CN116463056B - Composite varnish with self-cleaning function and preparation method thereof - Google Patents
Composite varnish with self-cleaning function and preparation method thereof Download PDFInfo
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- 239000002966 varnish Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000004140 cleaning Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 121
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 97
- 229920002545 silicone oil Polymers 0.000 claims description 63
- 239000005543 nano-size silicon particle Substances 0.000 claims description 56
- 235000012239 silicon dioxide Nutrition 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 47
- 239000003795 chemical substances by application Substances 0.000 claims description 41
- 230000002209 hydrophobic effect Effects 0.000 claims description 40
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 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 description 12
- 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 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 12
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical group OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000012974 tin catalyst Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229960001669 kinetin Drugs 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 238000006352 cycloaddition reaction Methods 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 210000003608 fece Anatomy 0.000 description 2
- DDKIXUQHRSUCMN-UHFFFAOYSA-N n-butylbutan-1-amine;propan-2-one Chemical compound CC(C)=O.CCCCNCCCC DDKIXUQHRSUCMN-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- HPOKESDSMZRZLC-UHFFFAOYSA-N propan-2-one;hydrochloride Chemical compound Cl.CC(C)=O HPOKESDSMZRZLC-UHFFFAOYSA-N 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- -1 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- Y02P20/10—Process efficiency
Abstract
The invention relates to the technical field of varnishes and discloses a composite varnish with self-cleaning function and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of varnishes, in particular to a composite varnish with self-cleaning function and a preparation method thereof.
Background
Along with economic development, the automobile gradually steps into the popular age, and the automobile protection film is one of the consumptive materials of automobile, and demand also rises gradually, and the automobile protection film that uses on the market at present mostly has multilayer structure, is pressure sensitive adhesive layer, substrate layer and coating from interior to exterior in proper order, and though the automobile protection film mainly plays the effect of protecting automobile body paint surface, prevents that the automobile from receiving erosion such as bird's droppings, acid rain because of parking outdoors, can also reduce driving in-process and the paint surface damage that slightly scrapes and rubs and lead to with barrier such as branch. In recent years, the large-scale popularization of vehicles leads to the shortage of indoor parking spaces, so that a large number of vehicle owners can only choose to park the vehicles outdoors, and therefore, the importance of the automobile protective film as the outermost barrier of the vehicles is self-evident, but the coating of the existing automobile protective film mostly does not have self-cleaning performance, dust and the like in the air can be adsorbed on the surface of the automobile protective film through electrostatic action, and then the automobile protective film is subjected to rain washing, so that unsightly water stains are extremely easy to remain, and bird droppings, tree oil and the like are easy to stay for a long time and easily grow bacteria, so that the service life of the automobile protective film is greatly shortened.
The Chinese patent application No. CN201911144985.4 discloses a fluorine-containing organopolysiloxane self-cleaning coating, which consists of a fluorine-containing siloxane precursor and a siloxane prepolymer, wherein the fluorine-containing siloxane precursor can greatly reduce the surface energy of the surface of the coating after being crosslinked with a polysiloxane main chain, so that higher self-cleaning performance is obtained, but on one hand, the fluorine-containing material has higher cost and poorer stability, and on the other hand, the fluorine-containing material has certain destructiveness to the environment and is unfavorable for environmental protection, so that the fluorine-containing organopolysiloxane self-cleaning coating still has a larger problem in practical application.
Based on the above, the invention provides a composite varnish which does not contain fluorine substances, has strong stability and can be directly used as an outer coating of an automobile protective film.
Disclosure of Invention
The invention aims to provide a composite varnish with self-cleaning function and a preparation method thereof, which solve the technical problem of poor self-cleaning effect of the outer coating of the conventional automobile protective film and simultaneously endow the composite varnish with good self-repairing and other comprehensive performances.
The aim of the invention can be achieved by the following technical scheme:
the composite varnish with the self-cleaning function comprises the following raw materials in parts by weight: 50-60 parts of furan modified silicone oil, 1-2 parts of hydrophobic nano silicon dioxide, 0.5-2 parts of organic tin catalyst, 10-25 parts of diisocyanate main curing agent, 5-10 parts of bismaleimide auxiliary curing agent and 10-15 parts of organic solvent;
the furan modified silicone oil is prepared by introducing furan groups at the tail end of a molecular chain of the terminal hydrogen-containing silicone oil;
the hydrophobic nano silicon dioxide is prepared by carrying out surface modification on the nano silicon dioxide and then connecting furan groups.
Further, the organotin catalyst is any one of dibutyltin dilaurate, stannous octoate or dibutyltin diacetate; the diisocyanate main curing agent is any one of toluene-2, 4-diisocyanate or diphenylmethane-4, 4' -diisocyanate; the bismaleimide auxiliary curing agent is N, N' -m-phenylene bismaleimide; the organic solvent is any one of acetone or tetrahydrofuran.
Further, the preparation method of the furan modified silicone oil specifically comprises the following steps:
step A: adding hydrogen-containing silicone oil and 1, 3-diglycidyl ether glycerin into toluene, stirring uniformly, introducing nitrogen for protection, adding an accelerator for mixing, raising the temperature of a reaction system to 80-95 ℃, stirring for 12-18h, and distilling under reduced pressure to remove a solvent after the reaction is finished to obtain epoxy-terminated silicone oil;
and (B) step (B): adding epoxy end-capped silicone oil into toluene, stirring, adding 2-furanmethanamine into the system, stirring uniformly, introducing nitrogen for protection, stirring for 4-8h at 60-75 ℃, after the reaction is finished, distilling under reduced pressure to remove the solvent, and discharging to obtain furan modified silicone oil.
Further, in the step A, the hydrogen content of the terminal hydrogen-containing silicone oil is 0.05-0.07%.
Further, in step a, the promoter is trifluoroacetic acid.
Through the technical scheme, under the catalysis of trifluoroacetic acid, a silicon hydrogen bond at the tail end of a molecular chain of hydrogen-containing silicone oil can react with hydroxyl in a 1, 3-diglycidyl ether glycerol molecule to obtain epoxy end-capped silicone oil with four equivalent epoxy groups at the tail end of the molecular chain, the 2-furanmethanamine structure contains active amino groups, ring-opening addition reaction can be carried out on the epoxy end-capped silicone oil with the epoxy groups at the tail end of the molecular chain of the epoxy end-capped silicone oil, the furanyl groups are introduced into the silicone oil structure, and meanwhile, the ring-opening reaction also generates corresponding active hydroxyl groups to obtain furan modified silicone oil.
Further, the preparation method of the hydrophobic nano silicon dioxide specifically comprises the following steps:
step I: dispersing nano silicon dioxide in anhydrous toluene by ultrasonic, adding toluene-2, 4-diisocyanate, mixing uniformly, raising the temperature to 70-85 ℃, stirring for 4-6 hours, naturally cooling the materials, centrifugally separating to obtain a solid sample, and washing and drying to obtain modified nano silicon dioxide;
step II: mixing the modified nano silicon dioxide with 1, 4-dioxane, adding furfuryl alcohol and a catalyst after ultrasonic treatment for 20-30min, stirring and uniformly mixing, placing the system in a temperature environment of 55-60 ℃ for stirring for 6-12h, discharging after the materials are cooled, and obtaining the hydrophobic nano silicon dioxide through centrifugation, washing and vacuum drying processes.
Further, in the step I, the particle size of the nano silicon dioxide is less than 50nm.
Further, in the step II, the mass ratio of the modified nano silicon dioxide to the furfuryl alcohol is 10:0.5-1.5.
Further, in the step II, the catalyst is dibutyl tin dilaurate.
According to the technical scheme, the surface of the nano silicon dioxide is rich in hydroxyl groups, the modified nano silicon dioxide with the surface containing isocyanate groups is obtained after toluene-2, 4-diisocyanate modification, the isocyanate groups can further react with the hydroxyl groups in the furfuryl alcohol structure under the catalysis of dibutyltin dilaurate, so that the furan groups are modified on the surface of the nano silicon dioxide, and the hydrophobic nano silicon dioxide with the surface simultaneously containing the isocyanate groups and the furan groups can be obtained by controlling the dosage of the modified nano silicon dioxide and furfuryl alcohol.
A preparation method of a composite varnish with self-cleaning function comprises the following steps:
step one: mixing furan modified silicone oil, hydrophobic nano silicon dioxide, diisocyanate main curing agent and organic solvent in parts by weight, uniformly stirring, adding organic tin catalyst in parts by weight, placing the system in a temperature environment of 50-55 ℃, stirring for 2-4h, and cooling the materials to room temperature to obtain a prepolymer;
step two: and pouring the bismaleimide auxiliary curing agent in parts by weight into the prepolymer, and uniformly stirring and mixing to obtain the composite varnish.
According to the technical scheme, as the furan modified silicone oil structure contains active hydroxyl groups and the surface of the hydrophobic nano silicon dioxide contains active isocyanate groups, diisocyanate curing agents can be used, urethanization reaction can be carried out between the furan modified silicone oil structure and the hydrophobic nano silicon dioxide under the action of an organotin catalyst, and the furan modified silicone oil and the hydrophobic nano silicon dioxide are gradually crosslinked to form a prepolymer, meanwhile, since the furan modified silicone oil and the hydrophobic nano silicon dioxide both contain furan groups, bismaleimide can be used as an auxiliary curing agent, and in the varnish curing process, reversible DA cycloaddition reaction can be carried out between the furan modified silicone oil and the furan groups, so that the further curing effect is achieved.
The invention has the beneficial effects that:
(1) According to the invention, the furan modified silicone oil and the hydrophobic nano silicon dioxide are prepared, and the cross-linked product with a special three-dimensional network structure generated by cross-linking reaction is used as a main film forming substance of the composite varnish, and the nano silicon dioxide can be uniformly dispersed in a composite varnish matrix due to chemical bond connection, so that the negative influence caused by agglomeration of the nano silicon dioxide is avoided. Because the silicone oil molecular chain has lower surface energy, the composite varnish can show good hydrophobic property, and the film forming substance has a three-dimensional network structure, so that the powder structure formed by curing the composite varnish has very high surface tension, cohesion and compactness, and water molecules are difficult to approach the surface of the composite varnish and penetrate into the coating, thereby generating stronger hydrophobic self-cleaning effect.
(2) The main film forming substance in the composite varnish prepared by the invention contains hydrophobic nano silicon dioxide which has a coating structure, and the outer layer is organic matter, so that the composite varnish has good hydrophobicity, the tension of water on the surface of the composite varnish is reduced, a good hydrophobic effect is generated, the roughness of the surface of the varnish can be improved by the nano silicon dioxide, the abrasion resistance of the composite varnish is improved, the nano silicon dioxide exists in the film forming substance in a cross-linked framework core mode, the composite varnish has higher hardness, and the phenomenon of serious scratch caused by slight scraping is avoided.
(3) The composite varnish prepared by the invention also contains the bismaleimide auxiliary curing agent, when the composite varnish generates scratches, molecular chains of the film forming substances are broken, as the furan modified silicone oil and the hydrophobic nano silicon dioxide both contain furan groups, reversible DA cycloaddition reaction can be generated at the scratches by heating the parts of the scratches, and the molecular chains of the film forming substances are reconnected, so that the self-repairing effect is realized, and the problem that dirt at the scratches is easy to remain, and the hydrophobic self-cleaning effect of the composite varnish is lost is avoided.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in the following examples, and it is apparent that the described examples are only some of the examples of the present invention, but not all of the examples. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The composite varnish with the self-cleaning function comprises the following raw materials in parts by weight: 50 parts of furan modified silicone oil, 1 part of hydrophobic nano silicon dioxide, 0.5 part of dibutyl tin dilaurate catalyst, 10 parts of toluene-2, 4-diisocyanate main curing agent, 5 parts of N, N' -m-phenylene bismaleimide auxiliary curing agent and 10 parts of organic solvent acetone;
the preparation method of the composite varnish comprises the following steps:
step one: mixing furan modified silicone oil, hydrophobic nano silicon dioxide, toluene-2, 4-diisocyanate main curing agent and organic solvent acetone in parts by weight, uniformly stirring, adding dibutyl tin dilaurate catalyst in parts by weight, placing the system in a temperature environment of 50 ℃, stirring for 2 hours, and cooling the materials to room temperature to obtain a prepolymer;
step two: and pouring the N, N' -m-phenylene bismaleimide auxiliary curing agent in parts by weight into the prepolymer, and uniformly stirring and mixing to obtain the composite varnish.
The preparation method of the furan modified silicone oil specifically comprises the following steps:
step A: adding 10g of terminal hydrogen-containing silicone oil and 1.2g of 1, 3-diglycidyl ether glycerin into toluene, uniformly stirring, introducing nitrogen for protection, adding 0.01g of trifluoroacetic acid for mixing, raising the temperature of a reaction system to 95 ℃, stirring for 16 hours, and distilling under reduced pressure to remove a solvent after the reaction is finished to obtain epoxy-terminated silicone oil, wherein the molecular weight of the terminal hydrogen-containing silicone oil is 4000, and the hydrogen content is 0.05%;
accurately weighing 0.2g of epoxy end-capped silicone oil sample, testing the epoxy value of the sample by adopting a hydrochloric acid-acetone method with reference to national standard GB/T1677-2008, and testing the epoxy value of the sample to 1.621mmol/g.
And (B) step (B): adding 5g of epoxy end-capped silicone oil into toluene, stirring uniformly, adding 0.5g of 2-furanmethanamine into the system, mixing uniformly, introducing nitrogen for protection, stirring for 6 hours at the temperature of 65 ℃, after the reaction is finished, distilling under reduced pressure to remove the solvent, and discharging to obtain the furan modified silicone oil.
The epoxy value of a sample of 0.2g furan-modified silicone oil is tested by the hydrochloric acid-acetone method, and the epoxy value of the sample is 0.105mmol/g through the test, because the epoxy group of the epoxy-terminated silicone oil reacts with the amino group of 2-furanmethylamine, and a large amount of epoxy groups are consumed.
The preparation method of the hydrophobic nano silicon dioxide specifically comprises the following steps:
step I: dispersing 5g of nano silicon dioxide in anhydrous toluene by ultrasonic, adding 12g of toluene-2, 4-diisocyanate, uniformly mixing, raising the temperature to 75 ℃, stirring for 5 hours, naturally cooling the materials, centrifugally separating to obtain a solid sample, and washing and drying to obtain modified nano silicon dioxide; wherein the particle size of the nano silicon dioxide is less than 50nm;
accurately weighing 0.3g of modified nano silicon dioxide sample, testing the isocyanate mass fraction of the sample by using an acetone-di-n-butylamine titration method, wherein the isocyanate mass fraction of the sample is 16.82% after the test.
Step II: mixing 2g of modified nano silicon dioxide with 1, 4-dioxane, adding 0.1g of furfuryl alcohol and dibutyltin dilaurate after ultrasonic treatment for 30min, stirring and mixing uniformly, placing the system in a temperature environment of 60 ℃ for stirring for 8h, discharging after the materials are cooled, and obtaining the hydrophobic nano silicon dioxide through centrifugation, washing and vacuum drying processes.
Accurately weighing 0.3g of hydrophobic nano silicon dioxide sample, and testing the isocyanate mass fraction of the sample again by using an acetone-di-n-butylamine titration method, wherein the isocyanate mass fraction of the sample is 3.57% by test, and the isocyanate group on the surface of the modified nano silicon dioxide reacts with furfuryl alcohol, so that the isocyanate group is consumed.
Example 2
The composite varnish with the self-cleaning function comprises the following raw materials in parts by weight: 55 parts of furan modified silicone oil, 2 parts of hydrophobic nano silicon dioxide, 1 part of stannous octoate catalyst, 15 parts of diphenylmethane-4, 4 '-diisocyanate main curing agent, 6 parts of N, N' -m-phenylene bismaleimide auxiliary curing agent and 12 parts of organic solvent tetrahydrofuran;
the preparation method of the composite varnish comprises the following steps:
step one: mixing furan modified silicone oil, hydrophobic nano silicon dioxide, diphenylmethane-4, 4' -diisocyanate main curing agent and tetrahydrofuran as an organic solvent, uniformly stirring, adding stannous octoate catalyst in parts by weight, placing the system in a temperature environment of 55 ℃, stirring for 3 hours, and cooling the materials to room temperature to obtain a prepolymer;
step two: and pouring the N, N' -m-phenylene bismaleimide auxiliary curing agent in parts by weight into the prepolymer, and uniformly stirring and mixing to obtain the composite varnish.
Wherein the preparation method of furan modified silicone oil and hydrophobic nano-silica is the same as in example 1.
Example 3
The composite varnish with the self-cleaning function comprises the following raw materials in parts by weight: 60 parts of furan modified silicone oil, 2 parts of hydrophobic nano silicon dioxide, 2 parts of dibutyltin diacetate catalyst, 25 parts of toluene-2, 4-diisocyanate main curing agent, 10 parts of N, N' -m-phenylene bismaleimide auxiliary curing agent and 15 parts of organic solvent tetrahydrofuran;
the preparation method of the composite varnish comprises the following steps:
step one: mixing furan modified silicone oil, hydrophobic nano silicon dioxide, toluene-2, 4-diisocyanate main curing agent and tetrahydrofuran as an organic solvent, uniformly stirring, adding dibutyltin diacetate catalyst in the weight part, placing the system in a temperature environment of 55 ℃, stirring for 4 hours, and cooling the materials to room temperature to obtain a prepolymer;
step two: and pouring the N, N' -m-phenylene bismaleimide auxiliary curing agent in parts by weight into the prepolymer, and uniformly stirring and mixing to obtain the composite varnish.
Wherein the preparation method of furan modified silicone oil and hydrophobic nano-silica is the same as in example 1.
Comparative example 1
The composite varnish with the self-cleaning function comprises the following raw materials in parts by weight: 55 parts of furan modified silicone oil, 2 parts of hydrophobic nano silicon dioxide, 1 part of stannous octoate catalyst, 15 parts of diphenylmethane-4, 4' -diisocyanate main curing agent and 12 parts of organic solvent tetrahydrofuran;
the preparation method of the composite varnish specifically comprises the following steps:
mixing furan modified silicone oil, hydrophobic nano silicon dioxide, diphenylmethane-4, 4' -diisocyanate main curing agent and tetrahydrofuran as an organic solvent, uniformly stirring, adding stannous octoate catalyst in parts by weight, placing the system in a temperature environment of 55 ℃, stirring for 3 hours, cooling the materials to room temperature, and discharging to obtain the composite varnish.
Wherein the preparation method of furan modified silicone oil and hydrophobic nano-silica is the same as in example 1.
Comparative example 2
The composite varnish with the self-cleaning function comprises the following raw materials in parts by weight: 55 parts of furan modified silicone oil, 2 parts of nano silicon dioxide, 1 part of stannous octoate catalyst, 15 parts of diphenylmethane-4, 4' -diisocyanate main curing agent and 12 parts of organic solvent tetrahydrofuran;
the preparation method of the composite varnish specifically comprises the following steps:
mixing furan modified silicone oil, nano silicon dioxide, diphenylmethane-4, 4' -diisocyanate main curing agent and tetrahydrofuran as an organic solvent, uniformly stirring, adding stannous octoate catalyst in parts by weight, placing the system in a temperature environment of 55 ℃, stirring for 3 hours, cooling the materials to room temperature, and discharging to obtain the composite varnish.
Wherein the preparation method of the furan-modified silicone oil is the same as in example 1.
Comparative example 3
The composite varnish with the self-cleaning function comprises the following raw materials in parts by weight: 55 parts of furan modified silicone oil, 1 part of stannous octoate catalyst, 15 parts of diphenylmethane-4, 4 '-diisocyanate main curing agent, 6 parts of N, N' -m-phenylene bismaleimide auxiliary curing agent and 12 parts of organic solvent tetrahydrofuran;
the preparation method of the composite varnish comprises the following steps:
step one: mixing furan modified silicone oil, diphenylmethane-4, 4' -diisocyanate main curing agent and tetrahydrofuran as organic solvent, stirring uniformly, adding stannous octoate catalyst in weight portions, placing the system in a temperature environment of 55 ℃, stirring for 3 hours, and cooling the materials to room temperature to obtain a prepolymer;
step two: and pouring the N, N' -m-phenylene bismaleimide auxiliary curing agent in parts by weight into the prepolymer, and uniformly stirring and mixing to obtain the composite varnish.
Wherein the preparation method of the furan-modified silicone oil is the same as in example 1.
Comparative example 4
The composite varnish with the self-cleaning function comprises the following raw materials in parts by weight: 55 parts of furan modified silicone oil, 1 part of stannous octoate catalyst, 15 parts of diphenylmethane-4, 4' -diisocyanate main curing agent and 12 parts of organic solvent tetrahydrofuran;
the preparation method of the composite varnish specifically comprises the following steps:
step one: mixing furan modified silicone oil, diphenylmethane-4, 4' -diisocyanate main curing agent and tetrahydrofuran as organic solvent, stirring uniformly, adding stannous octoate catalyst in weight portions, placing the system in a temperature environment of 55 ℃, stirring for 3h, and cooling the materials to room temperature to obtain the composite varnish.
Wherein the preparation method of the furan-modified silicone oil is the same as in example 1.
Performance detection
Coating the composite varnishes prepared in the examples 1-3 and the comparative examples 1-4 on the surface of a stainless steel plate, curing for 6 hours in an oven at 80 ℃ to form a coating with the thickness of 500um, cutting the coating into samples to be tested with the specification of 5cm multiplied by 5cm, testing the water contact angle of the samples by using a Theta Flex contact angle measuring instrument, marking 20 scratches with consistent intervals on the surface of the samples by using a blade and the length of 1cm and the depth of 100um after the test is completed, placing the scratches in the oven at 60 ℃ for 4 hours, taking out the scratches, and testing the contact angle of the samples again; the abrasion resistance of a sample is tested by referring to national standard GB/T1768-2006, method for measuring abrasion resistance of color paint and varnish, rotary rubber grinding wheel method; referring to national standard GB/T6739-2006, paint film hardness is measured by the method of colored paint and varnish pencil, hardness of a sample is tested, and test results are shown in the following table:
as can be seen from the above table, the composite varnish prepared in the examples 1-3 of the invention has good hydrophobic self-cleaning performance, high wear resistance and hardness, and good hydrophobic performance after repair, so the self-repair effect is good.
The composite varnish prepared in comparative example 1 is not added with bismaleimide auxiliary curing agent, and can not realize self-repairing performance through DA reversible cycloaddition reaction, so that the water contact angle change value after repairing is larger, the self-repairing effect is poor, and other performances are good.
The composite varnish prepared in comparative example 2 uses nano silica which is not subjected to surface hydrophobic modification, and does not add bismaleimide auxiliary curing agent, so that the hydrophobic self-cleaning performance and the self-repairing effect are poor, and other performances are still available.
The composite varnish prepared in comparative example 3 does not use nano silica, so that the hydrophobicity, the wear resistance and the hardness are poor, but the self-repairing effect is good because the bismaleimide auxiliary curing agent is added.
The composite varnish prepared in comparative example 4 was not added with nano silica and bismaleimide co-curing agent, so that each performance was the worst.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (7)
1. The composite varnish with the self-cleaning function is characterized by comprising the following raw materials in parts by weight: 50-60 parts of furan modified silicone oil, 1-2 parts of hydrophobic nano silicon dioxide, 0.5-2 parts of organic tin catalyst, 10-25 parts of diisocyanate main curing agent, 5-10 parts of bismaleimide auxiliary curing agent and 10-15 parts of organic solvent;
the furan modified silicone oil is prepared by introducing furan groups at the tail end of a molecular chain of the terminal hydrogen-containing silicone oil;
the preparation method of the furan modified silicone oil specifically comprises the following steps:
step A: adding hydrogen-containing silicone oil and 1, 3-diglycidyl ether glycerin into toluene, stirring uniformly, introducing nitrogen for protection, adding an accelerator for mixing, raising the temperature of a reaction system to 80-95 ℃, stirring for 12-18h, and distilling under reduced pressure to remove a solvent after the reaction is finished to obtain epoxy-terminated silicone oil;
and (B) step (B): adding epoxy end-capped silicone oil into toluene, stirring, adding 2-furanmethanamine into the system, stirring uniformly, introducing nitrogen for protection, stirring for 4-8 hours at the temperature of 60-75 ℃, after the reaction is finished, distilling under reduced pressure to remove the solvent, and discharging to obtain furan modified silicone oil;
the hydrophobic nano silicon dioxide is prepared by carrying out surface modification on the nano silicon dioxide and then connecting furan groups;
the preparation method of the hydrophobic nano silicon dioxide specifically comprises the following steps:
step I: dispersing nano silicon dioxide in anhydrous toluene by ultrasonic, adding toluene-2, 4-diisocyanate, mixing uniformly, raising the temperature to 70-85 ℃, stirring for 4-6 hours, naturally cooling the materials, centrifugally separating to obtain a solid sample, and washing and drying to obtain modified nano silicon dioxide;
step II: mixing the modified nano silicon dioxide with 1, 4-dioxane, adding furfuryl alcohol and a catalyst after ultrasonic treatment for 20-30min, stirring and uniformly mixing, placing the system in a temperature environment of 55-60 ℃ for stirring for 6-12h, discharging after the materials are cooled, and obtaining hydrophobic nano silicon dioxide through centrifugation, washing and vacuum drying processes;
the mass ratio of the modified nano silicon dioxide to the furfuryl alcohol is 10:0.5-1.5.
2. The composite varnish with self-cleaning function according to claim 1, wherein the organotin catalyst is any one of dibutyltin dilaurate, stannous octoate or dibutyltin diacetate; the diisocyanate main curing agent is any one of toluene-2, 4-diisocyanate or diphenylmethane-4, 4' -diisocyanate; the bismaleimide auxiliary curing agent is N, N' -m-phenylene bismaleimide; the organic solvent is any one of acetone or tetrahydrofuran.
3. The composite varnish with self-cleaning function according to claim 1, wherein in the step A, the hydrogen content of the terminal hydrogen-containing silicone oil is 0.05 to 0.07%.
4. A composite varnish with self-cleaning function according to claim 1, wherein in step a, the accelerator is trifluoroacetic acid.
5. A composite varnish with self-cleaning function according to claim 1, characterized in that in step i the nanosilica has a particle size < 50nm.
6. The composite varnish with self-cleaning function according to claim 1, wherein in the step II, the catalyst is dibutyl tin dilaurate.
7. A method for preparing a composite varnish with self-cleaning function according to claim 1, wherein the preparation method comprises the following steps:
step one: mixing furan modified silicone oil, hydrophobic nano silicon dioxide, diisocyanate main curing agent and organic solvent in parts by weight, uniformly stirring, adding organic tin catalyst in parts by weight, placing the system in a temperature environment of 50-55 ℃, stirring for 2-4h, and cooling the materials to room temperature to obtain a prepolymer;
step two: and pouring the bismaleimide auxiliary curing agent in parts by weight into the prepolymer, and uniformly stirring and mixing to obtain the composite varnish.
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