CN115109468A - Multifunctional water-based damping paint and preparation method thereof - Google Patents
Multifunctional water-based damping paint and preparation method thereof Download PDFInfo
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- 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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention provides a multifunctional water-based damping coating and a preparation method thereof. According to the invention, the paint prepared by grafting quaternary ammonium salt and carrying nano silver tetrapod-like zinc oxide whiskers is introduced into a paint system as an antibacterial material and a damping reinforcing filler, on one hand, hydrogen bond interaction exists between the paint and a polymer, so that resistance and limitation are caused by relative movement between polymer chain segments, internal consumption is increased, and the function of reinforcing the damping effect of the paint is achieved; on the other hand, the agglomeration phenomenon of nano silver is reduced, the synergistic antibacterial action of quaternary ammonium salt cation antibacterial action, nano silver metal contact sterilization action and zinc oxide sterilization action is formed, and the broad-spectrum antibacterial property and antibacterial effect of the coating are enhanced.
Description
Technical Field
The invention relates to the technical field of damping materials, in particular to a multifunctional water-based damping coating and a preparation method thereof.
Background
China is the world with the longest mileage of high-speed rail, and in the high-speed rail age representing speed and efficiency nowadays, the China high-speed rail is always in high-precision quality as a business card of China economy going to the world. However, with the pursuit of people for higher quality life, higher requirements are also placed on the comfort and safety of people sitting on high-speed rails for travelling. The problems of vibration and noise caused by high-speed movement of a high-speed rail are more and more serious, on one hand, the problems can affect the safety and the reliable stability of vehicle-mounted equipment, and on the other hand, the travelling comfort of passengers is greatly reduced. Aiming at the problem, a mechanical structure with a damping structure is utilized to damp vibration, and a polymer damping material is utilized to damp vibration and reduce noise. The polymer damping material can be divided into damping paint, damping sheet material, porous material and the like, and the damping paint is widely applied due to the advantages of easy construction, easy preparation, low cost and the like. In order to better meet the requirements of people in the prior art on the coating.
For example, chinese patent application No. CN201910971844.3 discloses a tetrapod-like zinc oxide whisker modified polyurethane resin coating, which is prepared from the following raw materials in parts by weight: 20-30 parts of polyether polyol, 3-6 parts of dimethylolpropionic acid, 40-60 parts of isophorone diisocyanate, 10-15 parts of toluene-2, 4-diisocyanate, 0.1-1 part of dibutyl tin dilaurate, 1-3 parts of dimethylaminoethanol, 2-5 parts of hydrogenated modified castor oil, 10-20 parts of polyacrylate precoated tetrapod-like zinc oxide whisker, 1-3 parts of trimethylolpropane, 5-10 parts of butyl acetate, 10-30 parts of ethanol, 1-5 parts of anti-settling agent, 20-25 parts of nano filler and 150 parts of water 120 and other materials; according to the technology, the tetrapod-like zinc oxide whiskers added in the coating are pre-coated by utilizing polyacrylate, and in the method, although polyacrylate used for coating and polyurethane have good compatibility, the problem of poor compatibility still exists between the tetrapod-like zinc oxide whiskers and the polyacrylate, so that a paint film can generate cracks in a long-term use process, later maintenance is increased, and a large amount of manpower and material resources are wasted.
Disclosure of Invention
Aiming at the problems, the invention provides a multifunctional water-based damping paint and a preparation method thereof. The invention carries out graft modification on the tetrapod-like zinc oxide whiskers, improves the compatibility of the tetrapod-like zinc oxide whiskers and a coating polymer, and prolongs the service life of the damping coating.
The specific technical scheme of the invention is as follows:
a multifunctional water-based damping paint is prepared from the following components in parts by weight:
20-25 parts of aqueous emulsion, 8-12 parts of water, 10-13 parts of pigment and filler, 40-50 parts of flame retardant, 1-5 parts of functional micromolecule, 5-10 parts of functional filler, 1-3 parts of coupling agent, 1-2 parts of defoaming agent, 2-3 parts of base material wetting agent, 1-2 parts of dispersing agent, 2-3 parts of film forming auxiliary agent and 1-2 parts of composite antibacterial material;
the functional micromolecules are hindered phenol compounds, the composite antibacterial material is an organic/inorganic synergistic antibacterial material, and the organic/inorganic synergistic antibacterial material is nano-silver-loaded tetrapod-like zinc oxide whiskers grafted with quaternary ammonium salt.
In the prior art, the tetrapod-like zinc oxide whiskers are added in the damping coating, and due to the unique three-dimensional tetrapod-like three-dimensional structure, the tetrapod-like zinc oxide whiskers are easily uniformly distributed in a base material, so that the physical properties of the material are isotropically improved, and meanwhile, a coating film of the coating is endowed with multiple unique functional characteristics, and the coating has excellent properties which cannot be compared with common zinc oxide, such as wear resistance, reinforcement, vibration reduction, skid resistance, noise reduction, wave absorption, ageing resistance, static resistance, bacteria resistance and the like; because of the compatibility of the tetrapod-like zinc oxide whiskers and the damping coating polymer, the tetrapod-like zinc oxide whiskers are pre-coated by polyacrylate, the compatibility of the tetrapod-like zinc oxide whiskers and the damping coating is improved, and a coating film is prevented from cracking in the using process; however, the compatibility of the zinc oxide whisker and the polymer coating the whisker is not high, and a paint film can crack in the using process, so that the quality of the paint is influenced.
In the technical scheme of the invention, the zinc oxide whisker is modified, and the quaternary ammonium salt is grafted, so that hydrogen bonds can be formed between the zinc oxide whisker and a coating polymer, the bonding performance between the tetrapod-like zinc oxide whisker and the coating polymer is enhanced, the tetrapod-like zinc oxide whisker and the polymer are prevented from falling off, the performance of a coating film is greatly improved, and the service life of the coating film is longer; the invention also loads nano silver particles with bactericidal effect on the tetrapod-like zinc oxide whiskers, has better bactericidal and antibacterial effects than the case of independently adding an antibacterial agent, forms the synergistic antibacterial effect of quaternary ammonium salt cation antibacterial, nano silver metal contact sterilization and zinc oxide sterilization, and enhances the broad-spectrum antibacterial property and antibacterial effect of the coating.
Preferably, the water-based emulsion is ethylene-vinyl acetate copolymer emulsion, the solid content of the ethylene-vinyl acetate copolymer emulsion is 50-60%, the viscosity of the ethylene-vinyl acetate copolymer emulsion is 1050-1150 mpa.s, and the glass transition temperature of the ethylene-vinyl acetate copolymer emulsion is 11-15 ℃.
Preferably, the flame retardant is a compound flame retardant, and the compound flame retardant is a mixture of ammonium polyphosphate, melamine and pentaerythritol.
Preferably, in the above technical solution of the present invention, the functional small molecule is selected from one or more of 4,4'- (butyl-1, 1-diyl) bis (2- (tert-butyl) -5-methylphenol), 4' -thiobis (6-tert-butyl-m-cresol), 4 '-methylenebis (2, 6-di-tert-butylphenol), and 6,6' -methylenebis (2- (tert-butyl) -4-methylphenol).
Preferably, in the above technical solution of the present invention, the functional filler is selected from one or more of tetrapod-like zinc oxide whiskers and basic magnesium sulfate whiskers.
Preferably, the coupling agent is one or more selected from gamma-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane and 3-aminopropyltrimethoxysilane.
Preferably, the damping coating further comprises 1-2 parts by weight of a composite antibacterial material, wherein the composite antibacterial material is an organic/inorganic synergistic antibacterial material, and the organic/inorganic synergistic antibacterial material is a grafted quaternary ammonium salt supported nano silver tetrapod-like zinc oxide whisker.
In the above aspect of the present invention, the base wetting agent is preferably selected from one of a modified silicone base wetting agent and an acetylene glycol base wetting agent, and the base wetting agent is further preferably selected from one of BYK346, BYK349, BYK381, and cast 3346.
Preferably, the dispersant is one or more selected from BYK-190, BYK163, TEGO760W, TEGO755W and CASTLE 4110.
Preferably, in the above technical solution of the present invention, the coalescing agent is esteman alcohol ester twelve.
Preferably, the defoaming agent is one or two of BASF 2437, BASF2410, TEGO4100 and TEGO 810.
The invention also aims to provide a preparation method of the multifunctional water-based damping paint, which comprises the following preparation steps:
step 1: dispersing the tetrapod-like zinc oxide whiskers into absolute ethyl alcohol to obtain tetrapod-like zinc oxide whisker dispersion liquid;
step 2: adding ammonia water into the silver nitrate solution to prepare a silver-ammonia solution, and adjusting the pH value of the silver-ammonia solution to 9.5-10.5;
and step 3: mixing the silver ammonia solution and the tetrapod-like zinc oxide whisker dispersion liquid, adding polyvinylpyrrolidone (PVP), stirring in a water bath condition at 60-70 ℃, slowly dripping glucose ethanol solution after 25-35 min, and continuously heating and stirring until the reaction is finished to obtain nano-silver-loaded tetrapod-like zinc oxide whisker turbid liquid;
and 4, step 4: taking the turbid solution of the nano-silver-loaded tetrapod-like zinc oxide crystal whisker in the step 3, and centrifuging, washing and drying to obtain nano-silver-loaded tetrapod-like zinc oxide crystal whisker;
and 5: weighing a proper amount of coupling agent and equimolar succinic anhydride, dispersing the coupling agent and the succinic anhydride in DMF to form a first solution, and dispersing the nano-silver-loaded tetrapod-like zinc oxide whiskers in the step 4 in a mixed solution consisting of DMF and deionized water to obtain a nano-silver-loaded tetrapod-like zinc oxide whisker suspension; mixing the first solution and the nano-silver-loaded tetrapod-like zinc oxide whisker suspension, reacting under a stirring condition, and filtering, washing and drying after the reaction is finished to obtain nano-silver-loaded tetrapod-like zinc oxide whiskers with carboxylated surfaces;
step 6: mixing the surface-carboxylated nano-silver-loaded tetrapod-like zinc oxide whiskers obtained in the step 5 with Polyethyleneimine (PEI) with equal mass, dispersing in deionized water, stirring at room temperature for reaction for 7.5-8.5 hours, and filtering, washing and drying after the reaction is finished to obtain surface-amidated nano-silver-loaded tetrapod-like zinc oxide whiskers;
and 7: dispersing the surface amidated nano silver-loaded tetrapod-like zinc oxide whiskers in the step 6 into deionized water to obtain a second solution, stirring at a low temperature of 1-8 ℃, slowly dropwise adding propylene oxide into the second solution, reacting for 7-8 hours, and filtering, washing and drying to obtain nano silver-loaded tetrapod-like zinc oxide whiskers with tertiary aminated surfaces; wherein the amount of the substance added with propylene oxide is at least twice of the amount of the substance carrying the nano silver tetrapod-like zinc oxide whiskers with amidation on the surface.
And 8: and (3) dispersing the nano silver-loaded tetrapod-like zinc oxide whisker product with the surface subjected to tertiary amination in the step (7) into acetone, stirring at the temperature of 45-55 ℃, and mixing in a molar ratio of 1: 1, slowly dripping n-butyl bromide into the mixture for alkylation, and filtering, washing and drying the mixture after the reaction is finished to obtain the nano-silver-loaded tetrapod-like zinc oxide whisker grafted with quaternary ammonium salt;
and step 9: according to the formula, the water-based ethylene-vinyl acetate copolymer emulsion is placed under a high-speed dispersion machine to be dispersed at 2500-3500 r/min, then water, a base material wetting agent, a dispersing agent, a film forming auxiliary agent, a pigment filler, a composite antibacterial material, a flame retardant, functional micromolecules and a functional filler are sequentially added into the water-based ethylene-vinyl acetate copolymer emulsion, after the sequential addition is completed, the temperature of a coating dispersion container is continuously reduced, the high-speed dispersion at 2500-3000 r/min is kept for 2.5-3.5 h, a small amount of defoaming agent is continuously added in the dispersion process according to the bubble state of the coating, and the multifunctional water-based damping coating can be obtained after the dispersion is finished.
In the technical scheme of the invention, silver particles with a bactericidal effect are loaded on the surface of the tetrapod-like zinc oxide whisker, so that the phenomenon of agglomeration in the coating caused by independently adding the silver particles is avoided; simultaneously, the four-needle-shaped crystal whisker is grafted by a four-step method, carboxylate radical is grafted on the surface of the silver-loaded four-needle-shaped zinc oxide crystal whisker by a coupling agent, then the silver-loaded four-needle-shaped zinc oxide crystal whisker is reacted with PEI for amidation, then the silver-loaded four-needle-shaped zinc oxide crystal whisker is reacted with propylene oxide for tertiary amination, and finally the silver-loaded four-needle-shaped zinc oxide crystal whisker is reacted with halogenated hydrocarbon to form the grafted quaternary ammonium salt.
In conclusion, the beneficial effects of the invention are as follows:
1. the nanometer silver-loaded tetrapod-like zinc oxide crystal whisker grafted with the quaternary ammonium salt is introduced into a coating system as an antibacterial material and a damping reinforcing filler, and hydrogen bond interaction exists between the nanometer silver-loaded tetrapod-like zinc oxide crystal grafted with the quaternary ammonium salt and a coating polymer, so that the compatibility of the nanometer silver-loaded tetrapod-like zinc oxide crystal grafted with the quaternary ammonium salt and the coating polymer is enhanced;
2. the tetrapod-like zinc oxide crystals are introduced, so that resistance and limitation are caused to relative movement between polymer chain segments, internal consumption is increased, and the function of enhancing the damping effect of the coating is achieved;
3. according to the invention, silver particles are loaded on the surface of the tetrapod-like zinc oxide whisker, so that the agglomeration phenomenon of nano silver is reduced, the synergistic antibacterial action of quaternary ammonium salt cation antibacterial, nano silver metal contact sterilization and zinc oxide sterilization is formed, and the broad-spectrum antibacterial property and antibacterial effect of the coating are enhanced;
4. the paint provided by the invention has the functions of fire prevention, antibiosis, damping and the like, avoids the traditional requirement of a multilayer spraying process, simplifies the spraying process, reduces the cost and the workload of spraying the paint, lightens the later maintenance cost, saves manpower and material resources, and accords with the development trend of environmental protection, diversification, functionalization and light weight of the current paint;
5. the preparation method of the coating provided by the invention is simple and suitable for industrial production.
Drawings
FIG. 1 is a scanning electron microscope image of tetrapod-like zinc oxide whiskers;
FIG. 2 is a scanning electron microscope image of silver-carrying tetrapod-like zinc oxide whiskers;
FIG. 3 is a coating damping test of example 1;
FIG. 4 is a graph of large panel combustion refractory time for various embodiments;
FIG. 5 is a graph of damping performance with the addition of various embodiments;
FIG. 6 is a graph of the antimicrobial performance of coatings from different examples.
Detailed Description
The invention will now be further illustrated by the following examples, without limiting the scope of the invention thereto.
Example 1
Preparation of (one) nano silver carried tetrapod-like zinc oxide whisker
Step 1: 10 g of tetrapod-like zinc oxide whiskers are added into 100 ml of absolute ethyl alcohol, and ultrasonic dispersion is carried out for 30 min for later use.
Step 2: weighing 2.7 ml of silver nitrate solution with the concentration of 0.5mol/L, adding the silver nitrate solution into a proper amount of deionized water, taking 15 ml of ammonia water, slowly pouring the solution while stirring until the solution is clear, and adjusting the pH value to 10.
And step 3: mixing the silver ammonia solution and the tetrapod-like zinc oxide whisker dispersion liquid, adding 5 g of polyvinylpyrrolidone (PVP), performing magnetic stirring in a 65 ℃ water bath kettle, slowly dripping 10 ml of 0.5mol/L glucose ethanol solution after 30 min, continuously heating and stirring for 2h, and finishing the reaction.
And 4, step 4: and after the reaction is finished, cooling to room temperature, centrifugally separating the product, washing for 3-5 times by using deionized water, and drying in an oven at 80 ℃ to obtain the nano silver-loaded tetrapod-like zinc oxide whisker.
Preparation of (II) grafted quaternary ammonium salt nano silver-carried tetrapod-like zinc oxide whisker
Step 1: weighing 1 g of coupling agent and equivalent succinic anhydride, dispersing the coupling agent and the succinic anhydride in 50ml of DMF, magnetically stirring for 2h, then adding the suspension of the nano-silver-loaded tetrapod-shaped zinc oxide whiskers fully dispersed in the mixed solution of the DMF and the deionized water inwards, magnetically stirring for 5h, washing a product with the deionized water and absolute ethyl alcohol after the reaction is finished, and drying to obtain the nano-silver-loaded tetrapod-shaped zinc oxide whiskers with the carboxylated surfaces.
Step 2: and (2) placing the nano-silver-loaded tetrapod-like zinc oxide whiskers with the carboxylated surfaces prepared in the step (1) into a flask, then adding Polyethyleneimine (PEI) with the same mass, adding deionized water, carrying out ultrasonic dispersion for 1 h, then carrying out magnetic stirring reaction for 8 h at room temperature, washing with deionized water and absolute ethyl alcohol after the reaction is finished, carrying out suction filtration, and drying, wherein the purpose of the step is to amidate carboxyl and realize grafting of PEI.
And step 3: and (3) dispersing the product obtained in the step (2) into 100 ml of deionized water, magnetically stirring at a low temperature of 5 ℃, slowly dropwise adding 10 g of propylene oxide into the mixture, reacting for 6 hours, washing with absolute ethyl alcohol and deionized water after the reaction is finished, performing suction filtration, and drying to perform tertiary amination on the surface.
And 4, step 4: and (3) dispersing a proper amount of the product obtained in the step (3) into 100 ml of acetone, slowly dropwise adding 10 g of n-butyl bromide into the acetone at the water bath temperature of 50 ℃ for alkylation, magnetically stirring the mixture for 8 hours, washing the mixture by using deionized water and absolute ethyl alcohol after the reaction is finished, carrying out suction filtration and drying to obtain the nano-silver-loaded tetrapod-like zinc oxide whisker grafted with quaternary ammonium salt.
(III) preparation of the coating
Weighing 22 g of water-based ethylene-vinyl acetate copolymer emulsion, placing the water-based ethylene-vinyl acetate copolymer emulsion in a high-speed dispersion machine for dispersion at 3000 r/min, then adding 9 g of water, a base material wetting agent BYK 3462 g, a dispersing agent BYK 1901 g, a film-forming additive elsinantol ester twelve 3 g, a pigment filler titanium dioxide 8 g, calcium carbonate 3 g, nano-silver-loaded tetrapod-like zinc oxide whisker grafted with quaternary ammonium salt 1.5 g, a compound flame retardant ammonium polyphosphate 22 g, melamine 12 g, pentaerythritol 12 g, functional micromolecule 4,4' - (butyl-1, 1-diyl) bis (2- (tert-butyl) -5-methylphenol) 2 g and a functional filler grafted quaternary ammonium salt tetrapod-like zinc oxide whisker 5 g in sequence, after the addition is finished, introducing flowing cooling water to continuously cool a coating container, keeping 3000 r/min high-speed dispersion for 3 h, and (3) paying attention to the bubble state of the coating in the dispersion process, continuously adding a small amount of defoaming agent, and obtaining the coating after dispersion is finished.
Example 2
Preparing nano silver-carrying tetrapod-like zinc oxide whiskers: same as example 1
(II) preparing the nano-silver-loaded tetrapod-like zinc oxide whisker grafted with the quaternary ammonium salt: same as example 1
(III) preparation of the coating
Weighing 22 g of water-based ethylene-vinyl acetate copolymer emulsion, placing the water-based ethylene-vinyl acetate copolymer emulsion in a high-speed dispersion machine for dispersion at 3000 r/min, then adding 9 g of water, a base material wetting agent BYK 3462 g, a dispersing agent BYK 1901 g, a film-forming additive elsinantol ester twelve 3 g, a pigment filler titanium dioxide 8 g, calcium carbonate 3 g, nano-silver-loaded tetrapod-like zinc oxide whiskers grafted with quaternary ammonium salt 1.5 g, a compound flame retardant ammonium polyphosphate 26 g, melamine 8 g, pentaerythritol 10 g, functional micromolecule 4,4' -thiobis (6-tert-butyl-m-cresol) 2 g and functional filler grafted with tetrapod-like zinc oxide whiskers grafted with quaternary ammonium salt 5 g, after the sequential addition, introducing flowing cooling water for continuously cooling a coating container, keeping 3000 r/min high-speed dispersion for 3 h, paying attention to the coating bubble state in the dispersion process, and continuously adding a small amount of defoaming agent, and obtaining the coating after dispersion is finished.
Example 3
Preparing nano silver-loaded tetrapod-like zinc oxide whiskers: same as example 1
(II) preparing the nano-silver-loaded tetrapod-like zinc oxide whisker grafted with the quaternary ammonium salt: same as example 1
(III) preparation of the coating
Weighing 22 g of water-based ethylene-vinyl acetate copolymer emulsion, placing the water-based ethylene-vinyl acetate copolymer emulsion in a high-speed dispersion machine for dispersion at 3000 r/min, then adding 9 g of water, a base material wetting agent BYK 3462 g, a dispersing agent BYK 1901 g, a film-forming additive elsinantol ester twelve 3 g, a pigment filler titanium dioxide 8 g, calcium carbonate 3 g, nano-silver-loaded tetrapod-like zinc oxide whiskers grafted with quaternary ammonium salt 1.5 g, a compound flame retardant ammonium polyphosphate 22 g, melamine 10 g, pentaerythritol 10 g, functional small molecule 4,4' -methylenebis (2, 6-di-tert-butylphenol) 2 g and functional filler grafted tetrapod-like zinc oxide whiskers grafted with quaternary ammonium salt 5 g, after the sequential addition, introducing flowing cooling water for continuously cooling a coating container, keeping 3000 r/min high-speed dispersion for 3 h, paying attention to the coating bubble state in the dispersion process, and continuously adding a small amount of defoaming agent, and obtaining the coating after the dispersion is finished.
Example 4
Preparing nano silver-loaded tetrapod-like zinc oxide whiskers: same as example 1
(II) preparing the nano-silver-loaded tetrapod-like zinc oxide whisker grafted with the quaternary ammonium salt: same as example 1
(III) preparation of the coating
Weighing 22 g of water-based ethylene-vinyl acetate copolymer emulsion, placing the water-based ethylene-vinyl acetate copolymer emulsion in a high-speed dispersion machine for dispersion at 3000 r/min, then adding 9 g of water, a substrate wetting agent BYK 3462 g, a dispersing agent BYK 1901 g, a film-forming additive elsinantol ester twelve 3 g, a pigment filler titanium dioxide 8 g, calcium carbonate 3 g, nano-silver-loaded tetrapod zinc oxide whiskers grafted with quaternary ammonium salt 1.5 g, a compound flame retardant ammonium polyphosphate 24 g, melamine 8 g, pentaerythritol 12 g, a functional micromolecule 6,6' -methylenebis (2- (tert-butyl) -4-methylphenol) 2 g and needle-shaped zinc oxide whiskers grafted with quaternary ammonium salt as a functional filler 5 g into the water-based ethylene-vinyl acetate copolymer emulsion in sequence, after the addition is finished, introducing flowing cooling water to continuously cool a coating container, keeping 3000 r/min for high-speed dispersion for 3 h, and (3) paying attention to the bubble state of the coating in the dispersion process, continuously adding a small amount of defoaming agent, and obtaining the coating after dispersion is finished.
Comparative example
The preparation method of the common water-based damping paint is as follows:
weighing 22 g of water-based ethylene-vinyl acetate copolymer emulsion, placing the water-based ethylene-vinyl acetate copolymer emulsion in a high-speed dispersion machine, dispersing at 3000 r/min, then sequentially adding 9 g of water, 9 g of a base material wetting agent BYK 3462 g, 1901 g of a dispersing agent BYK, twelve 3 g of film-forming aid Islammonium ester, 8 g of pigment filler titanium dioxide, 3 g of calcium carbonate, 20 g of compound flame retardant ammonium polyphosphate outside the preferable proportioning range, 6 g of melamine, 14 g of pentaerythritol and 5 g of functional filler tetrapod-shaped zinc oxide whiskers, after the sequential addition is finished, introducing flowing cooling water to continuously cool a coating container, keeping 3000 r/min high-speed dispersion for 3 h, paying attention to the bubble state of the coating in the dispersion process, continuously adding a small amount of defoaming agent, and after the dispersion is finished, thus obtaining the coating.
In the above examples 1 to 4 and comparative examples, the inventors conducted the following tests:
the scanning electron microscope was a Nova 450 field emission scanning electron microscope (Fei, USA) and the test was carried out at an accelerating voltage of 5 kV, as shown in FIGS. 1 and 2.
The coating vibration reduction test adopts an EDM-1000 electric vibration test system of Hangzhou hundred million constant technology limited company to test the actual vibration reduction performance of the coating, the test frequency is 5-400 Hz, the input acceleration is 0.5 g, and the test result is shown in figure 3.
The fire resistance time adopts a fire-retardant coating large plate combustion test system, a thermocouple temperature measurement sensing line is attached to the back of a large plate to be tested, the difference between the internal temperature of the test equipment and the back temperature of the large plate is monitored, the temperature in the equipment is controlled by adopting automatic program temperature rise, the time when the temperature of the large plate back plate reaches 500 ℃ is taken as the fire resistance time in the test, and the test result is shown in figure 4.
The damping performance is tested by adopting a dynamic thermal mechanical analyzer DMA 8000 produced by Kyoda limited company to test the damping coefficient of the coating, the temperature range is-30 ℃ to 100 ℃, the heating rate is 3 ℃/min, the frequency is 2 Hz, the sample is cut into 10 mm by 2mm, and the test result is shown in figure 5.
The antibacterial performance test adopts the HG/T3950-2007 antibacterial coating standard. The strains selected for the antibacterial test were Escherichia coli (Escherichia coli) representing gram-negative bacteria, Staphylococcus aureus (Staphylococcus aureus) representing gram-positive bacteria, and Aspergillus niger representing mold, and the test results are shown in FIG. 6.
Differences of example 1, example 2, example 3 and example 4: firstly, different proportions are selected to be combined in the preferable range of the three compound flame retardants, the fireproof effect of the coating in the preferable range of the compound flame retardants is verified, then different functional micromolecules are respectively added, and the improvement of the functional micromolecules on the damping performance of the coating is verified. Compared with the examples, the compound flame retardant of the comparative example is not combined in the preferable range, and the nano silver-loaded tetrapod zinc oxide whisker grafted with quaternary ammonium salt is not added.
As can be seen from fig. 1 (SEM of example), the left graph shows that the nano silver-free tetrapod-like zinc oxide whiskers are smooth-surfaced crystals, and after modification, the nano silver particles are successfully loaded on the surface of the tetrapod-like zinc oxide whiskers as shown in the right graph.
It can be found from fig. 2 (vibration test of embodiment 1 with the best damping effect) that the vibration reduction test is performed on the coating by using the electronic vibration test system, the input acceleration is 0.5 g, compared with an empty steel plate, a steel plate coated with a coating with a thickness of 1mm, and a steel plate coated with a coating with a thickness of 2mm, the test result shows that the vibration of the steel plate after coating is almost completely eliminated, because the coating has the excellent damping effect, when the vibration system vibrates with different frequencies, the relative displacement between the molecular chain of the polymer and the molecular chain in the coating and between the molecular chain and the filler is limited, most of the kinetic energy generated by the vibration is converted into heat energy, and the form consumption is almost exhausted, so that the vibration amplitude of the steel plate is reduced, and the vibration reduction effect is achieved.
As shown in the attached figure 3, when the compound flame retardant is in a preferred range, the fire resistance time of the coatings of different examples is 47.8 min (example 1), 43.5 min (example 2), 42.7 min (example 3) and 38.8 min (example 4), respectively, while the fire resistance time of the coatings of comparative examples is only 29.1 min, which shows that the fire resistance of the coatings can be obviously improved by the preferred compound flame retardant.
As can be seen from the attached figure 4, the damping performance tan delta peak height of the coating (examples 1 to 4) added with the functional micromolecules is improved by 13 to 38 percent compared with the coating (comparative example) not added with the functional micromolecules, because the functional micromolecules improve the crosslinking degree among resin matrix molecular chains, the relative motion of the molecular chains of the coating can be limited under the action of the crosslinking stress, so that more mechanical energy can be consumed, and the damping performance of the coating is improved.
As can be found in the attached figure 5, the coating of the nano-silver-loaded tetrapod-like zinc oxide whisker added with the composite antibacterial material grafted quaternary ammonium salt achieves the highest level of antibacterial effects on escherichia coli, staphylococcus aureus and aspergillus niger, which shows that the prepared organic-inorganic dual-load antibacterial material has broad-spectrum antibacterial property and strong antibacterial effect, while the coating without the composite antibacterial material in the comparative example has no antibacterial property.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. The multifunctional water-based damping paint is prepared from the following components in parts by weight:
20-25 parts of aqueous emulsion, 8-12 parts of water, 10-13 parts of pigment and filler, 40-50 parts of flame retardant, 1-5 parts of functional micromolecule, 5-10 parts of functional filler, 1-3 parts of coupling agent, 1-2 parts of defoaming agent, 2-3 parts of base material wetting agent, 1-2 parts of dispersing agent, 2-3 parts of film forming auxiliary agent and 1-2 parts of composite antibacterial material;
the functional micromolecules are hindered phenol compounds, the composite antibacterial material is an organic/inorganic synergistic antibacterial material, and the organic/inorganic synergistic antibacterial material is nano-silver-loaded tetrapod-like zinc oxide whiskers grafted with quaternary ammonium salt.
2. The multifunctional water-based damping paint as claimed in claim 1, wherein the water-based emulsion is an ethylene-vinyl acetate copolymer emulsion, the ethylene-vinyl acetate copolymer emulsion has a solid content of 50-60%, a viscosity of 1050-1150 mpa.s, and a glass transition temperature of 11-15 ℃.
3. The multifunctional water-based damping paint as claimed in claim 1, wherein the flame retardant is a compound flame retardant, and the compound flame retardant is a mixture of ammonium polyphosphate, melamine and pentaerythritol.
4. The multifunctional aqueous damping paint of claim 1, wherein the functional small molecule is selected from one or more of 4,4'- (butyl-1, 1-diyl) bis (2- (tert-butyl) -5-methylphenol), 4' -thiobis (6-tert-butyl-m-cresol), 4 '-methylenebis (2, 6-di-tert-butylphenol), and 6,6' -methylenebis (2- (tert-butyl) -4-methylphenol).
5. The multifunctional water-based damping paint as claimed in claim 1, wherein the functional filler is selected from one or more of tetrapod-like zinc oxide whiskers and basic magnesium sulfate whiskers.
6. The multifunctional water-based damping paint as claimed in claim 1, wherein the coupling agent is selected from one or more of gamma-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, and 3-aminopropyltrimethoxysilane.
7. The multifunctional water-based damping paint as claimed in claim 1, wherein the substrate wetting agent is selected from one of modified silicone substrate wetting agents and acetylene glycol substrate wetting agents.
8. The multifunctional aqueous damping paint of claim 1, wherein the dispersant is selected from one or more of BYK-190, BYK163, TEGO760W, TEGO755W, CASTLE 4110.
9. The preparation method of the multifunctional water-based damping coating material as claimed in any one of claims 1 to 8, comprising the following preparation steps:
step 1: dispersing the tetrapod-like zinc oxide whiskers into absolute ethyl alcohol to obtain tetrapod-like zinc oxide whisker dispersion liquid;
step 2: adding ammonia water into the silver nitrate solution to prepare a silver-ammonia solution, and adjusting the pH value of the silver-ammonia solution to 9.5-10.5;
and step 3: mixing the silver ammonia solution and the tetrapod-like zinc oxide whisker dispersion liquid, adding polyvinylpyrrolidone (PVP), stirring in a water bath condition at 60-70 ℃, slowly dripping glucose ethanol solution after 25-35 min, and continuously heating and stirring until the reaction is finished to obtain nano-silver-loaded tetrapod-like zinc oxide whisker turbid liquid;
and 4, step 4: taking the turbid solution of the nano-silver-loaded tetrapod-like zinc oxide crystal whisker in the step 3, and centrifuging, washing and drying to obtain nano-silver-loaded tetrapod-like zinc oxide crystal whisker;
and 5: weighing a proper amount of coupling agent and equimolar succinic anhydride, dispersing the coupling agent and the succinic anhydride in DMF to form a first solution, and dispersing the nano-silver-loaded tetrapod-like zinc oxide whiskers in the step 4 in a mixed solution consisting of DMF and deionized water to obtain a nano-silver-loaded tetrapod-like zinc oxide whisker suspension; mixing the first solution and the nano-silver-loaded tetrapod-like zinc oxide whisker suspension, reacting under a stirring condition, and filtering, washing and drying after the reaction is finished to obtain nano-silver-loaded tetrapod-like zinc oxide whiskers with carboxylated surfaces;
step 6: mixing the nano-silver-loaded tetrapod-like zinc oxide whiskers subjected to surface carboxylation in the step 5 with Polyethyleneimine (PEI) with equal mass, dispersing the mixed materials in deionized water, stirring and reacting for 7.5-8.5 hours at room temperature, and filtering, washing and drying the obtained product after the reaction is finished to obtain nano-silver-loaded tetrapod-like zinc oxide whiskers subjected to surface amidation;
and 7: dispersing the surface amidated nano silver-loaded tetrapod-like zinc oxide whiskers in the step 6 into deionized water to obtain a second solution, stirring at a low temperature of 1-8 ℃, slowly dropwise adding propylene oxide into the second solution, reacting for 7-8 hours, and filtering, washing and drying to obtain nano silver-loaded tetrapod-like zinc oxide whiskers with tertiary aminated surfaces; wherein the amount of the substance added with propylene oxide is at least twice of the amount of the substance carrying the nano silver tetrapod-like zinc oxide whiskers with amidation on the surface.
And 8: and (3) dispersing the nano silver-loaded tetrapod-like zinc oxide whisker product with the surface subjected to tertiary amination in the step (7) into acetone, stirring at the temperature of 45-55 ℃, and mixing in a molar ratio of 1: 1, slowly dripping n-butyl bromide into the mixture for alkylation, and filtering, washing and drying the mixture after the reaction is finished to obtain the nano-silver-loaded tetrapod-like zinc oxide whisker grafted with quaternary ammonium salt;
and step 9: according to the formula, the water-based ethylene-vinyl acetate copolymer emulsion is placed under a high-speed dispersion machine to be dispersed at 2500-3500 r/min, then water, a base material wetting agent, a dispersing agent, a film forming auxiliary agent, pigment and filler, a composite antibacterial material, a flame retardant, functional micromolecules and functional filler are sequentially added into the water-based ethylene-vinyl acetate copolymer emulsion, after the sequential addition is completed, the coating dispersion container is continuously cooled, the high-speed dispersion at 2500-3000 r/min is kept for 2.5-3.5 h, a small amount of defoaming agent is continuously added in the dispersion process according to the bubble state of the coating, and the multifunctional water-based damping coating can be obtained after the dispersion is finished.
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