarboxylic acid, 4,4'- diaminobenzene anilid, Thiophosphonate are dissolved in dimethyl sulfoxide and form solution,
Solution is added in reaction kettle again, with air in nitrogen displacement kettle, normal pressure lower 100 DEG C of reactions 3 hours, after be warming up to 230 DEG C, In
Carried out polycondensation reaction 18 hours under 100Pa, after be cooled to room temperature, be adjusted to normal pressure, then into reaction system be added 2- ethyoxyl -1-
Ethoxy carbonic acyl radical -1,2- dihydroquinoline and 4- ethylene aniline, are stirred to react 1 hour at 25 DEG C, after settle out in water, then successively
With ethanol washing, ethenyl blocking polyamide-based condensation polymer containing selenium is obtained after dry；The 2,2'- seleno dibenzoic acid, 2,5-
Thiophene dicarboxylic acid, 4,4'- diaminobenzene anilid, Thiophosphonate, dimethyl sulfoxide, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,
The ratio between 2- dihydroquinoline, amount of substance of 4- ethylene aniline are 0.3:0.7:1:0.3:6:0.1:0.05.
The preparation method of the Bi-Pr-Y-O includes the following steps: to add bismuth chloride 10g, praseodymium nitrate 1g, yttrium chloride 1g
Enter into water 200g and form solution, be then spray-dried solution, obtains the presoma being uniformly mixed on molecular level
Grain；Granular precursor is placed in 650 DEG C of Muffle furnaces and calcines 8h, after be cooled to room temperature, cross 100 mesh meshes, obtain Bi-Pr-Y-
O；The bismuth chloride, praseodymium nitrate, yttrium chloride, water mass ratio be 1:0.1:0.1:20.
The preparation method of the graphene oxide cladding metal powder, includes the following steps: to disperse metal powder 100g
In ethyl alcohol 300g, after silane coupling agent KH560 10g is added thereto, be stirred to react at 60 DEG C 2 hours, after add oxygen
Graphite alkene 200g and sodium hydroxide 30g is stirred to react 8 hours at 70 DEG C, rear to take out, dry after being eluted with water, and obtains oxygen
Graphite alkene coats metal powder；The metal powder is mixed by copper, aluminium, strontium 1:2:1 in mass ratio.
The preparation method of the Medical anti-radiation material includes the following steps: by weight to be uniformly mixed each raw material, after
Extrusion molding is added twin-screw extrude, Medical anti-radiation material is obtained；The extrusion molding double screw extruder is extruded into
The extrusion temperature in the area Xing Shige are as follows: the first 180 DEG C of area, 192 DEG C of the secondth area, 200 DEG C of third area, 212 DEG C of the 4th area, the 5th area
225 DEG C, die head temperature is 220 DEG C.
Embodiment 2
Each raw material of a kind of Medical anti-radiation material, following parts by weight is made: ethenyl blocking polyamide-based polycondensation containing selenium
35 parts of object, 12 parts of ultra high molecular weight polyethylene fiber, 6 parts of Bi-Pr-Y-O, graphene oxide coat 23 parts of metal powder, azo
Two 1.5 parts of different heptonitriles, KH5601.5 parts of silane coupling agent.
The preparation method of the ethenyl blocking polyamide-based condensation polymer containing selenium includes the following steps: 2,2'- seleno two
Benzoic acid, 2,5- thiophene dicarboxylic acid, 4,4'- diaminobenzene anilid, phosphorous acid are dissolved in N,N-dimethylformamide and being formed
Solution, then solution is added in reaction kettle, with air in helium replacement kettle, lower 103 DEG C of normal pressure are reacted 3.5 hours, after be warming up to
235 DEG C, carried out polycondensation reaction 19 hours at 150Pa, after be cooled to room temperature, be adjusted to normal pressure, then 2- is added into reaction system
Ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline and 4- ethylene aniline, are stirred to react 1.2 hours at 27 DEG C, after in water
It settles out, then successively uses ethanol washing, obtain ethenyl blocking polyamide-based condensation polymer containing selenium after dry；The 2,2'- seleno two
Benzoic acid, 2,5- thiophene dicarboxylic acid, 4,4'- diaminobenzene anilid, phosphorous acid, N,N-dimethylformamide, 2- ethyoxyl-
The ratio between 1- ethoxy carbonic acyl radical -1,2- dihydroquinoline, amount of substance of 4- ethylene aniline are 0.3:0.7:1:0.4:7:0.1:0.05.
The preparation method of the Bi-Pr-Y-O includes the following steps: to add bismuth chloride 10g, praseodymium nitrate 1g, yttrium chloride 1g
Enter into water 250g and form solution, be then spray-dried solution, obtains the presoma being uniformly mixed on molecular level
Grain；Granular precursor is placed in 700 DEG C of Muffle furnaces and calcines 8.5h, after be cooled to room temperature, cross 130 mesh meshes, obtain Bi-Pr-
Y-O；The bismuth chloride, praseodymium nitrate, yttrium chloride, water mass ratio be 1:0.1:0.1:25.
The preparation method of the graphene oxide cladding metal powder, includes the following steps: to disperse metal powder 100g
In ethyl alcohol 350g, after silane coupling agent KH560 10g is added thereto, be stirred to react at 65 DEG C 2.5 hours, after add
Graphene oxide 230g and sodium carbonate 35g is stirred to react 8.5 hours at 73 DEG C, rear to take out, dry after being eluted with water, and is obtained
Graphene oxide coats metal powder；The metal powder is that chromium, nickel, bismuth, barium 1:3:2:2 in mass ratio are mixed.
The preparation method of the Medical anti-radiation material includes the following steps: by weight to be uniformly mixed each raw material, after
Extrusion molding is added twin-screw extrude, Medical anti-radiation material is obtained；The extrusion molding double screw extruder is extruded into
The extrusion temperature in the area Xing Shige are as follows: the first 183 DEG C of area, 194 DEG C of the secondth area, 203 DEG C of third area, 214 DEG C of the 4th area, the 5th area
226 DEG C, die head temperature is 223 DEG C.
Embodiment 3
Each raw material of a kind of Medical anti-radiation material, following parts by weight is made: ethenyl blocking polyamide-based polycondensation containing selenium
40 parts of object, 15 parts of ultra high molecular weight polyethylene fiber, 7 parts of Bi-Pr-Y-O, graphene oxide coat 25 parts of metal powder, azo
2 parts of bis-isobutyronitrile, 2 parts of silane coupling agent KH570.
The preparation method of the ethenyl blocking polyamide-based condensation polymer containing selenium includes the following steps: 2,2'- seleno two
Benzoic acid, 2,5- thiophene dicarboxylic acid, 4,4'- diaminobenzene anilid, thio-phosphamide are dissolved in shape in N-Methyl pyrrolidone
Be added in reaction kettle at solution, then by solution, with air in neon displacement kettle, normal pressure lower 105 DEG C of reactions 4 hours, after be warming up to
240 DEG C, carried out polycondensation reaction 20 hours at 200Pa, after be cooled to room temperature, be adjusted to normal pressure, then 2- is added into reaction system
Ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline and 4- ethylene aniline, are stirred to react 1.5 hours at 29 DEG C, after in water
It settles out, then successively uses ethanol washing, obtain ethenyl blocking polyamide-based condensation polymer containing selenium after dry；The 2,2'- seleno two
Benzoic acid, 2,5- thiophene dicarboxylic acid, 4,4'- diaminobenzene anilid, thio-phosphamide, N-Methyl pyrrolidone, 2- ethoxy
The ratio between base -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline, amount of substance of 4- ethylene aniline are 0.3:0.7:1:0.45:8:0.1:
0.05。
The preparation method of the Bi-Pr-Y-O includes the following steps: to add bismuth chloride 10g, praseodymium nitrate 1g, yttrium chloride 1g
Enter into water 300g and form solution, be then spray-dried solution, obtains the presoma being uniformly mixed on molecular level
Grain；Granular precursor is placed in 720 DEG C of Muffle furnaces and calcines 9h, after be cooled to room temperature, cross 200 mesh meshes, obtain Bi-Pr-Y-
O；The bismuth chloride, praseodymium nitrate, yttrium chloride, water mass ratio be 1:0.1:0.1:30.
The preparation method of the graphene oxide cladding metal powder, includes the following steps: to disperse metal powder 100g
In ethyl alcohol 400g, after silane coupling agent KH560 10g is added thereto, be stirred to react at 70 DEG C 3 hours, after add oxygen
Graphite alkene 250g and potassium hydroxide 40g is stirred to react 9 hours at 75 DEG C, rear to take out, dry after being eluted with water, and obtains oxygen
Graphite alkene coats metal powder；The metal powder is zinc, cobalt, tungsten, magnesium 1:1:3:2 in mass ratio are mixed.
The preparation method of the Medical anti-radiation material includes the following steps: by weight to be uniformly mixed each raw material, after
Extrusion molding is added twin-screw extrude, Medical anti-radiation material is obtained；The extrusion molding double screw extruder is extruded into
The extrusion temperature in the area Xing Shige are as follows: the first 185 DEG C of area, 195 DEG C of the secondth area, 205 DEG C of third area, 216 DEG C of the 4th area, the 5th area
227 DEG C, die head temperature is 225 DEG C.
Embodiment 4
Each raw material of a kind of Medical anti-radiation material, following parts by weight is made: ethenyl blocking polyamide-based polycondensation containing selenium
45 parts of object, 9 parts of Bi-Pr-Y-O, 29 parts of metal powder of graphene oxide cladding, causes 18 parts of ultra high molecular weight polyethylene fiber
2.5 parts of agent, 2.7 parts of coupling agent；The initiator is azodiisobutyronitrile, azobisisoheptonitrile 3:5 in mass ratio is mixed；
The coupling agent is Silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570 1:3:4 in mass ratio mixing
It forms.
The preparation method of the ethenyl blocking polyamide-based condensation polymer containing selenium includes the following steps: 2,2'- seleno two
Benzoic acid, 2,5- thiophene dicarboxylic acid, 4,4'- diaminobenzene anilid, catalyst are dissolved in high boiling solvent and form solution, then
Solution is added in reaction kettle, with air in argon gas displacement kettle, normal pressure lower 108 DEG C of reactions 4.8 hours, after be warming up to 247 DEG C, In
Carried out polycondensation reaction 23 hours under 280Pa, after be cooled to room temperature, be adjusted to normal pressure, then into reaction system be added 2- ethyoxyl -1-
Ethoxy carbonic acyl radical -1,2- dihydroquinoline and 4- ethylene aniline, are stirred to react 1.9 hours at 33 DEG C, after settle out in water, then according to
It is secondary to use ethanol washing, ethenyl blocking polyamide-based condensation polymer containing selenium is obtained after dry；The 2,2'- seleno dibenzoic acid, 2,
5- thiophene dicarboxylic acid, 4,4'- diaminobenzene anilid, catalyst, high boiling solvent, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,
The ratio between 2- dihydroquinoline, amount of substance of 4- ethylene aniline are 0.3:0.7:1:0.53:9.5:0.1:0.05；The catalyst is
Thiophosphonate, phosphorous acid, thio-phosphamide 1:1:3 in mass ratio are mixed；The high boiling solvent is dimethyl sulfoxide, N,
Dinethylformamide, N-Methyl pyrrolidone 1:3:2 in mass ratio are mixed.
The preparation method of the Bi-Pr-Y-O includes the following steps: to add bismuth chloride 10g, praseodymium nitrate 1g, yttrium chloride 1g
Enter into water 350g and form solution, be then spray-dried solution, obtains the presoma being uniformly mixed on molecular level
Grain；Granular precursor is placed in 780 DEG C of Muffle furnaces and calcines 9.7h, after be cooled to room temperature, cross 280 mesh meshes, obtain Bi-Pr-
Y-O；The bismuth chloride, praseodymium nitrate, yttrium chloride, water mass ratio be 1:0.1:0.1:35.
The preparation method of the graphene oxide cladding metal powder, includes the following steps: to disperse metal powder 100g
In ethyl alcohol 450g, after silane coupling agent KH560 10g is added thereto, be stirred to react at 78 DEG C 3.7 hours, after add
Graphene oxide 280g and basic catalyst 48g is stirred to react 9.5 hours at 78 DEG C, rear to take out, dry after being eluted with water,
Obtain graphene oxide cladding metal powder；The basic catalyst is sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate are pressed
Mass ratio 1:2:4:3 is mixed.
The metal powder includes heavy metal powder and light metal powder；The heavy metal powder is copper, chromium, tungsten, barium are pressed
Mass ratio 1:2:1:3 is mixed；The light metal powder is aluminium, strontium, barium, magnesium 1:3:2:2 in mass ratio are mixed.
The preparation method of the Medical anti-radiation material includes the following steps: by weight to be uniformly mixed each raw material, after
Extrusion molding is added twin-screw extrude, Medical anti-radiation material is obtained；The extrusion molding double screw extruder is extruded into
The extrusion temperature in the area Xing Shige are as follows: the first 188 DEG C of area, 197 DEG C of the secondth area, 208 DEG C of third area, 219 DEG C of the 4th area, the 5th area
229 DEG C, die head temperature is 228 DEG C.
Embodiment 5
Each raw material of a kind of Medical anti-radiation material, following parts by weight is made: ethenyl blocking polyamide-based polycondensation containing selenium
50 parts of object, 20 parts of ultra high molecular weight polyethylene fiber, 10 parts of Bi-Pr-Y-O, 30 parts of metal powder of graphene oxide cladding, idol
Two 3 parts of different heptonitrile of nitrogen, 3 parts of silane coupling agent KH560.
The preparation method of the ethenyl blocking polyamide-based condensation polymer containing selenium includes the following steps: 2,2'- seleno two
Benzoic acid, 2,5- thiophene dicarboxylic acid, 4,4'- diaminobenzene anilid, phosphorous acid are dissolved in dimethyl sulfoxide and form solution, then will
Solution is added in reaction kettle, with air in nitrogen displacement kettle, normal pressure lower 110 DEG C of reactions 5 hours, after be warming up to 250 DEG C, In
Carried out polycondensation reaction 24 hours under 300Pa, after be cooled to room temperature, be adjusted to normal pressure, then into reaction system be added 2- ethyoxyl -1-
Ethoxy carbonic acyl radical -1,2- dihydroquinoline and 4- ethylene aniline, are stirred to react 2 hours at 35 DEG C, after settle out in water, then successively
With ethanol washing, ethenyl blocking polyamide-based condensation polymer containing selenium is obtained after dry；The 2,2'- seleno dibenzoic acid, 2,5-
Thiophene dicarboxylic acid, 4,4'- diaminobenzene anilid, phosphorous acid, dimethyl sulfoxide, 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- two
The ratio between amount of substance of hydrogen quinoline, 4- ethylene aniline is 0.3:0.7:1:0.6:10:0.1:0.05.
The preparation method of the Bi-Pr-Y-O includes the following steps: to add bismuth chloride 10g, praseodymium nitrate 1g, yttrium chloride 1g
Enter into water 400g and form solution, be then spray-dried solution, obtains the presoma being uniformly mixed on molecular level
Grain；Granular precursor is placed in 800 DEG C of Muffle furnaces and calcines 10h, after be cooled to room temperature, cross 300 mesh meshes, obtain Bi-Pr-Y-
O；The bismuth chloride, praseodymium nitrate, yttrium chloride, water mass ratio be 1:0.1:0.1:40.
The preparation method of the graphene oxide cladding metal powder, includes the following steps: to disperse metal powder 100g
In ethyl alcohol 500g, after silane coupling agent KH560 10g is added thereto, be stirred to react at 80 DEG C 4 hours, after add oxygen
Graphite alkene 300g and potassium carbonate 50g is stirred to react 10 hours at 80 DEG C, rear to take out, dry after being eluted with water, and obtains oxygen
Graphite alkene coats metal powder；The metal powder is that barium and magnesium 3:5 in mass ratio are mixed.
The preparation method of the Medical anti-radiation material includes the following steps: by weight to be uniformly mixed each raw material, after
Extrusion molding is added twin-screw extrude, Medical anti-radiation material is obtained；The extrusion molding double screw extruder is extruded into
The extrusion temperature in the area Xing Shige are as follows: the first 190 DEG C of area, 198 DEG C of the secondth area, 210 DEG C of third area, 220 DEG C of the 4th area, the 5th area
230 DEG C, die head temperature is 230 DEG C.
Comparative example 1
This example provides a kind of Medical anti-radiation material, and formula and preparation method are substantially the same manner as Example 1, unlike
Ethenyl blocking polyamide-based condensation polymer containing selenium is not added.
Comparative example 2
This example provides a kind of Medical anti-radiation material, and formula and preparation method are substantially the same manner as Example 1, unlike
Do not add ultra high molecular weight polyethylene fiber.
Comparative example 3
This example provides a kind of Medical anti-radiation material, and formula and preparation method are substantially the same manner as Example 1, unlike
Graphene oxide is replaced to coat metal powder with metal powder.
Comparative example 5
Commercially available Medical anti-radiation material.
The Medical anti-radiation material described in embodiment 1-5 and comparative example 1-5 is tested for the property, test method and test knot
Fruit is shown in Table 1.
Table 1
| Project | Radiation protection rate | Tensile strength | Limit oxygen index |
| Unit | % | MPa | % |
| Detection method | SJ20524 | GB/T1040.1-2006 | GB/T2406-1993 |
| Embodiment 1 | 97.5 | 48 | 40 |
| Embodiment 2 | 97.9 | 50 | 42 |
| Embodiment 3 | 98.4 | 51 | 45 |
| Embodiment 4 | 98.8 | 55 | 46 |
| Embodiment 5 | 99.2 | 40 | 48 |
| Comparative example 1 | 92.5 | 41 | 34 |
| Comparative example 2 | 94.0 | 42 | 35 |
| Comparative example 3 | 92.2 | 42 | 35 |
| Comparative example 4 | 92.8 | 41 | 32 |
| Comparative example 5 | 88.6 | 38 | 25 |
As it can be seen from table 1 Medical anti-radiation material mechanical mechanical property disclosed by the invention and flame retardant property are more preferably, prevent
Radiation effect is more preferable.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (10)
1. a kind of Medical anti-radiation material, which is characterized in that each raw material of following parts by weight is made: ethenyl blocking polyamides containing selenium
30-50 parts of amine condensation polymer, 10-20 parts of ultra high molecular weight polyethylene fiber, Bi-Pr-Y-O5-10 parts, graphene oxide cladding
20-30 parts of metal powder, 1-3 parts of initiator, 1-3 parts of coupling agent.
2. a kind of Medical anti-radiation material according to claim 1, which is characterized in that the ethenyl blocking polyamides containing selenium
The preparation method of amine condensation polymer includes the following steps: 2,2'- seleno dibenzoic acid, 2,5- thiophene dicarboxylic acid, 4,4'- bis-
Amino benzanilide, catalyst, which are dissolved in high boiling solvent, forms solution, then solution is added in reaction kettle, with nitrogen or lazy
Air in property gas displacement kettle, 100-110 DEG C reaction 3-5 hours under normal pressure, after be warming up to 230-250 DEG C, at 100-300Pa
Carry out polycondensation reaction 18-24 hour, after be cooled to room temperature, be adjusted to normal pressure, then into reaction system addition 2- ethyoxyl -1- ethoxy
Carbonic acyl radical -1,2- dihydroquinoline and 4- ethylene aniline, are stirred to react 1-2 hours at 25-35 DEG C, after settle out in water, then according to
It is secondary to use ethanol washing, ethenyl blocking polyamide-based condensation polymer containing selenium is obtained after dry.
3. a kind of Medical anti-radiation material according to claim 2, which is characterized in that 2, the 2'- seleno dibenzoic acid,
2,5- thiophene dicarboxylic acid, 4,4'- diaminobenzene anilid, catalyst, high boiling solvent, 2- ethyoxyl -1- ethoxy carbonic acyl radical -
The ratio between 1,2- dihydroquinoline, amount of substance of 4- ethylene aniline are 0.3:0.7:1:(0.3-0.6): (6-10): 0.1:0.05.
4. a kind of Medical anti-radiation material according to claim 2, which is characterized in that the catalyst is selected from phosphonothiolic acid
At least one of ester, phosphorous acid, thio-phosphamide；The high boiling solvent be selected from dimethyl sulfoxide, N,N-dimethylformamide,
At least one of N-Methyl pyrrolidone；The inert gas is selected from one of helium, neon, argon gas.
5. a kind of Medical anti-radiation material according to claim 1, which is characterized in that the preparation side of the Bi-Pr-Y-O
Method includes the following steps: that bismuth chloride, praseodymium nitrate, yttrium chloride are added to the water to form solution, is then done solution by spraying
It is dry, obtain the granular precursor being uniformly mixed on molecular level；Granular precursor is placed in 650-800 DEG C of Muffle furnace and calcines 8-
10h, after be cooled to room temperature, cross 100-300 mesh mesh, obtain Bi-Pr-Y-O；The bismuth chloride, praseodymium nitrate, yttrium chloride, water
Mass ratio is 1:0.1:0.1:(20-40).
6. a kind of Medical anti-radiation material according to claim 1, which is characterized in that the graphene oxide coats metal
The preparation method of powder includes the following steps: to disperse metal powder in ethyl alcohol, after silane coupling agent is added thereto
KH560 is stirred to react 2-4 hours at 60-80 DEG C, after add graphene oxide and basic catalyst, stirred at 70-80 DEG C
Reaction 8-10 hours is mixed, it is rear to take out, it is dry after being eluted with water, obtain graphene oxide cladding metal powder；The metal powder
End, ethyl alcohol, silane coupling agent KH560, graphene oxide, basic catalyst mass ratio be 1:(3-5): 0.1:(2-3):
(0.3-0.5)。
7. a kind of Medical anti-radiation material according to claim 6, which is characterized in that the metal powder includes at least one
Heavy metal species powder and a kind of light metal powder；The heavy metal powder in copper, chromium, nickel, bismuth, zinc, cobalt, tungsten, barium extremely
Few one kind；The light metal powder is selected from one of aluminium, strontium, barium, magnesium or a variety of；The basic catalyst is selected from hydroxide
At least one of sodium, sodium carbonate, potassium hydroxide, potassium carbonate.
8. a kind of Medical anti-radiation material according to claim 1, which is characterized in that it is different that the initiator is selected from azo two
At least one of butyronitrile, azobisisoheptonitrile；The coupling agent be selected from Silane coupling agent KH550, silane coupling agent KH560,
At least one of silane coupling agent KH570.
9. a kind of Medical anti-radiation material according to claim 1-8, which is characterized in that the Medical anti-radiation
The preparation method of material includes the following steps: by weight to be uniformly mixed each raw material, after add twin-screw extrude extrusion
Molding, obtains Medical anti-radiation material.
10. a kind of Medical anti-radiation material according to claim 9, which is characterized in that the extrusion molding twin-screw squeezes
The extrusion temperature in the area machine extrusion molding Shi Ge out are as follows: the first 180-190 DEG C of area, 192-198 DEG C of the secondth area, third area 200-210
DEG C, the 4th 212-220 DEG C of area, the 5th 225-230 DEG C of area, die head temperature be 220-230 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111053312A (en) * | 2019-12-28 | 2020-04-24 | 顾正明 | Anti-radiation antibacterial fabric |
| CN116533260A (en) * | 2023-04-28 | 2023-08-04 | 上海长征医院 | Anti-interference method of vein anesthesia robot system for ship |
-
2019
- 2019-07-22 CN CN201910659313.0A patent/CN110437607A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111053312A (en) * | 2019-12-28 | 2020-04-24 | 顾正明 | Anti-radiation antibacterial fabric |
| CN116533260A (en) * | 2023-04-28 | 2023-08-04 | 上海长征医院 | Anti-interference method of vein anesthesia robot system for ship |
| CN116533260B (en) * | 2023-04-28 | 2024-04-09 | 上海长征医院 | Anti-interference method of vein anesthesia robot system for ship |
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