CN106009944A - Element gradient combined anti-radiation rubber product and preparation method thereof - Google Patents
Element gradient combined anti-radiation rubber product and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D107/00—Coating compositions based on natural rubber
- C09D107/02—Latex
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- C—CHEMISTRY; METALLURGY
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D111/00—Coating compositions based on homopolymers or copolymers of chloroprene
- C09D111/02—Latex
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- 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
- C08J2307/00—Characterised by the use of natural rubber
- C08J2307/02—Latex
Abstract
The invention discloses an element gradient combined anti-radiation rubber product and a preparation method thereof, and aims to solve the problems that generally, all fillers of a conventional anti-radiation protection rubber product are mixed together and filled, the contents of different filling components are not high, the overall shielding effect can be degraded, if a shielding material is added, filler sedimentation or layering of different degrees can be caused in the product preparation process, and furthermore the physical and mechanical properties of a finished product can be also greatly degraded. The element gradient combined anti-radiation rubber product comprises N layers of single shielding layers compounded in a gradient manner, wherein N is a natural number; N is greater than or equal to 2. By adopting the element gradient combined anti-radiation rubber product disclosed by the invention, a uniform shielding effect on a wide-energy spectrum high-energy ray can be achieved, the shielding rate of gamma and X-rays is higher than 30%, and the product is friendly to human bodies and the environment. The element gradient combined anti-radiation rubber product is reasonable to design, convenient to use, good in anti-radiation effect, high in production efficiency and filler utilization rate, good in comprehensive shielding property, capable of meeting requirements on industrial, large-scale and on-batch production, relatively high in application value, and relatively good in application prospect.
Description
Technical field
The present invention relates to radiation protection field, especially radiation protection field of rubber materials, be specially a kind of graded elemental
Combination radiation-proof rubber goods and preparation method thereof.The rubber of the present invention uses multielement combination, gradient lamination structure multiple
Close, can effectively shield γ and X-ray, there is preferable application prospect.
Background technology
Produce in radiation medicine research, radiosurgery treatment, nuclear material processing, nuclear waste transmutation and radiation and detect work
In the industries such as industry, it is flooded with high energy gamma and X-radiation, needs to use radiation protector to reduce the ray spoke for personnel
Shoot evil and environmental pollution wounded.Radiation protection elastomeric material is the most wide variety of class radiation proof material, by extensively
General being used as protects human hands, forearm, head, trunk and the radiation-proof rubber glove of comprehensive protection, radioprotective headgear, radiation
Protective garment and radiation protection material etc..Radiation protection elastomeric material includes multiple rubber and high molecular polymer, wherein, in case
The application of radiation rubber product is the most universal.
Radiation-proof rubber glove, headgear and protective garment etc. are mainly included for individual radiation proof rubber；This kind of
Rubber generally by rubber substrate and have the filler of attenuation or shielding properties compound after, be through impregnation with or be prepared by Hot rolling
Obtaining, prepared finished product typically has excellent mechanical performance and preferable radiation shield performance, is widely used in X-ray, γ
Radiation and neutron shielding.Wherein, the base material of such radiation-proof rubber goods specifically includes that natural rubber (NR), neoprene rubber
Glue (CR), butyl rubber (IIR), nitrile rubber (NBR) and CSM (CSM) etc., the radiation shield used
Filler then includes the inorganic material such as oxide or the acid salt of detection device for multi metallic elements, lanthanide series and rare earth element.
At present, commercially available radiation-proof rubber goods mostly are lamination glove, and inside is filled with the lead unit of oxide or salt form
Element (Pb) is as packing material.Owing to lead element has higher mobility, big to harm, and environmental pollution is serious,
The discarded processing cost containing lead gloves is usually the decades of times without lead gloves.Therefore, unleaded is high-performance radioprotective from now on
The inexorable trend of rubber development.
Under a lot of environment, emittance is higher, as in Interventional radiology environment gamma-ray energy range be 35 ~
60keV, part industry CT energy is 59.6kev, and nuclear material processes and is 20 ~ 275keV in processing environment, wherein most position
Between 50 ~ 125keV.For tradition plumbum containing radiation protection material, it is limited to 88keV owing to the K of lead element absorbs, 50 ~
There is weak absorbing district in 88keV energy interval so that simple lead-containing materials has good shielding to the gamma-rays about 90keV energy
Performance, but to less than 90keV and relatively low higher than the gamma ray shielding rate of 100keV energy.As the substitute element of lead, the dilutest
Earth elements is better than lead to the shield effectiveness of low-energyγ-ray, as the K of lanthanum (La) absorbs the limit 38.9keV K absorption to lutecium (Lu)
Limit 63.3keV is respectively positioned on the weak absorbing district of lead, and the K of other lanthanide series such as tungsten (W) absorbs and is limited to 69.5keV, and gadolinium (Gd) is
50.2keV, major element bismuth (Bi) is 90.5keV.
Described in French Patent (FRP) FR 2911991, it is well recognized that, if use high-energy ray shielding properties lower than lead
Element filler as an alternative, with the radiation protection product containing lead stuffing, there is the situation of suitable screening ability guaranteeing to obtain
Under, need to increase the loading of substitute element filler, so will certainly reduce product mechanical property；Skin Kanggong department of France
Patent of invention CN 102549057 A disclose a kind of bismuth oxide (Bi mixed in appropriate proportions2O3), Tungstic anhydride.
(WO3) and lanthanum sesquioxide (La2O3) powder is filled in the multiple rubber substrates such as polychlorobutadiene and finally gives anti-as filler
The technology of radiation glove, the maximum loading of filler is up to 65 ~ 85%, and glove product has the radiation suitable with containing lead gloves and declines
Subtract character；It is to adopt that surface described in utility model patent CN 201717015 U has the radiation-proof rubber glove of radiation protection layer
With lead oxide (PbO), bismuth oxide (Bi2O3), antimony pentasulfide (Sb2S5), barium sulfate (BaSO4), tungsten disulfide (WS2In) one
Plant or for X-ray, there is the shielding rate more than 22% as radiation shield filler, glove, but include after multiple compounds mixing
Tungsten disulfide and lead oxide have toxic at interior compound to human body；The invention of Lan Aikexiesi Co., Ltd of Germany
Patent CN 1748263 A discloses comprise barium, indium, niobium, zirconium, tungsten and lanthanide series etc. that a kind of filling content is 10 ~ 64% and is permitted
The combination formula of the lead-free mixture that can be used for additive for shielding radiation of multiple shielding element, base material covers rubber, thermoplastic
Property the polymer such as material, polyurethane, it is achieved thereby that the most unleaded the most acceptant mixture more preferably in lighter, toxicology
Ground shielding γ or X-ray；Similarly, United States Patent (USP) US 2004/0262546 disclose one class use single filler bismuth oxide or
Use the bismuth oxide mixed with the material such as the tungsten oxide being filled in natural rubber, stannum oxide or stannum oxide/stibium oxide as spoke
Penetrate shielding filler.
Conventional filling procedures with above-mentioned patent as representative, is to mix all fillers to be filled with.Filling
Amount not can exceed that under the maximum premise that can have a strong impact on product pliability and wearing property, the content of each filling components is the highest, from
And cause shield effectiveness generally to reduce.To ensure that shielding properties then can only increase loading as far as possible, thus one side is the most easily
Cause that product preparation process occurs filling settlement or layering in various degree, be on the other hand substantially reduced the Physical Mechanical of finished product
Energy.Additionally, different filler elements need to reach the more preferable structural adhesion with base material needs specific combinational environment such as pH, temperature
Deng, so, it is likely to be due to the materialization phenomenon of diversity between particle after the mixing of multiple inorganic matter and causes rubber substrate that knot occurs
Structure defect.
Similarly, the one described in patent of invention CN 104425049 A is with polyacrylic acid gadolinium for shielding filler, filling
Amount reaches natural rubber or the neoprene radiation-resistant gloves of 45 ~ 65%, and patent of invention CN 101894596 B is disclosed containing lead oxide
And/or the radiation-proof rubber protective gloves of bismuth oxide (loading 40 ~ 70%) and patent of invention CN 101752019 A are public
The radioprotective rubber with natural rubber and/or butyl rubber as base material, with the mixture of lead tungstate and Tungstic anhydride. as filler of cloth
Rubber gloves, these patent coexpress go out to employ lead element as filler, or use single-element compound as shielding
Filler, or be filled with after the mixing of multiple filler, product is the best to the uniformity shield effectiveness of wide power spectrum high-energy ray.
To this end, in the urgent need to a kind of new rubber, to solve the problems referred to above.
Summary of the invention
The goal of the invention of the present invention is: generally all fillers are blended in one for existing radiation protection rubber
Rising and fill, the content of each filling components is the highest, and overall shield effectiveness reduces, and increases shielding material, the most easily causes product system
Filling settlement or layering in various degree, the problem that also can be substantially reduced finished product physical and mechanical properties, it is provided that occur during Bei
Plant graded elemental combination radiation-proof rubber goods and preparation method thereof.The present invention provides a kind of multielement combination, gradient lamination knot
Compound and to γ and X-ray the shielding rate of structure is higher than the compound radiation-proof rubber goods of 30%, and it is capable of wide power spectrum high energy
The uniformity shield effectiveness of ray, and product is to human body and environmental friendliness.The present invention is reasonable in design, easy to use, and radioprotective is imitated
The best, production efficiency and filler utilization rate are high, and comprehensive shielded performance is good, it is possible to meet industrialization, extensive, the need of batch production
Want, there is higher using value and preferable application prospect.
To achieve these goals, the present invention adopts the following technical scheme that
A kind of graded elemental combination radiation-proof rubber goods, form including N shell shielding monolayer graded composite, and described N is natural number,
And N >=2；
The rubber latex of described shielding monolayer is composited with radiation shield uniform filling by compound rubber；
Ground floor shielding monolayer is in n-th layer shielding monolayer, and in each layer, the atomic number of radiation shield filler is along ground floor to N
Successively decrease in the direction of layer.
Described radiation shield filler is the one in iodic acid gadolinium, Gadolinia., bismuth iodate, bismuth oxide and tungsten oxide.Above-mentioned fill out
The particle diameter of material granule is less than 50 microns, and preferable particle size scope is 0.1 ~ 10 micron.
The rubber latex of described shielding monolayer uses the component of following ratio of weight and number to make:
Compound rubber 100 parts；
Zinc oxide 0.2 ~ 15 part；
0.5 ~ 5.0 part of sulfur；
Accelerator 0.5 ~ 10 part；
0.1 ~ 5.0 part of age resistor；
Stabilizer 0.05 ~ 3.0 part；
Reinforcing filler 5.0 ~ 30 parts；
Radiation shield filler 25 ~ 400 parts；
Wherein, compound rubber weight by dry rubber.
As preferably, the rubber latex of described shielding monolayer uses the component of following ratio of weight and number to make:
Compound rubber 100 parts；
Zinc oxide 0.5 ~ 10 part；
1.0 ~ 5.0 parts of sulfur；
Accelerator 1.0 ~ 8.0 parts；
0.5 ~ 3.5 part of age resistor；
Stabilizer 0.1 ~ 2.0 part；
Reinforcing filler 5.0 ~ 25 parts；
Radiation shield filler 33 ~ 400 parts；Wherein, compound rubber weight by dry rubber.
Described compound rubber be the one in natural rubber (NR), neoprene (CR) or nitrile rubber (NBR) latex or
Multiple；Preferably natural rubber or anionic water solublity polychloroprene latex.
Described accelerator is tetramethylthiuram disulfide (Vulcanization accelerator TMTD or TT) and diethyldithiocar bamic acid
Zinc (accelerator ZDC) presses the mixture of 1:1 weight ratio, or N-N '-rhenocure CA (accelerant C A), or ethylene thiourea
One or both in (accelerant N A-22).
Described age resistor is N-Phenyl beta naphthylamine (antioxidant D) or N-phenyl-a-naphthylamine (antioxidant A).
Described stabilizer is potassium hydroxide or sodium hydroxide.
Described reinforcing filler be high abrasion furnace black, methylcellulose, Graphene or industry CNT in one or
Multiple；Preferably N330 white carbon black or methylcellulose.
The atomic number of the radiation shield filler in these radiation-proof rubber goods is successively decreased within outer successively.
The preparation method of aforementioned elements gradient combination radiation-proof rubber goods, comprises the steps:
(1) prepare ground floor respectively and shield the rubber latex of monolayer to n-th layer；
(2) mould is immersed in coagulator, be then dried, obtain the first mould；
(3) the first mould is immersed polyurethane adhesive Ruzhong, be then dried；
(4) dried for step (3) the first mould is immersed in the rubber latex containing shielding monolayer, be then dried, make rubber soak
Stain layer is shaped, and repeats step (4) repeatedly, makes the shielding monolayer of preparation reach desired thickness；
(5) successively decrease sequentially according to the atom of radiation shield filler, repeat step (3), step (4), be sequentially prepared ground floor shielding
Monolayer to n-th layer shields monolayer, after end to be impregnated,.
In described step (2), mould is immersed in the coagulator of 40 ~ 70 DEG C, at a temperature of 70 ~ 120 DEG C, then it is dried 2 ~
10 minutes, obtain the first mould.
In described step (3), the first mould is immersed the polyurethane adhesive Ruzhong 10 ~ 60 seconds of mass fraction 5 ~ 40%, after mentioning
Uniformly it is dried 0.5 ~ 5 minute at 55 ~ 85 DEG C.
In described step (4), by dried for step (3) the first mould immersion rubber latex containing shielding monolayer 5 ~ 45
Second, it is dried 5 ~ 25 minutes at a temperature of 70 ~ 120 DEG C after mentioning, makes rubber impregnated layer shape.
In described step (5), after end to be impregnated, mould and upper semi-finished product thereof are dried 5 ~ 60 at a temperature of 80 ~ 140 DEG C
Minute, make the complete molding of rubber；
After the complete molding of rubber, after its surface is uniformly coated with and spreads Pulvis Talci or starch, by its demoulding, then at 60 ~ 100 DEG C
Hot water in digestion 10 ~ 60 minutes, be then dried 5 ~ 30 minutes at a temperature of 70 ~ 100 DEG C, get product.
For foregoing problems, the present invention provides a kind of graded elemental combination radiation-proof rubber goods and preparation method thereof.Should
Rubber, forms including by N shell shielding monolayer graded composite, and N is natural number, and N >=2.Shielding monolayer rubber latex by
Compound rubber is composited with radiation shield uniform filling；Ground floor shielding monolayer shields in monolayer to n-th layer, radiates in each layer
The atomic number of shielding filler is successively decreased along ground floor to the direction of n-th layer.
The mode that the present invention uses multielement combination, gradient lamination structure compound fills problem to solve above-mentioned filler, if
Count each layer of rubber glue-line and fill the compound of certain single-element, control the thickness of each glue-line, the number of plies, group by calculating ratio
Conjunction order and the loading of filler, it is achieved multiple element is according to gradient-structure layered combination, and it is excellent which has the biggest technology
Gesture.First, use the mode of lamination gradient combination so that the filler loading of each monolayer is up to 85%；Due to often
Layer is filled only with single filler, and it is stable that behavior filled by filler, and filler grain is well combined with rubber substrate, can strengthen rubber product
Physical and mechanical properties, improve the radiation shield performance of product simultaneously further.Secondly, the K of element absorb limit can be complementary and reach
To uniformly shielding gamma-ray effect, make up the unleaded rear weak district of gamma-ray shielding of radiation-proof rubber goods simultaneously；The present invention
Can be by complementary for the absorption limit of different elements and realize uniformly shielding high energy at wide energy spectrum and penetrate by the way of gradient combination
The effect of beta radiation.Finally, the present invention uses the mode that gradient lamination structure combines, can be according to different application environment and purpose
Requirement, only just can need to realize neatly difference ray types by changing the quantity of each shielding monolayer, thickness and order
The protection of the radiation with energy, production efficiency and filler utilization rate are greatly improved.
Multielement of the present invention combination, gradient lamination structure compounded rubber radiation-resistant gloves comprise 2 layers and count above
Amount radiation shield monolayer, all shielding single layer of substrate material are not limited to use elastomeric material of the same race, can be used as required 2 kinds or
3 kinds of elastomeric materials carry out lamination superposition.
You need to add is that, the sequencing of different graded elemental combinations has the biggest shadow to its radiation shield performance
Ring.Usually, we fill, at outer layer, the element that atomic number is maximum, and inner layer is successively decreased according to this.Suitable at this gradient combination
Under sequence, the bremstrahlen of generation, secondary gamma ray etc. can be by internal layer phases after outer shield element is decayed for extraneous γ or X-ray
Lighter element is decayed further and shields.If on the contrary, outer layer uses the element that atomic number is low, its comprehensive shielded performance
To reduce to a certain extent.
The present invention absorbs limit according to the K of shielding element and carries out complementary targetedly, by the composite bed foundation containing different elements
Certain concentration and thickness ratio lamination superimposion, it is possible to achieve to gamma-ray wide power spectrum, all in certain energy range
Even property shield effectiveness.By changing different gradient combination monolayer filler concentration of element, thickness and built-up sequence, the present invention can obtain
, physical and mechanical properties higher radiation-proof rubber goods more preferable to shielding properties.
The radiation-proof rubber goods of the present invention utilize the absorption including the elements such as gadolinium (Gd), tungsten (W), bismuth (Bi) and iodine (I)
Limit complementarity carries out multielement gradient combination, it is achieved that radiation-proof rubber glove uniformity shield effectiveness, and radiation shield in each layer
The atomic number covering filler is successively decreased along ground floor to the direction of n-th layer, it is possible to the comprehensive shielded performance of rubber further.
After measured, rubber of the present invention is used to be capable of the uniformity shield effectiveness to wide power spectrum high-energy ray, right
The γ of wide energy spectrum and X-ray shield rate are higher than 30%, and to human body and environmental friendliness.
In sum, the radiation-proof rubber goods of the present invention possess good physical and mechanical properties, to personnel and environment friend
Good.It has higher radiation shield efficiency to gamma-rays and X-ray, wherein has the gamma-rays of energy range 20 ~ 250keV
There is the good shield effectiveness of uniformity, and shielding rate be more than 30%, thus product of the present invention has good integrated protection effect,
Can be applicable to multiple high-energy ray radiation occasion, there is the highest practical value.
Accompanying drawing explanation
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein:
Fig. 1 is the radiation-proof rubber glove cross section structure schematic diagram that embodiment 2 makes.
Wherein: 1-1 is outer water soluble layer of polyurethane；1-2 is internal layer soluble polyurethane layer；2-1 is that outer layer contains iodic acid
Bismuth shield neoprene monolayer；2-2 is that internal layer contains bismuth iodate shield neoprene monolayer；3 is to shield containing tungsten oxide natural rubber
Monolayer；4 is to shield monolayer containing iodic acid gadolinium natural rubber.
Detailed description of the invention
All features disclosed in this specification, or disclosed all methods or during step, except mutually exclusive
Feature and/or step beyond, all can combine by any way.
Any feature disclosed in this specification, unless specifically stated otherwise, all can by other equivalence or there is similar purpose
Alternative features is replaced.I.e., unless specifically stated otherwise, an example during each feature is a series of equivalence or similar characteristics
?.
In the embodiment of the present invention, use and include that the method for step in detail below prepares graded elemental combination radiation-proof rubber system
Product.
(1) dipping compounded latex is prepared
1. under the temperature conditions of 20 ~ 65 DEG C, by the rubber latex of formula ratio, sulfur, zinc oxide, accelerator, age resistor and benefit
Strong agent uniformly mixes, and obtains latex mixing.
The most first certain tailored radiation of formula ratio is shielded filler powder to grind, and fully dispersed in aqueous solvent, then holding
It is slowly added to latex mixing in the case of continuous stirring, obtains compounded latex.
The most according to actual needs, the compounded latex containing other tailored radiation shielding filler is carried out according to step (2) is similar.
(2) dipping of radiation-proof rubber goods
1. goods mould is immersed in the coagulant solution of 40 ~ 70 DEG C, at a temperature of 70 ~ 120 DEG C, be dried 2 ~ 10 minutes.
Mould is immersed the polyurethane adhesive Ruzhong 10 ~ 60 seconds of mass fraction 5 ~ 40% the most again, after mentioning at 55 ~ 85 DEG C,
Uniformly it is dried 0.5 ~ 5 minute.
3. it is then immersed in the compounded latex containing the shielding filler of high atomic number metal compound, immerses 5 ~ 45 seconds, carry
After Qiing at a temperature of 70 ~ 120 DEG C, it is dried 5 ~ 25 minutes, makes this rubber impregnated layer shape.
4., by the way of to same compounded latex dipping one or many, reach a certain lamination and preset the thickness of calculating.
5. impregnate the most successively according to the order of the decreasing atomic number of metallic element in shielding filler and contain other and single fill out
The compounded latex of material, dipping process is with reference to step 2., 3. carry out.
If glove need to comprise two kinds of natural rubber or above rubber substrate, then impregnating synthetic rubber every time
Compounded latex after mentioning mould, is submerged initially in the coagulant solution of 15 ~ 45 DEG C 5 ~ 45 seconds, then mentions the distillation with 10 ~ 60 DEG C
Water or soft water clean.
6. after all compounded rubber latex dippings terminate, with reference to step (2)-2. impregnating polyurethane latex.
(3) after impregnation steps completes, by mould at a temperature of 80 ~ 140 DEG C, it is dried 5 ~ 60 minutes, makes rubber complete
Molding.
(4) by the rubber demoulding after step (3) glove surface is uniformly coated with and spreads Pulvis Talci or starch, at 60 ~ 100 DEG C
Digestion 10 ~ 60 minutes in hot water, are dried 5 ~ 30 minutes at a temperature of 70 ~ 100 DEG C afterwards, obtain rubber product.
The multielement combination of the present invention, gradient lamination structure are combined in radiation-proof rubber goods preparation process, gathering of employing
The preferred aqueous polyurethane of urethane latex.
The multielement combination of the present invention, gradient lamination structure are combined in radiation-proof rubber glove preparation process, coagulating of employing
Gu agent is preferably containing 5% barium chloride, 10% calcium chloride and the aqueous solution of 1% starch.
Embodiment 1
(1) preparation dipping compounded latex
The most at ambient temperature, by 100 parts of TVR LATEX rubber latex (in terms of dry weight), 1.5 parts of sulfur, 0.8 part of zinc oxide,
1.5 parts of accelerator ZDC, 2.0 parts of antioxidant Ds, 0.3 part of sodium hydroxide and 5.0 parts of methylcellulose uniformly mix, 60 DEG C of insulations
Cool down after 30 minutes, i.e. obtain natural rubber latex mixing.
2. the 150 parts of Gadolinia .s, 185 parts of bismuth iodates and the 185 parts of tungsten oxide powder that mean diameter are less than 30 microns divide
It is not configured to the ammonia dispersion liquid that mass fraction is 40%, wherein ammonia concentration 5%.
The most under continuous stirring, step 2. 3 kinds shielding filler dispersion liquids are slowly added to step latex mixing 1.
In, obtain, respectively containing Gadolinia., bismuth iodate and the dipping compounded latex of tungsten oxide, i.e. respectively obtaining the dipping containing Gadolinia. and using
Compounded latex, the dipping compounded latex containing bismuth iodate, the dipping compounded latex containing tungsten oxide.
(2) dipping natural rubber radiation protective article
1., after goods mould is immersed the coagulator of 50 DEG C, at a temperature of 90 DEG C, it is dried 10 minutes.
Mould is immersed the water-soluble polyurethane latex 15 seconds of 25% mass fraction the most again, at 80 DEG C, is uniformly dried 2.5 points
Clock.
3. it is first dipped in the compounded latex containing bismuth iodate powder body 8 seconds, is dried 7 minutes at a temperature of 100 DEG C after mentioning,
Make this rubber impregnated layer shape, then immerse containing oxidation tungsten powder body compounded latex in 10 seconds, after mentioning at a temperature of 100 DEG C be dried
10 minutes, each 5 seconds of the compounded latex that 2 times immerse containing Gadolinia. powder body afterwards, it is dried 5 minutes at a temperature of 100 DEG C.
4. the last water-soluble polyurethane latex that mould immerses 25% mass fraction 10 seconds, are uniformly dried 2 points at 80 DEG C
Clock.
(3) mould after being completed by dipping is dried 15 minutes at a temperature of 100 DEG C, makes the complete molding of goods.
(4) product surface in molding carries out the demoulding after being uniformly coated with and spreading Pulvis Talci, digestion 20 points in the boiling water of 100 DEG C
Clock, afterwards at 100 DEG C, is dried 10 minutes, obtains natural rubber radiation protective article finished product.
The compound radiation-proof rubber goods of the present embodiment are with natural rubber as base material, and finished product thickness is 1.4 millimeters, and it is to 20
The gamma ray shielding rate minimum of ~ 60keV energy range is 46%, to the gamma-ray shielding rate of 60 ~ 140keV energy range
Low value is 38%, and the gamma-ray shielding rate minimum to 140 ~ 240keV energy range is 40%, to wide power spectrum 20 ~ 275keV model
Enclose gamma ray shielding curve and compare the more convergence uniform smooth of the product containing only single filler.Rubber prepared by the present embodiment
Hot strength be 15.4Mpa, elongation at break is 820%.
Embodiment 2
(1) preparation dipping compounded latex
1. when 25 DEG C, by 100 parts of anionic water solublity polychloroprene latexs (model 41F, in terms of dry weight), 5.0 parts of zinc oxide,
1.0 parts of sulfur, 1.0 parts of accelerator TT, 1.5 parts of accelerant N A-22,2.0 parts of antioxidant As, 0.2 part of sodium hydroxide, 0.1 part of hydrogen-oxygen
Change potassium and 5.0 parts of N330 white carbon blacks uniformly mix, obtain neoprene latex mixing.
The most at room temperature by 100 parts of TVR LATEX rubber latex (in terms of dry weight), 1.5 parts of sulfur, 2.0 parts of zinc oxide,
3.0 parts of accelerator ZDC+TT(1:1 mixing), 1.5 parts of antioxidant Ds and 0.1 part of sodium hydroxide uniformly mix, be incubated 30 points at 60 DEG C
Cool down after clock, i.e. obtain natural rubber latex mixing.
150 parts of bismuth iodate powder body, 3 parts of sodium lauryl sulphates and 225 parts that 3. mean diameter is less than 30 microns are soft
Water uniformly mixes, and continuously stirred, obtains bismuth iodate dispersion liquid.
185 parts of iodic acid gadoliniums and 185 parts of tungsten oxide powder that 4. mean diameter is less than 30 microns are configured to quality respectively
Mark is the ammonia dispersion liquid of 40%, and ammonia concentration is 5%.
The most under continuous stirring, step bismuth iodate dispersion liquid 3. is slowly added in step neoprene latex mixing 1.,
Obtain the dipping neoprene compounded latex containing bismuth iodate.
The most under continuous stirring, step iodic acid gadolinium 4. and tungsten oxide dispersion liquid are slowly added to step natural rubber 2.
In glue latex mixing, obtain the dipping natural rubber compounded latex respectively containing iodic acid gadolinium, and the dipping containing tungsten oxide is with natural
Rubber combined latex.
(2) dipping of compounded rubber radiation protective article
1., after goods mould is immersed the coagulator of 50 DEG C, at a temperature of 100 DEG C, it is dried 10 minutes.
Mould is immersed the water-soluble polyurethane latex 45 seconds of 30% mass fraction the most again, is uniformly dried 2 minutes at 80 DEG C.
3. it is submerged initially in the neoprene compounded latex containing bismuth iodate powder body 10 seconds, immerses afterwards in 30 DEG C of coagulator 5 seconds, use
The soft water of 60 DEG C rinses product surface, is dried 4 minutes at a temperature of 100 DEG C, makes neoprene dipping layer sizing.
The most again by mould immerse containing oxidation tungsten powder body natural rubber compounded latex in 10 seconds, 100 DEG C of temperature after mentioning
Under, it is dried 8 minutes；Immerse afterwards containing in iodic acid gadolinium natural rubber compounded latex 10 seconds, at a temperature of 100 DEG C, be dried 6 minutes.
5., after mold surface temperature is down to 60 DEG C, one layer of neoprene compounded latex is the most again impregnated with reference to step.
6. last, mould is immersed the water-soluble polyurethane latex 20 seconds of 25% mass fraction, at 80 DEG C, is uniformly dried 1
Minute.
(3) mould after being completed by dipping, at 90 DEG C, is dried 8 minutes, makes the complete molding of goods.
(4) product surface in molding is uniformly coated with starch dusting and carries out the demoulding, in the boiling water of 70 DEG C, and digestion 15 minutes, it
After at 100 DEG C, be dried 6 minutes, obtain neoprene/natural rubber and be combined radiation protective article.
The compound radiation-proof rubber goods of the present embodiment are with neoprene and natural rubber as base material, and wherein neoprene layer plays
Resistance to chemical attack, oil resistant etc. act on.Finished product thickness prepared by the present embodiment is 1.5 millimeters, to 20 ~ 60keV energy range
Gamma ray shielding rate minimum is 42%, and the gamma-ray shielding rate minimum to 60 ~ 140keV energy range is 35%, to 140 ~
The gamma-ray shielding rate minimum of 240keV energy range is 37%, to wide power spectrum 20 ~ 275keV scope gamma ray shielding curve
Compare the more convergence uniform smooth of the product containing only single filler.The hot strength of the rubber prepared by the present embodiment is
12.1Mpa, elongation at break is 670%.
It should be noted that and understand, in the feelings without departing from the spirit and scope of the present invention required by appended claims
Under condition, it is possible to the present invention of foregoing detailed description is made various modifications and improvements.It is therefore desirable to the model of the technical scheme of protection
Enclose and do not limited by given any specific exemplary teachings.All features disclosed in description of the invention, except arranging mutually
Beyond the feature scolded, all can combine by any way.Disclosed in this specification (including any accessory claim, summary)
Any feature, unless specifically stated otherwise, all can be by other equivalences or there is the alternative features of similar purpose replaced.That is, unless
Narration especially, each feature is an example in a series of equivalence or similar characteristics.
The invention is not limited in aforesaid detailed description of the invention.The present invention expands to any disclose in this manual
New feature or any new combination, and the arbitrary new method that discloses or the step of process or any new combination.
Claims (10)
1. graded elemental combination radiation-proof rubber goods, it is characterised in that include that N shell shielding monolayer graded composite forms,
Described N is natural number, and N >=2；
The rubber latex of described shielding monolayer is composited with radiation shield uniform filling by compound rubber；
Ground floor shielding monolayer is in n-th layer shielding monolayer, and in each layer, the atomic number of radiation shield filler is along ground floor to N
Successively decrease in the direction of layer.
Graded elemental combination radiation-proof rubber goods the most according to claim 1, it is characterised in that described radiation shield filler
For the one in iodic acid gadolinium, Gadolinia., bismuth iodate, bismuth oxide and tungsten oxide.
Graded elemental the most according to claim 1 or claim 2 combination radiation-proof rubber goods, it is characterised in that described shielding monolayer
Rubber latex use following ratio of weight and number component make:
Compound rubber 100 parts；
Zinc oxide 0.2 ~ 15 part；
0.5 ~ 5.0 part of sulfur；
Accelerator 0.5 ~ 10 part；
0.1 ~ 5.0 part of age resistor；
Stabilizer 0.05 ~ 3.0 part；
Reinforcing filler 5.0 ~ 30 parts；
Radiation shield filler 25 ~ 400 parts；
Wherein, compound rubber weight by dry rubber.
4. according to graded elemental combination radiation-proof rubber goods described in any one of claim 1 ~ 3, it is characterised in that described stable
Agent is potassium hydroxide or sodium hydroxide.
5. according to graded elemental combination radiation-proof rubber goods described in any one of claim 1 ~ 3, it is characterised in that described reinforcement
Filler is one or more in high abrasion furnace black, methylcellulose, Graphene or industry CNT.
6., according to the preparation method of graded elemental combination radiation-proof rubber goods described in any one of claim 1 ~ 3, its feature exists
In, comprise the steps:
(1) prepare ground floor respectively and shield the rubber latex of monolayer to n-th layer；
(2) mould is immersed in coagulator, be then dried, obtain the first mould；
(3) the first mould is immersed polyurethane adhesive Ruzhong, be then dried；
(4) dried for step (3) the first mould is immersed in the rubber latex containing shielding monolayer, be then dried, make rubber soak
Stain layer is shaped, and repeats step (4) repeatedly, makes the shielding monolayer of preparation reach desired thickness；
(5) successively decrease sequentially according to the atom of radiation shield filler, repeat step (3), step (4), be sequentially prepared ground floor shielding
Monolayer to n-th layer shields monolayer, after end to be impregnated,.
The preparation method of graded elemental combination radiation-proof rubber goods the most according to claim 6, it is characterised in that described step
Suddenly, in (2), mould is immersed in the coagulator of 40 ~ 70 DEG C, be then dried 2 ~ 10 minutes at a temperature of 70 ~ 120 DEG C, obtain first
Mould.
The most according to claim 6, preparation method, it is characterised in that in described step (3), immerse quality by the first mould and divide
10 ~ 60 seconds, the polyurethane adhesive Ruzhong of several 5 ~ 40%, is uniformly dried 0.5 ~ 5 minute after mentioning at 55 ~ 85 DEG C.
The most according to claim 6, preparation method, it is characterised in that in described step (4), by dried for step (3)
One mould immerse containing shielding monolayer rubber latex in 5 ~ 45 seconds, after mentioning at a temperature of 70 ~ 120 DEG C be dried 5 ~ 25 minutes, make
Rubber impregnated layer is shaped.
10. according to preparation method described in any one of claim 6 ~ 9, it is characterised in that in described step (5), end to be impregnated
After, mould and upper semi-finished product thereof are dried 5 ~ 60 minutes at a temperature of 80 ~ 140 DEG C, make the complete molding of rubber；
After the complete molding of rubber, after its surface is uniformly coated with and spreads Pulvis Talci or starch, by its demoulding, then at 60 ~ 100 DEG C
Hot water in digestion 10 ~ 60 minutes, be then dried 5 ~ 30 minutes at a temperature of 70 ~ 100 DEG C, get product.
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