CN113214731A - Durable plant oil-based anti-graffiti easy-to-clean coating and preparation method and application thereof - Google Patents
Durable plant oil-based anti-graffiti easy-to-clean coating and preparation method and application thereof Download PDFInfo
- Publication number
- CN113214731A CN113214731A CN202110455161.XA CN202110455161A CN113214731A CN 113214731 A CN113214731 A CN 113214731A CN 202110455161 A CN202110455161 A CN 202110455161A CN 113214731 A CN113214731 A CN 113214731A
- Authority
- CN
- China
- Prior art keywords
- coating
- vegetable oil
- graffiti
- easy
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000006119 easy-to-clean coating Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000010773 plant oil Substances 0.000 title description 2
- 238000000576 coating method Methods 0.000 claims abstract description 70
- 239000011248 coating agent Substances 0.000 claims abstract description 65
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 60
- 239000008158 vegetable oil Substances 0.000 claims abstract description 60
- 229920005862 polyol Polymers 0.000 claims abstract description 36
- 150000003077 polyols Chemical class 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003208 petroleum Substances 0.000 claims abstract description 7
- 239000011521 glass Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000003085 diluting agent Substances 0.000 claims description 11
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 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 6
- 239000012975 dibutyltin dilaurate 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 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 16
- 238000004140 cleaning Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 10
- 239000004205 dimethyl polysiloxane Substances 0.000 abstract description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 abstract description 9
- 239000004359 castor oil Substances 0.000 abstract description 6
- 235000019438 castor oil Nutrition 0.000 abstract description 6
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 5
- -1 polydimethylsiloxane Polymers 0.000 abstract description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 3
- 230000002940 repellent Effects 0.000 abstract description 3
- 239000005871 repellent Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229920006150 hyperbranched polyester Polymers 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 5
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 5
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 241000208720 Nepenthes Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of high polymer coatings, and discloses a durable vegetable oil-based anti-graffiti easy-to-clean coating, and a preparation method and application thereof. According to the invention, the renewable castor oil is used as a core to react with the 2, 2-bis-hydroxymethyl propionic acid to obtain the polyol with the hyperbranched structure, and the vegetable oil-based hyperbranched polyol replaces the traditional petroleum-based polyol, so that the biomass content of the material can be greatly increased, the crosslinking density of the coating can be increased, and the coating is ensured to have higher hardness and good wear resistance. The polydimethylsiloxane with low surface energy is introduced in a covalent bond combination mode, and the long chain of the polydimethylsiloxane spontaneously migrates to the surface of the coating in the curing process, so that the coating is endowed with excellent liquid repellent property and self-cleaning property. The oily ink is rapidly contracted into fine liquid drops on the surface of the coating, and the fine liquid drops can be easily wiped off by a paper towel.
Description
Technical Field
The invention belongs to the technical field of high polymer coatings, and particularly relates to a durable vegetable oil-based anti-graffiti easy-to-clean coating, and a preparation method and application thereof.
Background
Anti-graffiti, easy-to-clean coatings generally have a low surface energy, and aqueous and oily stain droplets are difficult to spread on their surface. At a certain inclination angle, the stain liquid drops can automatically roll off or slide off from the surface of the paint without leaving a pollution mark, and the function of keeping the surface of an object clean is achieved. The anti-graffiti and easy-to-clean coating surface has excellent liquid repellency and self-cleaning capability and is difficult to stain by pollutants, so that the anti-graffiti and easy-to-clean coating surface is applied to the surfaces of glass curtain walls of skyscrapers, solar cell panels, metal substrates, inner walls of petroleum pipelines, displays, kitchen appliances, public facilities and the like, plays roles in preventing fouling, resisting graffiti, self-cleaning and water-resisting protection, and has extremely high practicability and development prospect.
Generally, the methods for preparing low surface energy, hydrophobic, oleophobic coatings fall largely into two methods. One is to combine low surface energy substances to prepare a layered structure with micro/nano scale, and the inspiration is from the surface morphology of lotus leaves (ACS Applied Materials & interfaces.2014,6: 2629-. Contact angles of various liquids on the surface of such coatings can be as high as 150 °. However, the micro-nano structure is fragile, and the adhesion between the low surface energy component and the base material is poor, so that the long-term wear resistance of the composite material is poor. In addition, low transparency, complex manufacturing processes, and expensive materials limit the large-scale application of such coatings. The second method is to simulate the sliding function of the nepenthes labial structure to prepare a liquid-impregnated porous surface (SLIPS) by impregnating a lubricating oil such as a perfluoro liquid, a silicone oil or an ionic liquid into a substrate containing a porous or graded coarse structure which has been constructed in advance (Chemical Engineering journal.2020,401: 126137). On the SLIPS surface, the contact angle of the liquid may not be high, usually less than 120 °, but most liquids have a very low sliding angle on their surface, achieving liquid repellent, self-cleaning effects. However, SLIPS also has disadvantages, such as the lubricant on the surface evaporating or being dissolved and lost, leading to a drastic reduction in its antifouling effect. In addition, most low surface energy materials currently in use are specially tailored organofluorine-based lubricants, which are expensive and biohazardous to humans and the environment.
Disclosure of Invention
In order to overcome the defects of the existing anti-graffiti and easy-to-clean coating system, the invention mainly aims to provide the durable vegetable oil-based anti-graffiti and easy-to-clean coating. The vegetable oil-based hyperbranched polyol with a high hydroxyl value is adopted to replace the traditional petroleum-based polyol so as to improve the biomass content of the coating, prepare the smooth and transparent polyurethane anti-graffiti and easy-to-clean coating, and introduce the monohydroxy terminated polydimethylsiloxane (PDMS-OH) into the coating in a covalent bond combination mode to form a low surface energy substance, so that the coating has excellent anti-graffiti and easy-to-clean performances. Due to the fact that the hyperbranched polyol provides a large number of crosslinking sites and PDMS long chains introduced by covalent bonds, the coating is endowed with high crosslinking density and wear resistance. The material does not contain easily-yellowing polyol and isocyanate components, so that the durability of the coating is ensured.
The invention further aims to provide a preparation method of the durable vegetable oil-based anti-graffiti easy-to-clean coating.
Still another object of the present invention is to provide the use of the durable vegetable oil-based graffiti resistant, easy-to-clean coating described above. The coating has excellent optical transparency, hardness, wear resistance and durability, and also has good scrawling resistance and self-cleaning property.
The purpose of the invention is realized by the following technical scheme:
a durable vegetable oil-based anti-graffiti easy-to-clean coating is used as a functional coating, and the coating is prepared from the following components in a mass ratio of 1:1, component A and component B;
wherein the component A comprises the following components in parts by mass:
100.0 parts of vegetable oil-based polyol
170.0 parts of diluent
The component B comprises the following components in parts by mass:
the vegetable oil-based polyol has a structural formula shown as a formula (I):
wherein,
the diluent is at least one of N, N-Dimethylformamide (DMF) and N, N-Dimethylacetamide (DMAC);
the solvent is at least one of Methyl Ethyl Ketone (MEK), methyl isobutyl ketone (MBIK) and dimethyl carbonate (DMC);
the catalyst is one of dibutyltin dilaurate (DBTDL) and triethylene diamine (TEDA).
The preparation method of the durable vegetable oil-based anti-graffiti easy-to-clean coating as the functional coating comprises the following operation steps:
dissolving vegetable oil-based polyalcohol in a diluent to obtain a component A; uniformly mixing PDMS-OH, a solvent, an HDI trimer and a catalyst, sealing, and heating to 80 ℃ for 1h to obtain a component B; the component A and the component B are mixed according to the mass ratio of 1:1, uniformly mixing to obtain the durable vegetable oil-based anti-graffiti easy-to-clean coating.
The durable vegetable oil-based anti-graffiti, easy-to-clean coating is applied as a functional coating on the surfaces of glass curtain walls of skyscrapers, solar cell panels, metal substrates, inner walls of petroleum pipelines, displays, kitchen appliances and public facilities.
The application comprises the following steps: the coating is manually coated or machine sprayed on glass, metal, stone and wood substrates and is cured for 2 hours at the temperature of 80 ℃ to obtain the durable vegetable oil-based anti-graffiti and easy-to-clean coating.
The vegetable oil-based hyperbranched polyol is prepared by the following method:
adding 0.01moL of Castor Oil (CO) and a proper amount of catalyst P-TSA into a four-neck flask with a mechanical stirring paddle, a drying tube, a condensing tube, a nitrogen inlet and a water separator; heating the mixture to 145 ℃ in a constant-temperature oil bath kettle, adding 0.027moL of 2, 2-bis (hydroxymethyl) propionic acid (DMPA), reacting for 2 hours under the protection of continuous nitrogen, stopping introducing nitrogen, and vacuumizing to 800-1000 Pa to react for 1 hour; then adding 0.054moL of DMPA for 2 times at intervals of 30min every time, continuously introducing nitrogen for reaction for 2 hours, vacuumizing to 800-1000 Pa, and stopping reaction until the acid value is less than 10mg of KOH/g; after cooling, the vegetable oil-based hyperbranched polyol with the hydroxyl value of 315 +/-10 mg KOH/g is obtained.
The reaction principle for preparing the durable vegetable oil-based anti-graffiti easy-to-clean coating is as follows:
firstly, performing melt polycondensation reaction on castor oil and 2, 2-bis (hydroxymethyl) propionic acid to obtain hyperbranched polyol, and dissolving the hyperbranched polyol in a solvent to obtain a vegetable oil-based polyol component solution. Secondly, uniformly mixing the single hydroxyl end-blocked polydimethylsiloxane (PDMS-OH), the catalyst and the HDI trimer (HDIT) curing agent, sealing, and heating to 80 ℃ for 1h to obtain a curing agent component solution. And finally, uniformly mixing the vegetable oil-based polyol component solution and the curing agent component solution, manually coating or spraying the mixture on the surface of the base material, and curing for 2 hours at the temperature of 80 ℃ to obtain the smooth and transparent durable vegetable oil-based polyurethane graffiti-resistant easy-to-clean coating. The hyperbranched polyol and the isocyanate groups in the HDIT react during curing to form a highly crosslinked polymer film. Due to the low surface energy property of PDMS, the PDMS long chain can automatically migrate and be enriched to the surface of the coating in the curing process, so that the discharged material has the low surface energy property, and the effects of graffiti resistance and easiness in cleaning are achieved. Furthermore, since the surface roughness of the formed coating is extremely low (much less than the wavelength of visible light), the coating has little influence on light transmittance, and thus the coating has extremely high optical transparency.
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention obtains the polyol with the hyperbranched structure by using the renewable castor oil as the core and reacting with the 2, 2-bis-hydroxymethyl propionic acid, and the biomass content of the material can be greatly improved by using the vegetable oil-based hyperbranched polyol to replace the traditional petroleum-based polyol.
(2) The vegetable oil-based hyperbranched polyol is used as the polyol component of the coating, so that a large number of crosslinking sites are provided for improving the crosslinking density of the polyurethane coating, and the wear resistance, durability and anti-graffiti capability of the coating are improved.
(3) According to the invention, PDMS-OH with low surface energy is introduced in a covalent bond combination mode, and a PDMS long chain can spontaneously migrate and be enriched to the surface of the coating in the curing process, so that the coating is endowed with excellent liquid repellent property and self-cleaning property.
(4) The durable vegetable oil-based anti-graffiti easy-to-clean coating agent can be used as a functional coating applied to the surfaces of glass curtain walls of skyscrapers, solar cell panels, metal substrates, inner walls of petroleum pipelines, displays, kitchen appliances, public facilities and the like, and plays roles in preventing fouling, resisting graffiti, self-cleaning and water-resisting protection. The surface of the coating is smooth after being cured, the transparency is more than 95 percent, the pencil hardness can reach 3H, and the flexibility can reach 2 mm; the oil Mark pen ink automatically shrinks into fine liquid drops on the surface of the coating, and can be easily erased by a paper towel; the water drops and the n-hexadecane drops automatically slide on the inclined coating surface without leaving a mark of pollution; in addition, the dust can be easily taken away by water drops on the surface of the coating, the effect of keeping the surface of an object clean is achieved, and the coating has a good application prospect.
Drawings
FIG. 1 is a schematic synthesis of a vegetable oil-based hyperbranched polyol;
FIG. 2 is a schematic illustration of the preparation of a durable vegetable oil-based anti-graffiti, easy-to-clean coating;
FIG. 3 is an AFM image of the coating surface of example 2;
FIG. 4 is an XPS plot of the coating surface of example 2;
FIG. 5 is a test of the anti-graffiti performance of the glass slide, example 1 and example 2 coating surfaces;
FIG. 6 shows the self-cleaning performance of the coating of example 2 after film formation on stainless steel sheets.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The raw materials selected by the invention can be purchased from commercial sources, wherein the molecular weight of PDMS-OH is 3.0 kDa.
Example 1
(1) Synthesizing vegetable oil-based hyperbranched polyester polyol: CO (0.01moL) and catalyst P-TSA (0.1g) were charged to a four-necked flask equipped with a mechanical stirring blade, drying tube, condenser tube, nitrogen inlet, water separator. Heating the oil bath kettle to 145 ℃, adding DMPA (0.027moL), reacting for 2 hours under the protection of continuous nitrogen, stopping introducing nitrogen, and vacuumizing to 800-1000 Pa for reacting for 1 hour; and then adding DMPA (0.054moL) for 2 times at intervals of 30min every time, continuously introducing nitrogen to react for 2 hours, vacuumizing to 800-1000 Pa, stopping the reaction until the acid value is less than 10mg KOH/g, and cooling to obtain the vegetable oil-based hyperbranched polyol with the hydroxyl value of 315 +/-10 mg KOH/g. The synthetic schematic diagram of the vegetable oil-based hyperbranched polyester polyol is shown in figure 1.
(2) The preparation method of the component A of the vegetable oil-based anti-graffiti easy-to-clean coating comprises the following steps: weighing 100.0g of vegetable oil-based polyol and 170.0g of diluent DMF, and uniformly mixing in a stirrer to obtain a component A;
(3) preparation of the component B: 100.0g of HDIT, 77.6g of mixed solvent (m) were weighed outMEK：mDMC1: 3) and 0.26g DBTDL in a stirrer to obtain a component B;
(4) the component A and the component B are mixed according to the mass ratio of 1:1 mixing to obtain the coating.
Example 2
(1) Synthesizing vegetable oil-based hyperbranched polyester polyol: the same as example 1;
(2) the preparation method of the component A of the vegetable oil-based anti-graffiti easy-to-clean coating comprises the following steps: weighing 100.0g of the vegetable oil-based polyol obtained in the step (1) and 170.0g of diluent DMF, and uniformly mixing in a stirrer to obtain a component A;
(3) preparation of the component B: 100.0g of HDIT, 77.6g of mixed solvent (m) were weighed outMEK：mDMC＝1：3)，0.083g of PDMS-OH and 0.26g of DBTDL are uniformly mixed in a stirrer and react for 1 hour in a closed way at the temperature of 80 ℃ to obtain a component B;
(4) the component A and the component B are mixed according to the mass ratio of 1:1, obtaining the durable vegetable oil-based anti-graffiti easy-to-clean coating. The paint preparation is schematically shown in FIG. 2.
Example 3
(1) Synthesizing vegetable oil-based hyperbranched polyester polyol: the same as example 1;
(2) the preparation method of the component A of the vegetable oil-based anti-graffiti easy-to-clean coating comprises the following steps: weighing 100.0g of vegetable oil-based polyol and 170.0g of diluent DMF, and uniformly mixing in a stirrer to obtain a component A;
(3) preparation of the component B: 100.0g of HDIT, 77.6g of mixed solvent (m) were weighed outMEK：mDMC1: 3) 0.166g of PDMS-OH and 0.26g of DBTDL are uniformly mixed in a stirrer and react for 1 hour in a closed manner at the temperature of 80 ℃ to obtain a component B;
(4) the component A and the component B are mixed according to the mass ratio of 1:1, obtaining the durable vegetable oil-based anti-graffiti easy-to-clean coating.
Example 4
(1) Synthesizing vegetable oil-based hyperbranched polyester polyol: the same as example 1;
(2) the preparation method of the component A of the vegetable oil-based anti-graffiti easy-to-clean coating comprises the following steps: weighing 100.0g of vegetable oil-based polyol and 170.0g of diluent DMAC, and uniformly mixing in a stirrer to obtain a component A;
(3) preparation of the component B: 100.0g of HDIT, 77.6g of mixed solvent (m) were weighed outMBIK：mDMC1: 3) 0.332g of PDMS-OH and 0.26g of TEDA are uniformly mixed in a stirrer and react for 1 hour in a closed manner at the temperature of 80 ℃ to obtain a component B;
(4) the component A and the component B are mixed according to the mass ratio of 1:1, obtaining the durable vegetable oil-based anti-graffiti easy-to-clean coating.
Example 5
(1) Synthesizing vegetable oil-based hyperbranched polyester polyol: the same as example 1;
(2) the preparation method of the component A of the vegetable oil-based anti-graffiti easy-to-clean coating comprises the following steps: weighing 100.0g of vegetable oil-based polyol and 170.0g of diluent DMAC, and uniformly mixing in a stirrer to obtain a component A;
(3) preparation of group B: 100.0g of HDIT, 77.6g of mixed solvent (m) were weighed outMBIK：mDMC1: 3) 0.498g of PDMS-OH and 0.26g of TEDA are mixed uniformly in a stirrer and react for 1 hour in a closed manner at the temperature of 80 ℃ to obtain a component B;
(4) the component A and the component B are mixed according to the mass ratio of 1:1, obtaining the durable vegetable oil-based anti-graffiti easy-to-clean coating.
Effects of the embodiment
The durable vegetable oil-based anti-graffiti and easy-to-clean coating prepared in the embodiment 1-5 and the coating prepared in the comparative example are manually coated or sprayed on substrates such as glass, metal, stone, wood and the like by a machine, cured for 2 hours at the temperature of 80 ℃, cooled to room temperature to obtain a coating, and then a performance test can be carried out.
And (3) testing pencil hardness: according to ASTM 3363; and (3) testing the adhesive force: according to the ASTM 3359 standard, the grade is judged according to the area proportion of the coating falling off from the base material, and the total grade is 0-5B, wherein 5B is the optimal grade, and 0B is the worst grade; light transmittance test of the coating: testing the transmittance of the curing film in the range of 300-600nm by using a UV-2550 ultraviolet visible spectrometer, reading the transmittance value at 500nm, wherein the thickness of all the films is 75 +/-5 mu m, and the glass slide is used as a reference; flexibility test: testing by a paint film cylindrical bending tester according to the ASTM D522 standard; contact angle and sliding angle test: the test was carried out using a contact angle tester (JC2000D2) at room temperature, except that the sliding angle test with water used 40. mu.L droplets, and the other tests used 5. mu.L droplets, the experimental values being the average of 5 replicates; and (3) carrying out scrawling resistance test: the paint is scratched on the surface of a coating by adopting a morning gloss plate oil-based mark pen, the shrinkage condition of ink marks on the surface of the coating is observed, the ink marks shrink into fine liquid drops and can be erased by a paper towel without leaving marks, so that the mark is good, and the mark is poor when the ink marks do not shrink or shrink slightly but cannot be erased by the paper towel; and (3) wear resistance test: the ink is rubbed for 1000 cycles, the shrinkage of the oil Mark pen ink on the coating surface is observed, if the ink shrinks sharply, the ink can be erased by a paper towel without leaving marks, the ink is recorded as good, and if the ink does not shrink or shrinks only slightly, but cannot be erased by the paper towel, the ink is recorded as bad. Self-cleaning performance test: spraying rhodamine B powder on the surface of a stainless steel sheet sample with a coating, wherein the inclination of the surface is 35 degrees, sucking water and hexadecane by using a 3mL plastic suction pipe respectively, and marking the sample as good if the powder on the steel sheet can be cleaned and taken away by liquid drops, and marking the sample as poor if a large amount of powder cannot be cleaned. The results of the test are shown in Table 1.
TABLE 1 Performance test results for durable vegetable oil-based anti-graffiti, easy-to-clean coatings
Note: in the comparative example, the sliding angle cannot be measured by spreading n-hexadecane on the surface of the coating, and the abrasion resistance cannot be measured because it does not have the anti-graffiti property.
As can be seen from the data in Table 1, the durable vegetable oil-based graffiti-resistant easy-to-clean coating prepared by the method disclosed by the invention has excellent optical transmittance (more than 95%), pencil hardness of 3H, adhesive force of 5B grade, water contact angle of up to 105.6 degrees, water and n-hexadecane liquid drops can slide off at a lower inclination angle on the surface of the coating, and the coating also has good wear resistance, graffiti resistance and self-cleaning property.
FIG. 3 is an AFM image of the coating surface of example 2, and it can be seen from FIG. 3 that the root mean square roughness of the coating surface is only 0.446nm, which has little influence on the transmittance of visible light and ensures high transparency of the coating.
FIG. 4 is an XPS graph of the coating surface of example 2, in example 1, the mass fraction of PDMS-OH in the coating matrix is 0.5%, the content of Si element in the coating is 0.17%, and the XPS test result shows that the Si content on the coating surface is as high as 8.01%, which proves that the PDMS long chain automatically migrates and enriches to the surface during the curing process.
FIG. 5 is a test of the graffiti resistance of an oil pen on the surface of a glass slide, a comparative example and a coating of example 2. from FIG. 5 it can be seen that the coating of example 1 without PDMS-OH modification on the surface of the glass slide does not have graffiti resistance, leaves a uniform, clear mark after the oil pen is stroked, and cannot be wiped off with a paper towel; the paint in the embodiment 2 has obvious ink shrinkage capability after being coated on a glass slide, ink marks are immediately shrunk into fine liquid drops after oily strokes are passed, and the ink drops can be easily wiped off by using a paper towel, so that the paint has an excellent anti-graffiti effect.
FIG. 6 is a self-cleaning performance test of the coating of example 2 after film formation on a stainless steel sheet, and it can be seen from FIG. 6 that water-soluble rhodamine B powder can be washed clean by water and n-hexadecane droplets without obvious stains, indicating that the coating has good self-cleaning performance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. A durable vegetable oil-based anti-graffiti easy-to-clean coating is used as a functional coating, and is characterized in that: the coating is prepared from the following components in percentage by mass of 1:1, component A and component B;
wherein the component A comprises the following components in parts by mass:
100.0 parts of vegetable oil-based polyol
170.0 parts of diluent
The component B comprises the following components in parts by mass:
2. a durable vegetable oil-based anti-graffiti, easy-to-clean coating as a functional coating in accordance with claim 1, wherein:
the vegetable oil-based polyol has a structural formula shown as a formula (I):
wherein,
3. a durable vegetable oil-based anti-graffiti, easy-to-clean coating as a functional coating in accordance with claim 1, wherein:
the diluent is at least one of N, N-dimethylformamide and N, N-dimethylacetamide;
the solvent is at least one of butanone, methyl isobutyl ketone and dimethyl carbonate;
the catalyst is one of dibutyltin dilaurate and triethylene diamine.
4. The method for preparing the durable vegetable oil-based anti-graffiti easy-to-clean coating as the functional coating according to claim 1, characterized by comprising the following steps:
dissolving vegetable oil-based polyalcohol in a diluent to obtain a component A; uniformly mixing PDMS-OH, a solvent, an HDI trimer and a catalyst, sealing, and heating to 80 ℃ for 1h to obtain a component B; the component A and the component B are mixed according to the mass ratio of 1:1, uniformly mixing to obtain the durable vegetable oil-based anti-graffiti easy-to-clean coating.
5. Use of the durable vegetable oil-based anti-graffiti, easy-to-clean coating of claim 1 as a functional coating on the surfaces of glass curtain walls, solar panels, metal substrates, petroleum pipe interior walls, displays, kitchen appliances and public facilities of skyscrapers.
6. Use according to claim 5, characterized in that: the application comprises the following steps: the coating is manually coated or machine sprayed on glass, metal, stone and wood substrates and is cured for 2 hours at the temperature of 80 ℃ to obtain the durable vegetable oil-based anti-graffiti and easy-to-clean coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110455161.XA CN113214731A (en) | 2021-04-26 | 2021-04-26 | Durable plant oil-based anti-graffiti easy-to-clean coating and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110455161.XA CN113214731A (en) | 2021-04-26 | 2021-04-26 | Durable plant oil-based anti-graffiti easy-to-clean coating and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113214731A true CN113214731A (en) | 2021-08-06 |
Family
ID=77089159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110455161.XA Withdrawn CN113214731A (en) | 2021-04-26 | 2021-04-26 | Durable plant oil-based anti-graffiti easy-to-clean coating and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113214731A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124920A (en) * | 2022-08-05 | 2022-09-30 | 之江实验室 | Transparent self-repairing anti-contamination polyurethane coating and preparation method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1160613B (en) * | 1961-02-23 | 1964-01-02 | Mobay Chemical Corp | Process for the production of foams containing urethane groups |
| DE3439319A1 (en) * | 1983-10-27 | 1985-05-15 | Toyoda Gosei Co., Ltd., Haruhimura, Aichi | RUNNING RAIL FOR MOVABLE WINDOW WINDOWS OF MOTOR VEHICLES |
| WO2006086092A2 (en) * | 2005-01-14 | 2006-08-17 | Ndsu Research Foundation | Polymeric material that forms surface microdomains |
| CN101225150A (en) * | 2008-01-28 | 2008-07-23 | 浙江大学 | Method for synthesizing water-dispersion organosilicon-polyurethane block copolymer |
| US20150086713A1 (en) * | 2013-09-23 | 2015-03-26 | Tamkang University | Non-fluoro hydrophobic aqueous-based polyurethane resin dispersion, and production method and use thereof |
| CN105218801A (en) * | 2015-09-14 | 2016-01-06 | 华南理工大学 | A kind of urethane-organic silicon modified aqueous Synolac and preparation method and application |
| CN105802479A (en) * | 2016-06-04 | 2016-07-27 | 付学勇 | Wear-resistant self-cleaning coating and preparation method and application method thereof |
| CN106397719A (en) * | 2016-10-09 | 2017-02-15 | 华南农业大学 | Castor-oil-based hyperbranched UV curable polyurethane acrylate and preparation method and application thereof |
| CN109897175A (en) * | 2019-01-28 | 2019-06-18 | 中科院广州化灌工程有限公司 | A kind of castor oil-base hyperbranched epoxy resin and its preparation method and application |
| WO2020062036A1 (en) * | 2018-09-28 | 2020-04-02 | Dow Global Technologies Llc | Polyol composition |
| CN111417692A (en) * | 2017-11-07 | 2020-07-14 | 瓦克化学股份公司 | Anti-graffiti coating compositions |
| CN112210061A (en) * | 2020-09-23 | 2021-01-12 | 长春工业大学 | Preparation method of organic silicon modified castor oil based waterborne polyurethane film |
| CN112961302A (en) * | 2021-04-20 | 2021-06-15 | 浙江清优材料科技有限公司 | High-temperature and high-humidity resistant polyurethane foam material |
| CN113105815A (en) * | 2021-03-29 | 2021-07-13 | 华南理工大学 | Wear-resistant waterborne polyurethane matting coating and preparation method and application thereof |
-
2021
- 2021-04-26 CN CN202110455161.XA patent/CN113214731A/en not_active Withdrawn
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1160613B (en) * | 1961-02-23 | 1964-01-02 | Mobay Chemical Corp | Process for the production of foams containing urethane groups |
| DE3439319A1 (en) * | 1983-10-27 | 1985-05-15 | Toyoda Gosei Co., Ltd., Haruhimura, Aichi | RUNNING RAIL FOR MOVABLE WINDOW WINDOWS OF MOTOR VEHICLES |
| WO2006086092A2 (en) * | 2005-01-14 | 2006-08-17 | Ndsu Research Foundation | Polymeric material that forms surface microdomains |
| CN101225150A (en) * | 2008-01-28 | 2008-07-23 | 浙江大学 | Method for synthesizing water-dispersion organosilicon-polyurethane block copolymer |
| US20150086713A1 (en) * | 2013-09-23 | 2015-03-26 | Tamkang University | Non-fluoro hydrophobic aqueous-based polyurethane resin dispersion, and production method and use thereof |
| CN105218801A (en) * | 2015-09-14 | 2016-01-06 | 华南理工大学 | A kind of urethane-organic silicon modified aqueous Synolac and preparation method and application |
| CN105802479A (en) * | 2016-06-04 | 2016-07-27 | 付学勇 | Wear-resistant self-cleaning coating and preparation method and application method thereof |
| CN106397719A (en) * | 2016-10-09 | 2017-02-15 | 华南农业大学 | Castor-oil-based hyperbranched UV curable polyurethane acrylate and preparation method and application thereof |
| CN111417692A (en) * | 2017-11-07 | 2020-07-14 | 瓦克化学股份公司 | Anti-graffiti coating compositions |
| WO2020062036A1 (en) * | 2018-09-28 | 2020-04-02 | Dow Global Technologies Llc | Polyol composition |
| CN109897175A (en) * | 2019-01-28 | 2019-06-18 | 中科院广州化灌工程有限公司 | A kind of castor oil-base hyperbranched epoxy resin and its preparation method and application |
| CN112210061A (en) * | 2020-09-23 | 2021-01-12 | 长春工业大学 | Preparation method of organic silicon modified castor oil based waterborne polyurethane film |
| CN113105815A (en) * | 2021-03-29 | 2021-07-13 | 华南理工大学 | Wear-resistant waterborne polyurethane matting coating and preparation method and application thereof |
| CN112961302A (en) * | 2021-04-20 | 2021-06-15 | 浙江清优材料科技有限公司 | High-temperature and high-humidity resistant polyurethane foam material |
Non-Patent Citations (3)
| Title |
|---|
| DAIDONG WEI等: ""High-Performance Bio-Based Polyurethane Antismudge Coatings"", 《ACS APPLID POLYMETR MATERIALS》 * |
| YING LIANG ET.AL: ""Bio-based omniphobic polyurethane coating providing anti-smudge and anti-corrosion protection"", 《PROGRESS IN ORGANIC COATINGS》 * |
| 钟细明: ""无氟防沾污涂层的制备、性能及应用研究"", 《中国优秀博士学位论文电子期刊工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124920A (en) * | 2022-08-05 | 2022-09-30 | 之江实验室 | Transparent self-repairing anti-contamination polyurethane coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101035460B1 (en) | Coating composition | |
| Wei et al. | High-performance bio-based polyurethane antismudge coatings using castor oil-based hyperbranched polyol as superior cross-linkers | |
| Yong et al. | Synthesis and surface analysis of self-matt coating based on waterborne polyurethane resin and study on the matt mechanism | |
| AU2010200029B2 (en) | Ambient cure water-based coatings for writable-erasable surfaces | |
| WO2011140370A1 (en) | Writable-erasable surfaces | |
| WO1998022547A1 (en) | Non-staining coating composition | |
| CN101395191A (en) | High energy ray-curable composition | |
| WO2019199713A1 (en) | Methods for forming omniphobic thermoset compositions and related articles | |
| JP2012041558A (en) | Multi-component, waterborne coating composition, relating to coating and method | |
| CN109486393B (en) | Special high-gloss anti-fouling wear-resistant water-based paint for PVC surface decoration and preparation method thereof | |
| CN112852273B (en) | Water-based matte scratch-resistant paint and application thereof | |
| CN108976424A (en) | A kind of low-surface-energy scopiform silicone molecules and its preparation and application in the coating | |
| CN103635549B (en) | Aqueous polyurethane coating composition | |
| CN107936814A (en) | The net taste woodcare paint of high hardness polyurethane that a kind of POSS is modified | |
| CN114231153A (en) | Anti-pollution polyurethane matte clear coating and preparation method and application thereof | |
| CN113214731A (en) | Durable plant oil-based anti-graffiti easy-to-clean coating and preparation method and application thereof | |
| Luo et al. | Fabrication of UV-curable waterborne polyurethane coatings with self-cleaning, anti-graffiti performance, and corrosion resistance | |
| CN109439169A (en) | A kind of aqueous clear finish of biology base light with lotus leaf effect | |
| Yang et al. | A facile approach to fabricate omniphobic and robust polyurethane coatings for anti-smudge, anti-ink | |
| KR100895197B1 (en) | Functional silane curable urethane-modified polysiloxane paint composition | |
| Patel et al. | Synthesis and characterization of low volatile content polyurethane dispersion from depolymerised polyethylene terphthalate | |
| CN112143276B (en) | Antifouling auxiliary agent for automobile varnish and preparation method and application thereof | |
| CN113603881A (en) | Fluorinated polytetrahydrofuran diol and preparation method thereof, fluorinated polyurethane waterproof coating and composition thereof, and preparation method and application of fluorinated polyurethane waterproof coating | |
| Zhang et al. | Preparation of a novel melamine formaldehyde resin with palmitoylated melamine involved and its functional coating | |
| CN117511380B (en) | Graphene modified waterborne polyurethane coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210806 |
|
| WW01 | Invention patent application withdrawn after publication |