CN116200116B - Multifunctional coating with super-strong mechanical property and self-repairing function - Google Patents
Multifunctional coating with super-strong mechanical property and self-repairing function Download PDFInfo
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- CN116200116B CN116200116B CN202310286678.XA CN202310286678A CN116200116B CN 116200116 B CN116200116 B CN 116200116B CN 202310286678 A CN202310286678 A CN 202310286678A CN 116200116 B CN116200116 B CN 116200116B
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- 238000000576 coating method Methods 0.000 title claims abstract description 53
- 239000011248 coating agent Substances 0.000 title claims abstract description 50
- 239000003822 epoxy resin Substances 0.000 claims abstract description 44
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 44
- 229920002635 polyurethane Polymers 0.000 claims abstract description 41
- 239000004814 polyurethane Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 claims abstract description 28
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 230000002441 reversible effect Effects 0.000 claims abstract description 5
- 238000007115 1,4-cycloaddition reaction Methods 0.000 claims abstract description 4
- 210000000845 cartilage Anatomy 0.000 claims abstract description 4
- 150000001993 dienes Chemical class 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 claims abstract description 4
- 125000002541 furyl group Chemical group 0.000 claims abstract description 4
- 125000000879 imine group Chemical group 0.000 claims abstract description 4
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims abstract description 3
- 239000011347 resin Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 66
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 66
- 239000000203 mixture Substances 0.000 claims description 33
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 9
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 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
- 239000010949 copper Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000011527 polyurethane coating Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000001133 acceleration Effects 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000002313 adhesive film Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004593 Epoxy Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229920006334 epoxy coating Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a multifunctional coating with super-strong mechanical properties and a self-repairing function, and belongs to the technical field of self-repairing coatings. The coating matrix resin is epoxy resin and polyurethane, and the epoxy resin is introduced into polyurethane molecular chains through a self-repairing crosslinking agent to form a cross-linked network structure so as to simulate the fiber structure of animal cartilage tissues; the advantages of the epoxy resin and the polyurethane are fully exerted, and the adhesive strength, the tensile strength, the water resistance and the like of the adhesive film are effectively improved. The self-repairing cross-linking agent is composed of 2, 5-furandimethanol and 4,4 '-methylenebis (N-phenylmaleimide), and is polymerized with polyurethane firstly and then cross-linked with epoxy resin, and self-repairing is carried out by virtue of reversible reaction of [4+2] cycloaddition reaction of diene on furyl in 2, 5-furandimethanol and imine group dienophile in 4,4' -methylenebis (N-phenylmaleimide).
Description
Technical Field
The invention belongs to the technical field of self-repairing coatings.
Background
The broad field of application of polyurethanes is related to their characteristic properties, and the advantages of polyurethanes include: 1. abrasion resistance: the polyurethane material has high surface hardness and wear resistance, and is suitable for high-wear environment. 2. Excellent elasticity: the polyurethane has good elasticity, so that the material has good impact absorption capacity, and the vibration isolation and shock absorption effects are good. 3. Waterproof property: the polyurethane can form a seamless coating, and has strong waterproof property and good moisture resistance. 3. Weather resistance: the polyurethane material has good oxidation resistance and ultraviolet stability, is not easy to age, has long service life, and can keep the surface from fading and sagging. 4. Good insulating properties: polyurethane is an excellent insulating material, has good electrical insulation performance, and can be used in the electrical field. However, polyurethane has a low surface hardness and is susceptible to abrasion or impact when used as a floor coating or a car body coating. In addition, polyurethane has poor adhesion properties as compared with epoxy, and conventionally, in order to solve this disadvantage, epoxy-modified polyurethane is used.
The epoxy modified polyurethane has the following advantages that the epoxy modified polyurethane combines the advantages of epoxy resin and polyurethane, and has the following advantages: wear resistance: compared with pure polyurethane, the epoxy modified polyurethane has better wear resistance and can be used for manufacturing high-wear parts. Chemical resistance: compared with pure polyurethane, the epoxy modified polyurethane has better chemical corrosion resistance, and can be used for manufacturing chemical reactors, storage tanks and other equipment. Hardness: compared with pure polyurethane, the epoxy modified polyurethane has higher hardness and can be used for manufacturing parts with high strength and high rigidity. The thermal stability is higher: compared with pure polyurethane, the epoxy modified polyurethane has higher thermal stability and can be used for manufacturing parts capable of bearing high-temperature environments. The construction is convenient: the epoxy modified polyurethane can be used in a wider temperature range during construction than the pure polyurethane.
In a word, the epoxy modified polyurethane combines the advantages of epoxy resin and polyurethane, and has wider application range and better performance. However, the traditional epoxy modified polyurethane adopts a mixing method, but the properties of different parts of the coating are different due to the uneven mixing of the polyurethane and the epoxy resin. In addition, development of self-repairing coatings is necessary in that the materials can be made to have self-repairing ability, i.e., to be automatically repaired when fine damage occurs, which can effectively reduce damage to the materials and maintenance costs, and increase the service life of the materials. Without a self-healing coating, the material would need to be repaired or replaced once damaged, which can result in higher costs and time, affecting global economics. The necessity of the self-repairing coating is not only reflected in repairing damage to the material, but also can be improved in the aspects of maintaining the beauty, corrosion resistance, abrasion resistance and the like of the coating.
Disclosure of Invention
In order to meet the requirements, the technical scheme provided by the invention is to crosslink the epoxy and the polyurethane together through the self-repairing crosslinking agent, so that the coating has a self-repairing function, and meanwhile, the effective crosslinking of the polyurethane and the epoxy resin is completed. Improves the mechanical property of the coating and has the self-repairing function.
The matrix resin of the multifunctional coating with super-strong mechanical property and self-repairing function is epoxy resin and polyurethane, and the epoxy resin is introduced into a polyurethane molecular chain through a self-repairing crosslinking agent to form a cross-linked network structure so as to simulate the fiber structure of animal cartilage tissue; the self-repairing cross-linking agent is composed of 2, 5-furandimethanol and 4,4 '-methylenebis (N-phenylmaleimide), and is polymerized with polyurethane firstly and then cross-linked with epoxy resin, and self-repairing is carried out by virtue of reversible reaction of [4+2] cycloaddition reaction of diene on furyl in 2, 5-furandimethanol and imine group dienophile in 4,4' -methylenebis (N-phenylmaleimide).
The preparation steps of the multifunctional coating with the super-strong mechanical property and the self-repairing function are as follows:
1) Preparation of epoxy resin mixtures
Mixing epoxy resin and solvent ethyl acetate, adding a curing agent, reacting at 60 ℃ for 8 hours, adding ethyl acetate for dilution to enable the mass of the epoxy resin and furfuryl amine to account for 25-35% of the total mass of the mixture, bottling and sealing the obtained epoxy resin mixture, cooling to room temperature and storing; wherein the molar ratio of the epoxy resin to the curing agent is 1:1. The epoxy resin is preferably epoxy resin e51, and the curing agent is preferably furfuryl amine;
2) Preparation of polyurethane prepolymers
The isocyanate was poured into a reaction vessel, heated to 50 ℃ and polyol was added dropwise to the reaction vessel by nitrogen, reacted at 50 ℃ for 30 minutes, then the temperature was raised to 80 ℃ for 3 hours, and then the resulting polyurethane prepolymer was bottled and sealed, cooled to room temperature and stored.
The isocyanate is preferably 2, 4-toluene diisocyanate, the polyol is preferably polytetrahydrofuran ether glycol, and the mass ratio of the 2, 4-toluene diisocyanate to the polytetrahydrofuran ether glycol is 1:2.075; the reaction drop velocity is preferably 4 drops/sec;
3) Polyurethane prepolymer chain extension
A. Mixing polyurethane prepolymer and solvent Dimethylformamide (DMF), adding 2, 5-Furandimethanol (FDMO), heating to 60 ℃ to react until the 2, 5-furandimethanol is completely dissolved, adding ethyl acetate solvent, and stirring for 4 hours at 60 ℃ by nitrogen to obtain a mixture A; the mass ratio of the polyurethane prepolymer to the DMF to the 2, 5-furandimethanol is 1:1.56:0.105; the mass ratio of the polyurethane prepolymer to the ethyl acetate is 1 (0.6-2);
b. Dissolving 4,4' -methylenebis (N-phenyl maleimide) by using a solvent dimethylformamide, then adding the solvent dimethylformamide into the mixture A, and reacting for 30min at normal temperature to complete the chain extension reaction of the polyurethane prepolymer; the mass ratio of the 4,4' -methylenebis (N-phenyl maleimide) to the polyurethane prepolymer is 0.194:1; the mass ratio of the 4,4' -methylenebis (N-phenyl maleimide) to the dimethylformamide is 1:0.5-1.5;
4) Crosslinking reaction
Adding the epoxy resin mixture obtained in the step 1) into the product obtained in the step 3), adding ethyl acetate as a solvent for dilution to ensure that the solid content in the mixed system is 30%, and stirring for 1 hour at normal temperature to obtain the coating for preparing the multifunctional coating with super-strong mechanical property and self-repairing function; the epoxy resin mixture accounts for 10% of the total polyurethane coating mass.
5) Coating preparation
Coating the coating obtained in the step 4) on the surface of a substrate, and curing the coating in a vacuum furnace at 80 ℃ for 48 hours to obtain a multifunctional coating with super-strong mechanical property and self-repairing function; the substrate comprises: alloys of one or more of iron, copper, steel, magnesium, titanium, aluminum.
The invention has the beneficial effects that:
the multifunctional coating with super-strong mechanical property and self-repairing function provided by the invention adopts epoxy resin to simulate the fiber structure of animal cartilage tissue. The epoxy resin has the advantages of high strength, good dielectric resistance, strong adhesive force, good heat resistance and the like, and the epoxy resin is introduced into polyurethane molecular chains to form a cross-linked network structure, so that the advantages of the epoxy resin and the polyurethane molecular chains can be fully exerted, and the adhesive strength, the tensile strength, the water resistance and the like of the adhesive film are effectively improved.
The self-repairing function in the invention is realized mainly by Diels-Alder reaction (DA reaction). The DA reaction has thermal reversibility, mild reaction conditions, no need of adding a catalyst and small side reaction, and is commonly used for preparing self-repairing polymers. The DA reaction is a thermal induction of [4+2] cycloaddition of dienoids on furyl groups in 2, 5-furandimethanol and imine groups in 4,4' -methylenebis (N-phenylmaleimide), the resulting DA adduct will undergo cleavage reaction (DA inversion) at high temperature, then diene and dienophile structures are formed, and upon a decrease in temperature they undergo DA reaction, the DA adduct is reformed. In the invention, the sample is placed at 130 ℃ to cause DA reverse reaction, and then placed at 60 ℃ to cause DA reaction again, thereby realizing the self-repairing function of the coating.
Drawings
FIG. 1 coating tensile properties vs. graph
FIG. 2 10% epoxy coating before repair
FIG. 3 10% epoxy coating after repair for self-healing properties
Detailed Description
The technical scheme of the invention is further explained and illustrated in the following form of specific examples.
Example 1
The starting materials used in this example were toluene 2, 4-diisocyanate (TDI-100), polytetrahydrofuran ether glycol (PTMG, molecular weight 650), 2, 5-Furandimethanol (FDMO), 4' -methylenebis (N-phenylmaleimide) (BM), epoxy resin e51 (EP), furfuryl Amine (FA)
The raw materials are common in the market, the price is low, the synthesis method is simple, and the large-scale synthesis can be realized. The solvents used in the preparation of the coating were ethyl acetate and DMF.
1) Preparation of epoxy resin mixtures
12G of EP and 10g of ethyl acetate solvent were poured into a beaker, 3.1g of FA was added and the reaction was carried out at 60℃for 8 hours. Then 25.23g of ethyl acetate solvent was added to bring the mass of epoxy resin and furfuryl amine to approximately 30% of the total mass of the mixture. The epoxy resin mixture was bottled and sealed, cooled to room temperature and stored.
2) Preparation of polyurethane prepolymers
A. PTMG was first poured into a rotary bottle of a rotary evaporator and then distilled under vacuum at 120℃for 2 hours. After cooling to 60 ℃, the mixture was bottled and stored in a sealed state.
B. 40g of TDI-100 was poured into a four-necked flask, heated to 50℃and passed through nitrogen, 83g of PTMG was poured into a constant pressure dropping funnel, and dropped into the four-necked flask at a rate of 4 drops per second. The reaction was carried out at 50℃for 30 minutes. The temperature was then raised to 80℃and the reaction continued for 3 hours. The polyurethane prepolymer was bottled and sealed, cooled to room temperature and stored.
3) Chain extension of polyurethane prepolymers
A. 6g of polyurethane prepolymer and 1gDMF solvent were mixed, 0.638g of FDMO was added, heated to 60℃and stirred for 5min to FDMO to be completely dissolved, 10g of ethyl acetate solvent was further added, and stirred by nitrogen at 60℃for 4 hours to obtain a mixture.
B. 1.16g of BM was added to 1.46g of DMF and was completely dissolved, and then added to the above mixture, and the reaction was carried out at room temperature for 30 minutes to obtain a chain-extended polyurethane prepolymer.
3) Preparation of the coating
Adding 1.72g of epoxy resin mixture into the polyurethane prepolymer after chain extension, so that the epoxy resin accounts for 10% of the total mass of the finally prepared coating; 8.19g of ethyl acetate is added to ensure that the solid content in the coating is close to 30 percent, and the coating is stirred for 1 hour at normal temperature to obtain the coating for preparing the multifunctional coating with super-strong mechanical property and self-repairing function.
4) Finally, the coating is solidified in a vacuum furnace at 80 ℃ for 48 hours to obtain the multifunctional coating with super-strong mechanical property and self-repairing function.
FDMO and BM in the present invention are only soluble in DMF, but DMF cannot be excessive, and excessive DMF can affect the mechanical properties of materials, so that two solvents, namely DMF and ethyl acetate, are used in the present invention.
In the present invention, BM is added first followed by EP mixture in order to allow efficient chemical crosslinking of the prepolymer, BM and EP. This is because mixing the BM with the EP first causes a crosslinking reaction between the BM and the EP first, and the BM is linked to the EP at both ends, thereby losing the ability to crosslink with the prepolymer.
For comparative purposes to illustrate the effect of the invention, the following examples are chosen as comparative purposes:
comparative example 1:
1) PTMG was first poured into a rotary bottle of a rotary evaporator and then distilled under vacuum at 120℃for 2 hours. After cooling to 60 ℃, the mixture was bottled and stored in a sealed state.
2) 40G of TDI-100 was poured into a four-necked flask, heated to 50℃and passed through nitrogen, 83g of PTMG was poured into a constant pressure dropping funnel, and dropped into the four-necked flask at a rate of 4 drops per second. The reaction was carried out at 50℃for 30 minutes. The temperature was then raised to 80℃and the reaction continued for 3 hours. The polyurethane prepolymer obtained was bottled and sealed, cooled to room temperature and stored.
3) 6G of polyurethane prepolymer and 1g of solvent DMF were mixed, 0.638g of FDMO g of DMF was added, heated to 60℃and stirred for 5min to FDMO to dissolve completely, 10g of solvent ethyl acetate was added and stirred for 4 hours at 60℃by nitrogen.
4) 0.89G BM was added to 1.12g DMF and dissolved completely, then added to the above mixture, and 7.56g ethyl acetate was added and stirred at room temperature for 1 hour, resulting in a coating with a solids content of approximately 30%.
5) Finally, the coating was cured in a vacuum oven at 80 ℃ for 48 hours.
Comparative example 2:
1) 12g of EP and 10g of ethyl acetate as solvent were poured into a beaker, 3.1g of FA was added and the reaction was carried out at 60℃for 8 hours. Then 25.23g of ethyl acetate was added to bring the mass of EP and FA to approximately 30% of the total mass of the mixture. The epoxy resin mixture was bottled and sealed, cooled to room temperature and stored.
2) PTMG was first poured into a rotary bottle of a rotary evaporator and then distilled under vacuum at 120℃for 2 hours. After cooling to 60 ℃, the mixture was bottled and stored in a sealed state.
3) 40G of TDI-100 solution was poured into a four-necked flask, heated to 50℃and 83g of PTMG was poured into a constant pressure dropping funnel by nitrogen, and dropped into the four-necked flask at a rate of 4 drops per second. The reaction was carried out at 50℃for 30 minutes. The temperature was then raised to 80℃and the reaction continued for 3 hours. The polyurethane prepolymer obtained was bottled and sealed, cooled to room temperature and stored.
4) 6G of polyurethane prepolymer and 1g of DMF solvent were mixed, 0.638g of FDMO was added, heated to 60℃and stirred for 5min to FDMO to dissolve completely, 10g of ethyl acetate was added as solvent, and stirred by nitrogen at 60℃for 4 hours to obtain a mixture.
5) 1.5G BM was added to 1.89g DMF solvent and was completely dissolved, and then added to the above mixture, and the reaction was performed at normal temperature for 30 minutes. Obtaining the polyurethane prepolymer after chain extension.
6) 3.87G of an epoxy resin mixture was added to the polyurethane prepolymer after chain extension to obtain a mixture containing 20% of epoxy content of the solute. And 8.99g of ethyl acetate was added so that the solute was approximately 30% of the mass of the solution. The mixture was stirred at room temperature for 1 hour.
7) The mixture was cured in a vacuum oven at 80 ℃ for 48 hours.
And (3) effect verification:
1) Tensile test: as a result, as shown in FIG. 1, it can be seen that the tensile strength thereof was 37.8MPa when the EP content was 0%. With increasing EP content, the tensile strength of the polymer changes significantly. When the EP content was 10%, the tensile strength was 40.1MPa. But after that, as the EP content increases to 20%, the tensile strength tends to decrease, being only 38.4MPa. Therefore, the mechanical properties are best when the EP content is 10%.
2) Self-repair test:
A sample of the material containing 10% of epoxy in example 1 was taken, a scratch of 3mm was scratched on the surface thereof with a knife, and the sample was placed in a vacuum drying oven at 130℃for 30min and at 60℃for 24h, and the conditions before and after the repair of the crack of the sample were qualitatively observed with an optical microscope. As can be seen by comparing fig. 2 and 3, the scratch completely disappears after the high temperature treatment, due to the reversible crosslinking reaction bridging the cut surface. The mechanical properties and self-healing capacity of the coating are greatly improved by DA reaction.
Claims (5)
1. A multifunctional coating with super-strong mechanical property and self-repairing function is characterized in that matrix resin in the coating is epoxy resin and polyurethane, and the epoxy resin is introduced into polyurethane molecular chains through a self-repairing crosslinking agent to form a cross-linked network structure so as to simulate the fiber structure of animal cartilage tissues; the self-repairing cross-linking agent consists of 2, 5-furandimethanol and 4,4 '-methylenebis (N-phenylmaleimide), is polymerized with polyurethane firstly and then cross-linked with epoxy resin, and self-repairing is carried out by virtue of reversible reaction of [4+2] cycloaddition reaction of diene on furyl in 2, 5-furandimethanol and imine group dienophile in 4,4' -methylenebis (N-phenylmaleimide); the preparation method comprises the following specific steps:
1) Preparation of epoxy resin mixtures
Mixing epoxy resin and ethyl acetate serving as a solvent, adding a curing agent, reacting at 60 ℃ for 8 hours, adding ethyl acetate for dilution to enable the mass of the epoxy resin and the furfuryl amine to account for 25-35% of the total mass of the mixture, bottling and sealing the obtained epoxy resin mixture, cooling to room temperature, and storing; wherein the molar ratio of the epoxy resin to the curing agent is 1:1;
2) Preparation of polyurethane prepolymers
Pouring isocyanate into a reaction vessel, heating to 50 ℃, dropwise adding polyol into the reaction vessel through nitrogen, reacting for 30 minutes at 50 ℃, then raising the temperature to 80 ℃ for 3 hours, bottling and sealing the obtained polyurethane prepolymer, cooling to room temperature and storing; wherein the isocyanate is in excess;
3) Polyurethane prepolymer chain extension
A. Mixing polyurethane prepolymer and solvent dimethylformamide, adding 2, 5-furandimethanol, heating to 60 ℃ to react until the 2, 5-furandimethanol is completely dissolved, adding ethyl acetate solvent, and stirring for 4 hours at 60 ℃ through nitrogen to obtain a mixture A; the mass ratio of the polyurethane prepolymer to the dimethylformamide to the 2, 5-furandimethanol is 1:1.56:0.105; the mass ratio of the polyurethane prepolymer to the ethyl acetate is 1 (0.6-2);
b. Dissolving 4,4' -methylenebis (N-phenyl maleimide) by using a solvent dimethylformamide, then adding the solvent dimethylformamide into the mixture A, and reacting for 30min at normal temperature to complete the chain extension reaction of the polyurethane prepolymer; the mass ratio of the 4,4' -methylenebis (N-phenyl maleimide) to the polyurethane prepolymer is 0.194:1; the mass ratio of the 4,4' -methylenebis (N-phenyl maleimide) to the dimethylformamide is 1:0.5-1.5;
4) Crosslinking reaction
Adding the epoxy resin mixture obtained in the step 1) into the product obtained in the step 3), adding ethyl acetate as a solvent for dilution to ensure that the solid content in the mixed system is 30%, and stirring for 1 hour at normal temperature to obtain the coating for preparing the multifunctional coating with super-strong mechanical property and self-repairing function; the epoxy resin mixture accounts for 10% of the total polyurethane coating mass;
5) Coating preparation
And (3) coating the coating obtained in the step (4) on the surface of a substrate, and curing the coating in a vacuum furnace at 80 ℃ for 48 hours to obtain the multifunctional coating with super-strong mechanical property and self-repairing function.
2. The multifunctional coating with super-strong mechanical properties and self-repairing function according to claim 1, wherein the epoxy resin in the step 1) is epoxy resin e51, and the curing agent is furfuryl amine.
3. The multifunctional coating with super-strong mechanical properties and self-repairing function according to claim 1, wherein in the step 2), the isocyanate is 2, 4-toluene diisocyanate, the polyol is polytetrahydrofuran ether glycol, and the mass ratio of the 2, 4-toluene diisocyanate to the polytetrahydrofuran ether glycol is 1:2.075.
4. The multifunctional coating with superior mechanical properties and self-healing function according to claim 1, wherein the reaction drop acceleration in step 2) is 4 drops/sec.
5. The multifunctional coating with superior mechanical properties and self-healing function according to claim 1, wherein the substrate in step 5) comprises: alloys of one or more of iron, copper, steel, magnesium, titanium, aluminum.
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