CN115895299B - Self-repairing hydrophobic self-cleaning coating and preparation method thereof - Google Patents
Self-repairing hydrophobic self-cleaning coating and preparation method thereof Download PDFInfo
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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 43
- 238000000576 coating method Methods 0.000 title claims abstract description 42
- 239000011248 coating agent Substances 0.000 title claims abstract description 41
- 238000004140 cleaning Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 239000003094 microcapsule Substances 0.000 claims abstract description 18
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002808 molecular sieve Substances 0.000 claims abstract description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000013312 flour Nutrition 0.000 claims abstract description 10
- 239000004576 sand Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 8
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 8
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000010456 wollastonite Substances 0.000 claims abstract description 8
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 8
- 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 abstract description 7
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 6
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 18
- 229920002545 silicone oil Polymers 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 238000001723 curing Methods 0.000 claims description 9
- 239000003973 paint Substances 0.000 claims description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 6
- XKRPWHZLROBLDI-UHFFFAOYSA-N dimethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OC)OC XKRPWHZLROBLDI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920002050 silicone resin Polymers 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
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- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 235000013339 cereals Nutrition 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000160 oxazolidinyl group Chemical group 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000013638 trimer Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 239000011664 nicotinic acid Substances 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
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- 125000003277 amino group Chemical group 0.000 description 3
- 239000002775 capsule Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 230000005661 hydrophobic surface Effects 0.000 description 3
- -1 hydroxypropyl Chemical group 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
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- 150000001298 alcohols Chemical class 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The invention discloses a self-repairing hydrophobic self-cleaning coating, which comprises a component A and a component B, wherein the component A comprises inorganic silicon resin, hydroxy acrylic resin, 400-mesh wollastonite powder, 200-mesh talcum powder, sand flour, self-repairing microcapsules, a dispersing agent, a defoaming agent, ethanol, isopropanol, butyl acetate, hydrophobic fumed silica, a molecular sieve and a water conversion agent; the component B comprises a catalyst, butyl acetate and HDI trimer. The coating film has bionic hydrophobic self-cleaning performance, has a self-repairing function when scratched, and has excellent chemical corrosion resistance, adhesion and weather resistance.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a self-repairing hydrophobic self-cleaning coating, and a preparation method of the coating.
Background
The self-cleaning paint can prevent water drops from adhering to the surface of glass, ceramic, metal or plastic and other base materials by changing the surface properties of the base materials, thereby achieving the self-cleaning effect. The hydrophobic self-cleaning coating has a plurality of applications in the aspects of glass curtain walls, solar heat collection devices and the like by virtue of excellent anti-fog and anti-fouling properties. The super-hydrophobic phenomenon in nature is known for a long time, and the most representative is the hydrophobic phenomenon of lotus leaves. The lotus leaf surface has a rough micro-nano structure, and the specific micro-nano structure and the wax on the surface are important reasons for realizing the self-cleaning property. The bionic hydrophobic surface is established, so that dirt is taken away when water drops roll off, the cleaning cost can be greatly reduced, and the energy utilization rate is improved. However, under the conditions of physical abrasion and chemical corrosion, the ordinary hydrophobic material easily loses the hydrophobic property, thereby affecting the normal use thereof.
Disclosure of Invention
The self-repairing hydrophobic self-cleaning paint provided by the invention has bionic hydrophobic self-cleaning performance, has a self-repairing function when scratched, and has excellent chemical corrosion resistance, adhesion and weather resistance.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the self-repairing hydrophobic self-cleaning coating comprises a component A and a component B, wherein the component A consists of the following raw materials in parts by weight: inorganic silicon resin: 40-50, hydroxy acrylic resin: 12-17g,400 mesh wollastonite powder: 8-10, 200 mesh talcum powder: 6-8, sand flour: 7-10, self-repairing microcapsule: 6-8, dispersant: 0.5-1, defoamer: 0.5-1, ethanol: 9-12, isopropanol: 7-9, butyl acetate: 4-6, hydrophobic fumed silica: 2-3, molecular sieves: 3-6, water conversion agent: 0.1-0.3; the component B consists of the following raw materials in parts by weight: catalyst: 0.9-1.2, butyl acetate: 2-4, hdi trimer: 6-8.
The hydroxyl acrylic resin is preferably ZJ-225 of Cheng Jia resin Co.Ltd, the HDI trimer is Bayer N3900, inorganic silicon resin and hydroxypropyl resin are selected as main film forming substances, a multiple crosslinking curing mode is adopted, after the component A and the component B are mixed, the catalyst in the component B catalyzes the polymerization reaction of the inorganic silicon resin, isocyanate groups in the HDI trimer are crosslinked and cured with hydroxyl groups in the hydroxyl acrylic resin and hydroxyl groups in the inorganic silicon resin, and a crosslinking curing mode of an organic-inorganic mutual transmission network is formed, so that the excellent adhesive force and solvent resistance of a coating film are provided. The solvent of the invention contains ethanol and isopropanol, which can improve the storage stability of the resin, and can be combined with a molecular sieve and a water conversion agent to further improve the storage stability of the component A and prevent the coating from foaming. In addition, 400-mesh wollastonite powder, 200-mesh talcum powder, sand flour, self-repairing microcapsule and hydrophobic gas-phase white carbon black are added in the formula, so that the micro-nano filler can form a concave-convex surface on the surface of a coating film, reduce the contact area between water drops and the surface of the coating film, and the inorganic silicone resin has low surface tension and excellent hydrophobic property, and the two materials are matched in a synergistic way to provide the excellent bionic self-cleaning property of the coating film.
Preferably, the water conversion agent is an oxazolidine latent curing agent, the molecular sieve is a 4A molecular sieve, and the hydrophobic fumed silica is R972 of Desoxase. The oxazolidine latent hardener is preferably LH-101A from Suzhou non-Tech New Material technologies Co. The addition of the oxazolidine latent curing agent can react with water in the system to generate amino, so that on one hand, the influence of moisture on the stability of the system is reduced, the system gel caused by moisture curing is prevented, on the other hand, the generated amino can react with isocyanate groups in the curing agent to improve the crosslinking density of the system, and the molecular sieve can effectively adsorb the moisture in the system, thereby being beneficial to improving the storage stability of the system. Hydrophobic fumed silica is a silica surface that has been hydrophobically modified to provide the proper rheology of the system in a solvent containing alcohols.
Preferably, the self-repairing microcapsule is prepared by the following method: adding 2.5g of emulsifier OP-10, 100g of distilled water and 18g of urea into a reactor, stirring 500r/min until the emulsifier is dissolved, then adjusting the pH to 2.0-3.0 by hydrogen chloride, adding 37g of vinyl silicone oil, 1g of 2-hydroxy-2-methyl propiophenone, dispersing for 15min by 1500r/min, then adjusting the rotating speed to 500r/min, adding 2g of 0.5% ammonium chloride aqueous solution, dropwise adding 27g of 37% formaldehyde aqueous solution into the reactor at a uniform speed, dropwise adding the mixture for 20-25min, finishing the dropwise adding, reacting for 2h at the constant temperature of 70 ℃, filtering after the reaction is finished, and cleaning a product by using distilled water, dimethylbenzene and ethanol to obtain the self-repairing microcapsule. The vinyl silicone oil is preferably V421-1300 of Shandong Dayi chemical industry Co.
Preferably, the self-repairing microcapsule is added into the coating, on one hand, the self-repairing microcapsule can be combined with sand flour, 400-mesh wollastonite powder and 200-mesh talcum powder to form a micro-rough coating surface, so that the contact area between water drops and the coating is reduced, on the other hand, when the coating is scratched, vinyl methyl silicone oil of a microcapsule capsule core can be released, and the microcapsule capsule core is solidified into a film under the action of ultraviolet light and an initiator to form a new hydrophobic surface, so that the self-repairing function is realized.
Preferably, the inorganic silicon resin is composed of the following raw materials in parts by weight: propyl trimethoxysilane: 43-47, dimethyl dimethoxy silane: 7-9, methylpropyldimethoxy silane: 5-7, 3-aminopropyl trimethoxysilane: 3-5, acidic silica sol: 4-6, deionized water: 13-17, hydrogen chloride: 0.1-0.2, methyl silicone oil: 1-2, hydroxy silicone oil: 3-5.
Preferably, the inorganic silicone resin is prepared by the following method:
step 1: adding propyl trimethoxy silane, dimethyl dimethoxy silane, methyl propyl dimethoxy silane and 3-aminopropyl trimethoxy silane into a four-neck flask with a stirrer, a thermometer, a water diversion condensing device and a constant pressure dropping funnel according to the formula amount, heating to 50 ℃, and stirring at a speed of 800r/min;
step 2: evenly mixing deionized water and hydrogen chloride according to the formula amount to obtain a hydrochloric acid solution, and adding the hydrochloric acid solution into a constant-pressure dropping funnel;
step 3: dropping the hydrochloric acid solution in the constant-pressure dropping funnel into the four-necked flask at a constant speed within 20-30 minutes;
step 4: after the dripping is completed, the reaction temperature is raised to 65-80 ℃, hydroxyl silicone oil and acidic silica sol are added, a water diversion condensing device is used for discharging the reaction reflux, the reaction is carried out for 3 hours, and the heating is stopped;
step 5: cooling to below 30 ℃, adding methyl silicone oil, and stirring uniformly to obtain the inorganic silicone resin.
The inorganic silicon resin adopts four monomers of propyl trimethoxy silane, dimethyl dimethoxy silane, methyl propyl dimethoxy silane and 3-amino propyl trimethoxy silane, the addition amount of deionized water is strictly controlled, and the excellent hardness and flexibility of the coating are ensured, and meanwhile, the silicon resin has excellent storage stability. In addition, amino groups are introduced in the synthesis of the silicon resin, and when the component A and the component B are mixed, the amino groups in the silicon resin can be crosslinked and cured with HDI trimer in the curing agent component, so that the crosslinking density of a coating film is improved, the reaction speed of the amino groups and isocyanate groups is high, the reaction time is further accelerated, and the construction efficiency is improved. In the invention, the acidic silica sol is introduced into the inorganic silicon resin to form the organic-inorganic hybrid coating, the silica sol can construct a nano structure on the surface of the coating, and the nano structure is matched with other fillers to form the micro-nano coating surface, so that the hydrophobic property of the coating is enhanced.
Preferably, the viscosity of the methyl silicone oil is 300-500mPa.S, and the hydroxyl content of the hydroxyl silicone oil is 8%. The addition of the hydroxyl silicone oil can improve brittleness of the silicone resin, provide excellent flexibility of the coating film, and provide waxy micro-rough surface, reduce hydrophobic rolling angle of the coating film and provide excellent hydrophobic self-cleaning performance of the coating film. Preferably, the average particle size of the acidic silica sol is 40-60nm, and the PH is 2-4. KHAS-5030, a product of Kohne silicon Co., ltd, is preferred.
Preferably, the catalyst is isopropyl titanate and dibutyl tin dilaurate, and the ratio of the isopropyl titanate to the dibutyl tin dilaurate is 2:1.
Preferably, the average grain size of the sand flour is 85 mu m, and the Siluoer85 of Dongguan Sialol new material technology Co., ltd is preferred.
The preparation method of the self-repairing hydrophobic self-cleaning coating comprises the following steps:
s1: adding inorganic silicon resin, hydroxy acrylic resin and a dispersing agent and a defoaming agent according to the formula amount, and stirring uniformly at the rotating speed of 500-600 r/min;
s2: the rotating speed is regulated to 800-1000 r/min, hydrophobic gas-phase white carbon black is added, and the dispersion is carried out for 10-15 min;
s3: adding ethanol, isopropanol and butyl acetate, a molecular sieve, a water conversion agent, 400-mesh wollastonite powder, 200-mesh talcum powder, sand flour and self-repairing microcapsule, and stirring for 10-15 min at 500-600 r/min to obtain the component A;
s4: and weighing the catalyst, butyl acetate and HDI trimer according to the formula amount, and uniformly stirring at 500-600 r/min to obtain the component B, and subpackaging the component A and the component B to obtain the self-repairing hydrophobic self-cleaning coating.
The self-repairing hydrophobic self-cleaning coating prepared by the invention constructs a micro-nano rough surface, the coating film has lower surface tension and bionic hydrophobic self-cleaning performance, when the coating film is scratched, the microcapsule can release vinyl silicone oil with capsule cores, the vinyl silicone oil is repaired and cured under the action of a photoinitiator and ultraviolet light to form a new hydrophobic surface, and the adhesive force of the super-smooth self-cleaning coating on a metal substrate can reach 0 level, and the coating film has excellent chemical resistance and weather resistance.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The self-repairing microcapsule is prepared by the following method:
adding 2.5g of emulsifier OP-10, 100g of distilled water and 18g of urea into a reactor, stirring 500r/min until the mixture is dissolved, then adjusting the pH to 2.0-3.0 by hydrogen chloride, adding 37g of V421-1300 vinyl silicone oil, 1g of 2-hydroxy-2-methyl propiophenone, dispersing for 15min by 1500r/min, then adjusting the rotating speed to 500r/min, adding 2g of 0.5% ammonium chloride aqueous solution, dropwise adding 27g of 37% formaldehyde aqueous solution into the reactor at a constant speed, dropwise adding the mixture for 20-25min, reacting for 2h at a constant temperature of 70 ℃, filtering after the reaction is finished, and cleaning the product by distilled water, dimethylbenzene and ethanol to obtain the self-repairing microcapsule.
The inorganic silicon resin is self-made resin, and the following table lists the formulas of six inorganic silicon resins, which are respectively represented by resin a, resin b, resin c, resin d, resin e and resin f. As shown in table one below.
List one
The preparation method comprises the following steps:
step 1: adding propyl trimethoxy silane, dimethyl dimethoxy silane, methyl propyl dimethoxy silane and 3-aminopropyl trimethoxy silane into a four-neck flask with a stirrer, a thermometer, a water diversion condensing device and a constant pressure dropping funnel according to the formula amount, heating to 50 ℃, and stirring at a speed of 800r/min;
step 2: evenly mixing deionized water and hydrogen chloride according to the formula amount to obtain a hydrochloric acid solution, and adding the hydrochloric acid solution into a constant-pressure dropping funnel;
step 3: dropping the hydrochloric acid solution in the constant-pressure dropping funnel into the four-necked flask at a constant speed within 20-30 minutes;
step 4: after the dripping is completed, the reaction temperature is raised to 65-80 ℃, hydroxyl silicone oil and acidic silica sol are added, a water diversion condensing device is used for discharging the reaction reflux, the reaction is carried out for 3 hours, and the heating is stopped;
step 5: cooling to below 30 ℃, adding methyl silicone oil, and stirring uniformly to obtain the inorganic silicone resin.
The viscosity of the methyl silicone oil is 300-500mPa.S. The hydroxyl content of the hydroxyl silicone oil is 8%.
The following examples are provided to further illustrate embodiments of the invention.
Examples
Examples 1 to 3 respectively provide a self-repairing hydrophobic self-cleaning paint which consists of an A component and a B component, wherein the weight parts of the raw materials in the A component are shown in the following Table II, and five groups of comparative examples 1 to 5 are listed in the following Table II.
Watch II
The component B corresponding to the component A consists of the following raw materials in parts by weight:
watch III
Examples 1 to 3, and comparative examples 1 to 5 provide a method for preparing a coating material comprising the steps of:
s1: adding inorganic silicon resin, hydroxy acrylic resin ZJ-225, rotating at 500-600 r/min, sequentially adding dispersing agent and defoaming agent, and stirring uniformly;
s2: the rotating speed is regulated to 800-1000R/min, the hydrophobic gas phase white carbon black R972 is added, and the dispersion is carried out for 10-15 min;
s3: adding ethanol, isopropanol, butyl acetate, a 4A molecular sieve, a water conversion agent LH-101A, 400-mesh wollastonite powder, 200-mesh talcum powder, sand flour Siluoer85 and self-repairing microcapsules, and stirring for 10-15 min at 500-600 r/min to obtain a component A;
s4: and weighing the catalyst, butyl acetate and HDI trimer according to the formula amount, and uniformly stirring at 500-600 r/min to obtain the component B, and subpackaging the component A and the component B to obtain the self-repairing hydrophobic self-cleaning coating.
Comparative example 6
This comparative example provides a self-healing hydrophobic self-cleaning coating having a composition that is consistent with example 3 except that the 4A molecular sieve is removed, the remaining ingredients, amounts and preparation methods are the same as in example 3. The prepared paint film has foaming appearance, and is stored for 45 days at room temperature of 25 ℃ for gel curing.
Comparative example 7
This comparative example provides a self-healing hydrophobic self-cleaning coating having a composition similar to that of example 3, except that LH-101A was removed, the remaining ingredients, amounts and preparation methods were the same as in example 3. The prepared paint film has foaming appearance, and is stored for 50 days at room temperature of 25 ℃ for gel curing.
Comparative example 8
This comparative example provides a self-healing hydrophobic self-cleaning coating having a composition that is consistent with example 3 except that the ethanol is replaced with an equivalent amount of butyl acetate, i.e., 0 ethanol content, 15 butyl acetate content, and the remainder of the ingredients and preparation process are consistent with example 3. The gel of the system is solidified after being stored for 1 month at the room temperature of 25 ℃.
Comparative example 9
This comparative example provides a self-healing hydrophobic self-cleaning coating whose composition was the same as that of example 3 except that the isopropyl titanate of component B was replaced with an equivalent amount of dibutyltin dilaurate, i.e., the isopropyl titanate content was 0, the dibutyltin dilaurate content was 1.05, and the remaining components and preparation method were the same as those of example 3, and the cross-cut test (cross-cut distance 1 mm) was grade 2.
Test case
The self-repairing hydrophobic self-cleaning paint prepared in each example is subjected to relevant performance test, and specific test results are shown in the following table four.
Table four
The self-repairing hydrophobic self-cleaning paint prepared in each embodiment is subjected to relevant performance test, and specific test results are shown in the following table five:
TABLE five
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (4)
1. The self-repairing hydrophobic self-cleaning coating is characterized by comprising a component A and a component B, wherein the component A consists of the following raw materials in parts by weight: inorganic silicon resin: 40-50, hydroxy acrylic resin: 12-17g,400 mesh wollastonite powder: 8-10, 200 mesh talcum powder: 6-8, sand flour: 7-10, self-repairing microcapsule: 6-8, dispersant: 0.5-1, defoamer: 0.5-1, ethanol: 9-12, isopropanol: 7-9, butyl acetate: 4-6, hydrophobic fumed silica: 2-3, molecular sieves: 3-6, water conversion agent: 0.1-0.3; the component B consists of the following raw materials in parts by weight: catalyst: 0.9-1.2, butyl acetate: 2-4, hdi trimer: 6-8; the inorganic silicon resin consists of the following raw materials in parts by weight: propyl trimethoxysilane: 43-47, dimethyl dimethoxy silane: 7-9, methylpropyldimethoxy silane: 5-7, 3-aminopropyl trimethoxysilane: 3-5, acidic silica sol: 4-6, deionized water: 13-17, hydrogen chloride: 0.1-0.2, methyl silicone oil: 1-2, hydroxy silicone oil: 3-5; the viscosity of the methyl silicone oil is 300-500mPa.S, the hydroxyl content of the hydroxyl silicone oil is 8%, the average particle size of the acidic silica sol is 40-60nm, and the PH is 2-4; the catalyst is isopropyl titanate and dibutyl tin dilaurate, and the ratio of the isopropyl titanate to the dibutyl tin dilaurate is 2:1; the average grain diameter of the sand flour is 85 mu m, the water conversion agent is an oxazolidine latent curing agent,
the inorganic silicon resin is prepared by the following method:
step 1: adding propyl trimethoxy silane, dimethyl dimethoxy silane, methyl propyl dimethoxy silane and 3-aminopropyl trimethoxy silane into a four-neck flask with a stirrer, a thermometer, a water diversion condensing device and a constant pressure dropping funnel according to the formula amount, heating to 50 ℃, and stirring at a speed of 800r/min;
step 2: evenly mixing deionized water and hydrogen chloride according to the formula amount to obtain a hydrochloric acid solution, and adding the hydrochloric acid solution into a constant-pressure dropping funnel;
step 3: dropping the hydrochloric acid solution in the constant-pressure dropping funnel into the four-necked flask at a constant speed within 20-30 minutes;
step 4: after the dripping is completed, the reaction temperature is raised to 65-80 ℃, hydroxyl silicone oil and acidic silica sol are added, a water diversion condensing device is used for discharging the reaction reflux, the reaction is carried out for 3 hours, and the heating is stopped;
step 5: cooling to below 30 ℃, adding methyl silicone oil, and stirring uniformly to obtain the inorganic silicone resin.
2. The self-repairing hydrophobic self-cleaning paint according to claim 1, wherein the molecular sieve is a 4A molecular sieve, and the hydrophobic fumed silica is R972 of Desoxhlet.
3. The self-repairing hydrophobic self-cleaning paint according to claim 1, wherein the self-repairing microcapsule is prepared by the following method:
adding 2.5g of emulsifier OP-10, 100g of distilled water and 18g of urea into a reactor, stirring 500r/min until the emulsifier is dissolved, then adjusting the pH to 2.0-3.0 by using hydrogen chloride, adding 37g of vinyl silicone oil, 1g of 2-hydroxy-2-methyl propiophenone, dispersing 15min at 1500r/min, adjusting the rotating speed to 500r/min, adding 2g of 0.5% ammonium chloride aqueous solution, dropwise adding 27g of 37% formaldehyde aqueous solution into the reactor at a uniform speed, dropwise adding the mixture for 20-25min, reacting for 2h at a constant temperature of 70 ℃, filtering after the reaction is finished, and cleaning a product by using distilled water, dimethylbenzene and ethanol to obtain the self-repairing microcapsule.
4. A method of preparing a self-healing hydrophobic self-cleaning coating according to any one of claims 1 to 3, comprising the steps of:
s1: adding inorganic silicon resin, hydroxy acrylic resin and a defoaming agent according to the formula amount, and sequentially adding a dispersing agent and a defoaming agent and uniformly stirring at the rotating speed of 500-600 r/min;
s2: the rotating speed is regulated to 800-1000 r/min, hydrophobic fumed silica is added, and the dispersion is carried out for 10-15 min;
s3: adding ethanol, isopropanol and butyl acetate, a molecular sieve, a water conversion agent, 400-mesh wollastonite powder, 200-mesh talcum powder, sand flour and self-repairing microcapsules, and stirring for 10-15 min at 500-600 r/min to obtain a component A;
s4: and weighing the catalyst, butyl acetate and HDI trimer according to the formula amount, and uniformly stirring at 500-600 r/min to obtain the component B, and subpackaging the component A and the component B to obtain the self-repairing hydrophobic self-cleaning coating.
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