CN115160783B - Self-lubricating composite material applicable to wide-temperature-range polyurea/polyimide copolymer and preparation method thereof - Google Patents
Self-lubricating composite material applicable to wide-temperature-range polyurea/polyimide copolymer and preparation method thereof Download PDFInfo
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- 229920002396 Polyurea Polymers 0.000 title claims abstract description 133
- 239000004642 Polyimide Substances 0.000 title claims abstract description 96
- 229920001721 polyimide Polymers 0.000 title claims abstract description 96
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 238000004132 cross linking Methods 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims description 90
- 239000000243 solution Substances 0.000 claims description 85
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 66
- 238000003756 stirring Methods 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 40
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 39
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 32
- 239000002086 nanomaterial Substances 0.000 claims description 32
- 239000004952 Polyamide Substances 0.000 claims description 30
- 229920002647 polyamide Polymers 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 25
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 22
- 229910000831 Steel Inorganic materials 0.000 claims description 21
- 150000004985 diamines Chemical class 0.000 claims description 21
- 239000010959 steel Substances 0.000 claims description 21
- 229910021529 ammonia Inorganic materials 0.000 claims description 20
- -1 polytetrafluoroethylene Polymers 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- UNIBAJHMJGXVHL-UHFFFAOYSA-N 3-phenylbenzene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C=2C=CC=CC=2)=C1C(O)=O UNIBAJHMJGXVHL-UHFFFAOYSA-N 0.000 claims description 11
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000005461 lubrication Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 9
- 150000002513 isocyanates Chemical class 0.000 claims description 9
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- ALLIZEAXNXSFGD-UHFFFAOYSA-N 1-methyl-2-phenylbenzene Chemical group CC1=CC=CC=C1C1=CC=CC=C1 ALLIZEAXNXSFGD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920005575 poly(amic acid) Polymers 0.000 claims description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 2
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 238000012546 transfer Methods 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 4
- 238000005303 weighing Methods 0.000 description 27
- 239000000463 material Substances 0.000 description 10
- 150000008064 anhydrides Chemical class 0.000 description 9
- 238000010586 diagram Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a self-lubricating composite material applicable to a polyurea/polyimide copolymer with a wide temperature range and a preparation method thereof; according to the invention, multiple layers of titanium carbide are introduced in situ in a polyimide reaction system, so that the dispersibility of the titanium carbide in a polyimide matrix is improved, and the obtained titanium carbide/polyimide composite material and polyurea are subjected to cross-linking copolymerization. The composite material prepared by the invention has antifriction and antiwear properties, and the multilayer titanium carbide released at the interface in the friction test process can improve the bearing capacity of the transfer film, thereby greatly reducing the friction coefficient and the wear rate of the composite material.
Description
Technical Field
The invention relates to the technical field of lubrication, in particular to a self-lubricating composite material applicable to a polyurea/polyimide copolymer with a wide temperature range and a preparation method thereof.
Background
With the rapid development of modern manufacturing, frictional wear becomes one of the main factors of material damage and energy loss. It is counted that one third to one half of the energy in the world is consumed in various forms on friction, and that more than half of the part damage is due to wear. Therefore, reducing friction, reducing wear, and improving the lubrication performance of mechanical moving parts is one of the effective methods of saving energy and improving the service life and reliability of the equipment.
Polyimide (PI) as self-lubricating matrix material has the advantages of good mechanical property, thermal stability, radiation resistance, corrosion resistance and the like. However, pure PI has a high coefficient of friction, poor wear resistance, poor impact resistance, low fracture toughness, thus limiting its application in the field of self-lubrication. Copolymers are of great interest because of their controllable structure, which can enable the material to adapt to changing environments such as high temperature/low alternation. Therefore, the mechanical property defect of pure PI can be improved by introducing a third flexible monomer or adjusting the monomer proportion into polyimide. Polyurea (PUA) is an elastomer with excellent adhesion and low temperature brittleness. The PUA structural unit comprises an isocyanate component and an amino component, wherein the amino group can react with dianhydride in PI, so that the two polymers (PI/PUA) can be crosslinked and copolymerized to integrate the performance advantages of the two materials. In addition, the solid lubricant is introduced into the material system to improve the tribological property and mechanical property of the material. Chinese patent CN111040209A researches the tribological behavior of polyimide self-lubricating composite materials, and adds traditional carbon fiber and nano niobium carbide into a polyimide matrix to obtain the polyimide composite material, and the friction result shows that the friction coefficient and the wear rate of the composite material are reduced after the filler is added. Titanium carbide (Ti) 3 C 2 ) MXene is expected to improve the tribological properties of polyimide materials by forming a high load-bearing, easily shear-transferring film on the friction dual surface due to its higher mechanical properties and its layered structure.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
Aiming at the defect of single-structure polyimide tribological performance in a wide-temperature-range environment, the polyurea/polyimide copolymer is designed to be expected to adapt to the tribological performance at different temperatures, and meanwhile, titanium carbide (Ti 3 C 2 ) The MXene lamellar solid lubricant can improve the friction coefficient and the wear rate. Therefore, the invention provides a wide temperature range polyurea/polyimide self-lubricating composite material.
According to the preparation method, after the polyamide acid is prepared by introducing multiple layers of titanium carbide into polyimide monomers in situ, the polyamide acid and polyurea are subjected to cross-linking copolymerization under the action of a cross-linking agent, so that the polyurea/polyimide copolymer composite material is obtained. Etching of titanium carbide (Ti) by hydrofluoric acid 3 AlC 2 ) The surface of the obtained polyimide has carboxyl or hydroxyl groups, and the polyimide can react with diamine monomers in polyimide in the process of synthesizing polyimide, so that the aggregation of multiple layers of titanium carbide in polymer groups can be effectively avoided. The multilayer titanium carbide can improve the mechanical property of the copolymer after being introduced into the polyurea/polyimide copolymer due to the good mechanical property, so that the wear resistance of the copolymer is improved, and meanwhile, the multilayer titanium carbide at a friction interface is released, so that the formation of a transfer film is facilitated, and the bearing capacity of the transfer film is improved. The cross-linking copolymerization of polyurea and polyimide can integrate the performance advantages of the two materials, and is suitable for tribological properties at different temperatures. Therefore, the polyurea/polyimide copolymer composite material prepared by the invention has excellent antifriction and wear resistance in a wide temperature range environment, can greatly reduce the friction coefficient and wear rate of polyimide, and improves the reliability and service life of the polyimide/polyimide copolymer composite material.
To achieve these objects and other advantages and in accordance with the purpose of the invention, a self-lubricating composite material of polyurea/polyimide copolymer suitable for a wide temperature range is provided, in which titanium carbide is introduced in situ in polyimide and cross-linked and copolymerized with polyurea.
The invention also provides a self-lubricating composite material suitable for the wide temperature range polyurea/polyimide copolymer, which comprises the following steps:
step one, taking diamine monomer and Ti 3 C 2 Adding the mixture into a solvent, and performing ultrasonic treatment for 1-2 hours to obtain a mixed dispersion liquid; adding dianhydride monomer into the mixed dispersion liquid, and stirring and reacting for 18-36 hours under the conditions of ice bath and nitrogen to obtain acid anhydride end-capped polyamide acid viscous solution;
step two, adding diamine monomer into a solvent, and performing ultrasonic treatment for 1-2 hours to obtain a mixed solution; adding the isocyanate component into the mixed solution, and stirring and reacting for 5-8 hours at the temperature of 60-80 ℃ under the nitrogen condition to obtain an isocyanate-terminated polyurea viscous solution;
thirdly, adding the polyurea viscous solution into the polyamide acid viscous solution, stirring and reacting for 0.5-1.5 h at 60-80 ℃ under the nitrogen condition, adding diamine monomer, and continuously reacting for 4-6 h to obtain the polyurea/polyamide acid viscous solution;
uniformly coating the polyurea/polyamide acid viscous solution on the surface of a carrier, and placing the carrier on a constant-temperature heating table for treatment at 50-70 ℃ for 6-8 hours to completely evaporate the solvent; then placing the mixture into a tube furnace, preserving heat for 1-3 h at 75-85 ℃, preserving heat for 0.5-1.5 h at 95-105 ℃, 145-155 ℃ and 175-185 ℃ respectively, and obtaining the multilayer titanium carbide/polyurea/polyimide copolymer high-lubrication composite material, namely the self-lubrication composite material applicable to the wide-temperature-range polyurea/polyimide copolymer.
Preferably, the Ti is 3 C 2 The preparation method of (2) comprises the following steps: 1 to 2g of Ti 3 AlC 2 Placing the nano material into a polytetrafluoroethylene beaker containing 10-20 mL of HF solution with the concentration of 40wt%, magnetically stirring the nano material in a water bath at 25 ℃ for 24h, repeatedly washing the nano material with deionized water to pH 7 in a centrifugal way, performing suction filtration, and performing vacuum drying at 60 ℃ for 24 hours to obtain Al-stripped organ-shaped Ti 3 C 2 。
Preferably, for the Ti 3 C 2 The pretreatment is carried out, and the pretreatment process comprises the following steps: ti is mixed with 3 C 2 Adding the mixture into a high-pressure reaction kettle, simultaneously introducing ammonia into the high-pressure reaction kettle, and sealing the high-pressure reaction kettle; heating the high-pressure reaction kettle to reach the temperature and pressure of supercritical ammonia, preserving heat and pressure for 30-45 min, cooling and decompressing to obtain pretreated Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the supercritical ammonia is 145-165 ℃ and the pressure is 8-25 MPa.
Preferably, ti will be pretreated 3 C 2 Adding the mixture into hot water at the temperature of 80-90 ℃ and stirring for 10-15 min, then adding cyanuric acid, continuously stirring for 30-45 min at the temperature of 80-90 ℃, and filtering to obtain modified Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the The pretreatment Ti 3 C 2 The mass volume ratio of the water to the hot water is 1 g:10-15 mL; the saidPretreatment of Ti 3 C 2 The mass ratio of the epoxy resin to cyanuric acid is 1:0.5-1.
Preferably, in the first step, the molar ratio of the dianhydride monomer to the diamine monomer is 0.8-1.2:1, and the solid content of the obtained polyamide acid viscous solution is 10-20%;
in the first step, the solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the diamine monomer is one or more of 4,4' -diaminodiphenyl ether, p-phenylenediamine and 4,4' -diamino-2, 2' -methyl biphenyl; the dianhydride monomer is one or more of 3, 4' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride and cyclobutane tetracarboxylic dianhydride.
Preferably, in the second step, the molar ratio of the isocyanate component to the diamine monomer is 0.8-1.2:1, and the solid content of the obtained polyurea viscous solution is 10-20%;
in the second step, the solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the diamine monomer is one or more of 4,4' -diaminodiphenyl ether, p-phenylenediamine and 4,4' -diamino-2, 2' -methyl biphenyl; the isocyanate component is one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
Preferably, in the third step, the mass ratio of the polyurea in the polyurea viscous solution to the polyamic acid in the polyamic acid viscous solution is 1:4-8;
in the third step, the diamine monomer is one or more of 4,4' -diaminodiphenyl ether, p-phenylenediamine and 4,4' -diamino-2, 2' -methylbiphenyl;
in the third step, the diamine monomer is added in an amount such that the ratio of the total molar amount of the dianhydride monomer and the isocyanate component to the molar amount of the total diamine monomer is 0.8-1.2:1;
in the fourth step, the carrier is one or more of bearing steel, stainless steel, aluminum plate, glass and ceramic.
Preferably, the Ti is 3 C 2 The mass fraction of the multilayer titanium carbide/polyurea/polyimide copolymer high-lubrication composite material is 0-2.0%.
Preferably, the number of layers of the multilayer titanium carbide in the multilayer titanium carbide/polyurea/polyimide copolymer high-lubrication composite material is 10-30, and the interlayer spacing is 70-90 nm.
The invention at least comprises the following beneficial effects: according to the invention, the multilayer titanium carbide is introduced in situ into the synthesized polyimide matrix, so that the dispersibility of the multilayer titanium carbide in polyimide can be improved; according to the invention, multiple layers of titanium carbide are introduced into polyimide, and then copolymerization reaction is carried out with polyurea, so that the formation of a high-bearing and easily-sheared transfer film can be promoted. The multilayer titanium carbide/polyurea/polyimide copolymer composite material has good tribological performance in a wide-temperature-range environment.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 shows the composition of the present invention (a) Ti 3 AlC 2 SEM images of nanomaterials; (b) Ti (Ti) 3 C 2 SEM images of (a);
FIG. 2 is a light mirror dispersion diagram of a multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite prepared in example 1 of the present invention; (b) An optical lens dispersion diagram of the multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite prepared in example 2; (c) An optical lens dispersion diagram of the multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite prepared in example 3; (d) An optical lens dispersion diagram of the multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite prepared in example 4; (e) Optical lens dispersion diagram of the multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite prepared in example 5.
The specific embodiment is as follows:
the present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite prepared by the steps of:
step one, taking 2g of Ti 3 AlC 2 Placing the nano material in a polytetrafluoroethylene beaker containing 20mL of HF solution with the concentration of 40wt%, magnetically stirring the nano material in a water bath at 25 ℃ for 24h, repeatedly washing the nano material with deionized water to pH 7 by a centrifugal mode, performing suction filtration, and performing vacuum drying at 60 ℃ for 24 hours to obtain the organ-shaped Ti with the Al peeled off 3 C 2 ；
Step two, 50mL of N-methylpyrrolidone is added into a reaction vessel, and 3.430g of 4,4' -diaminodiphenyl ether and 0g of Ti are weighed 3 C 2 Adding into N-methyl pyrrolidone, completely dissolving ultrasonic 2 h-4, 4' -diaminodiphenyl ether, ti 3 C 2 Uniformly dispersing;
step three, adding 5.390g of 3, 4' -biphenyl tetracarboxylic dianhydride into the mixed solution obtained in the step two, stirring and reacting under the ice bath and nitrogen condition for 24h, and taking out to obtain an anhydride end-capped polyamide acid (PAA) viscous solution;
step four, adding 50mL of N-methylpyrrolidone into a reaction vessel, weighing 3.750g of 4,4' -diaminodiphenyl ether, adding the mixture into the N-methylpyrrolidone, and completely dissolving the amino compound by ultrasonic treatment 2 h;
step five, adding 5.070g of diphenylmethane diisocyanate into the mixed solution obtained in the step four, stirring and reacting at 70 ℃ under the condition of nitrogen to obtain 6h, and taking out to obtain isocyanate-terminated Polyurea (PUA) viscous solution;
step six, weighing 9.8g of the penta Polyurea (PUA) viscous solution in the step three-Phase Amic Acid (PAA) viscous solution, stirring and reacting at 70 ℃ under the condition of nitrogen for 1 h, weighing 0.2g of 4,4' -diaminodiphenyl ether, adding the obtained mixture into the obtained mixture, continuously reacting for 4.5 h, and taking out the obtained mixture to obtain polyurea/polyamide acid (PUA-PAA) viscous solution;
step seven, uniformly coating the PUA-PAA viscous solution obtained in the step six on the surface of the bearing steel, and putting the bearing steel on a constant-temperature heating table for treatment at 60 ℃ for 8 hours to completely evaporate the solvent; then placing into a tube furnace, preserving heat at 80deg.C for 2 h, respectively preserving heat at 100deg.C, 150deg.C and 180deg.C for 1 h, and relatively mild heating to obtain PUA-PAA-Ti 3 C 2 Imidizing the PAA to obtain the multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite material.
Example 2:
a multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite prepared by the steps of:
step one, taking 2g of Ti 3 AlC 2 Placing the nano material in a polytetrafluoroethylene beaker containing 20mL of HF solution with the concentration of 40wt%, magnetically stirring the nano material in a water bath at 25 ℃ for 24h, repeatedly washing the nano material with deionized water to pH 7 by a centrifugal mode, performing suction filtration, and performing vacuum drying at 60 ℃ for 24 hours to obtain the organ-shaped Ti with the Al peeled off 3 C 2 ；
Step two, 50mL of N-methylpyrrolidone is added into a reaction vessel, and 3.430g of 4,4' -diaminodiphenyl ether and 0.01 g of Ti are weighed 3 C 2 Adding into N-methyl pyrrolidone, completely dissolving ultrasonic 2 h-4, 4' -diaminodiphenyl ether, ti 3 C 2 Uniformly dispersing;
step three, adding 5.390g of 3, 4' -biphenyl tetracarboxylic dianhydride into the mixed solution obtained in the step two, stirring and reacting under the ice bath and nitrogen condition for 24h, and taking out to obtain an anhydride end-capped polyamide acid (PAA) viscous solution;
step four, adding 50mL of N-methylpyrrolidone into a reaction vessel, weighing 3.750g of 4,4' -diaminodiphenyl ether, adding the mixture into the N-methylpyrrolidone, and completely dissolving the amino compound by ultrasonic treatment 2 h;
step five, adding 5.070g of diphenylmethane diisocyanate into the mixed solution obtained in the step four, stirring and reacting at 70 ℃ under the condition of nitrogen to obtain 6h, and taking out to obtain isocyanate-terminated Polyurea (PUA) viscous solution;
step six, weighing 9.8g of the penta Polyurea (PUA) viscous solution in the step three-Phase Amic Acid (PAA) viscous solution, stirring and reacting at 70 ℃ under the condition of nitrogen for 1 h, weighing 0.2g of 4,4' -diaminodiphenyl ether, adding the obtained mixture into the obtained mixture, continuously reacting for 4.5 h, and taking out the obtained mixture to obtain polyurea/polyamide acid (PUA-PAA) viscous solution;
step seven, uniformly coating the PUA-PAA viscous solution obtained in the step six on the surface of the bearing steel, and putting the bearing steel on a constant-temperature heating table for treatment at 60 ℃ for 8 hours to completely evaporate the solvent; then placing into a tube furnace, preserving heat at 80deg.C for 2 h, respectively preserving heat at 100deg.C, 150deg.C and 180deg.C for 1 h, and relatively mild heating to obtain PUA-PAA-Ti 3 C 2 Imidizing the PAA to obtain the multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite material.
Example 3:
a multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite prepared by the steps of:
step one, taking 2g of Ti 3 AlC 2 Placing the nano material in a polytetrafluoroethylene beaker containing 20mL of HF solution with the concentration of 40wt%, magnetically stirring the nano material in a water bath at 25 ℃ for 24h, repeatedly washing the nano material with deionized water to pH 7 by a centrifugal mode, performing suction filtration, and performing vacuum drying at 60 ℃ for 24 hours to obtain the organ-shaped Ti with the Al peeled off 3 C 2 ；
Step two, 50mL of N-methylpyrrolidone is added into a reaction vessel, and 3.430g of 4,4' -diaminodiphenyl ether and 0.05g of Ti are weighed 3 C 2 Adding into N-methyl pyrrolidone, completely dissolving ultrasonic 2 h-4, 4' -diaminodiphenyl ether, ti 3 C 2 Uniformly dispersing;
step three, adding 5.390g of 3, 4' -biphenyl tetracarboxylic dianhydride into the mixed solution obtained in the step two, stirring and reacting under the ice bath and nitrogen condition for 24h, and taking out to obtain an anhydride end-capped polyamide acid (PAA) viscous solution;
step four, adding 50mL of N-methylpyrrolidone into a reaction vessel, weighing 3.750g of 4,4' -diaminodiphenyl ether, adding the mixture into the N-methylpyrrolidone, and completely dissolving the amino compound by ultrasonic treatment 2 h;
step five, adding 5.070g of diphenylmethane diisocyanate into the mixed solution obtained in the step four, stirring and reacting at 70 ℃ under the condition of nitrogen to obtain 6h, and taking out to obtain isocyanate-terminated Polyurea (PUA) viscous solution;
step six, weighing 9.8g of the penta Polyurea (PUA) viscous solution in the step three-Phase Amic Acid (PAA) viscous solution, stirring and reacting at 70 ℃ under the condition of nitrogen for 1 h, weighing 0.2g of 4,4' -diaminodiphenyl ether, adding the obtained mixture into the obtained mixture, continuously reacting for 4.5 h, and taking out the obtained mixture to obtain polyurea/polyamide acid (PUA-PAA) viscous solution;
step seven, uniformly coating the PUA-PAA viscous solution obtained in the step six on the surface of the bearing steel, and putting the bearing steel on a constant-temperature heating table for treatment at 60 ℃ for 8 hours to completely evaporate the solvent; then placing into a tube furnace, preserving heat at 80deg.C for 2 h, respectively preserving heat at 100deg.C, 150deg.C and 180deg.C for 1 h, and relatively mild heating to obtain PUA-PAA-Ti 3 C 2 Imidizing the PAA to obtain the multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite material.
Example 4:
a multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite prepared by the steps of:
step one, taking 2g of Ti 3 AlC 2 Placing the nano material in a polytetrafluoroethylene beaker containing 20mL of HF solution with the concentration of 40wt%, magnetically stirring the nano material in a water bath at 25 ℃ for 24h, repeatedly washing the nano material with deionized water to pH 7 by a centrifugal mode, performing suction filtration, and performing vacuum drying at 60 ℃ for 24 hours to obtain the organ-shaped Ti with the Al peeled off 3 C 2 ；
Step two, 50mL of N-methylpyrrolidone is added into a reaction vessel, and 3.430g of 4,4' -diaminodiphenyl ether and 0.102g of Ti are weighed 3 C 2 Adding into N-methyl pyrrolidone, completely dissolving ultrasonic 2 h-4, 4' -diaminodiphenyl ether, ti 3 C 2 Uniformly dispersing;
step three, adding 5.390g of 3, 4' -biphenyl tetracarboxylic dianhydride into the mixed solution obtained in the step two, stirring and reacting under the ice bath and nitrogen condition for 24h, and taking out to obtain an anhydride end-capped polyamide acid (PAA) viscous solution;
step four, adding 50mL of N-methylpyrrolidone into a reaction vessel, weighing 3.750g of 4,4' -diaminodiphenyl ether, adding the mixture into the N-methylpyrrolidone, and completely dissolving the amino compound by ultrasonic treatment 2 h;
step five, adding 5.070g of diphenylmethane diisocyanate into the mixed solution obtained in the step four, stirring and reacting at 70 ℃ under the condition of nitrogen to obtain 6h, and taking out to obtain isocyanate-terminated Polyurea (PUA) viscous solution;
step six, weighing 9.8g of the penta Polyurea (PUA) viscous solution in the step three-Phase Amic Acid (PAA) viscous solution, stirring and reacting at 70 ℃ under the condition of nitrogen for 1 h, weighing 0.2g of 4,4' -diaminodiphenyl ether, adding the obtained mixture into the obtained mixture, continuously reacting for 4.5 h, and taking out the obtained mixture to obtain polyurea/polyamide acid (PUA-PAA) viscous solution;
step seven, uniformly coating the PUA-PAA viscous solution obtained in the step six on the surface of the bearing steel, and putting the bearing steel on a constant-temperature heating table for treatment at 60 ℃ for 8 hours to completely evaporate the solvent; then placing into a tube furnace, preserving heat at 80deg.C for 2 h, respectively preserving heat at 100deg.C, 150deg.C and 180deg.C for 1 h, and relatively mild heating to obtain PUA-PAA-Ti 3 C 2 Imidizing the PAA to obtain the multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite material.
Example 5:
a multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite prepared by the steps of:
step one, taking 2g of Ti 3 AlC 2 Placing the nano material in a polytetrafluoroethylene beaker containing 20mL of HF solution with the concentration of 40wt%, magnetically stirring the nano material in a water bath at 25 ℃ for 24h, repeatedly washing the nano material with deionized water to pH 7 by a centrifugal mode, performing suction filtration, and performing vacuum drying at 60 ℃ for 24 hours to obtain the organ-shaped Ti with the Al peeled off 3 C 2 ；
Step two, 50mL of N-methylpyrrolidone is added into a reaction vessel, and 3.430g of 4,4' -diaminodiphenyl ether and 0.205 g of Ti are weighed 3 C 2 Adding into N-methyl pyrrolidone, completely dissolving ultrasonic 2 h-4, 4' -diaminodiphenyl ether, ti 3 C 2 Uniformity ofDispersing;
step three, adding 5.390g of 3, 4' -biphenyl tetracarboxylic dianhydride into the mixed solution obtained in the step two, stirring and reacting under the ice bath and nitrogen condition for 24h, and taking out to obtain an anhydride end-capped polyamide acid (PAA) viscous solution;
step four, adding 50mL of N-methylpyrrolidone into a reaction vessel, weighing 3.750g of 4,4' -diaminodiphenyl ether, adding the mixture into the N-methylpyrrolidone, and completely dissolving the amino compound by ultrasonic treatment 2 h;
step five, adding 5.070g of diphenylmethane diisocyanate into the mixed solution obtained in the step four, stirring and reacting at 70 ℃ under the condition of nitrogen to obtain 6h, and taking out to obtain isocyanate-terminated Polyurea (PUA) viscous solution;
step six, weighing 9.8g of the penta Polyurea (PUA) viscous solution in the step three-Phase Amic Acid (PAA) viscous solution, stirring and reacting at 70 ℃ under the condition of nitrogen for 1 h, weighing 0.2g of 4,4' -diaminodiphenyl ether, adding the obtained mixture into the obtained mixture, continuously reacting for 4.5 h, and taking out the obtained mixture to obtain polyurea/polyamide acid (PUA-PAA) viscous solution;
step seven, uniformly coating the PUA-PAA viscous solution obtained in the step six on the surface of the bearing steel, and putting the bearing steel on a constant-temperature heating table for treatment at 60 ℃ for 8 hours to completely evaporate the solvent; then placing into a tube furnace, preserving heat at 80deg.C for 2 h, respectively preserving heat at 100deg.C, 150deg.C and 180deg.C for 1 h, and relatively mild heating to obtain PUA-PAA-Ti 3 C 2 Imidizing the PAA to obtain the multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite material.
Example 6:
a multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite prepared by the steps of:
step one, taking 2g of Ti 3 AlC 2 Placing the nano material in a polytetrafluoroethylene beaker containing 20mL of HF solution with the concentration of 40wt%, magnetically stirring the nano material in a water bath at 25 ℃ for 24h, repeatedly washing the nano material with deionized water to pH 7 by a centrifugal mode, performing suction filtration, and performing vacuum drying at 60 ℃ for 24 hours to obtain the organ-shaped Ti with the Al peeled off 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the For Ti 3 C 2 The pretreatment is carried out, and the pretreatment process comprises the following steps: ti is mixed with 3 C 2 Adding the mixture into a high-pressure reaction kettle, simultaneously introducing ammonia into the high-pressure reaction kettle, and sealing the high-pressure reaction kettle; heating the high-pressure reaction kettle to reach the temperature and pressure of supercritical ammonia, preserving heat and pressure for 45min, cooling, and relieving pressure to obtain pretreated Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the supercritical ammonia condition is 155 ℃ and the pressure is 12MPa; supercritical ammonia is adopted for Ti 3 C 2 Processing and enriching Ti 3 C 2 Surface groups of (2) further improve Ti 3 C 2 Dispersibility in polyimide, effectively avoiding Ti 3 C 2 Agglomeration in the polymer groups is beneficial to reducing the friction coefficient and the wear rate of the finally prepared material;
step two, 50mL of N-methylpyrrolidone is added into a reaction vessel, and 3.430g of 4,4' -diaminodiphenyl ether and 0.05g of pretreated Ti are weighed 3 C 2 Adding into N-methyl pyrrolidone, completely dissolving ultrasonic 2 h-4, 4' -diaminodiphenyl ether, ti 3 C 2 Uniformly dispersing;
step three, adding 5.390g of 3, 4' -biphenyl tetracarboxylic dianhydride into the mixed solution obtained in the step two, stirring and reacting under the ice bath and nitrogen condition for 24h, and taking out to obtain an anhydride end-capped polyamide acid (PAA) viscous solution;
step four, adding 50mL of N-methylpyrrolidone into a reaction vessel, weighing 3.750g of 4,4' -diaminodiphenyl ether, adding the mixture into the N-methylpyrrolidone, and completely dissolving the amino compound by ultrasonic treatment 2 h;
step five, adding 5.070g of diphenylmethane diisocyanate into the mixed solution obtained in the step four, stirring and reacting at 70 ℃ under the condition of nitrogen to obtain 6h, and taking out to obtain isocyanate-terminated Polyurea (PUA) viscous solution;
step six, weighing 9.8g of the penta Polyurea (PUA) viscous solution in the step three-Phase Amic Acid (PAA) viscous solution, stirring and reacting at 70 ℃ under the condition of nitrogen for 1 h, weighing 0.2g of 4,4' -diaminodiphenyl ether, adding the obtained mixture into the obtained mixture, continuously reacting for 4.5 h, and taking out the obtained mixture to obtain polyurea/polyamide acid (PUA-PAA) viscous solution;
step seven, uniformly coating the PUA-PAA viscous solution obtained in the step six on the surface of the bearing steel, and putting the bearing steel on a constant-temperature heating table for treatment at 60 ℃ for 8 hours to completely evaporate the solvent; then placing into a tube furnace, preserving heat at 80deg.C for 2 h, respectively preserving heat at 100deg.C, 150deg.C and 180deg.C for 1 h, and relatively mild heating to obtain PUA-PAA-Ti 3 C 2 Imidizing the PAA to obtain the multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite material.
Example 7:
a multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite prepared by the steps of:
step one, taking 2g of Ti 3 AlC 2 Placing the nano material in a polytetrafluoroethylene beaker containing 20mL of HF solution with the concentration of 40wt%, magnetically stirring the nano material in a water bath at 25 ℃ for 24h, repeatedly washing the nano material with deionized water to pH 7 by a centrifugal mode, performing suction filtration, and performing vacuum drying at 60 ℃ for 24 hours to obtain the organ-shaped Ti with the Al peeled off 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the For Ti 3 C 2 The pretreatment is carried out, and the pretreatment process comprises the following steps: ti is mixed with 3 C 2 Adding the mixture into a high-pressure reaction kettle, simultaneously introducing ammonia into the high-pressure reaction kettle, and sealing the high-pressure reaction kettle; heating the high-pressure reaction kettle to reach the temperature and pressure of supercritical ammonia, preserving heat and pressure for 45min, cooling, and relieving pressure to obtain pretreated Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the 1g of pretreated Ti 3 C 2 Adding into 85deg.C 15mL hot water, stirring for 15min, adding 1g cyanuric acid, stirring at 85deg.C for 45min, and filtering to obtain modified Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the supercritical ammonia condition is 155 ℃ and the pressure is 12MPa; supercritical ammonia and melamine are adopted for preparing Ti 3 C 2 Is treated to further enrich Ti 3 C 2 Surface groups of (a) improve Ti 3 C 2 The dispersibility in polyimide is beneficial to reducing the friction coefficient and the wear rate of the finally prepared material;
step two, 50mL of N-methylpyrrolidone is added into a reaction vessel, and 3.430g of 4,4' -diaminodiphenyl ether and 0.05g of modified T are weighedi 3 C 2 Adding into N-methyl pyrrolidone, completely dissolving ultrasonic 2 h-4, 4' -diaminodiphenyl ether, ti 3 C 2 Uniformly dispersing;
step three, adding 5.390g of 3, 4' -biphenyl tetracarboxylic dianhydride into the mixed solution obtained in the step two, stirring and reacting under the ice bath and nitrogen condition for 24h, and taking out to obtain an anhydride end-capped polyamide acid (PAA) viscous solution;
step four, adding 50mL of N-methylpyrrolidone into a reaction vessel, weighing 3.750g of 4,4' -diaminodiphenyl ether, adding the mixture into the N-methylpyrrolidone, and completely dissolving the amino compound by ultrasonic treatment 2 h;
step five, adding 5.070g of diphenylmethane diisocyanate into the mixed solution obtained in the step four, stirring and reacting at 70 ℃ under the condition of nitrogen to obtain 6h, and taking out to obtain isocyanate-terminated Polyurea (PUA) viscous solution;
step six, weighing 9.8g of the penta Polyurea (PUA) viscous solution in the step three-Phase Amic Acid (PAA) viscous solution, stirring and reacting at 70 ℃ under the condition of nitrogen for 1 h, weighing 0.2g of 4,4' -diaminodiphenyl ether, adding the obtained mixture into the obtained mixture, continuously reacting for 4.5 h, and taking out the obtained mixture to obtain polyurea/polyamide acid (PUA-PAA) viscous solution;
step seven, uniformly coating the PUA-PAA viscous solution obtained in the step six on the surface of the bearing steel, and putting the bearing steel on a constant-temperature heating table for treatment at 60 ℃ for 8 hours to completely evaporate the solvent; then placing into a tube furnace, preserving heat at 80deg.C for 2 h, respectively preserving heat at 100deg.C, 150deg.C and 180deg.C for 1 h, and relatively mild heating to obtain PUA-PAA-Ti 3 C 2 Imidizing the PAA to obtain the multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite material.
Example 8:
a multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite prepared by the steps of:
step one, taking 2g of Ti 3 AlC 2 The nano material is placed in a polytetrafluoroethylene beaker containing 20mL of HF solution with the concentration of 40wt%, magnetically stirred in a water bath at 25 ℃ for 24h, and then repeatedly washed with deionized water by a centrifugal mode until the pH value is reached7, carrying out suction filtration, and vacuum drying at 60 ℃ for 24 hours to obtain the organ-shaped Ti with the Al peeled off 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the For Ti 3 C 2 The pretreatment is carried out, and the pretreatment process comprises the following steps: ti is mixed with 3 C 2 Adding the mixture into a high-pressure reaction kettle, simultaneously introducing ammonia into the high-pressure reaction kettle, and sealing the high-pressure reaction kettle; heating the high-pressure reaction kettle to reach the temperature and pressure of supercritical ammonia, preserving heat and pressure for 45min, cooling, and relieving pressure to obtain pretreated Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the supercritical ammonia condition is 155 ℃ and the pressure is 12MPa;
step two, 50mL of N-methylpyrrolidone is added into a reaction vessel, and 3.430g of 4,4' -diaminodiphenyl ether and 0.102g of pretreated Ti are weighed 3 C 2 Adding into N-methyl pyrrolidone, completely dissolving ultrasonic 2 h-4, 4' -diaminodiphenyl ether, ti 3 C 2 Uniformly dispersing;
step three, adding 5.390g of 3, 4' -biphenyl tetracarboxylic dianhydride into the mixed solution obtained in the step two, stirring and reacting under the ice bath and nitrogen condition for 24h, and taking out to obtain an anhydride end-capped polyamide acid (PAA) viscous solution;
step four, adding 50mL of N-methylpyrrolidone into a reaction vessel, weighing 3.750g of 4,4' -diaminodiphenyl ether, adding the mixture into the N-methylpyrrolidone, and completely dissolving the amino compound by ultrasonic treatment 2 h;
step five, adding 5.070g of diphenylmethane diisocyanate into the mixed solution obtained in the step four, stirring and reacting at 70 ℃ under the condition of nitrogen to obtain 6h, and taking out to obtain isocyanate-terminated Polyurea (PUA) viscous solution;
step six, weighing 9.8g of the penta Polyurea (PUA) viscous solution in the step three-Phase Amic Acid (PAA) viscous solution, stirring and reacting at 70 ℃ under the condition of nitrogen for 1 h, weighing 0.2g of 4,4' -diaminodiphenyl ether, adding the obtained mixture into the obtained mixture, continuously reacting for 4.5 h, and taking out the obtained mixture to obtain polyurea/polyamide acid (PUA-PAA) viscous solution;
step seven, uniformly coating the PUA-PAA viscous solution obtained in the step six on the surface of the bearing steel, and putting the bearing steel on a constant-temperature heating table for treatment at 60 ℃ for 8 hours to completely evaporate the solvent; then put into the tubeIn the furnace, the temperature is kept at 80 ℃ for 2 h, the temperature is kept at 100 ℃, the temperature is kept at 150 ℃ and the temperature is kept at 180 ℃ for 1 h respectively, and the temperature is raised relatively gently so that the PUA-PAA-Ti 3 C 2 Imidizing the PAA to obtain the multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite material.
Example 9:
a multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite prepared by the steps of:
step one, taking 2g of Ti 3 AlC 2 Placing the nano material in a polytetrafluoroethylene beaker containing 20mL of HF solution with the concentration of 40wt%, magnetically stirring the nano material in a water bath at 25 ℃ for 24h, repeatedly washing the nano material with deionized water to pH 7 by a centrifugal mode, performing suction filtration, and performing vacuum drying at 60 ℃ for 24 hours to obtain the organ-shaped Ti with the Al peeled off 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the For Ti 3 C 2 The pretreatment is carried out, and the pretreatment process comprises the following steps: ti is mixed with 3 C 2 Adding the mixture into a high-pressure reaction kettle, simultaneously introducing ammonia into the high-pressure reaction kettle, and sealing the high-pressure reaction kettle; heating the high-pressure reaction kettle to reach the temperature and pressure of supercritical ammonia, preserving heat and pressure for 45min, cooling, and relieving pressure to obtain pretreated Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the 1g of pretreated Ti 3 C 2 Adding into 85deg.C 15mL hot water, stirring for 15min, adding 1g cyanuric acid, stirring at 85deg.C for 45min, and filtering to obtain modified Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the supercritical ammonia condition is 155 ℃ and the pressure is 12MPa;
step two, 50mL of N-methylpyrrolidone is added into a reaction vessel, and 3.430g of 4,4' -diaminodiphenyl ether and 0.102g of modified Ti are weighed 3 C 2 Adding into N-methyl pyrrolidone, completely dissolving ultrasonic 2 h-4, 4' -diaminodiphenyl ether, ti 3 C 2 Uniformly dispersing;
step three, adding 5.390g of 3, 4' -biphenyl tetracarboxylic dianhydride into the mixed solution obtained in the step two, stirring and reacting under the ice bath and nitrogen condition for 24h, and taking out to obtain an anhydride end-capped polyamide acid (PAA) viscous solution;
step four, adding 50mL of N-methylpyrrolidone into a reaction vessel, weighing 3.750g of 4,4' -diaminodiphenyl ether, adding the mixture into the N-methylpyrrolidone, and completely dissolving the amino compound by ultrasonic treatment 2 h;
step five, adding 5.070g of diphenylmethane diisocyanate into the mixed solution obtained in the step four, stirring and reacting at 70 ℃ under the condition of nitrogen to obtain 6h, and taking out to obtain isocyanate-terminated Polyurea (PUA) viscous solution;
step six, weighing 9.8g of the penta Polyurea (PUA) viscous solution in the step three-Phase Amic Acid (PAA) viscous solution, stirring and reacting at 70 ℃ under the condition of nitrogen for 1 h, weighing 0.2g of 4,4' -diaminodiphenyl ether, adding the obtained mixture into the obtained mixture, continuously reacting for 4.5 h, and taking out the obtained mixture to obtain polyurea/polyamide acid (PUA-PAA) viscous solution;
step seven, uniformly coating the PUA-PAA viscous solution obtained in the step six on the surface of the bearing steel, and putting the bearing steel on a constant-temperature heating table for treatment at 60 ℃ for 8 hours to completely evaporate the solvent; then placing into a tube furnace, preserving heat at 80deg.C for 2 h, respectively preserving heat at 100deg.C, 150deg.C and 180deg.C for 1 h, and relatively mild heating to obtain PUA-PAA-Ti 3 C 2 Imidizing the PAA to obtain the multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite material.
Application example:
the invention adopts MDZ-1GL type high/low temperature and vacuum friction and wear testing machine to carry out rotary friction experiments on the embodiments 1-9; polyimide material (multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite material) is a lower-style disc, and bearing steel is an upper-style dual ball. The test conditions of the friction experiment are as follows: atmospheric environment, test lasting 1.0h, loading force 20.0N, speed 0.25m/s; the results obtained are shown in Table 1 (different mass fractions Ti over a broad temperature range) 3 C 2 The coefficient of friction of the polyurea/polyimide copolymer composite) of (a) Table 2 (different mass fractions Ti over a broad temperature range) 3 C 2 The wear rate of the polyurea/polyimide copolymer composite (10) -5 mm 3 N.m.); volumetric wear rate (mm) of polymer 3 N.m) is scanned and calculated by a white light three-dimensional scanner attached to a Rtec-MFT3000 type multifunctional frictional wear tester.
Prepared by the inventionDifferent mass fractions Ti at wide temperature ranges 3 C 2 As a result of comparing the polyurea/polyimide copolymer composite material, it was found that a proper amount of Ti was added 3 C 2 Can improve the tribological property of the polyurea/polyimide copolymer composite material and improve the mechanical property to a certain extent. Due to Ti 3 C 2 The weaker van der Waals force is arranged between the layers, and the weaker van der Waals force is sheared to form weaker sheets under the action of shearing force in the friction process, so that the self-lubricating film is formed, and the bearing capacity of the composite material transfer film is improved.
TABLE 1 different mass fractions Ti at broad temperature ranges 3 C 2 Coefficient of friction of polyurea/polyimide copolymer composites
| -100℃ | 25℃ | 100℃ | |
| Example 1 | 0.129 | 0.225 | 0.290 |
| Example 2 | 0.093 | 0.203 | 0.273 |
| Example 3 | 0.069 | 0.196 | 0.250 |
| Example 4 | 0.154 | 0.085 | 0.193 |
| Example 5 | 0.165 | 0.161 | 0.234 |
| Example 6 | 0.055 | 0.134 | 0.164 |
| Example 7 | 0.041 | 0.096 | 0.128 |
| Example 8 | 0.116 | 0.065 | 0.148 |
| Example 9 | 0.092 | 0.054 | 0.117 |
TABLE 2 different mass fractions Ti at broad temperature ranges 3 C 2 The wear rate of the polyurea/polyimide copolymer composite (10) - 5 mm 3 /N·m)
| -100℃ | 25℃ | 100℃ | |
| Example 1 | 6.82 | 8.27 | 13.72 |
| Example 2 | 4.26 | 6.94 | 8.63 |
| Example 3 | 3.66 | 6.42 | 8.19 |
| Example 4 | 4.13 | 4.56 | 5.91 |
| Example 5 | 6.45 | 8.06 | 10.12 |
| Example 6 | 3.12 | 5.89 | 7.75 |
| Example 7 | 2.85 | 5.06 | 6.95 |
| Example 8 | 3.35 | 3.58 | 4.95 |
| Example 9 | 3.06 | 3.19 | 4.11 |
It can be seen from tables 1 and 2 that the polyurea/polyimide copolymer composite obtained in example 4, which has a content of 1%, has the lowest coefficient of friction and wear rate over a wide temperature range, in particular at 25℃and 100 ℃. Example 1 the coefficient of friction and wear rate were highest for the pure polyurea/polyimide copolymer without the addition of multiple layers of titanium carbide. Pretreatment of Ti was used in examples 6 and 8 3 C 2 The obtained multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite material has lower friction coefficient and wear rate, and modified Ti is adopted in the same examples 7 and 9 3 C 2 The obtained multilayer titanium carbide/polyurea/polyimide copolymer self-lubricating composite material has lower friction coefficient and wear rate, and in addition, the friction performance of the composite materials obtained in examples 2,3 and 5 is better than that of the pure polyurea/polyimide copolymer.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (8)
1. A self-lubricating composite material suitable for polyurea/polyimide copolymer in wide temp. range is prepared through in-situ introducing titanium carbide in polyimide, cross-linking copolymerization with polyurea,
the preparation method of the self-lubricating composite material suitable for the wide temperature range polyurea/polyimide copolymer comprises the following steps:
step one, taking diamine monomer and Ti 3 C 2 Adding the mixture into a solvent, and performing ultrasonic treatment for 1-2 hours to obtain a mixed dispersion liquid; adding dianhydride monomer into the mixed dispersion liquid, and stirring and reacting for 18-36 hours under the conditions of ice bath and nitrogen to obtain acid anhydride end-capped polyamide acid viscous solution;
step two, adding diamine monomer into a solvent, and performing ultrasonic treatment for 1-2 hours to obtain a mixed solution; adding the isocyanate component into the mixed solution, and stirring and reacting for 5-8 hours at the temperature of 60-80 ℃ under the nitrogen condition to obtain an isocyanate-terminated polyurea viscous solution;
thirdly, adding the polyurea viscous solution into the polyamide acid viscous solution, stirring and reacting for 0.5-1.5 h at 60-80 ℃ under the nitrogen condition, adding diamine monomer, and continuously reacting for 4-6 h to obtain the polyurea/polyamide acid viscous solution;
uniformly coating the polyurea/polyamide acid viscous solution on the surface of a carrier, and placing the carrier on a constant-temperature heating table for treatment at 50-70 ℃ for 6-8 hours to completely evaporate the solvent; then placing the mixture into a tube furnace, and preserving heat for 1-3 hours at 75-85 ℃, and preserving heat for 0.5-1.5 hours at 95-105 ℃, 145-155 ℃ and 175-185 ℃ respectively to obtain a multi-layer titanium carbide/polyurea/polyimide copolymer high-lubrication composite material, namely the self-lubrication composite material applicable to the wide-temperature-range polyurea/polyimide copolymer;
the Ti is 3 C 2 The mass fraction of the multilayer titanium carbide/polyurea/polyimide copolymer high-lubrication composite material is 0-2.0%; and the mass fraction is not 0.
2. The polyurea/polyimide copolymer self-lubricating composite material suitable for use in a wide temperature range as claimed in claim 1, wherein the Ti 3 C 2 The preparation method of (2) comprises the following steps: 1 to 2g of Ti 3 AlC 2 Placing the nano material into a polytetrafluoroethylene beaker containing 10-20 mL of HF solution with the concentration of 40wt%, magnetically stirring the nano material in a water bath at 25 ℃ for 24h, repeatedly washing the nano material with deionized water to pH 7 in a centrifugal way, performing suction filtration, and performing vacuum drying at 60 ℃ for 24 hours to obtain Al-stripped organ-shaped Ti 3 C 2 。
3. The self-lubricating composite material suitable for use in a wide temperature range polyurea/polyimide copolymer according to claim 1, wherein the Ti is 3 C 2 The pretreatment is carried out, and the pretreatment process comprises the following steps: ti is mixed with 3 C 2 Adding the mixture into a high-pressure reaction kettle, simultaneously introducing ammonia into the high-pressure reaction kettle, and sealing the high-pressure reaction kettle; heating the high-pressure reaction kettle to reach the temperature and pressure of supercritical ammonia, preserving heat and pressure for 30-45 min, cooling and decompressing to obtain pretreated Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the supercritical ammonia is 145-165 ℃ and the pressure is 8-25 MPa.
4. The self-lubricating composite material suitable for use in a broad temperature range polyurea/polyimide copolymer as claimed in claim 3, wherein the Ti is to be pretreated 3 C 2 Adding the mixture into hot water at the temperature of 80-90 ℃ and stirring for 10-15 min, then adding cyanuric acid, continuously stirring for 30-45 min at the temperature of 80-90 ℃, and filtering to obtain modified Ti 3 C 2 The method comprises the steps of carrying out a first treatment on the surface of the The pretreatment Ti 3 C 2 The mass volume ratio of the water to the hot water is 1 g:10-15 mL; the pretreatment Ti 3 C 2 The mass ratio of the epoxy resin to cyanuric acid is 1:0.5-1.
5. The self-lubricating composite material for the wide temperature range polyurea/polyimide copolymer according to claim 1, wherein in the first step, the molar ratio of the dianhydride monomer to the diamine monomer is 0.8-1.2:1, and the solid content of the obtained polyamide acid viscous solution is 10-20%;
in the first step, the solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the diamine monomer is one or more of 4,4' -diaminodiphenyl ether, p-phenylenediamine and 4,4' -diamino-2, 2' -methyl biphenyl; the dianhydride monomer is one or more of 3, 4' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride and cyclobutane tetracarboxylic dianhydride.
6. The self-lubricating composite material applicable to the wide-temperature-range polyurea/polyimide copolymer according to claim 1, wherein in the second step, the molar ratio of the isocyanate component to the diamine monomer is 0.8-1.2:1, and the solid content of the obtained polyurea viscous solution is 10-20%;
in the second step, the solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the diamine monomer is one or more of 4,4' -diaminodiphenyl ether, p-phenylenediamine and 4,4' -diamino-2, 2' -methyl biphenyl; the isocyanate component is one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
7. The self-lubricating composite material applicable to the wide-temperature-range polyurea/polyimide copolymer according to claim 1, wherein in the third step, the mass ratio of the polyurea in the polyurea viscous solution to the polyamic acid in the polyamic acid viscous solution is 1:4-8;
in the third step, the diamine monomer is one or more of 4,4' -diaminodiphenyl ether, p-phenylenediamine and 4,4' -diamino-2, 2' -methylbiphenyl;
in the third step, the diamine monomer is added in an amount such that the ratio of the total molar amount of the dianhydride monomer and the isocyanate component to the molar amount of the total diamine monomer is 0.8-1.2:1;
in the fourth step, the carrier is one or more of bearing steel, stainless steel, aluminum plate, glass and ceramic.
8. The self-lubricating composite material applicable to the wide temperature range polyurea/polyimide copolymer according to claim 1, wherein the number of layers of the multilayer titanium carbide in the multilayer titanium carbide/polyurea/polyimide copolymer high-lubricating composite material is 10-30, and the interlayer spacing is 70-90 nm.
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