CN116535925A - Water-based flame-retardant anticorrosive coating and preparation method thereof - Google Patents

Water-based flame-retardant anticorrosive coating and preparation method thereof Download PDF

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CN116535925A
CN116535925A CN202310663429.8A CN202310663429A CN116535925A CN 116535925 A CN116535925 A CN 116535925A CN 202310663429 A CN202310663429 A CN 202310663429A CN 116535925 A CN116535925 A CN 116535925A
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monomer
flame
retardant
water
following
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徐添懿
陈祝都乐
黄卓
简懿璐
冯钰�
林祖达
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Zhejiang Tongji Vocational College of Science and Technology
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Abstract

The invention discloses a water-based flame-retardant anticorrosive coating and a preparation method thereof, comprising the following steps: (1) Mixing and dissolving hydrophobic vinyl monomer, polar vinyl monomer, flame-retardant functional monomer and co-stabilizer to form oil phase solution; (2) Dispersing the inorganic nano particles with the surface modified by vinyl into water to obtain aqueous dispersion liquid of the inorganic nano particles; (3) And then the flame-retardant nano composite anticorrosive coating is prepared through free radical copolymerization. According to the invention, surface modified inorganic nano particles are used as a stabilizer instead of an organic micromolecular emulsifier, a miniemulsion polymerization system is stabilized, and in monomer droplets, a hydrophobic vinyl monomer, a polar vinyl monomer and a flame-retardant functional monomer are subjected to free radical copolymerization reaction to prepare the nano composite anti-corrosion coating with flame retardant property.

Description

Water-based flame-retardant anticorrosive coating and preparation method thereof
Technical Field
The invention belongs to the field of coating preparation, and particularly relates to a water-based flame-retardant anticorrosive coating and a preparation method thereof.
Background
With the increasing demand of the green development of the anti-corrosion coating, the replacement of solvent-type anti-corrosion coating with aqueous anti-corrosion coating has become a development trend of the anti-corrosion coating industry, wherein the development of high-performance aqueous anti-corrosion coating emulsion has become an important development direction of the related field of anti-corrosion coating. However, aqueous corrosion protection coatings still suffer from deficiencies in overall adhesion properties, water resistance, etc. [ Langmuir 2011,27,3878-3888 ]. The reason for this is that, in addition to the molecular structure design of the anti-corrosion coating polymer itself, small molecule emulsifiers added during the synthesis of aqueous anti-corrosion coating emulsions also have an important impact on the adhesion properties of the anti-corrosion coating [ Journal ofApplied Polymer Science 2010,115,1125-1130 ]. The residue of the emulsifier in the anti-corrosive coating emulsion can be reduced by repeated centrifugation-washing, but the treatment method still exists: (1) complicated procedures, and a large amount of wastewater can be generated; (2) After removing part of the emulsifier, the stability of the anti-corrosion coating emulsion is reduced; (3) The residual emulsifier still deteriorates the adhesion properties of the corrosion-resistant coating.
With the progress of technology and the development of economy, in order to meet the demands of high-rise buildings, light weight automobiles, high-rise electrical appliances, high-grade furniture, and the like, adhesive connection is increasingly replacing mechanical connection. The materials used in the above application fields are required to have excellent flame retardant properties, so that imparting excellent flame retardant properties to the anticorrosive coating while maintaining high adhesion properties has become a research hotspot in the field of anticorrosive coating development. [ ACS Sustainable Chemistry & Engineering 2017,5,3353-3361 ]
Disclosure of Invention
The invention aims to provide a water-based flame-retardant anticorrosive coating and a preparation method thereof, wherein in a miniemulsion polymerization system, inorganic particles with surface vinyl modified replace micromolecular emulsifying agents to serve as colloid stabilizers, and a vinyl-containing flame-retardant functional monomer is introduced to prepare the water-based flame-retardant nano composite anticorrosive coating through free radical copolymerization reaction of the vinyl-containing flame-retardant functional monomer and a general monomer.
In order to solve the technical problems, the following technical scheme is adopted:
the water-based flame-retardant anticorrosive coating and the preparation method thereof are characterized by comprising the following steps:
(1) Mixing and dissolving a hydrophobic vinyl monomer, a polar vinyl monomer, a flame-retardant functional monomer and a co-stabilizer to form an oil phase solution, wherein the mass dosage of the hydrophobic vinyl monomer is 30-95% of the total mass dosage of the monomers (namely, the total mass of the hydrophobic vinyl monomer, the polar vinyl monomer and the flame-retardant functional monomer is the same as the following), the mass dosage of the polar vinyl monomer is 0.5-15% of the total mass dosage of the monomers, and the mass dosage of the flame-retardant monomer is 1-40% of the total mass dosage of the monomers; the mass consumption of the co-stabilizer is 0-12% of the total mass consumption of the monomers;
(2) Dispersing the surface modified inorganic nano particles in water to obtain aqueous dispersion of the inorganic nano particles, wherein the mass dosage of the inorganic nano particles is 1-20% of the total mass dosage of the monomers, the mass dosage of the water is 60-1900% of the total mass dosage of the monomers, and regulating the pH value of the dispersion to 4-11 by using a pH regulator;
(3) Adding the oil phase solution prepared in the step (1) into the aqueous dispersion of the inorganic particles obtained in the step (2), and pre-emulsifying under the stirring intensity of 100-1000 rpm to obtain coarse emulsion; finally, placing the container filled with the coarse emulsion in an ice-water bath, and performing ultrasonic treatment for 0.5 to 120 minutes under the power of 30 to 900W to prepare monomer miniemulsion; after nitrogen is introduced and deoxidized, the temperature is adjusted to 25 ℃ to 95 ℃ and reacts for 0.5h to 24h under the protection of nitrogen, so that the flame-retardant nano composite anti-corrosion coating is prepared;
preferably, after said step (1), the hydrophobic vinyl monomer is selected from at least one of the following: acrylate or methacrylate monomers represented by formula (I), vinyl acetate, styrene;
in the formula (I), R 1 Is H or CH 3 ；R 2 Is a C1-C20 aliphatic linear or branched alkyl or- (CH) 2 ) 3 -Si(OCH 3 ) 3 。
Preferably, after said step (1), the polar vinyl monomer is selected from at least one of the following: hydroxyalkyl methacrylates, hydroxyalkyl acrylates, acrylamides, N-hydroxyalkyl acrylamides, methacrylic acid, acrylic acid, dimethylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate.
Preferably, after the step (1), the flame retardant functional monomer is at least one selected from the group consisting of flame retardant-1 monomer to flame retardant-37 monomer, as shown in the following tables 1 and 2:
TABLE 1
(1) Monovinyl flame-retardant functional monomer.
TABLE 2
(2) A divinyl flame retardant functional monomer.
Preferably, the mass consumption of the flame-retardant functional monomer is 5-30% of the total mass consumption of the monomer.
Preferably, the co-stabilizer is selected from at least one of the following in view of the stability of the monomer droplets: C14-C22 fatty straight or branched chain alkanes, and C14-C22 fatty alcohols. Further preferred is at least one of the following: C16-C22 aliphatic linear or branched alkanes, more preferably n-hexadecane.
Preferably, after said step (2), the inorganic nanoparticles are selected from at least one of the following: silica, titania, zinc oxide; further preferred are silica nanoparticles.
Preferably, the size of the inorganic nanoparticles ranges from 10nm to 50nm.
Preferably, after the step (2), the surface modifier of the inorganic nanoparticle is selected from at least one of the following: contains vinyl silane coupling agent and methacrylic acid 2-isocyanic acid ethyl ester. The surface modifier is further preferably a silane coupling agent, the degree of modification of which is expressed in terms of coupling density, defined as TiO per unit square meter 2 The molar amount of modifier for modifying the surface of the particles is given in [ mu ] mol (m 2 TiO 2 ) -1 Wherein the range of coupling densityIs 0.2. Mu. Mol (m 2 TiO 2 ) -1 ～2.0μmol·(m 2 TiO 2 ) -1 . The TiO 2 Nanoparticles can be prepared by existing methods, for example: (1) Synthesizing TiO with particle size of 30 nm-100 nm by sol-gel method 2 Nanoparticles or (2) direct purchase of commercially available TiO in this particle size range 2 And (3) nanoparticles.
Preferably, after said step (2), the pH adjuster is selected from at least one of the following: citric acid, lactic acid, tartaric acid, sodium citrate, sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water, disodium hydrogen phosphate, sodium dihydrogen phosphate and borax.
Preferably, the initiator is then introduced by means a or b:
mode a: in the step (1), adding an oil-soluble initiator into the oil phase solution, wherein the mass dosage of the oil-soluble initiator is 0.05% -5% of the total mass dosage of the monomers;
mode b: in the step (3), a water-soluble initiator is added into the monomer miniemulsion, wherein the mass dosage of the water-soluble initiator is 0.05-5% of the total mass dosage of the monomers.
Preferably, the oil-soluble initiator is selected from at least one of the following: azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide and diisopropyl peroxydicarbonate.
Preferably, the water-soluble initiator is selected from at least one of the following: a redox system consisting of 2,2' -azobisisobutylamidine dihydrochloride, azobiscyano valeric acid, persulfate, an oxidant and a reducing agent; the reducing agent is selected from at least one of the following: sulfite, thiosulfate, bisulfite, ascorbate, oxalic acid; the oxidant is selected from at least one of the following: hydrogen peroxide, persulfates; the persulfate is preferably selected from at least one of the following: ammonium persulfate and potassium persulfate. The reducing agent is further preferably ascorbate or sulfite.
Preferably, the polymerization temperature is preferably 30 to 75 ℃ in consideration of the initiation temperature of the initiator; the reaction time is preferably 1 to 24 hours; in order to prevent the miniemulsion from overheating in the ultrasonic process, the container for containing the macroemulsion is placed in an ice-water bath for ultrasonic treatment, the ultrasonic power is preferably 60-500W, and the ultrasonic time is preferably 5-45 min.
Due to the adoption of the technical scheme, the method has the following beneficial effects:
in the invention, surface modified inorganic nano particles are used as a stabilizer instead of an organic micromolecular emulsifier to stabilize a miniemulsion polymerization system, and in monomer droplets, hydrophobic vinyl monomers, polar vinyl monomers and flame-retardant functional monomers are subjected to free radical copolymerization to prepare the nano composite anti-corrosion coating with flame-retardant performance. The inventor has intensively studied and found that in order to ensure that the vinyl modified inorganic nano particles spontaneously adsorb to the oil-water interface, the coupling density of the surface coupling agent needs to be strictly controlled. Inorganic nano particles with suitable oil-water amphipathy can stably exist on an oil-water interface to form a compact single-layer or multi-layer solid film, so that the bonding aggregation among liquid drops is prevented, and the effect of stabilizing the fine emulsion liquid drops is finally achieved. Inorganic particles with too high a surface coupling density are difficult to disperse uniformly in the aqueous phase and do not provide sufficient colloidal stability for the miniemulsion polymerization system. In a miniemulsion polymerization system with stable inorganic particles, a small molecular emulsifier is not added, so that the post-treatment process of the emulsion is greatly simplified, and on the other hand, the added inorganic particles can also improve the cohesive force of the anti-corrosion coating adhesive film and enhance the adhesive film strength. However, the research shows that the addition amount of the inorganic particles needs to be strictly controlled within a certain interval, the addition amount is too low, the stability capability is insufficient, and the miniemulsion polymerization system is easy to be unstable; the addition amount is too high, the cohesive force of the adhesive film is too strong, and the viscosity of the anti-corrosion coating is reduced.
The inventor has intensively studied and found that the combination and the proportion of the hydrophobic vinyl monomer/the polar vinyl monomer/the flame retardant monomer, the pH value of the system and the TiO 2 The reaction parameters such as dosage and the like can have important influence on the stability of a miniemulsion polymerization system, the size and distribution of nano composite anti-corrosion coating particles, the anti-corrosion coating and microstructure thereof, the adhesive property, the flame retardant property and the like. The introduction of a certain amount of flame-retardant monomer can endow the anticorrosive coating with flame-retardant property, and the flame-retardant property of the anticorrosive coating is obviously improved along with the increase of the dosage of the flame-retardant monomer, but the flame-retardant property of the ethylene-bis-vinylToo high a level of base flame retardant monomer can result in reduced adhesion properties of the corrosion resistant coating. The pH value of the polymerization reaction system is maintained in the range of 7.0-10.0, the effect of inorganic particles and liquid drops is strongest, and the stability of the polymerization system is better. The size of the inorganic nanoparticles as stabilizer is between 30nm and 80nm, which is optimal for the stabilization of the miniemulsion droplets, while with TiO 2 The content is increased, the flame retardant effect of the anti-corrosion coating is also improved, but the existence of excessive inorganic particles weakens the bonding performance.
Compared with the prior art, the invention has the beneficial effects that: the invention aims at stabilizing a miniemulsion polymerization system by adopting a surface-modified inorganic nano particle as a stabilizer to replace a small molecular emulsifier in the frame of a miniemulsion polymerization technology, and preparing the water-based flame-retardant nano composite anti-corrosion coating by introducing a vinyl-containing flame-retardant monomer to participate in a free radical copolymerization reaction. The method has the advantages that: (1) The method has the advantages that a small molecular emulsifier is not used, the post-treatment process of the emulsion is simplified, and the influence of the small molecular emulsifier on the comprehensive adhesive property of the anti-corrosion coating is avoided; (2) The anti-corrosion coating is endowed with excellent flame retardant property, so that the anti-corrosion coating has higher application value in the fields of military industry, electronic components, automobiles, buildings and the like; (3) The formula of the anticorrosive coating is various, the preparation process is simple, and the industrial implementation is easy.
Detailed Description
The invention aims to provide a water-based flame-retardant anticorrosive coating and a preparation method thereof.
The invention is further described below in connection with specific embodiments, but the scope of the invention is not limited thereto:
example 1:
8.87g of isooctyl acrylate, 1.4g of styrene, 0.86g of 2-hydroxyethyl methacrylate, 0.33g of glycidyl acrylate, 4.34g of flame-retardant-22 monomer and 1.06g of n-octadecane are weighed and mixed to obtain an oil phase solution.
1.0g of vinyl-modified TiO 2 Nanoparticles [ number average particle diameter of 50nm, coupling Density of 1.2. Mu. Mol (m 2 TiO 2 ) -1 Pre-dispersing in 95g water, and then weighing 1.54g sodium citrate to obtain pH regulator, to obtain TiO with pH value of 8.9 2 An aqueous dispersion.
Adding the monomer dispersion to TiO 2 Pre-emulsifying the aqueous dispersion liquid under magnetic stirring at 500rpm to obtain coarse emulsion, and placing a container filled with the coarse emulsion in an ice-water bath, and performing ultrasonic treatment for 8min under the power of 300W to obtain stable monomer miniemulsion; then adding 0.27g of water-soluble initiator potassium persulfate into the monomer miniemulsion, introducing nitrogen to remove oxygen, regulating the reaction temperature to 65 ℃, and reacting for 12 hours under the protection of nitrogen to obtain the flame-retardant polyacrylate/TiO 2 Nano composite anticorrosive coating emulsion.
The emulsion has high colloid stability, and no precipitate is generated after centrifugation at 5000rpm for 15 min. The Z average particle diameter of the nano composite anti-corrosion coating particles is 239nm and PDI is 0.118 measured by a dynamic light scattering nano particle size analyzer.
After the solid content of the emulsion was adjusted to 20wt%, 3g of the emulsion was taken, and 1.5g of PTE thickener (Datang resin Co., ltd., sanshui of Buddha) having a solid content of 3.0wt% was added to prepare an anticorrosive coating working solution. A polyethylene terephthalate (PET) film was cut into 20cm X26 cm pieces, and placed in a plasma treatment apparatus (HD-1B, hemsleyak Chang Tai plasma technologies Co., ltd.) and treated under an oxygen atmosphere at 200W for 5 minutes to prepare a PET hydrophilic film. Placing PET hydrophilic film on automatic coater (K control Coater model 202,R K Print Coat Instruments Ltd), selecting No. 3 roller, and processing at 100mm min -1 The anticorrosive coating working solution is applied under the condition of (1) and then baked for 2min at 100 ℃. The PET film after sizing was cut into 2.5cm by 26cm strip samples and subjected to flat angle butt joint with an area of 2.5cm by 25 cm. The shear strength of the adhesive film was measured by a universal stretcher, and the result showed that it was 100 mm.min -1 The shear strength of the film was 24.6MPa. Cutting the PET film after sizing into strips of 2.5cm multiplied by 12.5cmSample, holding the adhesive side of the adhesive tape outwards, making into a standard annular sample with a circumference of 98mm, contacting with a test steel plate specified in GB/T3280-2007, and measuring 300mm min -1 The initial tack of the sample was measured to be 0.78N by pulling up. Cutting PET film into strip sample with 2.5cm×26cm, and stretching at 300mm·min -1 T-peel strength test was conducted under the conditions of (1) to find that the peel strength of the sample was 22.8N.m -1 。
10g of the anti-corrosion coating emulsion is weighed and placed in a tetrafluoroethylene mold with grooves, and after being placed in a constant temperature and humidity box with the temperature of 70 ℃ and the RH of 60% for one week, the complete anti-corrosion coating adhesive film is obtained. According to the requirements of GB/T2406-80, cutting the anticorrosion coating adhesive film into the dimensions of 70mm multiplied by 6mm multiplied by 3.2mm, vertically fixing the sample in a combustion cylinder, enabling oxygen and nitrogen mixed gas flow to flow from bottom to top, igniting the top end of the sample, and simultaneously timing and observing the combustion length of the sample, and comparing with the specified standard criterion. A group of samples are tested in different oxygen concentrations, the lowest oxygen concentration of the anticorrosive coating when the anticorrosive coating just maintains stable combustion is measured, and the limiting oxygen index of the samples is measured to be 28.2% by volume percentage of oxygen in the mixed gas, so that the flame retardant effect is good.
Comparative example 1:
an oil phase solution was obtained by mixing 8.87g of isooctyl acrylate, 1.4g of styrene, 0.86g of 2-hydroxyethyl methacrylate, 0.33g of glycidyl acrylate and 1.06g of n-octadecane.
1.0g of vinyl-modified TiO 2 Nanoparticles [ number average particle diameter of 60nm, coupling Density of 1.2. Mu. Mol (m 2 TiO 2 ) -1 Pre-dispersing in 95g water, and then weighing 1.54g sodium citrate to obtain pH regulator, to obtain TiO with pH value of 8.9 2 An aqueous dispersion.
Adding the monomer dispersion to TiO 2 Pre-emulsifying the aqueous dispersion liquid under magnetic stirring at 500rpm to obtain coarse emulsion, and placing a container filled with the coarse emulsion in an ice-water bath, and performing ultrasonic treatment for 8min under the power of 300W to obtain stable monomer miniemulsion; subsequently, 0.27g of potassium persulfate as a water-soluble initiator was added to the monomer miniemulsion, and after deoxygenation by introducing nitrogen, the reaction temperature was adjusted to 65℃and under nitrogen protectionReacting for 12h to obtain the flame-retardant polyacrylate/TiO 2 Nano composite anticorrosive coating emulsion.
The emulsion has high colloid stability, and no precipitate is generated after centrifugation at 5000rpm for 15 min. The Z average particle diameter of the nano composite anti-corrosion coating particles is 210nm and the PDI is 0.100 measured by a dynamic light scattering nano particle sizer. The adhesive film had a shear strength of 23.9MPa, and the initial adhesion and peel strength of 0.82N and 23.0 N.multidot.m, respectively, using the same sizing process and test method as in example 1 -1 The limiting oxygen index of the sample is 18.4%, and the sample has no flame retardant effect.
Comparative example 2:
8.87g of isooctyl acrylate, 1.4g of styrene, 0.86g of 2-hydroxyethyl methacrylate, 0.33g of glycidyl acrylate, 4.34g of flame-retardant-22 monomer and 1.06g of n-octadecane are weighed and mixed to obtain an oil phase solution.
Dissolving 0.5g of sodium dodecyl sulfate in 95g of water, and then weighing 1.54g of sodium citrate to prepare a pH regulator to obtain TiO with the pH value of 8.9 2 An aqueous dispersion.
Adding the monomer dispersion to TiO 2 Pre-emulsifying the aqueous dispersion liquid under magnetic stirring at 500rpm to obtain coarse emulsion, and placing a container filled with the coarse emulsion in an ice-water bath, and performing ultrasonic treatment for 8min under the power of 300W to obtain stable monomer miniemulsion; then adding 0.27g of water-soluble initiator potassium persulfate into the monomer miniemulsion, introducing nitrogen to remove oxygen, regulating the reaction temperature to 65 ℃, and reacting for 12 hours under the protection of nitrogen to obtain the flame-retardant polyacrylate/TiO 2 Nano composite anticorrosive coating emulsion.
The emulsion has high colloid stability, and no precipitate is generated after centrifugation at 5000rpm for 15 min. The Z average particle diameter of the nano composite anti-corrosion coating particles is 439nm and PDI is 0.180 measured by a dynamic light scattering nano particle sizer. The adhesive film had a shear strength of 21.9MPa, and the initial adhesion and peel strength of 0.65N and 21.6 N.m, respectively, using the same sizing process and test method as in example 1 -1 The limiting oxygen index of the sample is 25.8%, and the flame retardant effect is good.
Example 2:
an oil phase mixed solution was obtained by mixing 5.9g of butyl acrylate, 1.6g of vinyl acetate, 0.05g of acrylamide, 0.03g of 2-hydroxyethyl acrylate, 2.42g of a flame retardant-23 monomer, 0.36g of n-hexadecane and 0.25g of dibenzoyl peroxide.
1.2g of vinyl-modified TiO 2 Nanoparticles [ number average particle diameter of 52nm, coupling Density of 1.4. Mu. Mol (m 2 TiO 2 ) -1 Pre-dispersing in 120g water, then weighing 0.41g disodium hydrogen phosphate and 0.39g sodium dihydrogen phosphate to prepare pH regulator, and obtaining TiO with pH value of 6.8 2 An aqueous dispersion.
Adding the monomer dispersion to TiO 2 Pre-emulsifying the aqueous dispersion liquid under magnetic stirring at 800rpm to obtain coarse emulsion, and placing a container filled with the coarse emulsion in an ice-water bath, and performing ultrasonic treatment for 7min under 400W power to obtain stable monomer miniemulsion; after nitrogen is introduced and deoxidized, the reaction temperature is adjusted to 78 ℃, and the reaction is carried out for 20 hours under the protection of nitrogen, thus preparing the flame-retardant polyacrylate/TiO 2 Nano composite anticorrosive coating emulsion.
The emulsion has high colloid stability, and no precipitate is generated after centrifugation at 5000rpm for 15 min. The Z average particle diameter of the nano composite anti-corrosion coating particles is 330nm and the PDI is 0.175 measured by a dynamic light scattering nano particle sizer. The adhesive film had a shear strength of 22.4MPa, and the initial adhesion and peel strength of 0.77N and 23.7 N.m, respectively, using the same sizing process and test method as in example 1 -1 The limiting oxygen index of the sample was 29.6%.
Example 3:
2.75g of methyl methacrylate, 3.00g of methyl acrylate, 5.5g of butyl acrylate, 0.27g of 2-hydroxypropyl methacrylate, 0.03g of glycidyl acrylate, 1.65g of flame retardant-25 monomer, 0.26g of hexadecane and 0.45g of azobisisobutyronitrile were weighed and mixed to obtain an oil phase solution.
0.5g of vinyl-modified TiO 2 Nanoparticles [ number average particle diameter of 60nm, coupling Density of 1.0. Mu. Mol (m 2 TiO 2 ) -1 Pre-dispersing in 100g water, and then weighing 0.055g disodium hydrogen phosphate and 0.985g sodium dihydrogen phosphate to prepare pH regulator to obtain TiO with pH value of 8.0 2 Moisture contentAnd (5) dispersing liquid.
Adding the monomer dispersion to TiO 2 Pre-emulsifying the aqueous dispersion liquid by magnetic stirring at 700rpm to obtain coarse emulsion, and then placing a container filled with the coarse emulsion in an ice-water bath, and performing ultrasonic treatment for 5min under the power of 450W to obtain stable monomer miniemulsion; after nitrogen is introduced and deoxidized, the reaction temperature is adjusted to 65 ℃, and the reaction is carried out for 10 hours under the protection of nitrogen, thus preparing the flame-retardant polyacrylate/TiO 2 Nano composite anticorrosive coating emulsion.
The emulsion has high colloid stability, and no precipitate is generated after centrifugation at 5000rpm for 15 min. The Z average particle diameter of the nano composite anti-corrosion coating particles is 508nm and the PDI is 0.152 as measured by a dynamic light scattering nano particle sizer. The adhesive film had a shear strength of 28.4MPa, and the initial adhesion and peel strength of 0.68N and 22.3 N.m, respectively, using the same sizing process and test method as in example 1 -1 The limiting oxygen index of the sample is 28.2%, and the flame retardant effect is good.
Example 4:
an oil phase mixed solution was obtained by mixing 7.6g of vinyl acetate, 1.33g of methyl methacrylate, 0.1g of dimethylaminoethyl methacrylate, 0.06g of methacrylic acid, 0.41g of a flame-retardant-32 monomer, 0.79g of n-hexadecane and 0.04g of azobisisoheptonitrile.
0.8g of vinyl-modified TiO 2 Nanoparticles [ number average particle diameter of 35nm, coupling Density of 0.6. Mu. Mol (m 2 TiO 2 ) -1 Pre-dispersing in 105g water, then weighing 0.215g sodium carbonate and 2.1g sodium bicarbonate to prepare pH regulator, obtaining TiO with pH value of 9.0 2 An aqueous dispersion.
Adding the monomer dispersion to TiO 2 Pre-emulsifying the aqueous dispersion liquid by magnetic stirring at 600rpm to obtain coarse emulsion, and then placing a container filled with the coarse emulsion in an ice-water bath, and performing ultrasonic treatment for 12min under the power of 200W to obtain stable monomer miniemulsion; after nitrogen is introduced and deoxidized, the reaction temperature is adjusted to 62 ℃, and the reaction is carried out for 7 hours under the protection of nitrogen, thus preparing the flame-retardant polyacrylate/TiO 2 Nano composite anticorrosive coating emulsion.
The emulsion has high colloidal stability and is centrifuged at 5000rpm for 15No precipitate formed after min. The Z average particle diameter of the nano composite anti-corrosion coating particles is 515nm and the PDI is 0.165 measured by a dynamic light scattering nano particle sizer. The adhesive film had a shear strength of 23.2MPa, and the initial adhesion and peel strength of 0.78N and 24.3 N.m, respectively, using the same sizing process and test method as in example 1 -1 The limiting oxygen index of the sample is 26.6%, and the flame retardant effect is good.
Example 5:
5.75g of methyl methacrylate, 3.3g of butyl acrylate, 2.2g of vinyl acetate, 0.27g of 2-hydroxypropyl methacrylate, 0.03g of methacrylic acid, 0.95g of flame-retardant-8 monomer and 0.26g of n-hexadecane are weighed respectively and mixed to obtain an oil phase mixed solution.
0.75g of vinyl-modified TiO 2 Nanoparticles [ number average particle diameter of 55nm, coupling Density of 0.8. Mu. Mol (m 2 TiO 2 ) -1 Pre-dispersing in 100g water, then weighing 0.16g sodium carbonate and 0.29g sodium bicarbonate to obtain pH regulator, and obtaining TiO with pH value of 9.6 2 An aqueous dispersion.
Adding the monomer dispersion to TiO 2 Pre-emulsifying the aqueous dispersion liquid by magnetic stirring at 700rpm to obtain coarse emulsion, and then placing a container filled with the coarse emulsion in an ice-water bath, and performing ultrasonic treatment for 5min under the power of 450W to obtain stable monomer miniemulsion; then adding 0.08g of water-soluble oxidant potassium persulfate and 0.08g of water-soluble reducing agent sodium sulfite into the monomer miniemulsion, introducing nitrogen to remove oxygen, regulating the reaction temperature to 30 ℃, and reacting for 24 hours under the protection of nitrogen to obtain the flame-retardant polyacrylate/TiO 2 Nano composite anticorrosive coating emulsion.
The emulsion has high colloid stability, and no precipitate is generated after centrifugation at 5000rpm for 15 min. The Z average particle diameter of the nano composite anti-corrosion coating particles is 526nm and the PDI is 0.146 measured by a dynamic light scattering nano particle sizer. The adhesive film had a shear strength of 20.8MPa, and the initial adhesion and peel strength of 0.72N and 22.5 N.m, respectively, using the same sizing process and test method as in example 1 -1 The limiting oxygen index of the sample is 27.3%, and the flame retardant effect is good.
Example 6:
6.67g of methyl methacrylate, 1.41g of butyl acrylate, 1.03g of hydroxyethyl acrylate, 0.22g of glycidyl acrylate, 2.56g of flame-retardant-17 monomer and 0.64g of n-hexadecane are weighed and mixed to obtain an oil phase mixed solution.
1.4g of vinyl-modified TiO 2 Nanoparticles [ number average particle diameter 58nm, coupling Density 0.5. Mu. Mol (m 2 TiO 2 ) -1 Pre-dispersing in 110g water, then weighing 0.23g disodium hydrogen phosphate and 0.98g sodium dihydrogen phosphate to prepare pH regulator, and obtaining TiO with pH value of 7.4 2 An aqueous dispersion.
Adding the monomer dispersion to TiO 2 Pre-emulsifying the aqueous dispersion liquid by magnetic stirring at 650rpm to obtain coarse emulsion, placing a container filled with the coarse emulsion in an ice-water bath, and performing ultrasonic treatment for 10min at a power of 280W to obtain stable monomer miniemulsion; then adding 0.15g of water-soluble oxidant ammonium persulfate and 0.15g of water-soluble reducing agent sodium ascorbate into the monomer miniemulsion, introducing nitrogen to remove oxygen, regulating the reaction temperature to 50 ℃, and reacting for 22 hours under the protection of nitrogen to obtain the flame-retardant polyacrylate/TiO 2 Nano composite anticorrosive coating emulsion.
The emulsion has high colloid stability, and no precipitate is generated after centrifugation at 5000rpm for 15 min. The Z average particle diameter of the nano composite anti-corrosion coating particles is 520nm and PDI is 0.163 measured by a dynamic light scattering nano particle sizer. The adhesive film had a shear strength of 20.4MPa, and the initial adhesion and peel strength of 0.62N and 21.8 N.m, respectively, using the same sizing process and test method as in example 1 -1 The limiting oxygen index of the sample is 26.9%, and the flame retardant effect is good.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions or modifications made on the basis of the present invention to solve the substantially same technical problems and achieve the substantially same technical effects are encompassed within the scope of the present invention.

Claims (10)

1. The water-based flame-retardant anticorrosive coating and the preparation method thereof are characterized by comprising the following steps:
(1) Mixing and dissolving a hydrophobic vinyl monomer, a polar vinyl monomer, a flame-retardant functional monomer and a co-stabilizer to form an oil phase solution, wherein the mass dosage of the hydrophobic vinyl monomer is 30-95% of the total mass dosage of the monomers (namely, the total mass of the hydrophobic vinyl monomer, the polar vinyl monomer and the flame-retardant functional monomer is the same as the following), the mass dosage of the polar vinyl monomer is 0.5-15% of the total mass dosage of the monomers, and the mass dosage of the flame-retardant monomer is 1-40% of the total mass dosage of the monomers; the mass consumption of the co-stabilizer is 0-12% of the total mass consumption of the monomers;
(2) Dispersing the surface modified inorganic nano particles in water to obtain aqueous dispersion of the inorganic nano particles, wherein the mass dosage of the inorganic nano particles is 1-20% of the total mass dosage of the monomers, the mass dosage of the water is 60-1900% of the total mass dosage of the monomers, and regulating the pH value of the dispersion to 4-11 by using a pH regulator;
(3) Adding the oil phase solution prepared in the step (1) into the aqueous dispersion of the inorganic particles obtained in the step (2), and pre-emulsifying under the stirring intensity of 100-1000 rpm to obtain coarse emulsion; finally, placing the container filled with the coarse emulsion in an ice-water bath, and performing ultrasonic treatment for 0.5 to 120 minutes under the power of 30 to 900W to prepare monomer miniemulsion; and (3) after nitrogen is introduced and deoxidized, the temperature is adjusted to 25-95 ℃, and the reaction is carried out for 0.5-24 hours under the protection of nitrogen, so that the flame-retardant nano composite anti-corrosion coating is prepared.
2. The aqueous flame retardant corrosion resistant coating and the preparation method thereof according to claim 1, wherein: said step (1), the hydrophobic vinyl monomer is selected from at least one of the following: acrylate or methacrylate monomers represented by formula (I), vinyl acetate, styrene;
in the formula (I), R 1 Is H or CH 3 ；R 2 Is C1-C20 aliphatic linear or branched alkyl or
(CH 2 ) 3 -Si(OCH 3 ) 3 。
3. The aqueous flame retardant corrosion resistant coating and the preparation method thereof according to claim 1, wherein: said step (1), polar vinyl monomer is selected from at least one of the following: hydroxyalkyl methacrylates, hydroxyalkyl acrylates, acrylamides, N-hydroxyalkyl acrylamides, methacrylic acid, acrylic acid, dimethylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate.
4. The aqueous flame retardant corrosion resistant coating and the preparation method thereof according to claim 1, wherein: the flame-retardant functional monomer in the step (1) is at least one from flame-retardant-1 monomer to flame-retardant-37 monomer.
5. The aqueous flame retardant corrosion resistant coating and the preparation method thereof according to claim 1, wherein: said step (1), the co-stabilizer is selected from at least one of the following: C14-C22 fatty straight or branched chain alkanes, and C14-C22 fatty alcohols.
6. The aqueous flame retardant corrosion resistant coating and the preparation method thereof according to claim 1, wherein: said step (2), the inorganic nanoparticles are selected from at least one of the following: silica, titania, zinc oxide; the size of the inorganic nano particles ranges from 10nm to 50nm.
7. The aqueous flame retardant corrosion resistant coating and the preparation method thereof according to claim 1, wherein: said step (2), the surface modifier of the inorganic nanoparticle is selected from at least one of the following: contains vinyl silane coupling agent and methacrylic acid 2-isocyanic acid ethyl ester.
8. The aqueous flame retardant corrosion resistant coating and the preparation method thereof according to claim 1, wherein: said step (2), the pH regulator is selected from at least one of the following: citric acid, lactic acid, tartaric acid, sodium citrate, sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water, disodium hydrogen phosphate, sodium dihydrogen phosphate and borax.
9. The aqueous flame retardant corrosion resistant coating and the preparation method thereof according to claim 1, wherein: introducing initiator by way a or way b:
mode a: in the step (1), adding an oil-soluble initiator into the oil phase solution, wherein the mass dosage of the oil-soluble initiator is 0.05% -5% of the total mass dosage of the monomers;
mode b: in the step (3), a water-soluble initiator is added into the monomer miniemulsion, wherein the mass dosage of the water-soluble initiator is 0.05-5% of the total mass dosage of the monomers.
10. The aqueous flame retardant corrosion resistant coating and the preparation method thereof according to claim 9, wherein: the oil-soluble initiator is selected from at least one of the following: azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, diisopropyl peroxydicarbonate; the water-soluble initiator is selected from at least one of the following: a redox system consisting of 2,2' -azobisisobutylamidine dihydrochloride, azobiscyano valeric acid, persulfate, an oxidant and a reducing agent; the reducing agent is selected from at least one of the following: sulfite, thiosulfate, bisulfite, ascorbate, oxalic acid; the oxidant is selected from at least one of the following: hydrogen peroxide, persulfates; the persulfate is preferably selected from at least one of the following: ammonium persulfate and potassium persulfate.
CN202310663429.8A 2023-06-06 2023-06-06 Water-based flame-retardant anticorrosive coating and preparation method thereof Pending CN116535925A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110157362A (en) * 2019-06-10 2019-08-23 浙江理工大学 A kind of preparation method of the nano combined binder of waterborne flame retardant type

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110157362A (en) * 2019-06-10 2019-08-23 浙江理工大学 A kind of preparation method of the nano combined binder of waterborne flame retardant type

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