WO2022121491A1 - Preparation method for low-temperature glue for low-temperature pump activated carbon adsorption material - Google Patents
Preparation method for low-temperature glue for low-temperature pump activated carbon adsorption material Download PDFInfo
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- WO2022121491A1 WO2022121491A1 PCT/CN2021/122946 CN2021122946W WO2022121491A1 WO 2022121491 A1 WO2022121491 A1 WO 2022121491A1 CN 2021122946 W CN2021122946 W CN 2021122946W WO 2022121491 A1 WO2022121491 A1 WO 2022121491A1
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- temperature
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- powder
- low
- polychlorotrifluoroethylene
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 22
- 239000003292 glue Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- -1 polytrifluorochloroethylene Polymers 0.000 claims abstract description 52
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 57
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 57
- 239000000843 powder Substances 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 31
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 229910021389 graphene Inorganic materials 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 239000012745 toughening agent Substances 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 9
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 8
- 229950000244 sulfanilic acid Drugs 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000009832 plasma treatment Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000003517 fume Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 4
- 235000010288 sodium nitrite Nutrition 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 229920001780 ECTFE Polymers 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 2
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical compound [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000002826 coolant Substances 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229920001875 Ebonite Polymers 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003949 liquefied natural gas Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FPBWSPZHCJXUBL-UHFFFAOYSA-N 1-chloro-1-fluoroethene Chemical group FC(Cl)=C FPBWSPZHCJXUBL-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical class 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920003247 engineering thermoplastic Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000013102 re-test Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
Definitions
- the invention belongs to the technical field of cryopumps, in particular to a preparation method of cryogenic glue for activated carbon adsorption materials of cryopumps.
- a cryopump is a vacuum pump that uses a cryogenic surface to condense and physically adsorb gases. Also known as condensate pump and cryogenic adsorption pump. At present, the low temperature pumping method has been widely used. Pumping with cryopumps is based on the condensation of gases on cryogenic surfaces, which are cooled to very low temperatures. The difference between cryopumps and cold traps is the refrigerant used. What cools the working surface of the cryopump is not liquid nitrogen (which has a boiling point of minus 196°C at standard pressure, but hydrogen or helium, which have a boiling point of minus 253°C and minus 269°C at standard pressure, respectively.
- Cool to The surface of liquid nitrogen temperature can make gas (including most of the decomposition products of oil diffusion pump) extremely easy to condense.
- a surface can be used as a cryopump, and cryopump needs to use adsorbent material to help it pump gas, and adsorbent material
- the bonding with the panel is achieved by adhesives, but the existing adhesives have poor low temperature resistance and low bonding strength.
- Activated carbon is one of the most widely used temperature adsorption materials for cryopumps. It strongly depends on the temperature characteristics. Therefore, if the temperature of the cooling surface of the cryopump rises only slightly, when a thick gas condensate with poor thermal conductivity is formed on the cooling surface, the temperature of the cooling surface will rise.
- the present invention aims to provide a preparation method of a cryogenic glue for a cryopump activated carbon adsorption material.
- a preparation method of cryogenic glue for cryogenic pump activated carbon adsorption material comprising the following steps: (1) in parts by weight, 3-5 parts of natural flake graphite powder, 2-2.5 parts of sodium nitrate and 100-115 parts of 98%
- the concentrated sulfuric acid is mixed and placed in the reaction kettle, stirred in an ice-water bath of -1 ⁇ 2°C to make it fully mixed, and then weigh 14 ⁇ 15 parts of potassium permanganate fine powder and slowly add it into the above-mentioned mixed solution, and the adding time is 0.5 ⁇ 1h, then raise the temperature of the water bath to 10-15°C, continue stirring for 1-2h, then raise the temperature of the water bath to 20-35°C, when the temperature reaches this temperature, continue stirring for 20-30min, using a constant pressure funnel Continuously and slowly add 200-230 parts of distilled water, the addition time is 30-60min, then the water bath is heated to 95-98 °C, the reaction solution continues to react for 10-15min, the reaction is completed, and then 12-15 parts of mass fraction
- the obtained product is graphene oxide hydrosol
- pour the hydrosol into a watch glass stir to level, vacuum dry in a vacuum drying box at 60°C, and wait until it is completely dried
- 8-10 parts of graphene oxide solution with a concentration of 1 mg/mL adjust the pH to 9-10 with anhydrous sodium carbonate solution with a mass fraction of 5%, ultrasonically treat, and then add 0.2 mol 15-20 parts/L of sodium borohydride solution, washed with water to neutrality after the reaction, to obtain a partially reduced graphene oxide solution, and adding 1.9-2.1 parts by weight of 4-aminobenzenesulfonic acid to 8-10 parts by weight Dissolve in 5% NaOH solution, dissolve 0.6-0.8 parts of sodium nitrite in 5-6 parts of deionized water, then add it to the mixed solution of 4-aminobenzenesulfonic acid and NaOH, at -1
- Plasma-induced grafting acrylic acid treatment of polychlorotrifluoroethylene powder use ZYHD-1A plasma processor to carry out plasma treatment of polychlorotrifluoroethylene powder, and place the pretreated polychlorotrifluoroethylene powder in the reaction In the reaction chamber between the two electrodes in the chamber, one end of the reaction chamber is connected to the vacuum pump, and the other end is connected to the air inlet system, close the reaction chamber cover and all vacuum valves, press the thermocouple vacuum gauge switch, measure the vacuum degree, and observe the vacuum gauge pointer at the same time.
- the regulating valve on the flowmeter adjusts the oxygen intake of the working gas.
- the pressure in the reaction chamber is stabilized to 25-28Pa, start the high-frequency power supply and process it at a power of 65W for 400-600s.
- the pressing pressure is 30-45Mpa, and the pressing time is 10-20min; after the mixed powder is pressed, it is taken out from the cold pressing mold, and it is trimmed to remove burrs to make it smooth and flat to obtain sulfonated graphite Graphene-polychlorotrifluoroethylene composite material sheet, the above-mentioned sulfonated graphene-polychlorotrifluoroethylene composite material sheet is placed on a low-temperature lining plate for heat treatment in a temperature-controlled electric furnace, and the temperature of the electric furnace is changed from room temperature to 5 °C/min. The heating rate was raised to 225°C, and the temperature was kept at 225°C for 30 minutes.
- the temperature of the electric furnace was lowered from 225°C to 200°C.
- the cooling process time was 2 to 3 minutes.
- the electric furnace was kept at 200°C for 20 to 35 minutes.
- the temperature is naturally cooled from 200°C to room temperature, and after the temperature of the electric furnace is naturally cooled to room temperature, the heat-treated sheet is taken out to obtain the low-temperature glue for the activated carbon adsorption material of the cryogenic pump.
- the toughening agent is one of vinylidene fluoride-chlorotrifluoroethylene copolymer and chlorotrifluoroethylene-ethylene copolymer.
- polychlorotrifluoroethylene is a powder with an average particle size of 300-500 ⁇ m.
- the preparation method of the low-temperature glue for the activated carbon adsorption material of the cryogenic pump disclosed by the invention is made of polychlorotrifluoroethylene, sulfonated graphene and a toughening agent, which has good cold flow resistance, wear resistance and dimensional stability, and has good processability. Good adhesion to metal.
- the low temperature resistance of PCTFE is particularly outstanding. It does not undergo embrittlement or creep in liquid nitrogen, liquid oxygen and liquefied natural gas. oxidizing agent.
- PCTFE has the lowest water vapor permeability and can not penetrate any gas. It is a good barrier polymer with excellent optical properties and good weather resistance. It can be uniformly coated on steel, brass, aluminum, zinc, etc.
- the surface of the metal low-temperature base plate is suitable for the adhesion of low-temperature adsorption materials such as activated carbon and does not absorb water, and is resistant to various acids, alkalis, oils and organic solvents. It has non-combustibility, mechanical, electrical insulation, aging resistance, radiation resistance, good dimensional stability, good adhesion to metal, and can be welded and welded.
- the present invention has the following advantages:
- the cryogenic glue for the activated carbon adsorption material of the cryogenic pump disclosed in the present invention can withstand extreme conditions, extreme temperature and its temperature change, and it does not undergo brittle cracking or creep in liquid nitrogen, liquid oxygen and liquefied natural gas, and can be used for a long time at temperature It has good mechanical and chemical properties in the range of -240 to 125 °C, making it an excellent engineering thermoplastic, resistant to almost all chemicals and oxidants, but slightly in halogenated ethers, esters and aromatic solutions. Has swelling, has the lowest water-vapor permeability of all plastics, does not penetrate any gas, does not burn, is a good barrier polymer, does not affect low temperature gas adsorption.
- the hydrosol was poured into a watch glass, and after stirring, it was vacuum-dried at 60°C in a vacuum drying oven. After drying was complete, it was taken out to obtain a solid oxide Graphene, then prepare 10 parts of graphene oxide solution with a concentration of 1 mg/mL, adjust the pH to 10 with anhydrous sodium carbonate solution of 5% by mass, ultrasonically treat, and then add 20 parts of 0.2 mol/L sodium borohydride solution to react After washing to neutrality, a partially reduced graphene oxide solution was obtained, 2.1 parts of 4-aminobenzenesulfonic acid in parts by weight were added to 10 parts of 5% NaOH solutions to dissolve, and 0.8 parts of sodium nitrite were dissolved in 6 parts of deionized water, then add it to the mixture of 4-aminobenzenesulfonic acid and NaOH, and add 3.1 parts of concentrated hydrochloric acid with a mass fraction of 36% and 10 parts of deionized water to the above reaction solution under the condition of
- (2) Plasma-induced grafting acrylic acid treatment of polychlorotrifluoroethylene powder use ZYHD-1A plasma treatment instrument to carry out plasma treatment of polychlorotrifluoroethylene powder, and the The pretreated polychlorotrifluoroethylene powder is placed in the reaction chamber between the two electrodes in the reaction chamber.
- One end of the reaction chamber is connected to the vacuum pump, and the other end is connected to the air intake system.
- the vacuum degree is pumped to 1Pa. Slowly unscrew the regulating valve on the rotameter to adjust the oxygen intake amount of the working gas.
- the prepared sulfonated graphene, the toughening agent and the acrylic acid grafted polychlorotrifluoroethylene powder were uniformly mixed and then poured into a 190°C molding die for compression molding, the compression pressure was 45Mpa, and the compression time was 20min; After the mixed powder is pressed, it is taken out from the cold molding die, and it is trimmed to remove burrs, so as to make it smooth and flat to obtain the sulfonated graphene-polychlorotrifluoro
- the temperature of the electric furnace is raised from room temperature to 225 °C at a heating rate of 5 °C/min, and kept at 225 °C for 30 minutes, and then the electric furnace is heated.
- the temperature is lowered from 225°C to 200°C, and the cooling process time is 2-3min.
- the electric furnace is kept at 200°C for 35min.
- the power of the electric furnace is turned off, so that the temperature is naturally cooled from 200°C to room temperature.
- the heat-treated sheet is taken out to obtain a low-temperature glue for cryopump activated carbon adsorption material.
- the toughening agent is a vinylidene fluoride-chlorotrifluoroethylene copolymer, and the polychlorotrifluoroethylene is a powder with an average particle size of 500 ⁇ m. .
- the obtained product is graphene oxide hydrosol, pour the hydrosol into a watch glass, stir to level, vacuum dry at 60 ° C in a vacuum drying box, take out after drying is complete, and obtain Solid graphene oxide, then prepare 8 parts of graphene oxide solution with a concentration of 1 mg/mL, adjust the pH to 9 with a mass fraction of 5% anhydrous sodium carbonate solution, ultrasonically treat, and then add 15 parts of 0.2 mol/L sodium borohydride solution , washed with water after the reaction to obtain a partially reduced graphene oxide solution, take 2.1 parts of 4-aminobenzenesulfonic acid in parts by weight and add it to 8 parts of 5% NaOH solution to dissolve, and 0.6 part of sodium nitrite is dissolved in 5 parts of deionized water, then add it to the mixture of 4-aminobenzenesulfonic acid and NaOH, under the condition of 2 °C ice-water bath, add 2.8 parts of concentrated hydrochlor
- Plasma-induced grafting acrylic acid treatment of polychlorotrifluoroethylene powder use ZYHD-1A plasma treatment instrument to carry out plasma treatment of polychlorotrifluoroethylene powder, and the The pretreated polychlorotrifluoroethylene powder is placed in the reaction chamber between the two electrodes in the reaction chamber. One end of the reaction chamber is connected to the vacuum pump, and the other end is connected to the air intake system.
- the chlorofluoroethylene composite material sheet is placed on a low-temperature lining plate for heat treatment in a temperature-controlled electric furnace.
- the temperature of the electric furnace is raised from room temperature to 225 °C at a heating rate of 5 °C/min, and kept at 225 °C for 30 minutes, and then the temperature of the electric furnace is increased from 225 Cool down to 200°C, the cooling process time is 2min, the electric furnace is kept at 200°C for 20min, and finally the power of the electric furnace is turned off, so that the temperature is naturally cooled from 200°C to room temperature, and the heat-treated sheet is taken out after the temperature of the electric furnace is naturally cooled to room temperature , that is, to obtain a low-temperature glue for a cryogenic pump activated carbon adsorption material, the toughening agent is a chlorotrifluoroethylene-ethylene copolymer, and the polychlorotrifluoroethylene is a powder with an average particle size of 300.
- step (3) the toughening agent is omitted, and other method steps are the same.
- step (3) the sulfonated graphene is omitted in this comparative example, and the other method steps are the same.
- cryopump activated carbon adsorption materials of Examples 1-2 and Comparative Examples 1-2 were tested with low-temperature glue, and the test results were shown in Table 1
- Example 1 Example 2 Comparative Example 1 Comparative Example 2 Low temperature embrittlement temperature °C -108.3 -105.2 -100.1 -98.5 Adhesion after UV irradiation no damage no damage no damage no damage no damage Fixed elongation adhesion after immersion in water no damage no damage no damage no damage no damage Elastic Recovery % 80 80 80 80 Fixed elongation adhesion no damage no damage no damage Adhesion after cold drawing-hot pressing after irradiation no damage no damage no damage no damage no damage no damage no damage Tensile strength MPa 34.3 32.9 31.4 30.5 Elongation at break% 67.5 68.6 65.4 69.4 Loss of strength temperature °C 278 270 275 265 Impact toughness KJ/m 2 13.5 13.2 14.8 12.5 Thermal Stability% 0.12 0.12 0.14 0.13 Hardness Shore A 85.4 82.8 82.4 80.2
- the adhesive ultraviolet irradiation box should comply with the provisions of 5.12.1 in JC/T485-1992, and it should be continuously illuminated for 300h under the condition of no immersion in water. Group test specimen retest.
- the inspection method of the test piece is the same; the fixed elongation adhesion after immersion in water is tested according to GB/T13477.11-2002; the performance at ultra-low temperature is determined according to the method specified in GJB2157-1994 Specification for Ultra-low Temperature Resistant Silicone Rubber Materials; cold drawing-hot pressing after irradiation Post-adhesion GB/T 13477.13-2002 Test Methods for Building Sealing Materials Part 13: Determination of Adhesion after Cold Drawing-Hot Pressing; Determination according to the method specified in HG/T3846-2008 Determination of Hardness of Hard Rubber; Tensile The strength is measured according to the method specified in HG/T3849-2008 Determination of Tensile Strength and Elongation at Break of Hard Rubber; Determination of the specified method; tear strength according to GB/T529-2008 Determination of vulcanized rubber or thermoplastic rubber tear strength specified method; HG 2167-1991 polychlorotrifluoroethylene resin.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention belongs to the technical field of low-temperature pumps, and specifically relates to a preparation method for a low-temperature glue for a low-temperature pump activated carbon adsorption material. The preparation method disclosed in the present invention comprises the blending modification of polytrifluorochloroethylene and sulfonated graphene. The low-temperature glue has excellent mechanical properties and good cold flow resistance, wear resistance, dimension stability and processability, has good adhesion to a metal bottom plate and a particularly outstanding low-temperature resistance, has no embrittlement and creep in a cooling medium such as liquid nitrogen, can be briefly used at the temperature close to zero degrees under certain conditions, is beneficial to prolonging the service life of a low-temperature pump panel and a low-temperature pump, has the lowest water vapor permeability in all plastics, has no gas permeation and does not combust, is a good barrier polymer and does not affect low-temperature gas adsorption.
Description
本发明属于低温泵技术领域，尤其是一种低温泵活性炭吸附材料用低温胶的制备方法。The invention belongs to the technical field of cryopumps, in particular to a preparation method of cryogenic glue for activated carbon adsorption materials of cryopumps.
低温泵是利用低温表面宋进行冷凝和物理吸附气体的真空泵。又称冷凝泵和低温吸附泵。在目前，低温抽气法获得了日益广泛的应用。用低温泵进行抽气是基于气体在低温表面上的冷凝，这种表面要冷却到很低的温度。低温泵与冷阱的区别在于使用的冷冻剂有所不同。对低温泵工作表面进行冷却的不是液态氮(在标准压力下液态氮的沸点为零下196℃，而是氢或氦，它们在标准压力下的沸点分别为零下253℃和零下269℃。冷却到液氮温度的表面能使气体(其中包括油扩散泵大部分的分解产物)极其容易地凝聚。这样的表面可以当作低温泵，低温泵需要通过吸附材料来帮助其抽除气体，而吸附材料与面板的粘合通过胶粘剂来实现，但现有的胶粘剂耐低温性能差、粘接强度低，活性炭是目前应用范围最广的低温泵的温吸附材料之一，另外，低温泵具有蒸气分压强烈地依从温度的特性。因此，低温泵的冷却表面的温度只要略为上升一些时，在冷却表面上凝聚一层厚厚的导热性很差的气体凝聚层时，就会使冷却表面的温度上升，极限真空度就要变差，胶粘剂的耐久性、粘接性能、耐低温性能对面板以及低温泵的使用性能和使用寿命有着重大影响，本领域技术人员亟待开发一种低温泵活性炭吸附材料用低温胶的制备方法。A cryopump is a vacuum pump that uses a cryogenic surface to condense and physically adsorb gases. Also known as condensate pump and cryogenic adsorption pump. At present, the low temperature pumping method has been widely used. Pumping with cryopumps is based on the condensation of gases on cryogenic surfaces, which are cooled to very low temperatures. The difference between cryopumps and cold traps is the refrigerant used. What cools the working surface of the cryopump is not liquid nitrogen (which has a boiling point of minus 196°C at standard pressure, but hydrogen or helium, which have a boiling point of minus 253°C and minus 269°C at standard pressure, respectively. Cool to The surface of liquid nitrogen temperature can make gas (including most of the decomposition products of oil diffusion pump) extremely easy to condense. Such a surface can be used as a cryopump, and cryopump needs to use adsorbent material to help it pump gas, and adsorbent material The bonding with the panel is achieved by adhesives, but the existing adhesives have poor low temperature resistance and low bonding strength. Activated carbon is one of the most widely used temperature adsorption materials for cryopumps. It strongly depends on the temperature characteristics. Therefore, if the temperature of the cooling surface of the cryopump rises only slightly, when a thick gas condensate with poor thermal conductivity is formed on the cooling surface, the temperature of the cooling surface will rise. , the ultimate vacuum degree will deteriorate, and the durability, bonding performance and low temperature resistance of the adhesive have a significant impact on the performance and service life of the panel and the cryopump. Those skilled in the art need to develop a cryopump activated carbon adsorption material. Preparation method of low temperature glue.
针对上述问题，本发明旨在提供一种低温泵活性炭吸附材料用低温胶的制备方法。In view of the above problems, the present invention aims to provide a preparation method of a cryogenic glue for a cryopump activated carbon adsorption material.
本发明通过以下技术方案实现：The present invention is achieved through the following technical solutions:
一种低温泵活性炭吸附材料用低温胶的制备方法，包括如下步骤：(1)按重量份数计，将3～5份天然鳞片石墨粉，2～2.5份硝酸钠和100～115份98％浓硫酸混合置于反应釜中，在-1～2℃冰水浴中搅拌，使其充分混合，再称取14～15份高锰酸钾细粉缓慢加入上述混合液中，加入时间为0.5～1h，然后升高水浴温度至10～15℃，再继续搅拌1～2h，再将水浴锅温度升高至20～35℃，待升温到该温度时，继续搅拌20～30min，使用恒压漏斗连续缓慢加入200～230份蒸馏水，加入时间30～60min，然后将水浴锅升温至95～98℃，反应液继续反应10～15min，反应结束，向反应釜中再加入12～15份质量分数30％的双氧水搅拌均匀，使溶液变为亮黄色，继续搅拌8～10min，然后加入130～140份蒸馏水稀释，静置1～2h后去除上清液，再用去离子水洗涤重复三次，然后溶于去离子水中直至pH为7.0～7.2，所得到产物为氧化石墨烯水溶胶，将水溶胶倒入表面皿内，搅拌平整后，在真空干燥箱中60℃条件下抽真空干燥，待干燥完全后取出，制得固体氧化石墨烯，然后配制浓度为1mg/mL氧化石墨烯溶液8～10份，用质量分数5％的无水碳酸钠溶液调至pH9～10，超声处理，然后加入0.2mol/L的硼氢化钠溶液15～20份，反应后水洗至中性，得到部分还原氧化石墨烯溶液，取重量份数计的1.9～2.1份4-氨基苯磺酸加入到8～10份的5％Na0H溶液中溶解，将0.6～0.8份亚硝酸钠溶解于5～6份去离子水中，然后将其加入4-氨基苯磺酸和NaOH的混合液中，在-1～2℃冰水浴条件下，向上述反应液中加入 2.8～3.1份质量分数36％的浓盐酸和8～10份去离子水，反应10～20min，然后取上述反应液加入到部分还原氧化石墨烯溶液中20～25℃反应，然后将反应液超声8～10min后向反应体系中加入次硫酸钠4～5份，90～95℃小搅拌反应15～20min后，水洗至中性，得磺化石墨烯；(2)聚三氟氯乙烯粉末的等离子体诱导接枝丙烯酸处理：采用ZYHD-1A等离子体处理仪对聚三氟氯乙烯粉末进行等离子体处理，将预处理的聚三氟氯乙烯粉末置于反应室内两电极间的反应室内，反应室一端与真空泵相连，另一端连接进气系统，关闭反应室盖板和全部真空阀门，按下热耦真空计开关，测量真空度，同时观察真空计指针，真空度抽至0.8～1Pa，慢慢旋开转子流量计上的调节阀，调节工作气体氧气进气量，待反应室内气压稳定至25～28Pa，启动高频电源，在功率65W下处理400～600s，处理完毕后，先关闭射频电源，然后再关闭进气气路和真空泵，取出聚三氟氯乙烯粉末并在空气中放置15～30min；在通风橱内，将上述等离子体处理后的聚三氟氯乙烯粉末加入到质量分数为8～10％的丙烯酸水溶液中，聚三氟氯乙烯粉末与丙烯酸水溶液的质量比为4～5.5∶100，通入氮气作为保护气体，并在65～70℃下磁力搅拌，得到悬浮液；搅拌反应24～30h后对悬浮液进行离心分离，离心机转速为3500～4000r/min，离心时间为8～10min，并用去离子水反复清洗以去除聚三氟氯乙烯粉末表面上的丙烯酸单体，然后置于烘箱中在65～70℃下干燥12h，即得到丙烯酸接枝处理的聚三氟氯乙烯粉末；(3)步骤(1)中制得的磺化石墨烯、步骤(2)中制得的丙烯酸接枝处理的聚三氟氯乙烯粉末和增韧剂；上述各原料用量有如下质量比例关系：磺化石墨烯∶丙烯酸接枝处理的聚三氟氯乙烯粉末∶增韧剂＝15～20∶80～95∶20～40；将步骤(1)制备的磺化石墨烯和增韧剂以及丙烯酸接枝处理的聚三氟氯乙烯粉末，均匀混后后倒入170～190℃模压模具中进行压制成型，压制压力为30～45Mpa，压制时间为10～20min；待混合粉末压制处理后，将其从冷模压模具中取出，对其进行修整去除毛刺，使其光滑平整，制得磺化石墨烯-聚三氟氯乙烯复合材料薄片，将上述磺化石墨烯-聚三氟氯乙烯复合材料薄片置于低温衬板在温控电炉中进行热处理，将电炉温度自室温以5℃/min的升温速率升至225℃，并在225℃保温30min，然后将电炉温度由225℃降温到200℃，降温过程时间为2～3min，电炉在200℃保温20～35min，最后关闭电炉电源，使其温度由200℃自然冷却至室温，待电炉温度自然冷却至室温后，将热处理后的薄片取出，即得到低温泵活性炭吸附材料用低温胶。A preparation method of cryogenic glue for cryogenic pump activated carbon adsorption material, comprising the following steps: (1) in parts by weight, 3-5 parts of natural flake graphite powder, 2-2.5 parts of sodium nitrate and 100-115 parts of 98% The concentrated sulfuric acid is mixed and placed in the reaction kettle, stirred in an ice-water bath of -1～2°C to make it fully mixed, and then weigh 14～15 parts of potassium permanganate fine powder and slowly add it into the above-mentioned mixed solution, and the adding time is 0.5～ 1h, then raise the temperature of the water bath to 10-15°C, continue stirring for 1-2h, then raise the temperature of the water bath to 20-35°C, when the temperature reaches this temperature, continue stirring for 20-30min, using a constant pressure funnel Continuously and slowly add 200-230 parts of distilled water, the addition time is 30-60min, then the water bath is heated to 95-98 ℃, the reaction solution continues to react for 10-15min, the reaction is completed, and then 12-15 parts of mass fraction 30 are added to the reaction kettle % hydrogen peroxide, stir evenly, make the solution turn bright yellow, continue stirring for 8 to 10 minutes, then add 130 to 140 parts of distilled water to dilute, let stand for 1 to 2 hours, remove the supernatant, and then wash with deionized water for three times, and then dissolve. In deionized water until the pH is 7.0 to 7.2, the obtained product is graphene oxide hydrosol, pour the hydrosol into a watch glass, stir to level, vacuum dry in a vacuum drying box at 60°C, and wait until it is completely dried Then take it out to obtain solid graphene oxide, then prepare 8-10 parts of graphene oxide solution with a concentration of 1 mg/mL, adjust the pH to 9-10 with anhydrous sodium carbonate solution with a mass fraction of 5%, ultrasonically treat, and then add 0.2 mol 15-20 parts/L of sodium borohydride solution, washed with water to neutrality after the reaction, to obtain a partially reduced graphene oxide solution, and adding 1.9-2.1 parts by weight of 4-aminobenzenesulfonic acid to 8-10 parts by weight Dissolve in 5% NaOH solution, dissolve 0.6-0.8 parts of sodium nitrite in 5-6 parts of deionized water, then add it to the mixed solution of 4-aminobenzenesulfonic acid and NaOH, at -1～2 ℃ ice water bath Under the conditions, add 2.8～3.1 parts of concentrated hydrochloric acid with a mass fraction of 36% and 8～10 parts of deionized water to the above-mentioned reaction solution, react for 10～20min, then take the above-mentioned reaction solution and add it to the partially reduced graphene oxide solution for 20～10 minutes. React at 25°C, then add 4-5 parts of sodium sulfoxylate to the reaction system after ultrasonicating the reaction solution for 8 to 10 minutes, and stir the reaction at 90 to 95°C for 15 to 20 minutes, then wash with water until neutral to obtain sulfonated graphene; ( 2) Plasma-induced grafting acrylic acid treatment of polychlorotrifluoroethylene powder: use ZYHD-1A plasma processor to carry out plasma treatment of polychlorotrifluoroethylene powder, and place the pretreated polychlorotrifluoroethylene powder in the reaction In the reaction chamber between the two electrodes in the chamber, one end of the reaction chamber is connected to the vacuum pump, and the other end is connected to the air inlet system, close the reaction chamber cover and all vacuum valves, press the thermocouple vacuum gauge switch, measure the vacuum degree, and observe the vacuum gauge pointer at the same time. Pump the vacuum to 0.8～1Pa, and slowly unscrew the rotor The regulating valve on the flowmeter adjusts the oxygen intake of the working gas. When the pressure in the reaction chamber is stabilized to 25-28Pa, start the high-frequency power supply and process it at a power of 65W for 400-600s. Close the air inlet and vacuum pump, take out the polychlorotrifluoroethylene powder and place it in the air for 15 to 30 minutes; in a fume hood, add the above plasma-treated polychlorotrifluoroethylene powder to a mass fraction of 8 to 10 In the acrylic acid aqueous solution of %, the mass ratio of polychlorotrifluoroethylene powder and acrylic acid aqueous solution is 4～5.5: 100, feed nitrogen as protective gas, and magnetic stirring at 65～70 ℃, obtains suspension; Stirring reaction 24～ After 30 hours, the suspension was centrifuged, the speed of the centrifuge was 3500~4000r/min, the centrifugation time was 8~10min, and the acrylic monomer on the surface of the polychlorotrifluoroethylene powder was removed by repeated washing with deionized water, and then placed in Drying in an oven at 65-70° C. for 12 hours, to obtain polychlorotrifluoroethylene powder grafted with acrylic acid; (3) the sulfonated graphene obtained in step (1) and the acrylic acid obtained in step (2) Grafted polychlorotrifluoroethylene powder and toughening agent; the above-mentioned raw material consumptions have the following mass ratio relationship: sulfonated graphene: acrylic acid grafted polychlorotrifluoroethylene powder: toughening agent=15～20: 80-95:20-40; the sulfonated graphene and the toughening agent prepared in step (1) and the acrylic acid-grafted polychlorotrifluoroethylene powder are uniformly mixed and then poured into a molding die at 170-190° C. Press molding, the pressing pressure is 30-45Mpa, and the pressing time is 10-20min; after the mixed powder is pressed, it is taken out from the cold pressing mold, and it is trimmed to remove burrs to make it smooth and flat to obtain sulfonated graphite Graphene-polychlorotrifluoroethylene composite material sheet, the above-mentioned sulfonated graphene-polychlorotrifluoroethylene composite material sheet is placed on a low-temperature lining plate for heat treatment in a temperature-controlled electric furnace, and the temperature of the electric furnace is changed from room temperature to 5 °C/min. The heating rate was raised to 225°C, and the temperature was kept at 225°C for 30 minutes. Then the temperature of the electric furnace was lowered from 225°C to 200°C. The cooling process time was 2 to 3 minutes. The electric furnace was kept at 200°C for 20 to 35 minutes. The temperature is naturally cooled from 200°C to room temperature, and after the temperature of the electric furnace is naturally cooled to room temperature, the heat-treated sheet is taken out to obtain the low-temperature glue for the activated carbon adsorption material of the cryogenic pump.
进一步的，所述的增韧剂为偏氟乙烯-三氟氯乙烯共聚物、三氟氯乙烯-乙烯共聚物中的其中一种。Further, the toughening agent is one of vinylidene fluoride-chlorotrifluoroethylene copolymer and chlorotrifluoroethylene-ethylene copolymer.
进一步的，所述的聚三氟氯乙烯为平均粒径300～500μm的粉末。Further, the polychlorotrifluoroethylene is a powder with an average particle size of 300-500 μm.
本发明的有益效果：Beneficial effects of the present invention:
本发明公开的低温泵活性炭吸附材料用低温胶的制备方法通过聚三氟氯乙烯、磺化石墨烯、增韧剂制成具有良好耐冷流性、耐磨性和尺寸稳定性，加工性好，与金属的粘接性好。PCTFE的耐低温性特别突出，在液氮、液氧和液化天然气中不发生脆裂、不蠕变，在一定条件下能在接近零度(-273℃)下使用，能耐几乎所有的化学物质和氧化剂。PCTFE的水蒸气渗透率是最低的，可不渗透任何气体，是一种良好的屏障聚合物，具有优良的光学性能及良好的耐气候性，可均匀涂覆于钢铁、黄铜、铝、锌等金属低温底板表面，适用作活性炭等低温吸附材料的粘附不吸水，能耐各种酸、碱、油类和有机溶剂。具有不燃性，力学、电绝缘、耐老化、耐辐照、尺寸稳定性能良好，与金属的粘接性好，并能熔接与焊接。The preparation method of the low-temperature glue for the activated carbon adsorption material of the cryogenic pump disclosed by the invention is made of polychlorotrifluoroethylene, sulfonated graphene and a toughening agent, which has good cold flow resistance, wear resistance and dimensional stability, and has good processability. Good adhesion to metal. The low temperature resistance of PCTFE is particularly outstanding. It does not undergo embrittlement or creep in liquid nitrogen, liquid oxygen and liquefied natural gas. oxidizing agent. PCTFE has the lowest water vapor permeability and can not penetrate any gas. It is a good barrier polymer with excellent optical properties and good weather resistance. It can be uniformly coated on steel, brass, aluminum, zinc, etc. The surface of the metal low-temperature base plate is suitable for the adhesion of low-temperature adsorption materials such as activated carbon and does not absorb water, and is resistant to various acids, alkalis, oils and organic solvents. It has non-combustibility, mechanical, electrical insulation, aging resistance, radiation resistance, good dimensional stability, good adhesion to metal, and can be welded and welded.
本发明相比现有技术具有如下优点：Compared with the prior art, the present invention has the following advantages:
本发明公开的低温泵活性炭吸附材料用低温胶能够承受极端条件，耐受极端的温度及其温度变化，它在液氮、液氧和液化天然气中不发生脆裂，不蠕变，长期使用温度范围-240～125℃，具有良好的机械性能和化学性能，因而使其成为一种优良的工程热塑性塑料，能耐几乎所有的化学物质和氧化剂，但在含卤醚、酯和芳香族溶液中稍有溶胀，具有在所有塑料中最低的水一汽渗透率，不渗透任何气体，不燃烧，是一种良好的屏障聚合物，不影响低温气体吸附。The cryogenic glue for the activated carbon adsorption material of the cryogenic pump disclosed in the present invention can withstand extreme conditions, extreme temperature and its temperature change, and it does not undergo brittle cracking or creep in liquid nitrogen, liquid oxygen and liquefied natural gas, and can be used for a long time at temperature It has good mechanical and chemical properties in the range of -240 to 125 °C, making it an excellent engineering thermoplastic, resistant to almost all chemicals and oxidants, but slightly in halogenated ethers, esters and aromatic solutions. Has swelling, has the lowest water-vapor permeability of all plastics, does not penetrate any gas, does not burn, is a good barrier polymer, does not affect low temperature gas adsorption.
下面用具体实施例说明本发明，但并不是对本发明的限制。The present invention is described below with specific examples, but is not intended to limit the present invention.
实施例1Example 1
(1)按重量份数计，将5份天然鳞片石墨粉，2.5份硝酸钠和115份98％浓硫酸混合置于反应釜中，在2℃冰水浴中搅拌，使其充分混合，再称取15份高锰酸钾细粉缓慢加入上述混合液中，加入时间为1h，然后升高水浴温度至15℃，再继续搅拌2h，再将水浴锅温度升高至35℃，待升温到该温度时，继续搅拌30min，使用恒压漏斗连续缓慢加入230份蒸馏水，加入时间60min，然后将水浴锅升温至98℃，反应液继续反应15min，反应结束，向反应釜中再加入15份质量分数30％的双氧水搅拌均匀，使溶液变为亮黄色，继续搅拌10min，然后加入140份蒸馏水稀释，静置2h后去除上清液，再用去离子水洗涤重复三次，然后溶于去离子水中直至pH为7.2，所得到产物为氧化石墨烯水溶胶，将水溶胶倒入表面皿内，搅拌平整后，在真空干燥箱中60℃条件下抽真空干燥，待干燥完全后取出，制得固体氧化石墨烯，然后配制浓度为1mg/mL氧化石墨烯溶液10份，用质量分数5％的无水碳酸钠溶液调至pH10，超声处理，然后加入0.2mol/L的硼氢化钠溶液20份，反应后水洗至中性，得到部分还原氧化石墨烯溶液，取重量份数计的2.1份4-氨基苯磺酸加入到10份的5％NaOH溶液中溶解，将0.8份亚硝酸钠溶解于6份去离子水中，然后将其加入4-氨基苯磺酸和NaOH的混合液中，在2℃冰水浴条件下，向上述反应液中加入3.1份质量分数36％的浓盐酸和10份去离子水，反应20min，然后取上述反应液加入到部分还原氧化石墨烯溶液中25℃反应，然后将反应液超声10min后向反应体系中加入次硫酸钠5份，90～95℃小搅拌反应20min后，水洗至中性，得磺化石墨烯；(2)聚三氟氯乙烯粉末的等离子体诱导接枝丙烯酸处理：采用ZYHD-1A等离子体处理仪对聚三氟氯乙烯粉末进行等离子体处理，将预处理的聚三氟氯乙烯粉末置于反应室内两电极间的反应室内，反应室一端与真空泵相连，另一端连接进气系统，关闭反应室盖板和全部真空阀门，按下热耦真空计开关，测量真空度，同时观察真空计指针，真空度抽至1Pa，慢慢旋开转子流量计上的调节阀，调节工作气体氧气进气量，待反应室内气压稳定至28Pa，启动高频电源，在功率65W下处理600s，处理完毕后，先关闭射频电源，然后再关闭进气气路和真空泵，取出聚三氟氯乙烯粉末并在空气中放置30min；在通风橱内，将上述等离子体处理后的聚三氟氯乙烯粉末加入到质量分数为10％的丙烯酸水溶液中，聚三氟氯乙烯粉末与丙烯酸水溶液的质量比为5.5∶100，通入氮气作为保护气体，并在70℃下磁力搅拌，得到悬浮液；搅拌反应30h后对悬浮液进行离心分离，离心机转速为4000r/min，离心时间为10min，并用去离子水反复清洗以去除聚三氟氯乙烯粉末表面上的丙烯酸单体，然后置于烘箱中在70℃下干燥12h，即得到丙烯酸接枝处理的聚三氟氯乙烯粉末；(3)步骤(1)中制得的磺化石墨烯、步骤(2)中制得的丙烯酸接枝处理的聚三氟氯乙烯粉末和增韧剂；上述各原料用量有如下 质量比例关系：磺化石墨烯∶丙烯酸接枝处理的聚三氟氯乙烯粉末∶增韧剂＝20∶95∶40；将步骤(1)制备的磺化石墨烯和增韧剂以及丙烯酸接枝处理的聚三氟氯乙烯粉末，均匀混后后倒入190℃模压模具中进行压制成型，压制压力为45Mpa，压制时间为20min；待混合粉末压制处理后，将其从冷模压模具中取出，对其进行修整去除毛刺，使其光滑平整，制得磺化石墨烯-聚三氟氯乙烯复合材料薄片，将上述磺化石墨烯-聚三氟氯乙烯复合材料薄片置于低温衬板在温控电炉中进行热处理，将电炉温度自室温以5℃/min的升温速率升至225℃，并在225℃保温30min，然后将电炉温度由225℃降温到200℃，降温过程时间为2～3min，电炉在200℃保温35min，最后关闭电炉电源，使其温度由200℃自然冷却至室温，待电炉温度自然冷却至室温后，将热处理后的薄片取出，即得到低温泵活性炭吸附材料用低温胶，所述的增韧剂为偏氟乙烯-三氟氯乙烯共聚物，所述的聚三氟氯乙烯为平均粒径500μm的粉末。(1) In parts by weight, 5 parts of natural flake graphite powder, 2.5 parts of sodium nitrate and 115 parts of 98% concentrated sulfuric acid are mixed and placed in a reactor, stirred in an ice-water bath at 2 °C, and fully mixed, and weighed again. Take 15 parts of potassium permanganate fine powder and slowly add it to the above mixture for 1 hour, then raise the temperature of the water bath to 15°C, continue stirring for 2 hours, and then raise the temperature of the water bath to 35°C, and wait until the temperature reaches this temperature. When the temperature is reached, continue to stir for 30min, use a constant pressure funnel to continuously and slowly add 230 parts of distilled water for 60min, then heat the water bath to 98°C, the reaction solution continues to react for 15min, the reaction is over, and then 15 parts of mass fraction are added to the reaction kettle Stir well with 30% hydrogen peroxide to make the solution turn bright yellow, continue stirring for 10 minutes, then add 140 parts of distilled water to dilute, let stand for 2 hours, remove the supernatant, wash with deionized water and repeat three times, and then dissolve in deionized water until The pH was 7.2, and the obtained product was graphene oxide hydrosol. The hydrosol was poured into a watch glass, and after stirring, it was vacuum-dried at 60°C in a vacuum drying oven. After drying was complete, it was taken out to obtain a solid oxide Graphene, then prepare 10 parts of graphene oxide solution with a concentration of 1 mg/mL, adjust the pH to 10 with anhydrous sodium carbonate solution of 5% by mass, ultrasonically treat, and then add 20 parts of 0.2 mol/L sodium borohydride solution to react After washing to neutrality, a partially reduced graphene oxide solution was obtained, 2.1 parts of 4-aminobenzenesulfonic acid in parts by weight were added to 10 parts of 5% NaOH solutions to dissolve, and 0.8 parts of sodium nitrite were dissolved in 6 parts of deionized water, then add it to the mixture of 4-aminobenzenesulfonic acid and NaOH, and add 3.1 parts of concentrated hydrochloric acid with a mass fraction of 36% and 10 parts of deionized water to the above reaction solution under the condition of 2 ℃ ice-water bath , react for 20min, then take the above-mentioned reaction solution and add it to the partially reduced graphene oxide solution to react at 25°C, then add 5 parts of sodium sulfoxylate to the reaction system after ultrasonicating the reaction solution for 10min, and stir for 20min at 90～95°C. (2) Plasma-induced grafting acrylic acid treatment of polychlorotrifluoroethylene powder: use ZYHD-1A plasma treatment instrument to carry out plasma treatment of polychlorotrifluoroethylene powder, and the The pretreated polychlorotrifluoroethylene powder is placed in the reaction chamber between the two electrodes in the reaction chamber. One end of the reaction chamber is connected to the vacuum pump, and the other end is connected to the air intake system. Close the reaction chamber cover plate and all vacuum valves, and press the thermocouple vacuum gauge. Switch on and off, measure the vacuum degree, and observe the pointer of the vacuum gauge at the same time. The vacuum degree is pumped to 1Pa. Slowly unscrew the regulating valve on the rotameter to adjust the oxygen intake amount of the working gas. When the pressure in the reaction chamber is stabilized to 28Pa, start the high-frequency power supply. , treated at 65W for 600s, after the treatment, first turn off the radio frequency power supply, then turn off the air inlet and vacuum pump, take out the polychlorotrifluoroethylene powder and place it in the air for 30min; in a fume hood, put the above plasma Treated polychlorotrifluoroethylene powder Finally, it was added to the acrylic acid aqueous solution with a mass fraction of 10%, the mass ratio of polychlorotrifluoroethylene powder and acrylic acid aqueous solution was 5.5:100, nitrogen was introduced as protective gas, and magnetic stirring was performed at 70 ° C to obtain a suspension; stirring; After the reaction for 30h, the suspension was centrifuged, the speed of the centrifuge was 4000r/min, the centrifugation time was 10min, and repeatedly washed with deionized water to remove the acrylic monomer on the surface of the polychlorotrifluoroethylene powder, and then placed in an oven at Dry at 70° C. for 12 h, to obtain polychlorotrifluoroethylene powder grafted with acrylic acid; (3) the sulfonated graphene obtained in step (1) and the polyacrylic acid grafted polymer obtained in step (2) Chlorotrifluoroethylene powder and toughening agent; above-mentioned each raw material consumption has following mass ratio relationship: sulfonated graphene: polychlorotrifluoroethylene powder of acrylic acid grafting treatment: toughening agent=20:95:40; 1) The prepared sulfonated graphene, the toughening agent and the acrylic acid grafted polychlorotrifluoroethylene powder were uniformly mixed and then poured into a 190°C molding die for compression molding, the compression pressure was 45Mpa, and the compression time was 20min; After the mixed powder is pressed, it is taken out from the cold molding die, and it is trimmed to remove burrs, so as to make it smooth and flat to obtain the sulfonated graphene-polychlorotrifluoroethylene composite material sheet, and the above-mentioned sulfonated graphene is - The polychlorotrifluoroethylene composite material sheet is placed on a low-temperature lining plate for heat treatment in a temperature-controlled electric furnace. The temperature of the electric furnace is raised from room temperature to 225 °C at a heating rate of 5 °C/min, and kept at 225 °C for 30 minutes, and then the electric furnace is heated. The temperature is lowered from 225°C to 200°C, and the cooling process time is 2-3min. The electric furnace is kept at 200°C for 35min. Finally, the power of the electric furnace is turned off, so that the temperature is naturally cooled from 200°C to room temperature. The heat-treated sheet is taken out to obtain a low-temperature glue for cryopump activated carbon adsorption material. The toughening agent is a vinylidene fluoride-chlorotrifluoroethylene copolymer, and the polychlorotrifluoroethylene is a powder with an average particle size of 500 μm. .
实施例2Example 2
(1)按重量份数计，将3份天然鳞片石墨粉，2份硝酸钠和100份98％浓硫酸混合置于反应釜中，在-1℃冰水浴中搅拌，使其充分混合，再称取14份高锰酸钾细粉缓慢加入上述混合液中，加入时间为0.5h，然后升高水浴温度至10℃，再继续搅拌1h，再将水浴锅温度升高至20℃，待升温到该温度时，继续搅拌20min，使用恒压漏斗连续缓慢加入200份蒸馏水，加入时间30min，然后将水浴锅升温至95℃，反应液继续反应10min，反应结束，向反应釜中再加入12份质量分数30％的双氧水搅拌均匀，使溶液变为亮黄色，继续搅拌8min，然后加入130份蒸馏水稀释，静置1h后去除上清液，再用去离子水洗涤重复三次，然后溶于去离子水中直至pH为7.0，所得到产物为氧化石墨烯水溶胶，将水溶胶倒入表面皿内，搅拌平整后，在真空干燥箱中60℃条件下抽真空干燥，待干燥完全后取出，制得固体氧化石墨烯，然后配制浓度为1mg/mL氧化石墨烯溶液8份，用质量分数5％的无水碳酸钠溶液调至pH9，超声处理，然后加入0.2mol/L的硼氢化钠溶液15份，反应后水洗至中性，得到部分还原氧化石墨烯溶液，取重量份数计的2.1份4-氨基苯磺酸加入到8份的5％NaOH溶液中溶解，将0.6份亚硝酸钠溶解于5份去离子水中，然后将其加入4-氨基苯磺酸和NaOH的混合液中，在2℃冰水浴条件下，向上述反应液中加入2.8份质量分数36％的浓盐酸和10份去离子水，反应10min，然后取上述反应液加入到部分还原氧化石墨烯溶液中20℃反应，然后将反应液超声8min后向反应体系中加入次硫酸钠5份，90℃小搅拌反应15min后，水洗至中性，得磺化石墨烯；(2)聚三氟氯乙烯粉末的等离子体诱导接枝丙烯酸处理：采用ZYHD-1A等离子体处理仪对聚三氟氯乙烯粉末进行等离子体处理，将预处理的聚三氟氯乙烯粉末置于反应室内两电极间的反应室内，反应室一端与真空泵相连，另一端连接进气系统，关闭反应室盖板和全部真空阀门，按下热耦真空计开关，测量真空度，同时观察真空计指针，真空度抽至0.8Pa，慢慢旋开转子流量计上的调节阀，调节工作气体氧气进气量，待反应室内气压稳定至25Pa，启动高频电源，在功率65W下处理400s，处理完毕后，先关闭射频电源，然后再关闭进气气路和真空泵，取出聚三氟氯乙烯粉末并在空气中放置15min；在通风橱内，将上述等离子体处理后的聚三氟氯乙烯粉末加入到质量分数为8％的丙烯酸水溶液中，聚三氟氯乙烯粉末与丙烯酸水溶液的质量比为4∶100，通入氮气作为保护气体，并在65℃下磁力搅拌，得到悬浮液；搅拌反应24h后对悬浮液进行离心分离，离心机转速为3500r/min，离心时间为8min，并用去离子水反复清洗以去除聚三氟氯乙烯粉末表面上的丙烯酸单体，然后置于烘箱中在65℃下干燥12h，即得到丙烯酸接枝处理的聚三氟氯乙烯粉末；(3)步骤(1)中制得的磺化石墨烯、步骤(2)中制得的丙烯 酸接枝处理的聚三氟氯乙烯粉末和增韧剂；上述各原料用量有如下质量比例关系：磺化石墨烯∶丙烯酸接枝处理的聚三氟氯乙烯粉末∶增韧剂＝15∶80∶20；将步骤(1)制备的磺化石墨烯和增韧剂以及丙烯酸接枝处理的聚三氟氯乙烯粉末，均匀混后后倒入170℃模压模具中进行压制成型，压制压力为30Mpa，压制时间为10min；待混合粉末压制处理后，将其从冷模压模具中取出，对其进行修整去除毛刺，使其光滑平整，制得磺化石墨烯-聚三氟氯乙烯复合材料薄片，将上述磺化石墨烯-聚三氟氯乙烯复合材料薄片置于低温衬板在温控电炉中进行热处理，将电炉温度自室温以5℃/min的升温速率升至225℃，并在225℃保温30min，然后将电炉温度由225℃降温到200℃，降温过程时间为2min，电炉在200℃保温20min，最后关闭电炉电源，使其温度由200℃自然冷却至室温，待电炉温度自然冷却至室温后，将热处理后的薄片取出，即得到低温泵活性炭吸附材料用低温胶，所述的增韧剂为三氟氯乙烯-乙烯共聚物，所述的聚三氟氯乙烯为平均粒径300的粉末。(1) In parts by weight, 3 parts of natural flake graphite powder, 2 parts of sodium nitrate and 100 parts of 98% concentrated sulfuric acid are mixed and placed in the reactor, stirred in a -1 ℃ ice-water bath, fully mixed, and then Weigh 14 parts of potassium permanganate fine powder and slowly add it to the above mixture for 0.5h, then raise the temperature of the water bath to 10°C, continue stirring for 1h, and then raise the temperature of the water bath to 20°C, wait for the temperature to rise. When the temperature reaches this temperature, continue to stir for 20min, use a constant pressure funnel to continuously and slowly add 200 parts of distilled water for 30min, then heat the water bath to 95°C, the reaction solution continues to react for 10min, the reaction ends, and then add 12 parts to the reaction kettle 30% mass fraction of hydrogen peroxide was stirred evenly to make the solution turn bright yellow, continued stirring for 8 minutes, then diluted with 130 parts of distilled water, left standing for 1 hour to remove the supernatant, washed with deionized water and repeated three times, and then dissolved in deionized water. In water until the pH is 7.0, the obtained product is graphene oxide hydrosol, pour the hydrosol into a watch glass, stir to level, vacuum dry at 60 ° C in a vacuum drying box, take out after drying is complete, and obtain Solid graphene oxide, then prepare 8 parts of graphene oxide solution with a concentration of 1 mg/mL, adjust the pH to 9 with a mass fraction of 5% anhydrous sodium carbonate solution, ultrasonically treat, and then add 15 parts of 0.2 mol/L sodium borohydride solution , washed with water after the reaction to obtain a partially reduced graphene oxide solution, take 2.1 parts of 4-aminobenzenesulfonic acid in parts by weight and add it to 8 parts of 5% NaOH solution to dissolve, and 0.6 part of sodium nitrite is dissolved in 5 parts of deionized water, then add it to the mixture of 4-aminobenzenesulfonic acid and NaOH, under the condition of 2 ℃ ice-water bath, add 2.8 parts of concentrated hydrochloric acid of 36% by mass and 10 parts of deionized water to the above reaction solution. Ionized water, reacted for 10min, then took the above reaction solution and added it to the partially reduced graphene oxide solution to react at 20°C, then ultrasonicated the reaction solution for 8min and added 5 parts of sodium sulfoxylate to the reaction system, and stirred at 90°C for 15min. (2) Plasma-induced grafting acrylic acid treatment of polychlorotrifluoroethylene powder: use ZYHD-1A plasma treatment instrument to carry out plasma treatment of polychlorotrifluoroethylene powder, and the The pretreated polychlorotrifluoroethylene powder is placed in the reaction chamber between the two electrodes in the reaction chamber. One end of the reaction chamber is connected to the vacuum pump, and the other end is connected to the air intake system. Close the reaction chamber cover plate and all vacuum valves, and press the thermocouple vacuum gauge. Switch on and off, measure the vacuum degree, and observe the pointer of the vacuum gauge at the same time. The vacuum degree is pumped to 0.8Pa. Slowly unscrew the regulating valve on the rotameter to adjust the oxygen intake amount of the working gas. When the pressure in the reaction chamber is stabilized to 25Pa, start the high frequency Power supply, process 400s at 65W power. After processing, first turn off the RF power supply, then turn off the air inlet and vacuum pump, take out the polychlorotrifluoroethylene powder and place it in the air for 15min; in the fume hood, put the above plasma The body-treated polychlorotrifluoroethylene powder is added to the mass In the 8% acrylic acid aqueous solution, the mass ratio of polychlorotrifluoroethylene powder and acrylic acid aqueous solution is 4:100, nitrogen is introduced as protective gas, and magnetic stirring is performed at 65 ° C to obtain a suspension; after stirring for 24 hours The suspension was centrifuged at 3500 r/min, the centrifugation time was 8 min, and repeatedly washed with deionized water to remove the acrylic monomer on the surface of the polychlorotrifluoroethylene powder, and then placed in an oven at 65 °C After drying for 12 h, the acrylic acid grafted polychlorotrifluoroethylene powder is obtained; (3) the sulfonated graphene obtained in step (1), the acrylic acid grafted polychlorotrifluoroethylene obtained in step (2) Ethylene powder and toughening agent; the amounts of the above-mentioned raw materials have the following mass ratio relationship: sulfonated graphene: polychlorotrifluoroethylene powder treated by acrylic acid grafting: toughening agent=15:80:20; prepare step (1) The sulfonated graphene and toughening agent and acrylic acid grafted polychlorotrifluoroethylene powder were uniformly mixed and then poured into a 170 ℃ molding die for compression molding, the compression pressure was 30Mpa, and the compression time was 10min; the powder to be mixed After pressing, it is taken out from the cold molding die, and it is trimmed to remove burrs, so that it is smooth and flat to obtain the sulfonated graphene-polychlorotrifluoroethylene composite sheet, and the above-mentioned sulfonated graphene-polytrifluoroethylene composite sheet is obtained. The chlorofluoroethylene composite material sheet is placed on a low-temperature lining plate for heat treatment in a temperature-controlled electric furnace. The temperature of the electric furnace is raised from room temperature to 225 °C at a heating rate of 5 °C/min, and kept at 225 °C for 30 minutes, and then the temperature of the electric furnace is increased from 225 Cool down to 200°C, the cooling process time is 2min, the electric furnace is kept at 200°C for 20min, and finally the power of the electric furnace is turned off, so that the temperature is naturally cooled from 200°C to room temperature, and the heat-treated sheet is taken out after the temperature of the electric furnace is naturally cooled to room temperature , that is, to obtain a low-temperature glue for a cryogenic pump activated carbon adsorption material, the toughening agent is a chlorotrifluoroethylene-ethylene copolymer, and the polychlorotrifluoroethylene is a powder with an average particle size of 300.
对比例1Comparative Example 1
本对比例与实施例2相比，在步骤(3)中，省去增韧剂，除此外的方法步骤均相同。Compared with Example 2, in this comparative example, in step (3), the toughening agent is omitted, and other method steps are the same.
对比例2Comparative Example 2
本对比例与实施例2相比，在步骤(3)中，省去磺化石墨烯，除此外的方法步骤均相同。Compared with Example 2, in step (3), the sulfonated graphene is omitted in this comparative example, and the other method steps are the same.
将实施例1～2和对比例1～2的低温泵活性炭吸附材料用低温胶性能测试，测试结果见表1The cryopump activated carbon adsorption materials of Examples 1-2 and Comparative Examples 1-2 were tested with low-temperature glue, and the test results were shown in Table 1
表1实施例和对比例的低温泵活性炭吸附材料用低温胶性能测试对比结果Table 1 embodiment and comparative example cryopump activated carbon adsorption material with low temperature glue performance test comparison results
| 实施例1Example 1 | 实施例2Example 2 | 对比例1Comparative Example 1 | 对比例2Comparative Example 2 | |
| 低温脆化温度℃Low temperature embrittlement temperature °C | -108.3-108.3 | -105.2-105.2 | -100.1-100.1 | -98.5-98.5 |
| 紫外线辐照后粘结性Adhesion after UV irradiation | 无破坏no damage | 无破坏no damage | 无破坏no damage | 无破坏no damage |
| 浸水后定伸粘结性Fixed elongation adhesion after immersion in water | 无破坏no damage | 无破坏no damage | 无破坏no damage | 无破坏no damage |
| 弹性回复率％Elastic Recovery % | 8080 | 8080 | 8080 | 8080 |
| 定伸粘结性Fixed elongation adhesion | 无破坏no damage | 无破坏no damage | 无破坏no damage | 无破坏no damage |
| 辐照后冷拉-热压后粘结性Adhesion after cold drawing-hot pressing after irradiation | 无破坏no damage | 无破坏no damage | 无破坏no damage | 无破坏no damage |
| 拉伸强度MPaTensile strength MPa | 34.334.3 | 32.932.9 | 31.431.4 | 30.530.5 |
| 断裂伸长率％Elongation at break% | 67.567.5 | 68.668.6 | 65.465.4 | 69.469.4 |
| 失强温度℃Loss of strength temperature °C | 278278 | 270270 | 275275 | 265265 |
| 冲击韧性KJ/m 2 Impact toughness KJ/m 2 | 13.513.5 | 13.213.2 | 14.814.8 | 12.512.5 |
| 热稳定性％Thermal Stability% | 0.120.12 | 0.120.12 | 0.140.14 | 0.130.13 |
| 硬度邵氏AHardness Shore A | 85.485.4 | 82.882.8 | 82.482.4 | 80.280.2 |
注：紫外线辐照后粘结性紫外线辐照箱应符合JC/T485-1992中5.12.1的规定，在不浸水的条件下连续光照300h，若有块试件破坏，则另取备用的一组试件复验。试件的检查方法同；浸水后定伸粘结性按GB/T13477.11-2002试验；超低温下性能按GJB2157-1994耐超低温硅橡胶材料规范规定的方法测定；辐照后冷拉-热压后粘结性GB/T 13477.13-2002建筑密封材料试验方法第13部分：冷拉-热压后粘结性的测定；按HG/T3846-2008硬质橡胶硬度的测定规定的方法测定；拉伸强度按HG/T3849-2008硬质橡胶拉伸强度和拉断伸长率的测定规定的方法测定；扯断伸长率按HG/T3849-2008硬质橡胶拉伸强度和拉断伸长率的 测定规定的方法测定；撕裂强度按GB/T529-2008硫化橡胶或热塑性橡胶撕裂强度的测定规定的方法测定；HG 2167-1991聚三氟氯乙烯树脂。Note: After ultraviolet irradiation, the adhesive ultraviolet irradiation box should comply with the provisions of 5.12.1 in JC/T485-1992, and it should be continuously illuminated for 300h under the condition of no immersion in water. Group test specimen retest. The inspection method of the test piece is the same; the fixed elongation adhesion after immersion in water is tested according to GB/T13477.11-2002; the performance at ultra-low temperature is determined according to the method specified in GJB2157-1994 Specification for Ultra-low Temperature Resistant Silicone Rubber Materials; cold drawing-hot pressing after irradiation Post-adhesion GB/T 13477.13-2002 Test Methods for Building Sealing Materials Part 13: Determination of Adhesion after Cold Drawing-Hot Pressing; Determination according to the method specified in HG/T3846-2008 Determination of Hardness of Hard Rubber; Tensile The strength is measured according to the method specified in HG/T3849-2008 Determination of Tensile Strength and Elongation at Break of Hard Rubber; Determination of the specified method; tear strength according to GB/T529-2008 Determination of vulcanized rubber or thermoplastic rubber tear strength specified method; HG 2167-1991 polychlorotrifluoroethylene resin.
Claims (3)
- 一种低温泵活性炭吸附材料用低温胶的制备方法，其特征在于，所述制备方法包括如下步骤：(1)按重量份数计，将3～5份天然鳞片石墨粉，2～2.5份硝酸钠和100～115份98％浓硫酸混合置于反应釜中，在-1～2℃冰水浴中搅拌，使其充分混合，再称取14～15份高锰酸钾细粉缓慢加入上述混合液中，加入时间为0.5～1h，然后升高水浴温度至10～15℃，再继续搅拌1～2h，再将水浴锅温度升高至20～35℃，待升温到该温度时，继续搅拌20～30min，使用恒压漏斗连续缓慢加入200～230份蒸馏水，加入时间30～60min，然后将水浴锅升温至95～98℃，反应液继续反应10～15min，反应结束，向反应釜中再加入12～15份质量分数30％的双氧水搅拌均匀，使溶液变为亮黄色，继续搅拌8～10min，然后加入130～140份蒸馏水稀释，静置1～2h后去除上清液，再用去离子水洗涤重复三次，然后溶于去离子水中直至pH为7.0～7.2，所得到产物为氧化石墨烯水溶胶，将水溶胶倒入表面皿内，搅拌平整后，在真空干燥箱中60℃条件下抽真空干燥，待干燥完全后取出，制得固体氧化石墨烯，然后配制浓度为1mg/mL氧化石墨烯溶液8～10份，用质量分数5％的无水碳酸钠溶液调至pH9～10，超声处理，然后加入0.2mol/L的硼氢化钠溶液15～20份，反应后水洗至中性，得到部分还原氧化石墨烯溶液，取重量份数计的1.9～2.1份4-氨基苯磺酸加入到8～10份的5％NaOH溶液中溶解，将0.6～0.8份亚硝酸钠溶解于5～6份去离子水中，然后将其加入4-氨基苯磺酸和NaOH的混合液中，在-1～2℃冰水浴条件下，向上述反应液中加入2.8～3.1份质量分数36％的浓盐酸和8～10份去离子水，反应10～20min，然后取上述反应液加入到部分还原氧化石墨烯溶液中20～25℃反应，然后将反应液超声8～10min后向反应体系中加入次硫酸钠4～5份，90～95℃小搅拌反应15～20min后，水洗至中性，得磺化石墨烯；(2)聚三氟氯乙烯粉末的等离子体诱导接枝丙烯酸处理：采用ZYHD-1A等离子体处理仪对聚三氟氯乙烯粉末进行等离子体处理，将预处理的聚三氟氯乙烯粉末置于反应室内两电极间的反应室内，反应室一端与真空泵相连，另一端连接进气系统，关闭反应室盖板和全部真空阀门，按下热耦真空计开关，测量真空度，同时观察真空计指针，真空度抽至0.8～1Pa，慢慢旋开转子流量计上的调节阀，调节工作气体氧气进气量，待反应室内气压稳定至25～28Pa，启动高频电源，在功率65W下处理400～600s，处理完毕后，先关闭射频电源，然后再关闭进气气路和真空泵，取出聚三氟氯乙烯粉末并在空气中放置15～30min；在通风橱内，将上述等离子体处理后的聚三氟氯乙烯粉末加入到质量分数为8～10％的丙烯酸水溶液中，聚三氟氯乙烯粉末与丙烯酸水溶液的质量比为4～5.5∶100，通入氮气作为保护气体，并在65～70℃下磁力搅拌，得到悬浮液；搅拌反应24～30h后对悬浮液进行离心分离，离心机转速为3500～4000r/min，离心时间为8～10min，并用去离子水反复清洗以去除聚三氟氯乙烯粉末表面上的丙烯酸单体，然后置于烘箱中在65～70℃下干燥12h，即得到丙烯酸接枝处理的聚三氟氯乙烯粉末；(3)步骤(1)中制得的磺化石墨烯、步骤(2)中制得的丙烯酸接枝处理的聚三氟氯乙烯粉末和增韧剂；上述各原料用量有如下质量比例关系：磺化石墨烯∶丙烯酸接枝处理的聚三氟氯乙烯粉末∶增韧剂＝15～20∶80～95∶20～40；将步骤(1)制备的磺化石墨烯和增韧剂以及丙烯酸接枝处理的聚三氟氯乙烯粉末，均匀混后后倒入170～190℃模压模具中进行压制成型，压制压力为30～45Mpa，压制时间为10～20min；待混合粉末压制处理后，将其从冷模压模具中取出，对其进行修整去除毛刺，使其光滑平整，制得磺化石墨烯-聚三氟氯乙烯复合材料薄片，将上述磺化石墨烯-聚三氟氯乙烯复合材料薄片置于低温衬板在温控电炉中进行热处理，将电炉温度自室温以5℃/min的升温速率升至225℃，并在225℃保温30min，然后将电炉温度由225℃降温到200℃，降温过程时间为2～3min，电炉在200℃保 温20～35min，最后关闭电炉电源，使其温度由200℃自然冷却至室温，待电炉温度自然冷却至室温后，将热处理后的薄片取出，即得到低温泵活性炭吸附材料用低温胶。A preparation method of cryogenic glue for cryogenic pump activated carbon adsorption material, characterized in that the preparation method comprises the following steps: (1) in parts by weight, 3-5 parts of natural flake graphite powder, 2-2.5 parts of nitric acid Sodium and 100-115 parts of 98% concentrated sulfuric acid are mixed and placed in a reactor, stirred in an ice-water bath of -1-2 °C to make them fully mixed, and then 14-15 parts of potassium permanganate fine powder are weighed and slowly added to the above mixing In the liquid, the addition time is 0.5~1h, then the temperature of the water bath is raised to 10~15°C, and stirring is continued for 1~2h, and then the temperature of the water bath is raised to 20~35°C. When the temperature reaches this temperature, continue stirring. For 20-30min, use a constant pressure funnel to continuously and slowly add 200-230 parts of distilled water for 30-60min, then heat the water bath to 95-98°C, and continue the reaction for 10-15min. Add 12-15 parts of hydrogen peroxide with a mass fraction of 30% and stir evenly, so that the solution turns bright yellow, continue to stir for 8-10 minutes, then add 130-140 parts of distilled water to dilute, let stand for 1-2 hours, remove the supernatant, and then use The ionized water washing was repeated three times, and then dissolved in deionized water until the pH was 7.0 to 7.2. The obtained product was a graphene oxide hydrosol. The hydrosol was poured into a watch glass, stirred to level, and then dried in a vacuum drying box at 60 ° C. Under vacuum drying, take out after drying to obtain solid graphene oxide, then prepare 8-10 parts of graphene oxide solution with a concentration of 1 mg/mL, and adjust the pH to 9-10 with anhydrous sodium carbonate solution with a mass fraction of 5% , ultrasonic treatment, then add 15-20 parts of 0.2mol/L sodium borohydride solution, wash with water to neutrality after the reaction, obtain a partially reduced graphene oxide solution, take 1.9-2.1 parts by weight of 4-aminobenzenesulfonic acid The acid is added to 8-10 parts of 5% NaOH solution to dissolve, 0.6-0.8 parts of sodium nitrite is dissolved in 5-6 parts of deionized water, and then it is added to the mixed solution of 4-aminobenzenesulfonic acid and NaOH, Add 2.8-3.1 parts of concentrated hydrochloric acid with a mass fraction of 36% and 8-10 parts of deionized water to the above reaction solution under -1～2°C ice-water bath condition, react for 10～20min, and then take the above reaction solution and add it to part of the The reduced graphene oxide solution is reacted at 20-25°C, then the reaction solution is ultrasonicated for 8-10min, and then 4-5 parts of sodium sulfoxylate are added to the reaction system. , to obtain sulfonated graphene; (2) Plasma-induced grafting acrylic acid treatment of polychlorotrifluoroethylene powder: ZYHD-1A plasma treatment instrument was used to carry out plasma treatment of polychlorotrifluoroethylene powder, and the pretreated polychlorofluoroethylene powder was treated with plasma. Chlorotrifluoroethylene powder is placed in the reaction chamber between the two electrodes in the reaction chamber. One end of the reaction chamber is connected to the vacuum pump, and the other end is connected to the air inlet system. Close the reaction chamber cover plate and all vacuum valves, press the thermocouple vacuum gauge switch, and measure the vacuum. while observing the pointer of the vacuum gauge, the vacuum degree is pumped to 0.8 ～1Pa, slowly unscrew the regulating valve on the rotameter to adjust the oxygen intake amount of the working gas. When the pressure in the reaction chamber is stabilized to 25～28Pa, start the high-frequency power supply, and process it at the power of 65W for 400～600s. , first turn off the radio frequency power supply, and then turn off the air inlet and vacuum pump, take out the polychlorotrifluoroethylene powder and place it in the air for 15-30min; in the fume hood, put the above plasma-treated polychlorotrifluoroethylene powder It is added to the acrylic acid aqueous solution with a mass fraction of 8-10%, the mass ratio of polychlorotrifluoroethylene powder and acrylic acid aqueous solution is 4-5.5:100, nitrogen is introduced as protective gas, and magnetic stirring is carried out at 65-70 ℃, A suspension is obtained; after stirring and reacting for 24-30 hours, the suspension is centrifuged, the rotating speed of the centrifuge is 3500-4000r/min, the centrifugation time is 8-10min, and repeatedly washed with deionized water to remove the surface of the polychlorotrifluoroethylene powder The acrylic monomer is then placed in an oven and dried at 65-70 ° C for 12 h, to obtain the polychlorotrifluoroethylene powder grafted with acrylic acid; (3) the sulfonated graphene prepared in step (1), the step (2) the polychlorotrifluoroethylene powder and the toughening agent of the acrylic acid grafting treatment obtained in the middle; above-mentioned each raw material consumption has following mass ratio relationship: sulfonated graphene: the polychlorotrifluoroethylene powder of the acrylic acid grafting treatment: Toughening agent=15～20:80～95:20～40; The sulfonated graphene and toughening agent prepared in step (1) and acrylic acid grafted polychlorotrifluoroethylene powder are uniformly mixed and then poured into Compression molding is carried out in a molding die at 170-190°C, the pressing pressure is 30-45Mpa, and the pressing time is 10-20min; after the mixed powder is pressed, it is taken out from the cold molding die, and it is trimmed to remove burrs to make it smooth and flat to obtain the sulfonated graphene-polychlorotrifluoroethylene composite material sheet, the above-mentioned sulfonated graphene-polychlorotrifluoroethylene composite material sheet is placed on a low-temperature lining plate for heat treatment in a temperature-controlled electric furnace, and the temperature of the electric furnace is Rising from room temperature to 225°C at a heating rate of 5°C/min, and holding at 225°C for 30min, then cooling the furnace temperature from 225°C to 200°C, the cooling process time is 2-3min, and the furnace is kept at 200°C for 20-35min , and finally turn off the power of the electric furnace to cool the temperature from 200°C to room temperature naturally. After the temperature of the electric furnace is naturally cooled to room temperature, the heat-treated sheet is taken out to obtain the low-temperature glue for the low-temperature pump activated carbon adsorption material.
- 根据权利要求1所述的一种低温泵活性炭吸附材料用低温胶的制备方法，其特征在于，所述的增韧剂为偏氟乙烯-三氟氯乙烯共聚物、三氟氯乙烯-乙烯共聚物中的其中一种。The method for preparing a cryogenic glue for a cryopump activated carbon adsorption material according to claim 1, wherein the toughening agent is a vinylidene fluoride-chlorotrifluoroethylene copolymer, a chlorotrifluoroethylene-ethylene copolymer one of them.
- 根据权利要求1所述的一种低温泵活性炭吸附材料用低温胶的制备方法，其特征在于，所述的聚三氟氯乙烯为平均粒径300～500μm的粉末。The method for preparing a cryogenic glue for a cryopump activated carbon adsorption material according to claim 1, wherein the polychlorotrifluoroethylene is a powder with an average particle size of 300-500 μm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112625625A (en) * | 2020-12-09 | 2021-04-09 | 安徽腾龙泵阀制造有限公司 | Preparation method of low-temperature adhesive for low-temperature pump activated carbon adsorption material |
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