CN115894916B - Polyarylene sulfide based shielding material for preventing X, gamma rays and neutrons from radiating and preparation thereof - Google Patents
Polyarylene sulfide based shielding material for preventing X, gamma rays and neutrons from radiating and preparation thereof Download PDFInfo
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- CN115894916B CN115894916B CN202211592327.3A CN202211592327A CN115894916B CN 115894916 B CN115894916 B CN 115894916B CN 202211592327 A CN202211592327 A CN 202211592327A CN 115894916 B CN115894916 B CN 115894916B
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229920000412 polyarylene Polymers 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 24
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 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
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000006227 byproduct Substances 0.000 claims abstract description 5
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- 238000003756 stirring Methods 0.000 claims description 29
- 229920001223 polyethylene glycol Polymers 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 24
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 19
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000002798 polar solvent Substances 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 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 8
- 229910052788 barium Inorganic materials 0.000 claims description 8
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- 229910052708 sodium Inorganic materials 0.000 claims description 8
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- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 2
- GWCFTYITFDWLAY-UHFFFAOYSA-N 1-ethylazepan-2-one Chemical compound CCN1CCCCCC1=O GWCFTYITFDWLAY-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
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- 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
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
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- 230000000052 comparative effect Effects 0.000 description 20
- 229910052979 sodium sulfide Inorganic materials 0.000 description 12
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 9
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
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- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 1
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- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Polymers C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
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- GKOZUEZYRPOHIO-IGMARMGPSA-N iridium-192 Chemical compound [192Ir] GKOZUEZYRPOHIO-IGMARMGPSA-N 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
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Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention relates to a polyarylene sulfide based shielding material for preventing X, gamma rays and neutrons from radiating and a preparation method thereof, belonging to the field of radiation-proof materials. The invention provides a preparation method of a polyarylene sulfide based shielding material, which comprises the following steps: firstly, barium sulfide 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 are polymerized with other conventional reaction monomers to prepare the polyarylene sulfide based shielding material. The obtained barium sulfate whisker polyarylene sulfide composite material is manufactured into barium sulfate whisker polyarylene sulfide composite material equipment and devices which have X-ray and gamma-ray shielding and absorption, high temperature resistance and neutron shielding function through processing methods such as injection molding, film drawing and the like, and are used for the use of radiation irradiation environment and the protection of equipment and human radiation irradiation.
Description
Technical Field
The invention relates to a polyarylene sulfide based shielding material for preventing X, gamma rays and neutrons from radiating and a preparation method thereof, belonging to the field of radiation-proof materials.
Background
With the rapid development of informatization and artificial intelligence, as well as the utilization of nuclear energy and space development, the range of nuclear radiation and electromagnetic radiation is becoming wider and wider.
The radiation is classified 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; a 241Am-Be source, a 24Na-Be source, a 124Sb-Be source and neutron rays generated by an electron accelerator with energy exceeding 10M; beta, alpha rays generated by non-sealed sources; various industrial and medical X-ray devices can generate X-rays, etc.
It has therefore been one of the hot spots and difficulties in materials research to investigate materials capable of absorbing and shielding various types of radiation and irradiation. And 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 oxide materials thereof are difficult to simultaneously satisfy the comprehensive shielding and protection of neutrons, gamma rays, X rays and other various radiations. The elements and materials corresponding to the absorption and shielding of three types of radiation of neutrons, gamma rays and X rays are not completely the same, and how to enable multiple elements to form a multifunctional stable material with molecular level, enable different elements to play a synergistic effect and play a role in superposition of multiple radiation absorption and shielding is a core problem in the design and preparation of the existing radiation protection materials.
In order to solve the problem that multiple radiations exist simultaneously, the composite material is one of 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. Based on the matrix of the composite materials used for the radiation material, mainly conventional 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 ℃), which is excellent in heat resistance, corrosion resistance and self-lubricating properties, and which is relatively poor in radiation resistance; thermosetting plastics such as epoxy resin, imide and the like, and cannot be deformed and secondarily molded after being cured; the rubber (including natural rubber, silicone rubber such as polydimethylsiloxane, 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, can have phase separation, causes instability of materials, has good elasticity and low strength, and can not meet the requirements in a high-stress environment.
Disclosure of Invention
Aiming at the defects, the invention provides a polyarylene sulfide based composite material which has X-ray and gamma-ray shielding and absorption, high temperature resistance and neutron shielding function and an integrated preparation method thereof; namely, the barium sulfate whisker is prepared in an organic system, and the X-ray can not penetrate through the barium sulfate whisker by utilizing the strong X-ray absorption capacity of the barium sulfate whisker, so that the performances of X-rays and Y-rays can be effectively shielded; and the reaction by-product generated in the process of preparing the barium sulfate whisker is used as one of the 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; the barium sulfate whisker polyarylene sulfide composite material equipment and device with X-ray and gamma-ray shielding and absorption, high temperature resistance and neutron shielding function can be formed through injection molding and film drawing, and the equipment and device are used for radiation irradiation environment use and equipment and human body radiation irradiation protection.
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 based shielding material, which comprises the following steps: firstly, barium sulfide 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 polyarylene sulfide based shielding material can be prepared by polymerizing the sulfur-containing compounds with other conventional reaction monomers (such as dihalogenated aromatic compounds).
Further, the metal in the metal sulfate is alkali metal elements 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, performing an interface reaction, and controlling the dropping speed, stirring speed and temperature to form barium sulfate whiskers; wherein, the proportion of barium sulfide to metal sulfate is 1:1 to 1.20mol; 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: 5-20 ml; the concentration of the PEG aqueous solution is 1-25%, and the ratio of the metal sulfate to the PEG aqueous solution is 1g: 2.5-20 ml.
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-ethyl pyrrolidone, hexamethylphosphoramide (HMPA), N-dimethylacetamide, N-ethylcaprolactam, N-vinylpyrrolidone, caprolactam, tetramethylurea, dimethylsulfoxide or sulfolane; the dosage is as follows: the solvent is used in an amount of 250 to 1500ml per mole of barium sulfide.
Further, in order to prevent the hydrolysis of barium sulfide (BaS, 170.4), 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 during the dissolution of barium sulfide in the aqueous polyvinyl alcohol solution.
Further, in the above-mentioned production method, a sulfur-containing compound required for producing polyarylene sulfide may be additionally added as needed.
Further, the preparation method of the polyarylene sulfide based shielding material comprises the following steps:
1) 2.5 to 7.5L of aprotic polar solvent is measured and added into a reaction kettle, nitrogen or inert gas is introduced into the reaction kettle, 20 to 220 weight parts of alkali is added, and stirring is started, wherein the rotating speed is 50 to 100r/min; gradually dripping 0.5-5.0L barium sulfide-polyvinyl alcohol solution and 0.5-5.0L metal sulfate-PEG solution into aprotic polar solvent, and controlling the dripping speed to be 10-20 ml/min; after the dripping is finished, stirring is continued for 30-60 minutes, then the temperature is gradually increased to 190-200 ℃ for dehydration, and then the mixture is cooled to below 100 ℃;
2) Under the protection of nitrogen or inert gas, the stirring rotation 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 ℃ to react for 2-12 h; then cooling to below 120 ℃ to finish 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 a polyarylene sulfide based 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
Or-O-; x=f, cl, br or I.
Preferably, the reaction monomer 1 is: 2, 4-Dihalobenzene/> Or 4,4' -dihalobiphenyl/>
The reaction monomer 2 is: 4,4' -dihalodiphenylsulfones4,4' -DihalobenzophenoneOr 4,4' -dihalodiphenyl ether/>Etc.
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 as needed according to the ratio.
Preferably, in the step 2), 200 to 5000 parts by weight of the sulfur-containing compound is added, and 2.5 to 25L of the aprotic polar solvent is added.
Further, in the above 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, and stirring to completely dissolve to form barium sulfide-polyvinyl alcohol solution.
Further, in the above 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 to form sodium sulfate-PEG solution.
Further, the process of step 3) is: adding the reaction monomer 1 and the reaction monomer 2, stirring and heating under the protection of nitrogen or inert gas, and keeping for 1.5-5.5 hours after the temperature reaches 200-260 ℃; then heating to 220-300 ℃ and keeping for 1-5 hours.
The second technical problem to be solved by the invention is to provide a polyarylene sulfide based 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, the polyarylene sulfide based shielding material is formed into a film by tape casting, wherein the film drawing temperature is 290-350 ℃ and the speed is 10-300 mm/min; the thickness of the obtained film is 0.1-0.5 mm.
Further, the polyarylene sulfide based 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 whisker, 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 aprotic polar solvent under stirring, performing interface reaction, and controlling the dropping speed, stirring speed and temperature to form barium sulfate whisker; wherein, the proportion 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 ℃.
The fifth technical problem to be solved by the invention is to provide a barium sulfate whisker which is prepared by adopting the method.
Further, the diameter of the barium sulfate whisker is 0.5-5 mu m, and the length is 10-100 mu m.
The invention has the beneficial effects that:
In the process of preparing the barium sulfate whisker, the byproduct generated in the preparation process is used as a sulfur-containing compound required by polyarylene sulfide preparation, and the sulfur-containing compound and other conventional reaction monomers are continuously subjected to polymerization reaction of polyarylene sulfide to form the barium sulfate whisker polyarylene sulfide composite material; the barium sulfate whisker polyarylene sulfide composite material equipment and device with X-ray and gamma-ray shielding and absorption, high temperature resistance and neutron shielding function are manufactured by processing methods such as injection molding, film drawing and the like, and are used for the use of radiation irradiation environment and the protection of equipment and human radiation irradiation.
Detailed Description
The above-described aspects of the present invention will be described in further detail below by way of specific embodiments of the present invention. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. Various substitutions and alterations are also possible, without departing from the spirit of the invention, and are intended to be within the scope of the invention.
Example 1:
The polyarylene sulfide based shielding material of the invention is prepared by:
1) 250g of medium viscosity PVA was dissolved in 5L of deionized water and 10g of sodium hydroxide was added; then 852g of barium sulfide is added and stirred to be completely dissolved to form barium sulfide-PVA solution; dissolving 100g of PEG8000 in 5L of deionized water, adding 710g of sodium sulfate, and stirring to dissolve completely to form a sodium sulfate-PEG solution;
Weighing 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, and starting stirring at a rotating speed of 80r/min; 2L of barium sulfide PVA aqueous solution is measured; 2L of sodium sulfate-PEG solution is measured; gradually dripping the two solutions into NMP, controlling the dripping speed to be 10-20 ml/min, and finishing dripping in 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 temperature 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 (rotating/min), gradually heating to 198 ℃, removing 400ml of water, and cooling to 100-150 ℃;
3) Adding 1470g of paradichlorobenzene, stirring for 5 minutes under the protection of nitrogen, increasing the speed to 120r/min, and sealing the reaction kettle; after the temperature reaches 215-235 ℃, keeping for 3 hours; then heating to 260 ℃ and keeping for 3 hours; then cooling to below 120 ℃ to finish the reaction.
4) And (3) 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 barium sulfate whisker polyarylene sulfide complex (W-BaSO 4-PAS)1500g;W-BaSO4 mass ratio is about 30%).
Taking part of barium sulfate whisker polyarylene sulfide complex for thermal performance test, and partially injecting into mechanical sample strips through an injection molding machine; partial pressure is used for preparing X-ray and gamma-ray protection test samples; the properties obtained are shown in tables 1 to 3.
Example 2
Other steps are the same as in example 1; except that in step 3) p-dichlorobenzene 1396.5g,143.5g of 4, 4-dichlorodiphenyl sulfone are added; the barium sulfate whisker polyarylene sulfide complex (W-BaSO 4-PAS)1560g;W-BaSO4 mass percent is about 30%) is obtained.
Example 3
The other steps are the same as in example 1, except that in step 1): 100g of PEG4000 is dissolved in 5L of deionized water, 545g of lithium sulfate is added, and the mixture is stirred to be completely dissolved to form a lithium sulfate-PEG solution; the W-BaSO 4 mass ratio was about 18%.
Example 4:
The other steps are the same as in example 1, except that in step 1): 100g of PEG8000 is dissolved in 5L of deionized water, 600g of sodium bisulfate (NaHSO 4) is added, and the mixture is stirred and completely dissolved to form NaHSO 4 -PEG solution;
Weighing 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 accounts for about 30% by mass.
Example 5
The other steps are the same as in example 1, except that in step 2): 2340g of sodium sulfide (60%) and NMP7.5L g of sodium sulfide are added;
In the step 3), 2940g of paradichlorobenzene is added; 2600g of barium sulfate whisker polyarylene sulfide complex (W-BaSO 4 -PAS) was obtained; the W-BaSO 4 in the obtained material accounts for about 18% by mass.
Example 6:
The other steps are the same as in example 1, except that in step 2): 4290g of sodium sulfide (60%) and NMP12.5L g of sodium sulfide are added; in the step 3), 5145g of paradichlorobenzene is added; the barium sulfate whisker polyarylene sulfide complex (W-BaSO 4-PAS)4240g;W-BaSO4 accounts for about 10% by mass) is obtained.
Example 7:
the other steps are the same as in example 1, except that in step 2): 585g of sodium sulfide (60%) and 5L of NMP were added; in the step 3), 955.5g of p-dichlorobenzene was added to obtain a barium sulfate whisker polyarylene sulfide complex (W-BaSO 4-PAS)1150g;W-BaSO4 accounts for about 40% by mass.
Example 8:
The other steps are the same as in example 1, except that in step 2): 585g of sodium sulfide (60%) and 5L of NMP were added; in step 3), 882g of p-dichlorobenzene, 143.5g of 4, 4-dichlorodiphenyl sulfone are added; the barium sulfate whisker polyarylene sulfide complex (W-BaSO 4-PAS)1200g;W-BaSO4 accounts for about 40% by mass) is obtained.
Example 9:
The other steps are the same as in example 1, except that in step 2): 4290g of sodium sulfide (60%) and NMP12.5L g of sodium sulfide are added; in step 3), p-dichlorobenzene 4487.8g,1502.2g of 4, 4-dichlorodiphenyl sulfone was added; the barium sulfate whisker polyarylene sulfide complex (W-BaSO 4-PAS)4350g;W-BaSO4 accounts for about 10% by mass) is obtained.
Comparative example 1: synthesis and performance of W-BaSO 4.
1) 250G of medium viscosity PVA was dissolved in 5L of deionized water and 10g of sodium hydroxide was added; then 852g of barium sulfide is added and stirred to be completely dissolved to form barium sulfide-PVA solution;
Dissolving 100g of PEG8000 in 5L of deionized water, adding 710g of sodium sulfate, and stirring to dissolve completely to form a sodium sulfate-PEG solution;
Weighing 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, and starting stirring at a rotating speed of 80r/min; 2L of barium sulfide PVA aqueous solution is measured; 2L of sodium sulfate-PEG solution is measured; gradually dropwise adding the two solutions into NMP for 30 minutes to finish dropwise adding; 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 temperature is cooled to below 100 ℃.
2) Transferring the product into 30L of deionized water, stirring for 20 minutes, and filtering; washing with 60 ℃ deionized water for 5 times, and drying at 100 ℃ for 10 hours; the barium sulfate 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 mold and can not be used as a film or a plate for testing.
Comparative example 2: traditional PPS preparation and Properties
15L N-methyl-2-pyrrolidone (NMP), 50g NaOH,200g C 7H5NaO2, sodium sulfide (60%, na 2 S) 3.9kg were charged into a 30L reactor, stirred under nitrogen, heated to 195℃and fractionated water and NMP amounting to 1.8L; then cooling to 150 ℃; then adding 4.4kg of paradichlorobenzene, reacting for 3 hours at 220 ℃, heating to 260 ℃ and reacting for 3 hours; and cooling the polymerization reaction kettle to below 120 ℃, separating, recovering the solvent, washing the product with deionized water at 60-90 ℃ for 5-6 times, and drying the product in a 110 ℃ oven for 12 hours after washing is completed to obtain 3.0kg of white powder product. The test results are shown in tables 1 to 3.
Comparative example 3: traditional PPS preparation and Properties
15L N-methyl-2-pyrrolidone (NMP), 50g NaOH,200g C 7H5NaO2, sodium sulfide (60%, na 2 S) 3.9kg were charged into a 30L reactor, stirred under nitrogen, heated to 195℃and fractionated water and NMP amounting to 1.8L; then cooling to 150 ℃, then adding 0.43kg of p-dichlorobenzene 4.18kg, 4-dichloro diphenyl sulfone, reacting for 3 hours at 220 ℃, and then heating to 260 ℃ for reacting for 3 hours; and cooling the polymerization reaction kettle to below 120 ℃, separating, recovering the solvent, washing the product with deionized water at 60-90 ℃ for 5-6 times, and drying the product in a 110 ℃ oven for 12 hours after washing is completed, thus obtaining 3.3kg of white powder product. The test results of the obtained materials are shown in tables 1 to 3.
Comparative example 4: traditional blend material of PPS and barium sulfate powder (PPS/BaSO 4)
Preparing a PPS/BaSO 4 composite material by taking 2kg of PPS and 1 kg of barium sulfate powder synthesized in comparative example 2 through a double screw extruder; the speed of the twin-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 homogenization section temperature is 300-320 ℃. The test results of the obtained materials are shown in tables 1 to 3.
Comparative example 5: PAS barium sulfate powder blend material (PAS/BaSO 4)
Preparing a PPS/BaSO 4 composite material by taking 2kg of PAS and 1 kg of barium sulfate powder synthesized in comparative example 3 through a double screw extruder; the speed of the twin-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 homogenization section temperature is 300-320 ℃. The test results of the obtained materials are shown in tables 1 to 3.
Performance test:
performing injection molding on the dried barium sulfate whisker polyarylene sulfide composite material to obtain a spline for testing; the specific parameters of the injection molding process are as follows: mold temperature: 120-150 ℃, charging barrel temperature: front section: 290-320 ℃, middle section: 300-350 ℃, and the rear section: 310-340 ℃; and (3) a nozzle: 310-330 ℃, injection molding pressure: 80-150MPa (70-95%), injection molding speed: medium-high speed; pressure maintaining pressure: 30-70MPa (20-45%) metering: setting the residual quantity to be 5-10mm; loosening and backing: 3-5mm. The test results are shown in the table.
The barium sulfate whisker polyarylene sulfide composite material is subjected to injection molding into standard sample strips by using an injection molding machine; the density is measured according to the measurement method of GB/T1033; the tensile strength and the elongation at break are tested according to the method for measuring the tensile property of GB/T1040 plastic; the bending strength, the bending modulus and the cantilever notched impact strength are tested according to the method for measuring the bending performance of GB/T9341 plastic;
Thermal performance test: 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 again and finally raised to 300 ℃. The rate of temperature change in both stages was 10deg.C/min. Thermogravimetric analysis was performed on a TGA Q500V 6.4 Build 193 at a temperature ranging from room temperature to 800℃and at a temperature rise rate of 10℃per minute under nitrogen atmosphere.
Irradiation radiation performance test (X-ray, gamma-ray): is completed by a professional testing organization. Gamma rays were generated using 241Am,60 Co and 137 Cs sources with activities of about 3X 10 5 Bq. Table 5.2 shows Gamma energy for the different sources. The source is surrounded by a lead block and photons pass through a small hole of 3mm diameter and are collimated by the small hole. The photons then pass through the composite material and are attenuated by the composite material. The attenuated photons are detected with a NaI (TI) scintillator detector. The total count of photons was set to 10 4-105. Each sample was tested in triplicate so that the photon count error was less than 1%. The calculation statistics have test units completed and give the result: (1) Describing the attenuation of the radiation by the unit mass medium using a mass attenuation coefficient (μm); (2) Half Value Areal Density (HVAD) is the areal density of a material that shields half of the gamma rays.
TABLE 1 Mass attenuation coefficient of materials obtained in examples and comparative examples
| 59.5keV(cm2/g) | 80keV(cm2/g) | 356keV(cm2/g) | 662keV(cm2/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 area density of the materials obtained in examples and comparative examples
| 59.5keV(cm2/g) | 80keV(cm2/g) | 356keV(cm2/g) | 662keV(cm2/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 examples and comparative examples
Claims (12)
1. The preparation method of the polyarylene sulfide based shielding material is characterized by comprising the following steps: firstly, barium sulfide 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 are polymerized with other conventional reaction monomers to prepare the polyarylene sulfide based shielding material.
2. The method for preparing a polyarylene sulfide based shielding material according to claim 1, wherein the metal in the metal sulfate is lithium, sodium, potassium or rubidium; the other conventional reactive monomer is a dihaloaromatic compound.
3. The method for preparing the polyarylene sulfide based shielding material according to claim 1 or 2, wherein the method for preparing the barium sulfate whisker by using barium sulfide and metal sulfate as raw materials is as follows: 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, performing an interface reaction, and controlling the dropping speed, stirring speed and temperature to form barium sulfate whiskers; wherein, the mole ratio of barium sulfide to metal sulfate is 1:1 to 1.20; 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 according to claim 3, wherein the mass concentration of the aqueous solution of polyvinyl alcohol is 2.5-7.5%, and the ratio of barium sulfide to the aqueous solution of polyvinyl alcohol is 1g: 5-20 ml; the concentration of the PEG aqueous solution is 1-25%, and the ratio of the metal sulfate to the PEG aqueous solution is 1g: 2.5-20 ml;
the PEG in the PEG aqueous solution is PEG4000 or PEG8000;
The aprotic polar solvent is selected from: n-methyl-2-pyrrolidone, N-ethyl pyrrolidone, hexamethylphosphoramide, N-dimethylacetamide, N-ethylcaprolactam, N-vinylpyrrolidone, tetramethylurea, dimethylsulfoxide or sulfolane;
The dosage of the aprotic polar solvent is as follows: the usage amount of the solvent in each mole of barium sulfide is 250-1500 ml;
alkali accounting for 0.5-2.5% of the weight of the barium sulfide is also added in the process of dissolving the barium sulfide in the polyvinyl alcohol aqueous solution.
5. The method for producing a polyarylene sulfide based shielding material according to claim 4, wherein the method for producing a polyarylene sulfide based shielding material comprises the steps of:
1) 2.5 to 7.5L of aprotic polar solvent is measured and added into a reaction kettle, nitrogen or inert gas is introduced into the reaction kettle, 20 to 220 weight parts of alkali is added, and stirring is started, wherein the rotating speed is 50 to 100 r/min; gradually dripping 0.5-5.0L barium sulfide-polyvinyl alcohol solution and 0.5-5.0L metal sulfate-PEG solution into aprotic polar solvent, and controlling the dripping speed to be 10-20 ml/min; after the dripping is finished, stirring is continued for 30-60 minutes, then the temperature is gradually increased to 190-200 ℃ for dehydration, and then the mixture is cooled to below 100 ℃;
2) Under the protection of nitrogen or inert gas, the stirring rotation 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 ℃ to react for 2-12 h; then cooling to below 120 ℃ to finish 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 based shielding material;
wherein the structural general formula of the reaction monomer 1 is ，
The structural general formula of the reaction monomer 2 is，
M=、 />、/>Or-O-; x=f, cl, br or I.
6. The method for producing a polyarylene sulfide based shielding material according to claim 5, wherein,
The reaction monomer 2 is:、 /> or (b) 。
7. The method for preparing a polyarylene sulfide based shielding material according to claim 5, wherein in step 2), a sulfur-containing compound and an aprotic polar solvent are additionally added according to actual needs; 200 to 5000 parts by weight of sulfur-containing compound and 2.5 to 25L of aprotic polar solvent are added.
8. The method for preparing a polyarylene sulfide based shielding material according to claim 5, wherein in 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, and stirring to completely dissolve to form barium sulfide-polyvinyl alcohol solution;
In the step 1), the metal 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 to form metal sulfate-PEG.
9. The method for preparing a polyarylene sulfide based shielding material according to claim 5, wherein the process of step 3) is: adding the reaction monomer 1 and the reaction monomer 2, stirring and heating under the protection of nitrogen or inert gas, and keeping for 1.5-5.5 hours after the temperature reaches 200-260 ℃; then heating to 220-300 ℃ and keeping for 1-5 hours.
10. A polyarylene sulfide based shielding material, characterized in that the polyarylene sulfide based shielding material is produced by the production method according to any one of claims 1 to 9.
11. An article fabricated using the polyarylene sulfide based shielding material of claim 10.
12. An article according to claim 11, wherein,
The processing temperature is 290-350 ℃;
Casting the polyarylene sulfide based shielding material into a film, wherein the film drawing temperature is 290-350 ℃ and the speed is 10-300 mm/min; the thickness of the obtained film is 0.1-0.5 mm; or:
Hot-pressing the polyarylene sulfide based shielding material into a sheet, wherein the pressing temperature is 290-350 ℃ and the pressure is 20-100 MPa; the thickness of the obtained sheet is 0.5-2 mm.
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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 |
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