CN108586777A - A kind of preparation method of unleaded anti-ray radiation rubber composite material - Google Patents
A kind of preparation method of unleaded anti-ray radiation rubber composite material Download PDFInfo
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- CN108586777A CN108586777A CN201810352427.6A CN201810352427A CN108586777A CN 108586777 A CN108586777 A CN 108586777A CN 201810352427 A CN201810352427 A CN 201810352427A CN 108586777 A CN108586777 A CN 108586777A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2307/00—Characterised by the use of natural rubber
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Abstract
The present invention relates to a kind of preparation methods of unleaded anti-ray radiation rubber composite material, it includes：It is prepared by radiation shield extender paste body；Emulsion blending step；Solidification demulsification step；Drying steps；Vulcanisation step.The present invention is prepared into the modified shielding filler slurry being stably dispersed in water by filler is shielded, and is mixed with rubber latex, not only can guarantee that filler is evenly dispersed in rubber, but also improve filler and combined with rubber interface, easy to operate feasible, is easy to industrialize.The preparation method of the present invention, which avoids caused by shielding filler directly mixedly appears demulsification with latex, disperses uneven phenomenon, is conducive to high concentration shielding uniform filling and is filled in rubber matrix.Since high concentration shielding filler is evenly dispersed in rubber, and interface cohesion is good, therefore the present invention has very high ray radiation shield effectiveness, and the mechanical property of the rubber composite material of high concentration shielding filler filling is not in apparent deterioration, can be satisfied with the performance requirement of actual use.
Description
Technical field
The invention belongs to anti-ray radiation Material Field, more particularly to a kind of unleaded anti-ray radiation rubber composite material
Preparation method.
Background technology
Since roentgen has found X-ray, various radioactive rays are in national defence, medicine, scientific and technical research, nuclear industry and original
The sub- technical application of energy deepens continuously and develops.Especially application of the X ray image technology on medical domain, carries for doctor
For indispensable clinical diagnosis foundation, already become the important component in the field.However, obtaining people using ray
While various information needed, Long Term Contact or the passive ray radiation that receives can cause the body of people impaired.Therefore, in abundant profit
While with ray, its harm to human body is reduced, it is very necessary to take certain safeguard procedures.
Traditional ray radiation shielding material mainly based on lead or lead-containing materials, has been continued to use more than 100 in history
Year, there is extraordinary anti-ray radiation effect.And the radiation protection protector for being used for human body is also mainly lead clothing or lead rubber etc..Lead
Rubber is that the one kind prepared through mixing, vulcanization is anti-to penetrate with the leaded metal oxide such as lead oxide or filled rubber containing lead salts
Beta radiation material.With era development and technological progress, these safety devices made by lead rubber because of its toxicity and are dressed not
Convenient disadvantage, and gradually replaced by other radiation proof materials.
The novel anti-ray radiation rubber material of prior art preparation, mainly with the heavy metal of various non-lead, rare earth metal
And its oxide or salt prepare the rubber material of anti-ray radiation as gum filler by mixing, vulcanization.
Existing disclosed pertinent literature is as follows：
Entitled " the active Bi of document2O3The preparation and the research of gamma Rays barrier propterty of/rubber composite material ", disclosure
Main contents be：Using mechanical attrition method particle diameter distribution uniformly activity Bi is prepared by the way that complexed surfactant is added2O3
Micro-/ nano powder is added with slurry form in Heveatex, prepares the activity with good mechanical strength and radiation protection performance
Bi2O3/ rubber composite material.It (is sponsored quoted from Xinan Science and Technology Univ.《Functional material》2013,2 (44) .216-220, author：Wei
Rosy clouds, Zhou Yuanlin, Li Yingjun).
Document is entitled：“Bi3B5O12Preparation and its research of neutron-gamma ray collaboration shielding properties ", it is disclosed to lead
Wanting content is：The Bi of different luminous intensities is prepared by self-propagating high-temperature combustion method3B5O12Crystal, and filled out as function
Charge is added in Heveatex, obtains the Bi with excellent mechanical performances and gamma-rays-thermal neutron barrier propterty3B5O12/
Rubber composite material.It (is sponsored quoted from Xinan Science and Technology Univ.《Master thesis》.2015, author:Liang Feng, Zhou Yuanlin, Li Ying
Army).
Entitled " the Gd (AA) of document2The research of/NR composite material X-ray-preventing shielding properties summer mechanical properties ", disclosed in
To the effect that：Acrylic acid gadolinium [Gd (AA)2] with NR by one peroxide crosslinking of mechanical blending molding composite material is made；It grinds
Study carefully its Phase stracture, shielding property and mechanical property, finds Gd (AA)2, it is scattered in rubber, particle is small, interface make
With strong, with Gd (AA)2, the increase of additive amount, the shielding property raising of composite material, the material mechanical performance under height filling
It still is able to meet application requirement.It (is prepared and processing key lab quoted from Beijing University of Chemical Technology, Beijing's novel high polymer material
It sponsors《China Synthetic Rubber Industry》2004,27 (1) .49, author：Yang Cheng, Liu Li, Sui Yiwei, He Lei, Zhang Liqun)
Document is entitled：" core is developed with protective gloves ", disclosed main contents are：Neutron/γ composite shielding gloves exist
Nuclear industry field has wide practical use, and the country there is no relevant manufacturers to produce with boron carbide (B4) and tungsten oxide (WO C3) it is screen
Cover absorbing material, modified natural rubber latex is matrix, development neutron/gamma shielding composite material, using dipping or mould pressing method, preparation
The core protective gloves for going out function admirable, to neutron absorption rate be >=20%, 59.5keV gamma-ray shielding rate >=
23%；Breaking strength >=10MPa.It (is sponsored quoted from China Engineering Physics Research Institute《Chinese radiation protection branch of core association is academic
Annual meeting》.2013, author：Li Li, Xu Lijun)
Above documents disclose unleaded anti-ray radiation rubber composite material is prepared, there is certain radiation-proof effect,
But the preparation methods of these materials is complicated, is not easy industrialized production, and cost is higher, and filler filled in rubber matrix number compared with
Low (<40 parts), cause anti-ray radiation effect poor.
Invention content
A kind of unleaded anti-ray radiation rubber composite wood is provided it is an object of the invention to overcome the shortcomings of background technology
The method of material.The present invention provides one kind being easy to industrialized production, at low cost, and the rubber that high concentration fills non-lead screen filler is multiple
Condensation material, both so that high concentration shielding filler it is evenly dispersed in rubber, and with the preferable interface interaction of rubber matrix, it
While ensureing that rubber composite material basic performance meets actual operation requirements, and it can realize higher ray radiation shielding effect
Fruit.
The technical scheme is that：
A kind of preparation method of unleaded anti-ray radiation rubber composite material, it is characterised in that：It includes the following steps：
(1), prepared by radiation shield extender paste body：
By 50 parts of radiation shield fillers, 0.1-4 parts of emulsifiers, 0-2 parts of surface modifiers, 0.1-0.5 parts of thickeners, 0.1-
0.5 part of antifoaming agent, 0.5-2 parts of ammonium hydroxide and 40-300 parts of deionized waters are mixed；And it is stirred with dispersion by high speed machine；Ultrasound
Wavelength-division dissipates or cell crushing instrument disperses 10-60min；Obtain being stably dispersed in the radiation shield filler slurry in water；
(2), emulsion blending step：
The 40-150 part radiation shield filler slurries being prepared in step (1) are added based on radiation shield packing quality
Enter into the rubber latex of 100 parts of rubber (weight by dry rubber)；Machinery is carried out to stir with 30-60min；Evenly dispersed shielding is obtained to fill out
Material/rubber mix lotion；
(3), solidification demulsification step：
Calcium chloride or calcium nitrate solution that mass fraction is 2-20% are added to the shielding prepared in step (2)
In filler/rubber mix lotion；The solidification until the shielding filler/rubber mix lotion is demulsified completely；
(4), drying steps：
Shielding filler/the rubber composition prepared in step (3) is filtered, is washed；Then, at 60-120 DEG C into
Row drying, drying time 20min-60min；
(5), vulcanisation step：
By 100 parts be prepared in step (4) shielding filler/rubber compositions and 100 parts of rubber and 0.1-2.5 parts
Vulcanizing agent, 0.5-6 part vulcanization accelerator, 0.1-1 parts of anti-aging agents are mixed；And it is kneaded out in two-roll mill or mixer
Piece；Then, it places it in 100-160 DEG C of mold and vulcanizes；Obtain unleaded anti-ray radiation rubber composite material.
Wherein, the radiation shield filler is one kind of following material or in which several mixtures：Native sulfate of barium,
Precipitation method barium sulfate, modified barium sulphate, bismuth oxide, tungsten carbide, barium tungstate.
Preferably, the shielding packing material size is 50-4000nm.
The emulsifier is one kind of following material or in which several mixtures：Neopelex, octyl
Phenol polyethenoxy ether emulsifier op-10, casein.
The thickener is one kind of following material or in which several mixtures：Hydroxyethyl cellulose, carboxymethyl are fine
Tie up element, polyacrylic acid, polyacrylamide.
The surface modifier is one kind of following material or in which several mixtures：γ-aminopropyl-triethoxy
Silane (KH550), γ-methacryloxypropyl trimethoxy silane (KH570), double-[γ-(triethoxysilicane) propyl]
Tetrasulfide (Si69), polypyrrole alkanone (PVP).
The antifoaming agent, it includes：Dimethyl silicone polymer class, mineral oils, polyethers antifoaming agent.
It is 500-20000r/min that the high speed machine, which is stirred with dispersion rotating speed,；Ultrasonic wave disperses or ultrasonic cell-break
It is 100-2000KW that instrument, which disperses power,.
The rubber latex, it includes：Natural rubber latex, styrene-butadiene latex, carboxylic styrene butadiene latex, NBR latex, carboxylic
Base NBR latex.
The vulcanizing agent is sulphur.
The vulcanization accelerator is one kind of following material or in which several mixtures：2, bis- thio dibenzo of 2'-
Thiazole (altax), N- cyclohexyl -2- benzothiazole sulfonamides (accelerant CZ), zinc diethyl dithiocarbamate,
Zinc oxide, hard acid acid, thiocarbamide.
The anti-aging agent is one kind of following material or in which several mixtures：2-mercaptobenzimidazole (anti-aging agent
MB), N- phenyl-2-naphthylamines (antioxidant D), 2,2,4- trimethyl -1,2- dichloride quinoline polymers (anti-aging agent RD), 2,2,4-
- 1,2 hydrogenated quinoline polymer (antioxidant H PG) of dimethyl.
The advantage of the invention is that：The present invention is prepared into the modified shielding extender paste being stably dispersed in water by filler is shielded
Body is mixed with rubber latex, not only can guarantee that filler is evenly dispersed in rubber, but also improve filler and combined with rubber interface,
It is easy to operate feasible, it is easy to industrialize.It is directly mixedly appeared with latex in addition, the preparation method of the present invention avoids shielding filler
Disperse uneven phenomenon caused by demulsification, is conducive to high concentration shielding uniform filling and is filled in rubber matrix.Just because of highly concentrated
Degree shielding filler is evenly dispersed in rubber, and interface cohesion is good, and the rubber prepared by method provided by the present invention is multiple
Condensation material has very high ray radiation shield effectiveness, and the mechanics of the rubber composite material of high concentration shielding filler filling
Performance is not in apparent deterioration, can be satisfied with the performance requirement of actual use.
Description of the drawings
Fig. 1 (a) is CT scan photo in the embodiment of the present invention 1.
Fig. 1 (b) is CT scan photo in the embodiment of the present invention 2.
Fig. 1 (c) is CT scan photo in the embodiment of the present invention 3.
Fig. 1 (d) is CT scan photo in the embodiment of the present invention 4.
Fig. 1 (e) is CT scan photo in the embodiment of the present invention 5.
Specific implementation mode
With reference to the accompanying drawings of the specification and embodiment, the present invention is further illustrated.But embodiments of the present invention
It is without being limited thereto.
Embodiment 1：
The preparation method of the unleaded anti-ray radiation rubber composite material of the present invention, it includes the following steps：
(1) prepared by radiation shield dry load slurry：
By 50 part of 3000 mesh native sulfate of barium, 3 parts of emulsifier op-10s, 1 part of PVP, 0.2 part of carboxymethyl cellulose, 0.3 part
Dimethyl silicone polymer antifoaming agent, 1 part of ammonium hydroxide and 44.5 parts of deionized waters are mixed；It is stirred by 10000r/min high speed machines
With dispersion 30min；Obtain being stably dispersed in the radiation shield filler slurry in water；
(2) emulsion blending step：
40 parts of radiation shield filler slurries being prepared in step (1) are added to based on native sulfate of barium quality
In the natural rubber latex of 100 parts of rubber (weight by dry rubber)；And it carries out machinery and stirs with 30min；Obtain evenly dispersed natural sulphur
Sour barium/natural rubber mixed emulsion；
(3) solidification demulsification step：
Calcium chloride or calcium nitrate solution that mass fraction is 5% are added to the native sulfate of barium/day prepared in step (2)
In T PNR mixed emulsion；The solidification until mixed emulsion is demulsified completely；
(4) drying steps：
Native sulfate of barium/the natural rubber compound being prepared in step (3) is filtered, is washed；Then, by it
It is dried at 80 DEG C, dry 40min.
(5) vulcanisation step：
By 100 parts of native sulfate of barium/natural rubber compounds being prepared in step (4) and 100 parts of natural rubbers,
It is carried out with 1.5 parts of sulphur, 1.5 parts of altaxes, 1 part of accelerant CZ, 5 parts of stearic acids, 1 part of zinc oxide and 0.5 part of anti-aging agent RD
Mixing；And slice is kneaded in two-roll mill；Then, it places it in 140 DEG C of molds and is vulcanized；Obtain unleaded anti-penetrate
Beta radiation rubber composite material.
As shown in Fig. 1-a, the tensile strength of the native sulfate of barium/native rubber composite material is 19.3MPa；It is disconnected
It is 620% to split elongation.It is 0.015mmPb that its lead equivalent is detected under the X-ray of 120KV.
Embodiment 2：
The preparation method of the unleaded anti-ray radiation rubber composite material of the present invention, it includes the following steps：
(1) prepared by radiation shield dry load slurry：
By 50 parts of precipitation method barium sulfate, 2 parts of emulsifier neopelexes, 1 part of KH550,0.2 part of hydroxy ethyl fiber
Element, 0.3 part of dimethyl silicone polymer antifoaming agent, 1 part of ammonium hydroxide and 100 parts of deionized waters are mixed；And pass through 10000r/min
High speed machine is stirred with dispersion 30min；Obtain being stably dispersed in the radiation shield filler slurry in water；
(2) emulsion blending step：
The 120 parts of radiation shield filler slurries that will be prepared in step (1) are added based on precipitation method barium sulfate quality
Into the natural rubber latex of 100 parts of rubber (weight by dry rubber)；Machinery is carried out to stir with 30min；By the evenly dispersed precipitation method,
Obtain barium sulfate/natural rubber mixed emulsion；
(3) solidification demulsification step：
Calcium chloride or calcium nitrate solution that mass fraction is 5% are added to the barium sulfate/natural rubber prepared in step (2)
In glue mixed emulsion；The solidification until mixed emulsion is demulsified completely；
(4) drying steps：
Precipitation method barium sulfate/the natural rubber compound being prepared in step (3) is filtered, is washed；Then, will
It is dried at 80 DEG C, dry 40min.
(5) vulcanisation step：
By 100 parts of precipitation method barium sulfate/natural rubber compounds being prepared in step (4) and 100 parts of natural rubbers
Glue is carried out with 1 part of sulphur, 1 part of altax, 0.5 part of accelerant CZ, 5 parts of stearic acids, 1 part of zinc oxide and 0.5 part of antioxidant D
Mixing；And it is kneaded slice in two-roll mill；Then, it places it in 140 DEG C of molds and is vulcanized；It obtains unleaded
Anti- ray radiation rubber composite material.
As shown in Fig. 1-b, the tensile strength of precipitation method barium sulfate/native rubber composite material is 17.2MPa；Its
Elongation at break is 610%.It is 0.058mmPb that its lead equivalent is detected under the X-ray of 120KV.
Embodiment 3：
The preparation method of the unleaded anti-ray radiation rubber composite material of the present invention, it includes the following steps：
(1) prepared by radiation shield dry load slurry：
By 50 parts of average grain diameters be the tungsten carbide of 200nm, 2 parts of emulsifier neopelexes, 1 part of PVP, 0.2 part
Polyacrylamide, 0.3 part of mineral oil defoaming agent, 1 part of ammonium hydroxide and 200 parts of deionized waters are mixed；And it is super by 1000KW
Sound wave cell crushing instrument disperses 30min；Obtain being stably dispersed in the radiation shield filler slurry in water；
(2) emulsion blending step：
80 parts of radiation shield filler slurries being prepared in step (1) are added to 100 parts based on tungsten carbide quality
In the natural rubber latex of rubber (weight by dry rubber)；Machinery is carried out to stir with 30min；Obtain evenly dispersed tungsten carbide/natural rubber
Glue mixed emulsion；
(3) solidification demulsification step：
Calcium chloride or calcium nitrate solution that mass fraction is 5% are added to the tungsten carbide/natural rubber prepared in step (2)
In glue mixed emulsion；The solidification until mixed emulsion is demulsified completely；
(4) drying steps：
Tungsten carbide/the natural rubber compound being prepared in step (3) is filtered, is washed；Then, by it 80
It is dried at DEG C, dry 40min.
(5) vulcanisation step：
By 100 parts of tungsten carbide/natural rubber compounds being prepared in step (4) and 100 parts of natural rubbers, with 1.5
Part sulphur, 1.5 parts of altaxes, 0.5 part of accelerant CZ, 5 parts of stearic acids, 1 part of zinc oxide and 0.5 part of antioxidant H PG are mixed
It closes；And slice is kneaded in two-roll mill；Then, it places it in 140 DEG C of molds and is vulcanized；Obtain unleaded anti-ray
Radiate rubber composite material.
As shown in fig 1-c, the tensile strength of tungsten carbide/native rubber composite material is 18.3MPa；Its elongation at break is
520%.It is 0.025mmPb that its lead equivalent is detected under the X-ray of 120KV.
Embodiment 4：
The preparation method of the unleaded anti-ray radiation rubber composite material of the present invention, it includes the following steps：
(1) prepared by radiation shield dry load slurry：
By 25 parts of average grain diameters be 50nm bismuth oxide and 25 parts of precipitation method barium sulfate, 2 parts of emulsifier caseins, 1 part
KH570,0.2 part of hydroxyethyl cellulose, 0.3 part of dimethyl silicone polymer class antifoaming agent, 1 part of ammonium hydroxide and 50 parts of deionized waters carry out
Mixing；And it is stirred with dispersion 10min by 20000r/min high speed machines；Obtain being stably dispersed in the radiation shield extender paste in water
Body；
(2) emulsion blending step：
The 150 parts of radiation shield filler slurries that will be prepared in step (1), by bismuth oxide and the total matter of precipitation method barium sulfate
Gauge is added in the natural rubber latex of 100 parts of rubber (weight by dry rubber)；And it carries out machinery and stirs with 30min；Uniformly divided
Scattered tungsten carbide/natural rubber mixed emulsion；
(3) solidification demulsification step：
The calcium nitrate solution that mass fraction is 5% is added in the mixed emulsion prepared in step (2)；Until described
Mixed emulsion is demulsified solidification completely；
(4) drying steps：
Bismuth oxide/barium sulfate/the natural rubber compound being prepared in step (3) is filtered, is washed；Then,
It is dried at 80 DEG C, dry 40min.
(5) vulcanisation step：
By 100 parts of bismuth oxide/barium sulfate/natural rubber compounds being prepared in step (4) and 100 parts of natural rubbers
Glue, with 0.8 part of sulphur, 0.5 part of altax, 0.5 part of accelerant CZ, 4 parts of stearic acids, 1 part of zinc oxide and 0.5 part of antioxidant MB
It is mixed；And slice is kneaded in two-roll mill；Then, it places it in 140 DEG C of molds and is vulcanized；It obtains unleaded
Anti- ray radiation rubber composite material.
As shown in Fig. 1-d, the tensile strength of bismuth oxide and precipitation method barium sulfate/native rubber composite material is 16.3MPa；
Its elongation at break is 580%.It is 0.075mmPb that its lead equivalent is detected under the X-ray of 120KV.
Embodiment 5：
The preparation method of the unleaded anti-ray radiation rubber composite material of the present invention, it includes the following steps：
(1) prepared by radiation shield dry load slurry：
By 50 parts of average grain diameters be the bismuth oxide of 50nm, 2 parts of emulsifier caseins, 1 part of Si69,0.2 part of hydroxyethyl cellulose,
0.3 part of dimethyl silicone polymer antifoaming agent, 1 part of ammonium hydroxide and 100 parts of deionized waters are mixed；And it is thin by 1000KW ultrasonic waves
Born of the same parents are crushed instrument and disperse 30min；Obtain being stably dispersed in the radiation shield filler slurry in water；
(2) emulsion blending step：
100 parts of radiation shield filler slurries being prepared in step (1) are added to 100 parts based on bismuth oxide quality
In the natural rubber latex of rubber (weight by dry rubber)；And it carries out machinery and stirs with 30min；Obtain evenly dispersed bismuth oxide/natural
Rubber mix lotion；
(3) solidification demulsification step：
Calcium chloride or calcium nitrate solution that mass fraction is 5% are added in the mixed emulsion prepared in step (2)；Directly
It is demulsified completely solidification to the mixed emulsion；
(4) drying steps：
Bismuth oxide/the natural rubber compound being prepared in step (3) is filtered, is washed；Then, by it 80
It is dried at DEG C, dry 40min.
(5) vulcanisation step：
By 100 parts of bismuth oxide/natural rubber compounds being prepared in step (4) and 100 parts of natural rubbers, with 0.5
Part sulphur, 1 part of altax, 0.5 part of accelerant CZ, 5 parts of stearic acids, 1 part of zinc oxide and 0.5 part of antioxidant D are mixed；And
Slice is kneaded in two-roll mill；Then, it places it in 140 DEG C of molds and is vulcanized；Obtain unleaded anti-ray radiation
Rubber composite material.
If the tensile strength of Fig. 1-e institutes, bismuth oxide/native rubber composite material is 16.2MPa；Its elongation at break is
450%.It is 0.089mmPb that its lead equivalent is detected under the X-ray of 120KV.The present embodiment is preferred embodiment.
Claims (10)
1. a kind of preparation method of unleaded anti-ray radiation rubber composite material, it is characterised in that：It includes the following steps：
(1), prepared by radiation shield extender paste body：
By 50 parts of radiation shield fillers, 0.1-4 parts of emulsifiers, 0-2 parts of surface modifiers, 0.1-0.5 parts of thickeners, 0.1-0.5
Part antifoaming agent, 0.5-2 parts of ammonium hydroxide and 40-300 parts of deionized waters are mixed；And it is stirred with dispersion by high speed machine；Ultrasonic wave
Dispersion or cell crushing instrument disperse 10-60min；Obtain being stably dispersed in the radiation shield filler slurry in water；
(2), emulsion blending step：
The 40-150 part radiation shield filler slurries being prepared in step (1) are added to based on radiation shield packing quality
In the rubber latex of 100 parts of rubber；Machinery is carried out to stir with 30-60min；Obtain evenly dispersed shielding filler/rubber mix breast
Liquid；
(3), solidification demulsification step：
Calcium chloride or calcium nitrate solution that mass fraction is 2-20% are added to the shielding prepared in step (2) to fill out
In material/rubber mix lotion；The solidification until the shielding filler/rubber mix lotion is demulsified completely；
(4), drying steps：
Shielding filler/the rubber composition prepared in step (3) is filtered, is washed；Then, it is done at 60-120 DEG C
It is dry, drying time 20min-60min；
(5), vulcanisation step：
By 100 parts be prepared in step (4) shielding filler/rubber compositions and 100 parts of rubber and 0.1-2.5 parts of vulcanizations
Agent, 0.5-6 parts of vulcanization accelerators, 0.1-1 parts of anti-aging agents are mixed；And it is kneaded slice in two-roll mill or mixer；
Then, it places it in 100-160 DEG C of mold and vulcanizes；Obtain unleaded anti-ray radiation rubber composite material.
2. the preparation method of unleaded anti-ray radiation rubber composite material according to claim 1, it is characterised in that：It is described
Radiation shield filler be following material one kind or in which several mixtures：Native sulfate of barium, precipitation method barium sulfate, modification
Barium sulfate, bismuth oxide, tungsten carbide, barium tungstate.
3. the preparation method of unleaded anti-ray radiation rubber composite material according to claim 1, it is characterised in that：It is described
Shielding packing material size be 50-4000nm.
4. the preparation method of unleaded anti-ray radiation rubber composite material according to claim 1, it is characterised in that：It is described
Emulsifier be following material one kind or in which several mixtures：Neopelex, octyl phenol polyoxyethylene ether
Emulsifier op-10, casein.
5. the preparation method of unleaded anti-ray radiation rubber composite material according to claim 1, it is characterised in that：It is described
Thickener be following material one kind or in which several mixtures：Hydroxyethyl cellulose, carboxymethyl cellulose, polypropylene
Acid, polyacrylamide.
6. the preparation method of unleaded anti-ray radiation rubber composite material according to claim 1, it is characterised in that：It is described
Surface modifier be following material one kind or in which several mixtures：γ-aminopropyl triethoxysilane, γ-methyl
Acryloyloxypropyltrimethoxysilane, double-[γ-(triethoxysilicane) propyl] tetrasulfide, polypyrrole alkanone.
7. the preparation method of unleaded anti-ray radiation rubber composite material according to claim 1, it is characterised in that：It is described
Antifoaming agent, it includes：Dimethyl silicone polymer class, mineral oils, polyethers antifoaming agent.
8. the preparation method of unleaded anti-ray radiation rubber composite material according to claim 1, it is characterised in that：It is described
High speed machine stir with dispersion rotating speed be 500-20000r/min；Ultrasonic wave disperses or ultrasonic cell disruption instrument dispersion power is
100-2000KW。
9. the preparation method of unleaded anti-ray radiation rubber composite material according to claim 1, it is characterised in that：It is described
Rubber latex, it includes：Natural rubber latex, styrene-butadiene latex, carboxylic styrene butadiene latex, NBR latex, carboxylic acrylonitrile butadiene rubber latex.
10. the preparation method of unleaded anti-ray radiation rubber composite material according to claim 1, it is characterised in that：Institute
The vulcanization accelerator stated is one kind of following material or in which several mixtures：2,2'- dithio-bis-benzothiazoles, N- rings be
Base -2- benzothiazole sulfonamides, zinc diethyl dithiocarbamate, zinc oxide, hard acid acid, thiocarbamide.
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Application publication date: 20180928 |