CN115894916A - Polyarylene sulfide shielding material for preventing X, gamma ray and neutron radiation and preparation thereof - Google Patents
Polyarylene sulfide shielding material for preventing X, gamma ray and neutron radiation and preparation thereof Download PDFInfo
- Publication number
- CN115894916A CN115894916A CN202211592327.3A CN202211592327A CN115894916A CN 115894916 A CN115894916 A CN 115894916A CN 202211592327 A CN202211592327 A CN 202211592327A CN 115894916 A CN115894916 A CN 115894916A
- Authority
- CN
- China
- Prior art keywords
- barium
- polyarylene sulfide
- sulfide
- aqueous solution
- peg
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229920000412 polyarylene Polymers 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000005855 radiation Effects 0.000 title abstract description 25
- 230000005251 gamma ray Effects 0.000 title abstract description 11
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 108
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 239000006227 byproduct Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 229920001223 polyethylene glycol Polymers 0.000 claims description 31
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 28
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000002798 polar solvent Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 229910052788 barium Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 230000001502 supplementing effect Effects 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 claims description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 4
- 238000010406 interfacial reaction Methods 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 3
- GWCFTYITFDWLAY-UHFFFAOYSA-N 1-ethylazepan-2-one Chemical compound CCN1CCCCCC1=O GWCFTYITFDWLAY-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 15
- 238000001746 injection moulding Methods 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 241000282414 Homo sapiens Species 0.000 abstract description 6
- 238000003672 processing method Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 20
- 238000012360 testing method Methods 0.000 description 12
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 9
- 229910052979 sodium sulfide Inorganic materials 0.000 description 9
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000005670 electromagnetic radiation Effects 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 2
- 208000032467 Aplastic anaemia Diseases 0.000 description 1
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 1
- 102100037709 Desmocollin-3 Human genes 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 101000968042 Homo sapiens Desmocollin-2 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- TVFDJXOCXUVLDH-RNFDNDRNSA-N cesium-137 Chemical compound [137Cs] TVFDJXOCXUVLDH-RNFDNDRNSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- GKOZUEZYRPOHIO-IGMARMGPSA-N iridium-192 Chemical compound [192Ir] GKOZUEZYRPOHIO-IGMARMGPSA-N 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000005025 nuclear technology Methods 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000009725 powder blending Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 208000017443 reproductive system disease Diseases 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention relates to a polyarylene sulfide shielding material for preventing X, gamma-ray and neutron radiation and a preparation method thereof, belonging to the field of radiation-proof materials. The invention provides a preparation method of a polyarylene sulfide shielding material, which comprises the following steps: barium sulfate and metal sulfate are used as raw materials to prepare barium sulfate whiskers, then byproducts generated in the preparation process of the barium sulfate whiskers are used as sulfur-containing compounds required for preparing polyarylene sulfide, and the sulfur-containing compounds and other conventional reaction monomers are polymerized to prepare the polyarylene sulfide based shielding material. The barium sulfate whisker polyarylene sulfide composite material is prepared into barium sulfate whisker polyarylene sulfide composite material equipment and devices which have X-ray and gamma-ray shielding and absorption functions, high temperature resistance and neutron shielding functions by processing methods such as injection molding, film drawing and the like, and is used for the use of radiation irradiation environment and the protection of equipment and human body radiation irradiation.
Description
Technical Field
The invention relates to a polyarylene sulfide shielding material for preventing X, gamma-ray and neutron radiation and a preparation method thereof, belonging to the field of radiation-proof materials.
Background
With the rapid development of informatization and artificial intelligence, the utilization of nuclear energy and the development of space, the range of nuclear radiation and electromagnetic radiation is wider and wider, and the environment and people are seriously influenced. After long-term radiation exposure, the human body is uncomfortable, and serious injury to organs and systems of the human body can cause various diseases, such as leukemia, aplastic anemia, various tumors, eyeground pathological changes, reproductive system diseases, premature senility and the like.
Radiation is divided into electromagnetic radiation and nuclear radiation. Nuclear radiation hazards such as gamma rays generated by cobalt-60, cesium-137, iridium-192 sources, and the like; beta rays generated by a kr-85 source and the like; 241Am-Be source, 24Na-Be source, 124Sb-Be source and neutron rays generated by an electron accelerator with energy more than 10M; beta, alpha rays generated by a non-sealed source; x rays generated by various industrial and medical X-ray equipment, and the like. With the great application of nuclear energy and nuclear technology in industrial and nuclear radiation agricultural production, medical health, scientific research and national defense, more and more people are irradiated, and the radiation hazard is not ignored. The consequences of major accidents in the chernobeli nuclear power station of the last century were difficult to eliminate until now; the influence caused by major accidents of nuclear leakage in the Japanese Fudao in this century can not be completely solved so far, and the discharge of nuclear wastewater into the Pacific ocean causes pollution to the whole ocean and brings great harm to organisms and human beings.
Therefore, the research of materials capable of absorbing and shielding various types of radiation and irradiation has been one of the hot and difficult points of the material research. Each element has a certain weak absorption area for shielding and absorbing high-energy rays, and the composition, structure and performance of a single metal element and an oxide material thereof are difficult to simultaneously meet the comprehensive shielding and protection of neutrons, gamma rays, X rays and other multiple radiations. The elements corresponding to the radiation absorption and shielding of neutrons, gamma rays and X rays are not completely the same as the materials, so how to form a multifunctional stable material with multiple elements at a molecular level, and how to make different elements play a synergistic role and play a superposition effect of multiple radiation absorption and shielding is a core problem in the design and preparation of the current radiation protection materials.
In order to solve the problem of simultaneous existence of multiple radiations, the composite material is one of the alternative ways, and can combine the advantages of multiple elements and multiple materials to form multiple materials for protecting and shielding rays or electromagnetic waves. From the perspective of the matrix of the composite material used for the radiation material, mainly traditional plastics and rubbers: plastic plastics such as PE (polyethylene), PS (polystyrene), PMMA (polymethyl methacrylate), which generally use PTFE (polytetrafluoroethylene) having a low heat temperature (not more than 150 ℃) and excellent heat resistance, corrosion resistance and self-lubricating property, and having relatively poor radiation resistance; thermosetting plastics, such as epoxy resin, imide and the like, cannot be deformed and secondarily molded after being cured; the rubber (including natural rubber, silicone rubber such as polydimethylsilane, PDMS, and copolymerized synthetic rubber such as styrene-ethylene-butadiene-styrene, SEBS) generally has no active group, is difficult to form chemical bond combination with various metal elements, has no stable interface combination, may have phase separation and cause instability of materials, and has good elasticity, low strength and can not meet the requirement in high stress environment.
Disclosure of Invention
Aiming at the defects, the invention provides a polyarylene sulfide based composite material which has the functions of shielding and absorbing X rays and gamma rays, has high temperature resistance and can be processed into a neutron shielding material and an integrated preparation method thereof; the barium sulfate whisker is prepared in an organic system, and by utilizing the strong X-ray absorption capacity of the barium sulfate whisker, X rays cannot penetrate through the barium sulfate whisker, so that the barium sulfate whisker can effectively shield the X rays and the Y rays; and the reaction by-product produced in the process of preparing the barium sulfate whisker is used as one of reaction monomers for polymerizing the polyarylene sulfide, and the polymerization reaction of the polyarylene sulfide is continuously carried out in the process of preparing the barium sulfate whisker, so that the barium sulfate whisker polyarylene sulfide composite material (namely the polyarylene sulfide-based shielding material) is finally prepared; and the barium sulfate whisker polyarylene sulfide composite material equipment and device which have X-ray and gamma-ray shielding and absorption, high temperature resistance and neutron shielding function and can be processed are formed by injection molding and film drawing and are used for the use of radiation irradiation environment and the protection of radiation irradiation of equipment and human bodies.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide a preparation method of a polyarylene sulfide shielding material, which comprises the following steps: barium sulfate and metal sulfate are used as raw materials to prepare barium sulfate whiskers, then byproducts generated in the preparation process of the barium sulfate whiskers are used as sulfur-containing compounds required for preparing the polyarylene sulfide, and the sulfur-containing compounds and other conventional reaction monomers (such as dihalo aromatic compounds) are polymerized to prepare the polyarylene sulfide based shielding material.
Further, the metal in the metal sulfate is an alkali metal element such as lithium, sodium, potassium or rubidium.
Further, the method for preparing the barium sulfate whisker by taking barium sulfide and metal sulfate as raw materials comprises the following steps: dissolving barium sulfide in a polyvinyl alcohol aqueous solution, dissolving metal sulfate in a PEG aqueous solution, dropwise adding the two solutions into an aprotic polar solvent under stirring to perform an interfacial reaction, and controlling the dropwise adding speed, the stirring speed and the temperature to form barium sulfate whiskers; wherein the ratio of barium sulfide to metal sulfate is 1: 1-1.20 mol; the dropping speed is 10-20 ml/min, the stirring speed is 30-80 r/min, and the reaction temperature is room temperature-50 ℃.
Further, the mass concentration of the polyvinyl alcohol aqueous solution is 2.5-7.5%, and the ratio of barium sulfide to the polyvinyl alcohol aqueous solution is 1g:5 to 20ml; the concentration of the PEG aqueous solution is 1-25%, the proportion of the metal sulfate to the PEG aqueous solution is 1g:2.5 to 20ml.
Further, the PEG in the PEG aqueous solution is PEG4000 (HO (CH 2O) nH) or PEG8000 (HO (CH 2O) nH).
Further, the aprotic polar solvent is selected from: n-methyl-2-pyrrolidone (NMP), N-ethylpyrrolidone, hexamethylphosphoramide (HMPA), N-dimethylacetamide, N-ethylcaprolactam, N-vinylpyrrolidone, caprolactam, tetramethylurea, dimethyl sulfoxide or sulfolane; the dosage is as follows: the usage amount of the solvent in each mole of barium sulfide is 250-1500 ml.
Further, in order to prevent the hydrolysis of barium sulfide (BaS, 170.4), an alkali (such as sodium hydroxide (potassium, lithium)) is added in an amount of 0.5 to 2.5% by weight based on the weight of barium sulfate in the process of dissolving barium sulfide in the aqueous solution of polyvinyl alcohol.
Further, in the above production method, a sulfur-containing compound required for producing the polyarylene sulfide may be additionally added as necessary.
Further, the preparation method of the polyarylene sulfide shielding material comprises the following steps:
1) Weighing 2.5-7.5L of aprotic polar solvent, adding into a reaction kettle, introducing nitrogen or inert gas into the reaction kettle, adding 20-220 parts by weight of alkali, starting stirring at the rotating speed of 50-100 r/min; gradually dripping 0.5-5.0L of barium sulfide-polyvinyl alcohol solution and 0.5-5.0L of metal sulfate-PEG solution into the aprotic polar solvent, wherein the dripping speed is controlled to be 10-20 ml/min; after the dropwise addition is finished, continuously stirring for 30-60 minutes, then gradually heating to 190-200 ℃ for dehydration, and then cooling to below 100 ℃;
2) Under the protection of nitrogen or inert gas, the stirring speed is kept at 100-200 r/min, the temperature is gradually increased to 190-210 ℃, water in the system is removed, and then the system is cooled to 100-150 ℃;
3) Adding 500-5000 parts by weight of reaction monomer 1 and 100-2000 parts by weight of reaction monomer 2, and sealing the reaction kettle; heating to 200-300 ℃ and reacting for 2-12 h; then cooling to below 120 ℃, and finishing the reaction;
4) Opening the reaction kettle, washing the product with deionized water at 50-90 ℃ for 5-8 times, and drying at 80-120 ℃ for 10-20 hours to obtain the polyarylene sulfide shielding material (polyarylene sulfide/barium sulfate whisker complex);
wherein, the structural general formula of the reaction monomer 1 is
The structural general formula of the reaction monomer 2 is
Preferably, the reactive monomer 1 is:
2, 4-dihalobenzene/halogen combination>
Or 4,4' -dihalobiphenyl->
The reactive monomer 2 is: 4,4' -Dihalodiphenylsulfone
4,4' -dihalobenzophenone
Or 4,4' -dihalodiphenyl ether->
And so on.
Further, in the above preparation process, in the step 2), a sulfur-containing compound (such as sodium sulfide) and an aprotic polar solvent are additionally added according to the proportion as the case requires.
Preferably, in the step 2), 200 to 5000 parts by weight of the sulfur-containing compound is supplemented, and 2.5 to 25L of the aprotic polar solvent is supplemented.
Further, in the step 1), the barium sulfide-polyvinyl alcohol solution is prepared by the following method: 100 to 500 parts by weight of polyvinyl alcohol (PVA,
) Dissolving in 2.0-10.0L deionized water, and adding 2.5-25 parts by weight of alkali; then adding 250-1500 parts by weight of barium sulfide, stirring and completely dissolving to form barium sulfide-polyvinyl alcohol solution.
Further, in the step 1), the sodium sulfate-PEG solution is prepared by the following method: dissolving 25-250 parts by weight of PEG in 2.0-10L of deionized water, adding 250-1000 parts by weight of metal sulfate, and stirring for complete dissolution to form a sodium sulfate-PEG solution.
Further, the process of step 3) is: adding a reaction monomer 1 and a reaction monomer 2, heating under the protection of nitrogen or inert gas while stirring, and keeping the temperature for 1.5-5.5 hours after the temperature reaches 200-260 ℃; then the temperature is raised to 220 to 300 ℃ and kept for 1 to 5 hours.
The second technical problem to be solved by the invention is to provide a polyarylene sulfide shielding material, which is prepared by adopting the preparation method.
The third technical problem to be solved by the invention is to process the polyarylene sulfide based shielding material into corresponding products, such as film forming materials, sheet materials or injection molding parts.
Further, the processing conditions are as follows: the processing temperature is 290-350 ℃.
Further, casting the polyarylene sulfide shielding material into a film at 290-350 ℃ at the speed of 10-300 mm/min; the thickness of the obtained film is 0.1-0.5 mm.
Further, the polyarylene sulfide shielding material is hot-pressed into a sheet, the pressing temperature is 290-350 ℃, and the pressure is 20-100MPa; the thickness of the obtained sheet is 0.5-2 mm.
The fourth technical problem to be solved by the invention is to provide a preparation method of barium sulfate whiskers, which comprises the following steps: dissolving barium sulfide in aqueous solution of polyvinyl alcohol, dissolving metal sulfate in aqueous solution of PEG, dropwise adding the two solutions into an aprotic polar solvent under stirring to perform an interfacial reaction, and controlling the dropwise adding speed, stirring speed and temperature to form barium sulfate whiskers; wherein the proportion of the barium sulfide to the metal sulfate is 1-1.20 mol; the dropping speed is 10-20 ml/min, the stirring speed is 30-80 r/min, and the reaction temperature is room temperature-50 ℃.
The fifth technical problem to be solved by the invention is to provide the barium sulfate whisker prepared by the method.
Furthermore, the diameter of the barium sulfate whisker is 0.5-5 μm, and the length is 10-100 μm.
The invention has the beneficial effects that:
in the process of preparing the barium sulfate whisker, the by-product generated in the preparation process is used as the sulfur-containing compound required by the preparation of the polyarylene sulfide, and the sulfur-containing compound and other conventional reaction monomers are continuously subjected to the polymerization reaction of the polyarylene sulfide to form the barium sulfate whisker polyarylene sulfide composite material; the barium sulfate whisker polyarylene sulfide composite material equipment and device which have X-ray and gamma-ray shielding and absorption, high temperature resistance and neutron shielding function and can be prepared by processing methods such as injection molding, film drawing and the like are used for the use of radiation irradiation environment and the protection of equipment and human body radiation irradiation.
Detailed Description
The above-mentioned contents of the present invention will be further described in detail by the following specific embodiments of examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. Various substitutions and alterations according to the general knowledge and the conventional means in the art are included in the scope of the present invention without departing from the technical idea of the present invention.
Example 1:
the preparation of the polyarylene sulfide shielding material of the invention comprises the following steps:
1) Dissolving 250g of medium viscosity PVA in 5L of deionized water, and adding 10g of sodium hydroxide; then 852g of barium sulfide is added and stirred to be completely dissolved, so that a barium sulfide-PVA solution is formed; dissolving 100g of PEG8000 in 5L of deionized water, adding 710g of sodium sulfate, and stirring to completely dissolve to form a sodium sulfate-PEG solution;
measuring 5L of N-methyl-2-pyrrolidone (NMP), adding into a reaction kettle with a magnetic rotor, introducing nitrogen into the reaction kettle, adding 20g of sodium hydroxide, starting stirring at the rotating speed of 80r/min; weighing 2L of barium sulfide PVA aqueous solution; measuring 2L of sodium sulfate-PEG solution; gradually dripping the two solutions into NMP, controlling the dripping speed to be 10-20 ml/min, and finishing the dripping within 30 minutes; after the dropwise addition, stirring is continued for 45 minutes under the protection of nitrogen, then the temperature is gradually increased to 198 ℃, 4.9L of dehydrated water is kept for 45 minutes, and then the mixture is cooled to below 100 ℃.
2) Under the protection of nitrogen, opening the reaction kettle, taking out the magnetic rotor, supplementing 1040g of sodium sulfide (60%), supplementing 5L of NMP, starting mechanical stirring, increasing the speed to 120r/min (r/min), gradually heating to 198 ℃, removing 400ml of water, and cooling to 100-150 ℃;
3) 1470g of p-dichlorobenzene is added, the mixture is stirred for 5 minutes under the protection of nitrogen, the speed is increased to 120r/min, and the reaction kettle is sealed; after the temperature rises to 215-235 ℃, keeping for 3 hours; then heating to 260 ℃ and keeping for 3 hours; then the temperature is reduced to below 120 ℃, and the reaction is finished.
4) Opening the reaction kettle, washing the product with deionized water at 50-90 ℃ for 5-8 times, and drying at 80-120 ℃ for 10-20 hours to obtain a barium sulfate whisker polyarylene sulfide complex (W-BaSO) 4 -PAS)1500g；W-BaSO 4 The mass ratio is about 30%.
Taking part of the barium sulfate whisker polyarylene sulfide complex for thermal performance test, and forming a mechanical sample strip by injection molding of part of the barium sulfate whisker polyarylene sulfide complex through an injection molding machine; partially pressing into an X-ray and gamma-ray protection test sample; the properties obtained are shown in tables 1 to 3.
Example 2
The other steps are the same as example 1; except that 1396.5g of p-dichlorobenzene, 143.5g of 4, 4-dichlorodiphenyl sulfone was added in the step 3); to obtain barium sulfate crystalWhisker polyarylene sulfide complex (W-BaSO) 4 -PAS)1560g；W-BaSO 4 The mass ratio is about 30%.
Example 3
The other steps are the same as example 1, except that in step 1): dissolving 100g of PEG4000 in 5L of deionized water, adding 545g of lithium sulfate, and stirring to completely dissolve the lithium sulfate to form a lithium sulfate-PEG solution; W-BaSO 4 The mass ratio is about 18 percent.
Example 4:
the other steps are the same as example 1, except that in step 1): 100g of PEG8000 were dissolved in 5L of deionized water, and sodium bisulfate (NaHSO) was added 4 ) 600g, dissolved completely with stirring to form NaHSO 4 -a PEG solution;
measuring 5L of N-methyl-2-pyrrolidone (NMP), adding into a reaction kettle with a magnetic rotor, introducing nitrogen into the reaction kettle, and adding 220g of sodium hydroxide; W-BaSO 4 Is about 30% by mass.
Example 5
The other steps are the same as example 1, except that in step 2): 2340g of sodium sulfide (60%) is supplemented, and NMP7.5L is supplemented;
in the step 3), 2940g of p-dichlorobenzene is added; to obtain barium sulfate whisker polyarylene sulfide complex (W-BaSO) 4 -PAS) 2600g; W-BaSO in the resulting material 4 Is about 18% by mass.
Example 6:
the other steps are the same as example 1, except that in step 2): supplementing 4290g of sodium sulfide (60%) and supplementing NMP12.5L; in the step 3), 5145g of p-dichlorobenzene is added; to obtain barium sulfate whisker polyarylene sulfide complex (W-BaSO) 4 -PAS)4240g；W-BaSO 4 Is about 10% by mass.
Example 7:
the other steps are the same as example 1, except that in step 2): adding 585g of sodium sulfide (60%), and adding 5L of NMP; in the step 3), 955.5g of p-dichlorobenzene is added to obtain a barium sulfate whisker polyarylene sulfide complex (W-BaSO) 4 -PAS)1150g；W-BaSO 4 Is about 40% by mass.
Example 8:
the other steps are the same as example 1, except that in step 2): adding 585g of sodium sulfide (60%), and adding 5L of NMP; in the step 3), 882g of p-dichlorobenzene, 143.5g of 4, 4-dichlorodiphenyl sulfone are added; obtaining barium sulfate whisker polyarylene sulfide complex (W-BaSO) 4 -PAS)1200g；W-BaSO 4 Is about 40% by mass.
Example 9:
the other steps are the same as example 1, except that in step 2): supplementing 4290g of sodium sulfide (60%), and supplementing NMP12.5L; in the step 3), adding 4487.8g of p-dichlorobenzene, 1502.2g4, 4-dichlorodiphenyl sulfone; obtaining barium sulfate whisker polyarylene sulfide complex (W-BaSO) 4 -PAS)4350g；W-BaSO 4 Is about 10% by mass.
Comparative example 1: W-BaSO 4 Synthesis and performance of (c).
1) Dissolving 250g of PVA with medium viscosity in 5L of deionized water, and adding 10g of sodium hydroxide; then 852g of barium sulfide is added and stirred to be completely dissolved, so that a barium sulfide-PVA solution is formed;
dissolving 100g of PEG8000 in 5L of deionized water, adding 710g of sodium sulfate, stirring and completely dissolving to form a sodium sulfate-PEG solution;
measuring 5L of N-methyl-2-pyrrolidone (NMP), adding into a reaction kettle with a magnetic rotor, introducing nitrogen into the reaction kettle, adding 20g of sodium hydroxide, starting stirring at the rotating speed of 80r/min; weighing 2L of barium sulfide PVA aqueous solution; measuring 2L of sodium sulfate-PEG solution; gradually dripping the two solutions into NMP for 30 minutes; after the dropwise addition, stirring is continued for 45 minutes under the protection of nitrogen, then the temperature is gradually increased to 198 ℃, 4.9L of dehydrated water is kept for 45 minutes, and then the mixture is cooled to be below 100 ℃.
2) Transferring the product into 30L of deionized water, stirring for 20 minutes, and filtering; then washing the mixture for 5 times by using deionized water at 60 ℃, and drying the mixture for 10 hours at 100 ℃; the barium sulfate crystal whisker with the diameter of 0.5-5 mu m and the length of 10-100 mu m is obtained.
The barium sulfate whisker is difficult to form and cannot be used as a film or a plate for testing.
Comparative example 2: conventional PPS preparation and Performance
In a 30L reactor add15l of N-methyl-2-pyrrolidone (NMP), 50g of NaOH,200g of C 7 H 5 NaO 2 Sodium sulfide (60%, na) 2 S) 3.9kg, stirring under the protection of nitrogen, heating to 195 ℃, and fractionating to obtain 1.8l of water and NMP; then cooling to 150 ℃; then adding 4.4kg of p-dichlorobenzene, reacting for 3 hours at 220 ℃, then heating to 260 ℃ and reacting for 3 hours; cooling the polymerization reaction kettle to below 120 ℃, separating, recovering the solvent, washing the product for 5-6 times by using deionized water at the temperature of 60-90 ℃, and drying the product in a drying oven at the temperature of 110 ℃ for 12 hours after the washing is finished to obtain 3.0kg of a white powder product. The test results are shown in tables 1-3.
Comparative example 3: conventional PPS preparation and Performance
15L of N-methyl-2-pyrrolidone (NMP), 50g of NaOH,200g of C were charged into a 30L reactor 7 H 5 NaO 2 Sodium sulfide (60%, na) 2 S) 3.9kg, stirring under the protection of nitrogen, heating to 195 ℃, and fractionating to obtain 1.8l of water and NMP; then cooling to 150 ℃, adding 4.18kg of p-dichlorobenzene and 0.43kg of 4, 4-dichlorodiphenyl sulfone, reacting for 3 hours at 220 ℃, then heating to 260 ℃ and reacting for 3 hours; cooling the polymerization reaction kettle to below 120 ℃, separating, recovering the solvent, washing the product for 5-6 times by using deionized water at the temperature of 60-90 ℃, and drying the product in an oven at the temperature of 110 ℃ for 12 hours after the washing is finished to obtain 3.3kg of a white powder product. The test results of the obtained materials are shown in tables 1 to 3.
Comparative example 4: traditional PPS and barium sulfate powder blended material (PPS/BaSO) 4 )
PPS/BaSO was prepared by passing 2kg of the PPS synthesized in comparative example 2 and 1 kg of barium sulfate powder through a twin-screw extruder 4 A composite material; the speed of the double screw is 20-30r/min; the temperature of the conveying section is 280-290 ℃, the temperature of the melting section is 300-340 ℃, and the temperature of the mixing section is as follows: 300-330 ℃ and the temperature of the homogenization section is 300-320 ℃. The results of the material tests are shown in tables 1 to 3.
Comparative example 5: PAS barium sulfate powder blending material (PAS/BaSO) 4 )
2kg of PAS synthesized in comparative example 3 and 1 kg of barium sulfate powder were taken and subjected to a twin-screw extruder to prepare PPS/BaSO 4 A composite material; the speed of the double screw is 20-30r/min; the temperature of the conveying section is 280-290 ℃, the temperature of the melting section is 300-340 ℃, and the temperature of the mixing section is as follows: 300-330 ℃ and the temperature of the homogenization section is 300-320 ℃. The results of the material tests are shown in tables 1 to 3.
And (3) performance testing:
carrying out injection molding on the dried barium sulfate whisker polyarylene sulfide composite material to obtain a sample strip for testing; the specific parameters of the injection molding process are as follows: temperature of the die: 120-150 ℃, cylinder temperature: front section: 290-320 ℃, middle section: 300-350 ℃, and the rear section: 310-340 ℃; a nozzle: 310-330 ℃, injection molding pressure: 80-150MPa (70-95%), injection speed: medium speed-high speed; pressure maintaining: 30-70MPa (20-45%) metering: setting the residual amount to be 5-10mm; loosening: 3-5mm. The test results are shown in the table.
The barium sulfate whisker polyarylene sulfide composite material is injection molded into a standard sample strip by using an injection molding machine; the density is measured according to the measuring method of GB/T1033; the tensile strength and the elongation at break are tested according to the measuring method of the tensile property of GB/T1040 plastics; the bending strength, the bending modulus and the cantilever beam notch impact strength are tested according to a method for measuring the bending performance of GB/T9341 plastics;
and (3) testing thermal performance: differential Scanning Calorimetry (DSC) analysis was performed using a METTLER TOLEDO DSC3+/500 thermal analyzer. All sample measurements were as follows: the temperature rise rate is 50 ℃/min from room temperature to 300 ℃. Then cooled to room temperature and finally raised to 300 ℃. The temperature change rate for both stages was 10 deg.C/min. Thermogravimetric analysis was carried out on a TGA Q500V 6.4 Build 193, measuring temperature ranging from room temperature to 800 ℃, heating rate 10 ℃/min, measuring in an atmosphere of nitrogen.
Irradiation radiation performance test (X-ray, γ -ray): is finished by a professional testing organization. Gamma ray adoption 241 Am, 60 Co and 137 cs radioactive source having an activity of about 3 x 10 5 Table 5.2 shows the gamma ray energies for the different sources. The source was wrapped with lead and photons passed through a small hole 3mm in diameter and collimated by the hole. The photons then pass through the composite material, being attenuated by the composite material. NaI (TI) scintillator detector for attenuated photonsAnd (5) detecting. The total count of photons is set to 10 4 -10 5 . Each sample was tested in triplicate, resulting in a photon count error of less than 1%. The calculation and statistics are completed by test units and result is given: (1) The attenuation of the medium to the ray per unit mass is described by using a mass attenuation coefficient (mum); (2) The median areal density (HVAD) is the areal density of a material that is shielded from half of the gamma rays.
TABLE 1 Mass attenuation coefficient of the materials obtained in the examples and comparative examples
| 59.5keV(cm 2 /g) | 80keV(cm 2 /g) | 356keV(cm 2 /g) | 662keV(cm 2 /g) | |
| Example 1 | 1.399 | 2.055 | 0.122 | 0.069 |
| Example 2 | 1.406 | 2.078 | 0.128 | 0.070 |
| Example 3 | 1.229 | 1.865 | 0.120 | 0.071 |
| Example 4 | 1.396 | 2.079 | 0.128 | 0.073 |
| Example 5 | 1.233 | 1.886 | 0.125 | 0.076 |
| Example 6 | 0.208 | 0.130 | 0.083 | 0.069 |
| Example 7 | 1.728 | 2.409 | 0.130 | 0.073 |
| Example 8 | 1.730 | 2.405 | 0.133 | 0.071 |
| Example 9 | 0.209 | 0.128 | 0.085 | 0.069 |
| Comparative example 1 | / | / | / | / |
| Comparative example 2 | 0.185 | 0.115 | 0.078 | 0.058 |
| Comparative example 3 | 0.181 | 0.113 | 0.075 | 0.060 |
| Comparative example 4 | 0.785 | 1.110 | 0.100 | 0.062 |
| Comparative example 5 | 0.775 | 1.089 | 0.101 | 0.071 |
TABLE 2 half-value areal densities of the materials obtained in the examples and comparative examples
| 59.5keV(cm 2 /g) | 80keV(cm 2 /g) | 356keV(cm 2 /g) | 662keV(cm 2 /g) | |
| Example 1 | 0.591 | 0.150 | 4.351 | 8.255 |
| Example 2 | 0.588 | 0.150 | 4.345 | 8.156 |
| Example 3 | 0.621 | 0.216 | 4.550 | 7.912 |
| Example 4 | 0.590 | 0.149 | 4.345 | 8.160 |
| Example 5 | 0.625 | 0.215 | 4.533 | 7.912 |
| Example 6 | 4.755 | 3.913 | 5.501 | 8.225 |
| Example 7 | 0.419 | 0.112 | 4.150 | 8.230 |
| Example 8 | 0.431 | 0.109 | 4.133 | 8.015 |
| Example 9 | 4.792 | 3.956 | 5.521 | 8.374 |
| Comparative example 1 | / | / | / | / |
| Comparative example 2 | 5.301 | 3.028 | 5.232 | 8.133 |
| Comparative example 3 | 5.215 | 3.012 | 5.216 | 8.125 |
| Comparative example 4 | 1.621 | 0.355 | 5.011 | 8.002 |
| Comparative example 5 | 1.721 | 0.345 | 5.001 | 8.003 |
TABLE 3 mechanical and thermal Properties of the materials obtained in the examples and comparative examples
Claims (10)
1. A preparation method of a polyarylene sulfide shielding material is characterized by comprising the following steps: barium sulfate and metal sulfate are used as raw materials to prepare barium sulfate whiskers, then byproducts generated in the preparation process of the barium sulfate whiskers are used as sulfur-containing compounds required for preparing polyarylene sulfide, and the sulfur-containing compounds and other conventional reaction monomers are polymerized to prepare the polyarylene sulfide based shielding material.
2. The method of claim 1, wherein the metal in the metal sulfate is lithium, sodium, potassium or rubidium; the other conventional reaction monomer is a dihalo aromatic compound.
3. The method for preparing the polyarylene sulfide based shielding material according to claim 1 or 2, wherein the method for preparing barium sulfate whiskers by using barium sulfide and metal sulfate as raw materials comprises the following steps: dissolving barium sulfide in a polyvinyl alcohol aqueous solution, dissolving metal sulfate in a PEG aqueous solution, dropwise adding the two solutions into an aprotic polar solvent under stirring to perform an interfacial reaction, and controlling the dropwise adding speed, the stirring speed and the temperature to form barium sulfate whiskers; wherein the ratio of barium sulfide to metal sulfate is 1: 1-1.20 mol; the dropping speed is 10-20 ml/min, the stirring speed is 30-80 r/min, and the reaction temperature is room temperature-50 ℃.
4. The method for preparing a polyarylene sulfide based shielding material as claimed in claim 3, wherein the mass concentration of the polyvinyl alcohol aqueous solution is 2.5-7.5%, and the ratio of barium sulfide to polyvinyl alcohol aqueous solution is 1g:5 to 20ml; the concentration of the PEG aqueous solution is 1-25%, the proportion of the metal sulfate to the PEG aqueous solution is 1g:2.5 to 20ml;
further, the PEG in the PEG water solution is PEG4000 or PEG8000;
further, the aprotic polar solvent is selected from: n-methyl-2-pyrrolidone, N-ethylpyrrolidone, hexamethylphosphoramide, N-dimethylacetamide, N-ethylcaprolactam, N-vinylpyrrolidone, caprolactam, tetramethylurea, dimethyl sulfoxide or sulfolane;
further, the aprotic polar solvent is used in an amount of: the usage amount of the solvent in each mole of barium sulfide is 250-1500 ml;
further, alkali accounting for 0.5 to 2.5 percent of the weight of the barium sulfate is added in the process of dissolving the barium sulfide in the polyvinyl alcohol aqueous solution.
5. The method of any of claims 1 to 4, wherein the method of producing a polyarylene sulfide shielding material comprises the steps of:
1) Weighing 2.5-7.5L of aprotic polar solvent, adding into a reaction kettle, introducing nitrogen or inert gas into the reaction kettle, adding 20-220 parts by weight of alkali, starting stirring, and rotating at 50-100 r/min; gradually dripping 0.5-5.0L of barium sulfide-polyvinyl alcohol solution and 0.5-5.0L of metal sulfate-PEG solution into the aprotic polar solvent, wherein the dripping speed is controlled to be 10-20 ml/min; after the dropwise addition is finished, continuously stirring for 30-60 minutes, then gradually heating to 190-200 ℃ for dehydration, and then cooling to below 100 ℃;
2) Under the protection of nitrogen or inert gas, the stirring speed is kept at 100-200 r/min, the temperature is gradually increased to 190-210 ℃, water in the system is removed, and then the system is cooled to 100-150 ℃;
3) Adding 500-5000 parts by weight of reaction monomer 1 and 100-2000 parts by weight of reaction monomer 2, and sealing the reaction kettle; heating to 200-300 ℃ and reacting for 2-12 h; then cooling to below 120 ℃, and finishing the reaction;
4) Opening the reaction kettle, washing the product with deionized water at 50-90 ℃ for 5-8 times, and drying at 80-120 ℃ for 10-20 hours to obtain the polyarylene sulfide shielding material;
wherein, the structural general formula of the reaction monomer 1 is
/>
The structural general formula of the reaction monomer 2 is
6. The method of claim 5, wherein the reactive monomer 1 is:
the reactive monomer 2 is:
further, in the step 2), additionally supplementing a sulfur-containing compound and an aprotic polar solvent according to actual needs;
preferably, in the step 2), 200 to 5000 parts by weight of the sulfur-containing compound is supplemented, and 2.5 to 25L of the aprotic polar solvent is supplemented;
further, in the step 1), the barium sulfide-polyvinyl alcohol solution is prepared by the following method: dissolving 100-500 parts by weight of polyvinyl alcohol in 2.0-10.0L of deionized water, and adding 2.5-25 parts by weight of alkali; then adding 250-1500 parts by weight of barium sulfide, stirring and completely dissolving to form a barium sulfide-polyvinyl alcohol solution;
further, in the step 1), the sodium sulfate-PEG solution is prepared by the following method: dissolving 25-250 parts by weight of PEG in 2.0-10L of deionized water, adding 250-1000 parts by weight of metal sulfate, and stirring to completely dissolve the PEG to form a sodium sulfate-PEG solution;
further, the process of step 3) is: adding a reaction monomer 1 and a reaction monomer 2, heating under the protection of nitrogen or inert gas while stirring, and keeping the temperature for 1.5-5.5 hours after the temperature reaches 200-260 ℃; then the temperature is raised to 220 to 300 ℃ and kept for 1 to 5 hours.
7. A polyarylene sulfide based shielding material, characterized in that the polyarylene sulfide based shielding material is prepared by the preparation method of any one of claims 1 to 6.
8. The polyarylene sulfide-based shielding material of claim 7 processed into a corresponding article;
further, the processing temperature is 290-350 ℃;
further, casting the polyarylene sulfide shielding material into a film at 290-350 ℃ at the speed of 10-300 mm/min; the thickness of the obtained film is 0.1-0.5 mm;
further, the polyarylene sulfide shielding material is hot-pressed into a sheet material, the pressing temperature is 290-350 ℃, and the pressure is 20-100MPa; the thickness of the obtained sheet is 0.5-2 mm.
9. A preparation method of barium sulfate whiskers is characterized by comprising the following steps: dissolving barium sulfide in a polyvinyl alcohol aqueous solution, dissolving metal sulfate in a PEG aqueous solution, dropwise adding the two solutions into an aprotic polar solvent under stirring to perform an interfacial reaction, and controlling the dropwise adding speed, the stirring speed and the temperature to form barium sulfate whiskers; wherein the ratio of barium sulfide to metal sulfate is 1: 1-1.20 mol; the dropping speed is 10-20 ml/min, the stirring speed is 30-80 r/min, and the reaction temperature is room temperature-50 ℃;
further, the mass concentration of the polyvinyl alcohol aqueous solution is 2.5-7.5%, and the ratio of barium sulfide to the polyvinyl alcohol aqueous solution is 1g:5 to 20ml; the concentration of the PEG aqueous solution is 1-25%, the proportion of the metal sulfate to the PEG aqueous solution is 1g:2.5 to 20ml;
further, the PEG in the PEG aqueous solution is PEG4000 or PEG8000;
further, the aprotic polar solvent is selected from: n-methyl-2-pyrrolidone, N-ethylpyrrolidone, hexamethylphosphoramide, N-dimethylacetamide, N-ethylcaprolactam, N-vinylpyrrolidone, caprolactam, tetramethylurea, dimethyl sulfoxide or sulfolane;
further, the aprotic polar solvent is used in an amount of: the usage amount of the solvent in each mole of barium sulfide is 250-1500 ml;
further, alkali accounting for 0.5 to 2.5 percent of the weight of the barium sulfate is added in the process of dissolving the barium sulfide in the polyvinyl alcohol aqueous solution.
10. A barium sulfate whisker, characterized in that it is produced by the production method according to claim 9;
furthermore, the diameter of the barium sulfate whisker is 0.5-5 μm, and the length of the barium sulfate whisker is 10-100 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211592327.3A CN115894916B (en) | 2022-12-13 | 2022-12-13 | Polyarylene sulfide based shielding material for preventing X, gamma rays and neutrons from radiating and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211592327.3A CN115894916B (en) | 2022-12-13 | 2022-12-13 | Polyarylene sulfide based shielding material for preventing X, gamma rays and neutrons from radiating and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115894916A true CN115894916A (en) | 2023-04-04 |
| CN115894916B CN115894916B (en) | 2024-05-03 |
Family
ID=86470985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211592327.3A Active CN115894916B (en) | 2022-12-13 | 2022-12-13 | Polyarylene sulfide based shielding material for preventing X, gamma rays and neutrons from radiating and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115894916B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08157718A (en) * | 1994-12-07 | 1996-06-18 | Tonen Chem Corp | Polyarylene sulfide resin composition |
| JP2015219170A (en) * | 2014-05-20 | 2015-12-07 | 松山毛織株式会社 | Radiation shield material |
| KR20160142634A (en) * | 2015-06-03 | 2016-12-13 | 주식회사 알에스엠테크 | Radiation sheilding composition and method for preparing the same |
| CN108179477A (en) * | 2018-01-29 | 2018-06-19 | 辽宁工程技术大学 | A kind of method that calcium sulfate crystal whiskers are prepared in magnetic field |
| CN108976795A (en) * | 2018-05-31 | 2018-12-11 | 四川大学 | A kind of polyarylphosphorus ether radiation protection composite material and preparation method thereof |
| CN110564154A (en) * | 2019-10-23 | 2019-12-13 | 四川大学 | bonded polyarylene sulfide metal composite material with nuclear radiation protection function and preparation method thereof |
| KR102219045B1 (en) * | 2019-10-31 | 2021-02-23 | 서울과학기술대학교 산학협력단 | Radiation shielding block and method for manufacturing of radiation shielding block |
| CN112852380A (en) * | 2021-01-18 | 2021-05-28 | 竹山县秦巴钡盐有限公司 | Barium sulfate electronic pouring sealant and preparation method and application thereof |
| CN112909424A (en) * | 2021-01-18 | 2021-06-04 | 帕特克(武汉)科技有限公司 | In-situ modified barium sulfate whisker, preparation method thereof and lithium ion battery diaphragm |
| CN114213659A (en) * | 2021-12-27 | 2022-03-22 | 中鼎凯瑞科技成都有限公司 | Heat-resistant silicon-containing polyarylene sulfide and preparation method thereof |
-
2022
- 2022-12-13 CN CN202211592327.3A patent/CN115894916B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08157718A (en) * | 1994-12-07 | 1996-06-18 | Tonen Chem Corp | Polyarylene sulfide resin composition |
| JP2015219170A (en) * | 2014-05-20 | 2015-12-07 | 松山毛織株式会社 | Radiation shield material |
| KR20160142634A (en) * | 2015-06-03 | 2016-12-13 | 주식회사 알에스엠테크 | Radiation sheilding composition and method for preparing the same |
| CN108179477A (en) * | 2018-01-29 | 2018-06-19 | 辽宁工程技术大学 | A kind of method that calcium sulfate crystal whiskers are prepared in magnetic field |
| CN108976795A (en) * | 2018-05-31 | 2018-12-11 | 四川大学 | A kind of polyarylphosphorus ether radiation protection composite material and preparation method thereof |
| CN110564154A (en) * | 2019-10-23 | 2019-12-13 | 四川大学 | bonded polyarylene sulfide metal composite material with nuclear radiation protection function and preparation method thereof |
| KR102219045B1 (en) * | 2019-10-31 | 2021-02-23 | 서울과학기술대학교 산학협력단 | Radiation shielding block and method for manufacturing of radiation shielding block |
| CN112852380A (en) * | 2021-01-18 | 2021-05-28 | 竹山县秦巴钡盐有限公司 | Barium sulfate electronic pouring sealant and preparation method and application thereof |
| CN112909424A (en) * | 2021-01-18 | 2021-06-04 | 帕特克(武汉)科技有限公司 | In-situ modified barium sulfate whisker, preparation method thereof and lithium ion battery diaphragm |
| CN114213659A (en) * | 2021-12-27 | 2022-03-22 | 中鼎凯瑞科技成都有限公司 | Heat-resistant silicon-containing polyarylene sulfide and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115894916B (en) | 2024-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE60116628T2 (en) | EPOXY RESIN SYSTEMS WITH LOW MOISTURE ABSORPTION | |
| KR101145703B1 (en) | Radiation shield sheet | |
| CN101696316B (en) | Method for preparing radiation protection materials | |
| CN108659469B (en) | Organosilicon resin modified epoxy resin-based neutron shielding material, preparation and application thereof | |
| CN105566556A (en) | Anti-radiation organic glass | |
| EP3650483B1 (en) | Halogen-containing polymer and production method for same | |
| Wang et al. | Preparation and radiation shielding properties of Gd2O3/PEEK composites | |
| CN104262527B (en) | A kind of radioprotective liquid organic glass | |
| CN115894916A (en) | Polyarylene sulfide shielding material for preventing X, gamma ray and neutron radiation and preparation thereof | |
| CN101486809B (en) | Preparation of rare-earth oxide / natural rubber composite material for X radiation protection | |
| Wu et al. | Flexible stretchable low-energy X-ray (30–80 keV) radiation shielding material: Low-melting-point Ga1In1Sn7Bi1 alloy/thermoplastic polyurethane composite | |
| CN109161203A (en) | A kind of radiation hardness job that requires special skills graphene compounded rubber and preparation method | |
| Liao et al. | B4C/NRL flexible films for thermal neutron shielding | |
| KR101450677B1 (en) | Additive composition comprising counteragent | |
| CN113861414A (en) | Self-cleaning transparent nylon material for shielding radioactive rays and preparation method thereof | |
| Liao et al. | Preparation and characterization of Bi2O3/XNBR flexible films for attenuating gamma rays | |
| CN107880362A (en) | A kind of preparation method of neutron irradiation shielding composite | |
| CN110197734B (en) | Preparation method of X-ray shielding material based on natural leather | |
| CN112812498A (en) | Preparation method of functionalized carbon nanotube modified resin-based composite radiation protection material | |
| CN116574335A (en) | Gamma ray and neutron radiation protection rubber material based on rare earth material | |
| CN109438897B (en) | Gamma-ray radiation protection composite material and preparation method thereof | |
| DE68917817T2 (en) | Process for the preparation of crosslinked polycarbonates and compositions thereof. | |
| CN115746537A (en) | Nuclear radiation protection material with high temperature resistance and preparation method thereof | |
| CN106674579B (en) | The preparation method of engineering plastics cross-linked accelerating agent for irradiation | |
| Aycik et al. | Effect of polymer matrix type on electromagnetic radiation shielding performances of PbO reinforced/polyethylene, isophytalic polyester and bisphenol A vinylester based composites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |