CN111303713A - Ultraviolet light aging resistant environment-friendly coating and preparation method thereof - Google Patents
Ultraviolet light aging resistant environment-friendly coating and preparation method thereof Download PDFInfo
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- CN111303713A CN111303713A CN202010343712.9A CN202010343712A CN111303713A CN 111303713 A CN111303713 A CN 111303713A CN 202010343712 A CN202010343712 A CN 202010343712A CN 111303713 A CN111303713 A CN 111303713A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention belongs to the technical field of coatings, and particularly relates to an ultraviolet light aging resistant environment-friendly coating and a preparation method thereof.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to an ultraviolet light aging resistant environment-friendly coating and a preparation method thereof.
Background
The exterior wall coating is required to have elegant and fresh decorative effect and nontoxic and tasteless environmental protection function, and the performances of the exterior wall coating comprise weather resistance, stain resistance, color retention, water resistance, alkali resistance, scrubbing resistance, covering power, freezing and thawing performance and the like; meanwhile, the workability, the storage property, the film forming property and the anti-corrosion property during low-temperature construction are considered. In recent years, as the environment deteriorates, exterior wall coatings applied to buildings are affected by, for example, acid rain, ultraviolet ray enhancement due to ozone layer destruction, and the like in addition to exposure to sunlight and rain, and these factors have been required to be higher in weather resistance and stain resistance of exterior wall coatings. Therefore, improvement of weather resistance and stain resistance is a development direction of exterior wall coatings.
At present, emulsion of the latex paint for the exterior wall of the building mainly comprises styrene-acrylic emulsion, pure acrylic emulsion, silicone-acrylic emulsion and fluorocarbon emulsion, wherein the fluorocarbon emulsion has excellent weather resistance, chemical resistance, corrosion resistance, heat resistance, cold resistance, wear resistance, non-adhesiveness and pollution resistance, and has stronger resistance to temperature change and humidity change of the exterior wall. The fluorocarbon emulsion serving as a new and developing novel coating has excellent corrosion resistance, maintenance-free performance, self-cleaning performance, strong adhesion and ultra-long weather resistance, and the excellent performances can fully exert the fluorocarbon coating originally, but the defects of the fluorocarbon emulsion under the advantages are not negligible. When the fluorocarbon paint is applied to an outer wall, the paint has high requirements on construction conditions and matched materials, has rigid coating, does not have good elasticity, has unstable performance, has cracking and peeling phenomena, is easy to pollute the environment, has common long-term decoration and high manufacturing cost, contains a large amount of Volatile Organic Compounds (VOC) in solvent type paint, has serious environmental pollution, wastes resources and energy, is safe and nontoxic below the decomposition temperature, but generates dozens of harmful gases such as virulent phosgene, fluoroolefin and the like due to thermal decomposition when a building is in a fire disaster, and is different from the safety environmental protection paint advocated at present.
The styrene-acrylic emulsion, the pure acrylic emulsion, the silicone-acrylic emulsion and the polyurethane emulsion have good environmental friendliness, and the low organic volatile matters and the non-toxic safety make the styrene-acrylic emulsion, the pure acrylic emulsion, the silicone-acrylic emulsion and the polyurethane emulsion become the current mainstream coatings. The pure acrylic emulsion paint has certain folding and weather resistance, but is generally used as an inner wall paint due to the ultraviolet light resistance; the silicone-acrylic emulsion paint combines the advantages of organosilicon and pure acrylic emulsion, so that the silicone-acrylic emulsion paint has the environment-friendly building emulsion and paint with high weather resistance, high water resistance and pollution resistance. The aqueous polyurethane emulsion has the advantages of no pollution, safety, reliability, excellent mechanical property, good compatibility, easy modification and the like, so that the aqueous polyurethane emulsion is widely developed, but because the volatility of water is poorer than that of an organic solvent, the aqueous polyurethane adhesive is slower to dry, the water resistance of the material is poorer, and the aqueous polyurethane emulsion serving as an outer wall coating is easy to age by ultraviolet light.
The silicone-acrylate emulsion coating is an emulsion formed by adding an organosilicon monomer containing unsaturated bonds and an acrylic monomer into a proper auxiliary agent and polymerizing through a core-shell coating polymerization process, and an ultraviolet light absorber is usually required to be added into a formula for resisting ultraviolet light aging. Therefore, the compatibility of the ultraviolet absorbent and the emulsion is improved, and the ultraviolet resistance of the coating is greatly improved.
The patent application with the application number of 201811132060.3 discloses a self-healing ultraviolet shielding coating and a preparation method thereof, and the invention provides a preparation method of the self-healing ultraviolet shielding coating, which comprises the following steps of 1, ultrasonically dispersing titanium dioxide into cyclodextrin water solution to prepare β -CD-TiO2Step 2, mixing β -CD-TiO2Carrying out ultrasonic reaction on the obtained product and adamantane methyl methacrylate to prepare an inclusion solution, and freeze-drying the inclusion solution to obtain HEMA-Ad/β -CD-TiO2Step 3, the HEMA-Ad/β -CD-TiO is added2And the self-healing ultraviolet shielding coating is generated by copolymerization reaction of methyl methacrylate, butyl acrylate and an initiator. The invention solves the technical problems that the existing ultraviolet-proof coating has no self-healing performance, so that the coating of the cable is scratched in the installation and construction process, and the scratch position cannot be self-healed, so that the effect of preventing ultraviolet light aging is lost.
The patent application with the application number of 201910040992.3 discloses a modified polypropylene with ultraviolet aging resistanceThe preparation method of the olefine acid coating comprises the following steps: s1 preparation of TiO2β -cyclodextrin graft, S2, layered hydrotalcite, S3, TiO preparation2Grafting β -layered hydrotalcite with cyclodextrin intercalation, S4, adding defoamer and dispersant into dimethylbenzene for even dispersion, and adding into the step S3 to prepare TiO2The β -cyclodextrin intercalated layered hydrotalcite is added with organic silicon modified acrylic resin after being dispersed at a high speed, and then dispersed at a low speed to obtain the acrylic coating.
The patent application with the application number of 201410480734.4 discloses a coating for protecting an external wall and a preparation method thereof, wherein the coating comprises the following components in parts by mass: 11.5-24 parts of silicone-acrylate resin, 3-6.5 parts of organic silicone oil, 0.5-1.5 parts of protective adhesive, 1-4 parts of polyoxyethylene stearate, 0.7-1.5 parts of sodium dodecyl benzene sulfonate, 0.2-0.45 part of lauroyl peroxide, 0.08-0.13 part of sodium bicarbonate, 1.5-3.5 parts of low-wax asphalt, 0.1-0.3 part of dodecyl glycol ester, 0.5-1 part of ethyl acetate and 15-29 parts of deionized water. The paint provided by the invention has high weather resistance, strong adhesive force and high water resistance, is suitable for coating building outer walls, has a good beautifying effect on buildings, can prevent the buildings from being damaged by external atmosphere, ultraviolet rays, rainwater and chemical substances, and prolongs the service life of the outer walls.
The patent application with the application number of 200610036145.2 discloses a water-based long-acting anticorrosive coating and a preparation method thereof. The invention aims to solve the technical problem of how to provide a long-acting water-based long-acting anticorrosive coating with long effective period, sunlight resistance and ultraviolet resistance. The invention adopts the mature electrodialysis technology to prepare the high-modulus potassium lithium silicate composite solution, then uses the monomethyl triethoxysilane and the waterborne epoxy modified silicone-acrylate resin for modification to prepare the organic silicon modified composite silicate inorganic resin, and applies the dispersion coupling technology to fully disperse the powder and the auxiliary agent into the composite film-forming substance to form a composite compatible, stable and uniform coating system. The paint has van der Waals force on steel and cement base materials, and mainly has chemical bonding force, strong adhesive force, high strength, ageing resistance, radiation resistance, long-acting rust prevention and corrosion prevention. The water-based long-acting anticorrosive paint is an ideal substitute product of the existing anticorrosive paint, and is particularly suitable for being used as an outdoor anticorrosive paint.
The patent application with the application number of 97106656.6 discloses a silicone-acrylate resin for paint and a production method thereof, wherein the silicone-acrylate resin is prepared by copolymerizing a linear organosilicon intermediate and an acrylate monomer, wherein the linear organosilicon intermediate is generated by the catalytic polymerization reaction of octavinylcyclotetrasiloxane and octaalkylcyclotetrasiloxane. The silicone-acrylate resin product has regular structure, high transparency and good stability. The production process of the silicone-acrylic resin is simple and convenient, energy-saving and low in cost. The paint prepared by the silicone-acrylate resin can form a film at normal temperature or low temperature, has excellent stain resistance, aging resistance and ultraviolet irradiation resistance, and is hard in film coating and good in adhesive force.
The patent application with the application number of 201811640991.4 discloses a preparation process of an anticorrosive paint, which comprises the following steps: preparing a first mother solution from polyamide resin, isocyanate, phenolic resin and carbon nano powder; preparing a second mother solution by using methyl MQ silicon resin, fluorosilicone resin, silicone-acrylic resin and quartz powder; preparing a third mother liquor by using isobutyl triethoxysilane and alumina powder; and slowly adding the first mother liquor and the second mother liquor into the third mother liquor at the same time to obtain the finished anticorrosive paint. The anticorrosive paint prepared by the process has the characteristics of good high and low temperature resistance, water resistance, moisture resistance, ultraviolet resistance, good metal cementation, good wear resistance and the like, can effectively resist the damage of sun and rain to the paint when being used on outdoor equipment, and prolongs the service time of the paint.
Disclosure of Invention
Aiming at the problem that the weather resistance of the coating is affected due to poor compatibility of the ultraviolet light absorber in the coating caused by direct addition of the ultraviolet light absorber in the prior art, the invention aims to disclose a preparation method of an ultraviolet light aging resistant environment-friendly coating.
In order to achieve the purpose, the preparation method of the ultraviolet light aging resistant environment-friendly coating comprises the following steps:
(1) adding β -cyclodextrin and N-hydroxymethyl acrylamide into a dilute hydrochloric acid solution, reacting for 15-30 minutes at 75-80 ℃, cooling to room temperature, adding acetone, standing for 2-3 hours until the acetone is completely precipitated to form a supernatant, filtering and washing the acetone, and drying at 35-40 ℃ to obtain β -cyclodextrin composite N-hydroxymethyl acrylamide;
(2) dispersing an ultraviolet light absorber in water, adding β -cyclodextrin composite N-methylolacrylamide prepared in the step (1), ultrasonically dispersing for 1-2 hours, and filtering and drying to obtain β -cyclodextrin for absorbing the ultraviolet light absorber;
(3) adopting seed emulsion polymerization, mixing an acrylic monomer, water, an emulsifier and a water-soluble initiator, and reacting at 65-85 ℃ for 1-3 hours to perform nucleation polymerization to generate emulsion particles; then, continuously adding water, an emulsifier, an organic silicon monomer containing unsaturated bonds and a water-soluble initiator into the emulsion particles, supplementing the emulsifier once every 1 hour at the temperature of 75-85 ℃, and reacting for 3-4 hours;
(4) adding β -cyclodextrin adsorbing the ultraviolet light absorbent prepared in the step (2) into a polymerization kettle along with the last time of adding the emulsifier in the step (3) until the reaction is finished to obtain β -cyclodextrin grafted silicone-acrylic resin;
(5) and (3) uniformly mixing the β -cyclodextrin grafted silicone acrylic resin obtained in the step (4), acrylic resin, diethylene glycol butyl ether, a leveling agent, mica powder, xylene, a pinhole eliminating agent and a defoaming agent to prepare the weather-resistant environment-friendly exterior wall coating.
The ultraviolet absorbent can be a conventional ultraviolet absorbent on the market, and can strongly absorb ultraviolet rays with the wavelength of 290-400 nm. Preferably, the material has good thermal stability and chemical stability, and does not react with the material components in the product; EVERSORB SB1, available from Taiwan Yongguang, Inc., which has good miscibility and can be uniformly dispersed in the coating material.
Preferably, the β -cyclodextrin, the N-methylolacrylamide, the dilute hydrochloric acid and the acetone in the step (1) are 1-3: 2-5: 10-20: 5-10 parts by weight.
Preferably, the weight parts of the ultraviolet light absorber, the water and the β -cyclodextrin composite N-methylolacrylamide in the step (2) are 2-6: 15-20: 3-8.
Preferably, the weight parts of the acrylic monomer, the water, the emulsifier, the water-soluble initiator and the unsaturated bond-containing organosilicon monomer in the step (3) are 3-8: 15-30: 10-20: 1-3: 5-10.
Preferably, the β -cyclodextrin grafted silicone-acrylic resin, the diethylene glycol butyl ether, the leveling agent, the mica powder, the xylene, the pinhole eliminating agent and the defoaming agent in the step (5) are 20-40: 30-50: 2-5: 0.5-1: 10-25: 15-30: 2-3: 1-2 in parts by weight.
Preferably, the acrylic monomer in step (3) is at least one of acrylic acid, methyl acrylate and ethyl acrylate; the emulsifier is at least one of sodium stearate and sodium dodecyl sulfate; the water-soluble initiator is at least one of hydrogen peroxide and sodium sulfite; the organosilicon monomer containing unsaturated bonds is at least one of methyl vinyl chlorosilane and vinyl trichlorosilane.
Preferably, the leveling agent in the step (5) is polydimethylsiloxane; the pinhole eliminating agent is acrylic ester; the defoaming agent is polyethylene glycol ether.
Preferably, the temperature of standing in the step (1) is 0-5 ℃.
Preferably, the ultraviolet light absorber described in step (2) is EVERSORB SB1 manufactured by taiwan permanent light company.
The invention also aims to provide the environment-friendly paint with ultraviolet light aging resistance.
In order to achieve the second object of the invention, the environment-friendly ultraviolet light aging resistant coating is prepared by the preparation method of the environment-friendly ultraviolet light aging resistant coating.
Has the advantages that:
according to the invention, β -cyclodextrin grafted silicone-acrylate resin is used for improving the oil absorption performance of the silicone-acrylate resin, the hydrophilic characteristic of the hydrophobic surface of the inner cavity of β -cyclodextrin is utilized for adsorbing the oily ultraviolet light absorber, the compatibility of the ultraviolet light absorber and the paint is improved, and the dispersion uniformity of the ultraviolet light absorber in the paint is improved, so that the ultraviolet resistance of the paint does not influence the weather resistance of the silicone-acrylate paint, and the silicone-acrylate resin grafted silicone-acrylate resin has the following remarkable advantages:
according to the invention, an oily ultraviolet absorber is adsorbed by utilizing the hydrophilic characteristic of the hydrophobic surface of the inner cavity of β -cyclodextrin, and then the oily ultraviolet absorber is grafted to the surface of the silicone-acrylate emulsion in a modification mode, so that the ultraviolet absorber and the silicone-acrylate emulsion have better compatibility and the dispersion uniformity in the paint is improved, which is beneficial to improving the ultraviolet light aging resistance of the paint, meanwhile, the flexible silicone-acrylate emulsion is obtained by polymerizing a seed emulsion through preparing an elastic emulsion through an acrylic monomer and introducing an organic silicon monomer with low surface energy to the surface of emulsion particles, so that the paint has better elasticity and higher weather resistance.
Drawings
FIG. 1 a is a picture of example 1 without ultraviolet irradiation, and b is a picture after ultraviolet irradiation for 15 h;
FIG. 2 c is a photograph of comparative example 1 when no UV light was used, and d is a photograph after 15 hours of UV light irradiation;
FIG. 3 is a schematic structural diagram of β -cyclodextrin grafted silicone-acrylate resin of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
The preparation of the environment-friendly paint with ultraviolet light aging resistance comprises the following steps:
(1) adding β -cyclodextrin 500g and N-hydroxymethyl acrylamide 1000g into 5000g of dilute hydrochloric acid solution, reacting at 75 ℃ for 30 minutes, cooling to room temperature, adding acetone 5000g, placing into a refrigerator, standing at 4 ℃ for 2 hours until the supernatant is completely precipitated, filtering and washing with acetone, and drying at 35 ℃ to obtain β -cyclodextrin composite N-hydroxymethyl acrylamide;
(2) dispersing 500g of EVERSORB SB1 ultraviolet light absorbent produced by Taiwan Yongguang company in 5000g of water, adding 1000g of β -cyclodextrin composite N-methylolacrylamide prepared in the step (1), ultrasonically dispersing for 1.5 hours, filtering and drying to obtain β -cyclodextrin for adsorbing the ultraviolet light absorbent;
(3) adopting seeded emulsion polymerization, mixing 400g of acrylic monomer acrylic acid, 200g of water, 100g of emulsifier sodium dodecyl sulfate and 10g of water-soluble initiator sodium sulfite, and reacting at 80 ℃ for 2 hours to carry out nucleation polymerization to generate emulsion particles; then, continuously adding 1800g of water, 300g of emulsifier, 600g of organosilicon monomer methyl vinyl chlorosilane containing unsaturated bonds and 90g of water-soluble initiator into the emulsion particles, supplementing 300g of emulsifier every 1 hour at 75 ℃, and reacting for 3 hours;
(4) adding β -cyclodextrin adsorbing the ultraviolet light absorbent prepared in the step (2) into a polymerization kettle along with the last time of adding the emulsifier in the step (3) until the reaction is finished to obtain β -cyclodextrin grafted silicone-acrylic resin;
(5) and (3) uniformly mixing 2000g of β -cyclodextrin grafted silicone acrylic resin obtained in the step (4), 3000g of acrylic resin, 250g of diethylene glycol butyl ether, 60g of flatting agent polydimethylsiloxane, 1000g of mica powder, 1500g of xylene, 200g of pinhole eliminating agent acrylate and 100g of defoaming agent polyethylene glycol ether to prepare the weather-resistant environment-friendly exterior wall coating.
Example 2
The preparation of the environment-friendly paint with ultraviolet light aging resistance comprises the following steps:
(1) adding β -cyclodextrin 1000g and N-hydroxymethyl acrylamide 1000g into 5000g of dilute hydrochloric acid solution, reacting at 75 deg.C for 30 min, cooling to room temperature, adding acetone 5000g, standing in refrigerator at 4 deg.C for 2 hr until the upper layer is completely precipitated to obtain clear solution, filtering and washing with acetone, and drying at 35 deg.C to obtain β -cyclodextrin composite N-hydroxymethyl acrylamide;
(2) dispersing 500g of EVERSORB SB1 ultraviolet light absorbent produced by Taiwan Yongguang company in 5000g of water, adding 2000g of β -cyclodextrin composite N-methylolacrylamide prepared in the step (1), ultrasonically dispersing for 1.5 hours, filtering and drying to obtain β -cyclodextrin for adsorbing the ultraviolet light absorbent;
(3) adopting seeded emulsion polymerization, mixing 400g of acrylic monomer acrylic acid, 200g of water, 100g of emulsifier sodium dodecyl sulfate and 10g of water-soluble initiator sodium sulfite, and reacting at 75 ℃ for 2 hours to carry out nucleation polymerization to generate emulsion particles; then, continuously adding 1800g of water, 300g of emulsifier, 600g of organosilicon monomer methyl vinyl chlorosilane containing unsaturated bonds and 90g of water-soluble initiator into the emulsion particles, supplementing 300g of emulsifier every 1 hour at 75 ℃, and reacting for 3 hours;
(4) adding β -cyclodextrin adsorbing the ultraviolet light absorbent prepared in the step (2) into a polymerization kettle along with the last time of adding the emulsifier in the step (3) until the reaction is finished to obtain β -cyclodextrin grafted silicone-acrylic resin;
(5) and (3) uniformly mixing 2000g of β -cyclodextrin grafted silicone acrylic resin obtained in the step (4), 3000g of acrylic resin, 250g of diethylene glycol butyl ether, 60g of flatting agent polydimethylsiloxane, 1000g of mica powder, 1500g of xylene, 200g of pinhole eliminating agent acrylate and 100g of defoaming agent polyethylene glycol ether to prepare the weather-resistant environment-friendly exterior wall coating.
Example 3
The preparation of the environment-friendly paint with ultraviolet light aging resistance comprises the following steps:
(1) adding β -cyclodextrin 1500g and N-methylolacrylamide 1000g into 5000g of dilute hydrochloric acid solution, reacting at 80 ℃ for 30 minutes, cooling to room temperature, adding acetone 4000g, placing into a refrigerator, standing at 4 ℃ for 2 hours until the supernatant is completely precipitated, filtering and washing with acetone, and drying at 40 ℃ to obtain β -cyclodextrin composite N-methylolacrylamide;
(2) dispersing 500g of EVERSORB SB1 ultraviolet light absorbent produced by Taiwan Yongguang company in 5000g of water, adding 1500g of β -cyclodextrin composite N-methylolacrylamide prepared in the step (1), ultrasonically dispersing for 2 hours, filtering and drying to obtain β -cyclodextrin for adsorbing the ultraviolet light absorbent;
(3) adopting seeded emulsion polymerization, mixing 400g of acrylic monomer acrylic acid, 200g of water, 100g of emulsifier sodium stearate and 10g of water-soluble initiator sodium sulfite, and reacting at 80 ℃ for 2 hours to carry out nucleation polymerization to generate emulsion particles; then, continuously adding 1800g of water, 300g of emulsifier, 600g of organosilicon monomer methyl vinyl chlorosilane containing unsaturated bonds and 90g of water-soluble initiator into the emulsion particles, supplementing 300g of emulsifier sodium stearate every 1 hour at 75 ℃, and reacting for 3 hours;
(4) adding β -cyclodextrin adsorbing the ultraviolet light absorbent prepared in the step (2) into a polymerization kettle along with the last time of adding the emulsifier in the step (3) until the reaction is finished to obtain β -cyclodextrin grafted silicone-acrylic resin;
(5) and (3) uniformly mixing 2000g of β -cyclodextrin grafted silicone acrylic resin obtained in the step (4), 3000g of acrylic resin, 250g of diethylene glycol butyl ether, 60g of flatting agent polydimethylsiloxane, 1000g of mica powder, 1500g of xylene, 200g of pinhole eliminating agent acrylate and 100g of defoaming agent polyethylene glycol ether to prepare the weather-resistant environment-friendly exterior wall coating.
Example 4
The preparation of the environment-friendly paint with ultraviolet light aging resistance comprises the following steps:
(1) adding β -cyclodextrin 1500g and N-hydroxymethyl acrylamide 1500g into 5000g of dilute hydrochloric acid solution, reacting at 85 deg.C for 20 min, cooling to room temperature, adding acetone 5000g, standing in refrigerator at 4 deg.C for 3 hr until the upper layer is completely precipitated to obtain clear solution, filtering and washing with acetone, and drying at 35 deg.C to obtain β -cyclodextrin compound N-hydroxymethyl acrylamide;
(2) dispersing 500g of EVERSORB SB1 ultraviolet light absorbent produced by Taiwan Yongguang company in 5000g of water, adding 2500g of β -cyclodextrin composite N-methylolacrylamide prepared in the step (1), ultrasonically dispersing for 1.5 hours, filtering and drying to obtain β -cyclodextrin for adsorbing the ultraviolet light absorbent;
(3) adopting seeded emulsion polymerization, mixing 400g of acrylic monomer ethyl acrylate, 200g of water, 100g of emulsifier sodium dodecyl sulfate and 10g of water-soluble initiator sodium sulfite, and reacting at 80 ℃ for 1.5 hours to carry out nucleation polymerization to generate emulsion particles; then, continuously adding 1800g of water, 300g of emulsifier, 600g of organosilicon monomer methyl vinyl chlorosilane containing unsaturated bonds and 90g of water-soluble initiator into the emulsion particles, supplementing 300g of emulsifier every 1 hour at the temperature of 80 ℃, and reacting for 3 hours;
(4) adding β -cyclodextrin adsorbing the ultraviolet light absorbent prepared in the step (2) into a polymerization kettle along with the last time of adding the emulsifier in the step (3) until the reaction is finished to obtain β -cyclodextrin grafted silicone-acrylic resin;
(5) and (3) uniformly mixing 3000g of β -cyclodextrin grafted silicone acrylic resin obtained in the step (4), 3000g of acrylic resin, 250g of diethylene glycol monobutyl ether, 60g of flatting agent polydimethylsiloxane, 1000g of mica powder, 1500g of xylene, 200g of pinhole eliminating agent acrylate and 100g of defoaming agent polyethylene glycol ether to prepare the weather-resistant environment-friendly exterior wall coating.
Comparative example 1
2000g of silicone-acrylic resin, 3000g of acrylic resin, 250g of diethylene glycol monobutyl ether, 60g of flatting agent polydimethylsiloxane, 1000g of mica powder, 1500g of dimethylbenzene, 200g of pinhole eliminating agent acrylate and 100g of defoaming agent polyglycol ether are uniformly mixed to prepare the weather-resistant environment-friendly exterior wall coating.
The test method comprises the following steps: the coatings obtained in example 1 and comparative example 1 were applied to glass plates of 100X 100mm thickness of 0.5mm after stirring with water, and after drying, they were irradiated with UV lamps of 280nm distance of 0.5m each for 15 h. And (3) testing results: FIG. 1 a is a picture of example 1 without ultraviolet irradiation, and b is a picture after ultraviolet irradiation for 15 h; fig. 2 c is a picture of comparative example 1 when no ultraviolet light was used for irradiation, and d is a picture after 15 hours of ultraviolet light irradiation.
Through an ultraviolet aging test, the surface of the coating prepared in example 1 is almost unchanged after the coating is irradiated by ultraviolet light, and the coating prepared in comparative example 1 has serious aging phenomena such as spots and the like.
Claims (10)
1. The preparation method of the ultraviolet light aging resistant environment-friendly coating is characterized by comprising the following steps:
(1) adding β -cyclodextrin and N-hydroxymethyl acrylamide into a dilute hydrochloric acid solution, reacting for 15-30 minutes at 75-80 ℃, cooling to room temperature, adding acetone, standing for 2-3 hours until the acetone is completely precipitated to form a supernatant, filtering and washing the acetone, and drying at 35-40 ℃ to obtain β -cyclodextrin composite N-hydroxymethyl acrylamide;
(2) dispersing an ultraviolet light absorber in water, adding β -cyclodextrin composite N-methylolacrylamide prepared in the step (1), ultrasonically dispersing for 1-2 hours, and filtering and drying to obtain β -cyclodextrin for absorbing the ultraviolet light absorber;
(3) adopting seed emulsion polymerization, mixing an acrylic monomer, water, an emulsifier and a water-soluble initiator, and reacting at 65-85 ℃ for 1-3 hours to perform nucleation polymerization to generate emulsion particles; then, continuously adding water, an emulsifier, an organic silicon monomer containing unsaturated bonds and a water-soluble initiator into the emulsion particles, supplementing the emulsifier once every 1 hour at the temperature of 75-85 ℃, and reacting for 3-4 hours;
(4) adding β -cyclodextrin adsorbing the ultraviolet light absorbent prepared in the step (2) into a polymerization kettle along with the last time of adding the emulsifier in the step (3) until the reaction is finished to obtain β -cyclodextrin grafted silicone-acrylic resin;
(5) and (3) uniformly mixing the β -cyclodextrin grafted silicone acrylic resin obtained in the step (4), acrylic resin, diethylene glycol butyl ether, a leveling agent, mica powder, xylene, a pinhole eliminating agent and a defoaming agent to prepare the weather-resistant environment-friendly exterior wall coating.
2. The preparation method of the ultraviolet light aging resistant environment-friendly coating material as claimed in claim 1, wherein the β -cyclodextrin, the N-methylolacrylamide, the dilute hydrochloric acid and the acetone in the step (1) are 1-3: 2-5: 10-20: 5-10 parts by weight.
3. The preparation method of the ultraviolet light aging resistant environment-friendly coating material as claimed in claim 1 or 2, wherein the weight parts of the ultraviolet light absorber, water and β -cyclodextrin composite N-methylolacrylamide in the step (2) are 2-6: 15-20: 3-8.
4. The preparation method of the ultraviolet light aging resistant environment-friendly coating material as claimed in claim 1 or 2, wherein the weight parts of the acrylic monomer, water, the emulsifier, the water-soluble initiator and the unsaturated bond-containing organosilicon monomer in the step (3) are 3-8: 15-30: 10-20: 1-3: 5-10.
5. The preparation method of the ultraviolet light aging resistant environment-friendly coating material as claimed in claim 1 or 2, wherein the β -cyclodextrin grafted silicone-acrylic resin and acrylic resin, diethylene glycol monobutyl ether, the leveling agent, the mica powder, the xylene, the pinhole eliminating agent and the defoaming agent in the step (5) are 20-40: 30-50: 2-5: 0.5-1: 10-25: 15-30: 2-3: 1-2 in parts by weight.
6. The method for preparing the environment-friendly paint resisting ultraviolet light aging according to claim 1 or 2, characterized in that the acrylic monomer in the step (3) is at least one of acrylic acid, methyl acrylate and ethyl acrylate; the emulsifier is at least one of sodium stearate and sodium dodecyl sulfate; the water-soluble initiator is at least one of hydrogen peroxide and sodium sulfite; the organosilicon monomer containing unsaturated bonds is at least one of methyl vinyl chlorosilane and vinyl trichlorosilane.
7. The method for preparing the environment-friendly paint with ultraviolet light aging resistance according to claim 1 or 2, wherein the leveling agent in the step (5) is polydimethylsiloxane; the pinhole eliminating agent is acrylic ester; the defoaming agent is polyethylene glycol ether.
8. The method for preparing the environment-friendly paint resisting ultraviolet light aging according to claim 1 or 2, characterized in that the standing temperature in the step (1) is 0-5 ℃.
9. The method for preparing the environmentally friendly paint resistant to ultraviolet light aging according to claim 1 or 2, wherein the ultraviolet light absorber in the step (2) is EVERSORB SB1 manufactured by taiwan permanent magnet company.
10. The environment-friendly paint with ultraviolet light aging resistance is characterized by being prepared by the preparation method of the environment-friendly paint with ultraviolet light aging resistance according to any one of claims 1 to 9.
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| CN202010343712.9A CN111303713A (en) | 2020-04-27 | 2020-04-27 | Ultraviolet light aging resistant environment-friendly coating and preparation method thereof |
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| CN202010343712.9A CN111303713A (en) | 2020-04-27 | 2020-04-27 | Ultraviolet light aging resistant environment-friendly coating and preparation method thereof |
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| CN106590310A (en) * | 2017-02-21 | 2017-04-26 | 中国科学院成都生物研究所 | Uvioresistant paint with self-repairing function and preparation method and application thereof |
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| US6624238B1 (en) * | 1998-09-12 | 2003-09-23 | Basf Coatings Ag | Intrinsically viscous clear powder coating slurry which is free of organic solvents and external emulsifiers, method for producing said slurry and use of the same |
| US20030203991A1 (en) * | 2002-04-30 | 2003-10-30 | Hydromer, Inc. | Coating composition for multiple hydrophilic applications |
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