CN112029369A - SiO (silicon dioxide)2Composite anticorrosive material of grafted water-based acrylic epoxy resin and preparation method thereof - Google Patents

SiO (silicon dioxide)2Composite anticorrosive material of grafted water-based acrylic epoxy resin and preparation method thereof Download PDF

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CN112029369A
CN112029369A CN202010945912.1A CN202010945912A CN112029369A CN 112029369 A CN112029369 A CN 112029369A CN 202010945912 A CN202010945912 A CN 202010945912A CN 112029369 A CN112029369 A CN 112029369A
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epoxy resin
sio
water
anticorrosive material
silicon dioxide
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冯程程
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Suma Branch Of Anhui Shengyuan Environmental Protection New Material Co Ltd
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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
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    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
    • C09D5/08—Anti-corrosive paints
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K2201/011—Nanostructured additives

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Abstract

The invention relates to the technical field of anticorrosive materials, and discloses SiO2The composite anticorrosive material of grafted water-base acrylic epoxy resin is prepared with ethyl orthosilicate as silicon source and nanometer SiO containing great amount of hydroxyl radical2Reacting with triethylene tetramine to obtain aminated silicon dioxide, and reacting with epoxy resin under the action of initiatorReacting with methacrylic acid, copolymerizing styrene, butyl acrylate and methacrylic acid to obtain the aqueous acrylic epoxy resin, and reacting with SiO2Reacting to obtain SiO2Grafting aqueous acrylic acid epoxy resin emulsion, nano SiO2Uniformly dispersing, improving the mechanical strength of the waterborne acrylic epoxy resin, increasing the carboxyl content of acrylic acid, improving the hydrophilicity of the composite anticorrosive material, and preparing nano SiO2Has nanometer size effect, fills up the microporous structure of the composite anticorrosive material, and reduces H in the environment2O、O2And the composite anticorrosive material has excellent hydrophilicity, mechanical performance and chemical anticorrosive performance by permeating to the surface of the metal through the micropores.

Description

SiO (silicon dioxide)2Composite anticorrosive material of grafted waterborne acrylic epoxy resin and composite anticorrosive materialMethod for producing
Technical Field
The invention relates to the technical field of anticorrosive materials, in particular to SiO2A composite anticorrosive material grafted with water-based acrylic epoxy resin and a preparation method thereof.
Background
When the metal substrate works, due to the fact that corrosive substances such as air, water, ions and the like are contained in the environment, chemical or electrochemical reaction can occur to cause corrosion and damage, the phenomenon is very common, great influence is caused to industrial development, living environment and the like, the most common method for preventing corrosion is a coating protection method, and the method has the advantages of being low in cost, obvious in effect, simple in construction, simple to use and the like, and the application range is wide.
The epoxy resin coating has excellent corrosion resistance and chemical resistance, but the toughness and impact resistance of the coating after the coating is crosslinked are poor, the solvent type epoxy resin coating easily pollutes the environment and influences the human health, the water-based coating has the advantages of low volatile organic matter content, zero pollution, safe transportation and use and wide application, the acrylic resin has the advantages of excellent weather resistance, hydrophilicity, corrosion resistance and the like, the nano SiO has the advantages of improving the weather resistance, the hydrophilicity, the corrosion resistance and the like of the epoxy resin, and the like2The high-toughness high-temperature-resistant SiO polymer has the advantages of high toughness, excellent corrosion resistance, high temperature resistance and the like, is widely applied to the fields of coatings, composite materials and the like, but is easy to agglomerate in a polymer matrix, so that the application of the high-toughness high-temperature-resistant SiO polymer is limited, and therefore, SiO is adopted2The method for grafting the water-based acrylic epoxy resin solves the problems.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides SiO2The composite anticorrosive material grafted with water-thinned acrylic epoxy resin and its preparation process solve the problems of limited anticorrosive performance and relatively poor mechanical strength of epoxy resin.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: SiO (silicon dioxide)2Composite waterproof of grafted water-based acrylic epoxy resinCorrosion material of said SiO2The preparation method of the composite anticorrosive material grafted with the water-based acrylic epoxy resin comprises the following steps:
(1) adding deionized water, strong ammonia water and isopropanol into a reaction bottle, placing the reaction bottle in a water bath device, uniformly stirring at 55-65 ℃, adding tetraethoxysilane, continuously stirring until the precipitate is completely precipitated, centrifugally washing the precipitate with deionized water and absolute ethyl alcohol, and drying the precipitate to obtain silicon dioxide;
(2) adding thionyl chloride and silicon dioxide into a reaction bottle, carrying out chlorination, distilling under reduced pressure at 25-35 ℃ to remove thionyl chloride, washing with tetrahydrofuran, and drying to obtain chlorinated silicon dioxide;
(3) adding triethylene tetramine and chloro-silicon dioxide into a reaction bottle, carrying out an amination process, cooling to room temperature, washing with absolute ethyl alcohol, and drying in vacuum at room temperature to obtain aminated silicon dioxide;
(4) adding epoxy resin into a reaction bottle, heating to 120 ℃ for 100-2Grafting water-based acrylic acid epoxy resin emulsion;
(5) adding SiO into a reaction bottle2Grafting water-based acrylic epoxy resin emulsion, film-forming additive dipropylene glycol ethyl ether, defoaming agent Z-4933, flatting agent EFKA-3777 and curing agent triethylene tetramine, fully stirring, spraying the mixture on a tin plate polished by sand paper, and standing and culturing at room temperature for 4-6 days to obtain SiO2A composite anticorrosive material grafted with water-based acrylic epoxy resin.
Preferably, the water bath device in the step (1) comprises a main body, a motor is movably connected to the bottom of the main body, a connecting rod is movably connected to the top of the motor, a first gear is movably connected to the right side of the top of the connecting rod, a second gear is movably connected to the left side of the first gear, a third gear is movably connected to the left side of the second gear, a magnet is movably connected to the top of the third gear, a partition board is movably connected to the middle of the main body, and a beaker is movably connected to the top of the.
Preferably, the chlorination process in the step (2) is stirring reaction at 65-75 ℃ for 12-36 h.
Preferably, the amination in the step (3) is carried out for 24-72 hours at the temperature of 90-110 ℃ by stirring.
Preferably, in the step (4), the mass ratio of the epoxy resin, the ethylene glycol butyl ether, the n-butyl alcohol, the methacrylic acid, the styrene, the butyl acrylate, the dibenzoyl peroxide and the aminated silicon dioxide is 100:17-20:35-40:6.5-7.5:4-4.8:4-6:1-2: 1-4.
Preferably, SiO in the step (5)2The mass ratio of the grafted waterborne acrylic epoxy resin emulsion to the film-forming additive dipropylene glycol ethyl ether to the defoaming agent Z-4933 to the leveling agent EFKA-3777 to the curing agent triethylene tetramine is 100:3.5-3.8:0.5-0.6:0.3-0.4: 10-13.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the SiO2The composite anticorrosive material of grafted water-base acrylic epoxy resin is prepared with ethyl orthosilicate as silicon source and through water bath2The surface of the material contains a large number of hydroxyl groups, and then the material is placed in thionyl chloride solution, Cl replaces SiO2Hydroxyl on the surface forms Si-Cl bond, the Si-Cl bond reacts with amino of triethylene tetramine through water bath reaction, and the triethylene tetramine is grafted to nano SiO2Surface of, thereby in SiO2Introducing a large amount of amino groups on the surface to obtain the aminated silicon dioxide.
The SiO2Under the action of dibenzoyl peroxide as initiator, active methylene near ether bond in epoxy resin is in activated state and reacts with carbon-carbon double bond in methacrylic acid while styrene, butyl acrylate and methacrylic acid are copolymerized to make water-thinned acrylic resin connectedBranching to the molecular chain of epoxy resin to obtain water-based acrylic epoxy resin, SiO2The amino group on the surface and the epoxy group of the epoxy resin generate ring-opening reaction, so that the nano SiO2Covalently grafting with water-based acrylic epoxy resin to obtain SiO2Grafting aqueous acrylic acid epoxy resin emulsion, nano SiO2Uniformly dispersed in the molecular chain of the water-based acrylic epoxy resin, reduces the agglomeration phenomenon and adopts nano SiO with excellent mechanical property2As a crosslinking site, the mechanical strength such as impact resistance of the water-based acrylic epoxy resin is obviously improved.
The SiO2The three components are covalently grafted, Si, O, Si and C form a matched bond and have the property of partial double bonds, so that the system energy of the composite anticorrosive material is reduced, the thermal stability is increased, the content of hydrophilic group carboxyl of the composite anticorrosive material is increased by grafting acrylic acid, the hydrophilicity of the composite anticorrosive material is improved, and the grafted nano SiO is2Has nanometer size effect, can form a closely-packed protective layer after film forming, effectively fills up the microporous structure of the composite anticorrosive material, and reduces H in the environment2O、O2When corrosive substances permeate to the metal surface through the micropores, the chemical corrosion resistance is improved, and meanwhile, the nano SiO2The composite anticorrosive material has high surface energy, so that the exposed atoms have high unsaturation, a bonding structure is easily formed with other atoms, the adhesive force between the composite anticorrosive material and a metal matrix is improved, water vapor is prevented from entering, and the composite anticorrosive material has excellent hydrophilicity, mechanical property and chemical anticorrosive property.
Drawings
FIG. 1 is a schematic front view of a water bath apparatus;
fig. 2 is a gear structure schematic.
1. A main body; 2. a motor; 3. a connecting rod; 4. a first gear; 5. a second gear; 6. a third gear; 7. a magnet; 8. a partition plate; 9. a separator.
Detailed Description
To achieve the above objects, the present invention provides the following embodiments and implementationsExample (c): SiO (silicon dioxide)2Composite anticorrosive material of grafted water-base acrylic epoxy resin, SiO2The preparation method of the composite anticorrosive material grafted with the water-based acrylic epoxy resin comprises the following steps:
(1) adding deionized water, concentrated ammonia water and isopropanol into a reaction bottle, placing the reaction bottle in a water bath device, wherein the water bath device comprises a main body, the bottom of the main body is movably connected with a motor, the top of the motor is movably connected with a connecting rod, the right side of the top of the connecting rod is movably connected with a first gear, the left side of the first gear is movably connected with a second gear, the left side of the second gear is movably connected with a third gear, the top of the third gear is movably connected with a magnet, the middle of the main body is movably connected with a partition plate, the top of the partition plate is movably connected with a beaker, uniformly stirring the mixture at 55-65 ℃, adding tetraethoxysilane, continuously stirring the mixture until the mixture is completely precipitated, centrifugally;
(2) adding thionyl chloride and silicon dioxide into a reaction bottle, and carrying out chlorination process, wherein the chlorination process is that stirring reaction is carried out for 12-36h at 65-75 ℃, thionyl chloride is removed by reduced pressure distillation at 25-35 ℃, tetrahydrofuran is used for washing and drying, and the chlorinated silicon dioxide is obtained;
(3) adding triethylene tetramine and chloro-silicon dioxide into a reaction bottle, and carrying out an amination process, wherein the amination process is to stir and react for 24-72h at 90-110 ℃, cool to room temperature, wash with absolute ethyl alcohol, and carry out vacuum drying at room temperature to obtain aminated silicon dioxide;
(4) adding epoxy resin into a reaction bottle, heating to 120 ℃ for 100-The ratio of 100:17-20:35-40:6.5-7.5:4-4.8:4-6:1-2:1-4, refluxing and stirring for 4-8h to obtain SiO2Grafting water-based acrylic acid epoxy resin emulsion;
(5) adding SiO into a reaction bottle2Grafting water-based acrylic epoxy resin emulsion, film-forming additive dipropylene glycol ethyl ether, defoaming agent Z-4933, flatting agent EFKA-3777 and curing agent triethylene tetramine, wherein the mass ratio of the five components is 100:3.5-3.8:0.5-0.6:0.3-0.4:10-13, fully stirring, spraying the mixture on a tin plate polished by sand paper, standing and culturing at room temperature for 4-6 days to obtain SiO2A composite anticorrosive material grafted with water-based acrylic epoxy resin.
Example 1
(1) Adding deionized water, concentrated ammonia water and isopropanol into a reaction bottle, placing the reaction bottle in a water bath device, wherein the water bath device comprises a main body, the bottom of the main body is movably connected with a motor, the top of the motor is movably connected with a connecting rod, the right side of the top of the connecting rod is movably connected with a first gear, the left side of the first gear is movably connected with a second gear, the left side of the second gear is movably connected with a third gear, the top of the third gear is movably connected with a magnet, the middle of the main body is movably connected with a partition plate, the top of the partition plate is movably connected with a beaker, stirring is uniformly at 55 ℃, adding tetraethoxysilane, continuously stirring until complete precipitation, centrifugally washing with deionized water and absolute;
(2) adding thionyl chloride and silicon dioxide into a reaction bottle, and carrying out chlorination process, wherein the chlorination process is that stirring reaction is carried out for 12 hours at 65 ℃, thionyl chloride is removed by reduced pressure distillation at 25 ℃, tetrahydrofuran is used for washing and drying, and the chlorinated silicon dioxide is obtained;
(3) adding triethylene tetramine and chloro-silicon dioxide into a reaction bottle, and carrying out an amination process, wherein the amination process is to stir and react for 24 hours at 90 ℃, cool to room temperature, wash with absolute ethyl alcohol, and dry in vacuum at room temperature to obtain aminated silicon dioxide;
(4) adding epoxy resin into a reaction bottle, heating to 100 ℃, adding ethylene glycol monobutyl ether and n-butyl alcohol while stirring when the epoxy resin is in a molten state, fully stirring, introducing nitrogen, and dropwise adding the mixture within 1hAdding methacrylic acid, styrene, butyl acrylate and dibenzoyl peroxide, heating to 110 ℃, reacting at constant temperature for 3h, cooling to 50 ℃, adding N, N-dimethylethanolamine while stirring, controlling the pH of the solution to be neutral, reacting at constant temperature for 30min, adding aminated silica, wherein the mass ratio of the epoxy resin, the ethylene glycol butyl ether, the N-butyl alcohol, the methacrylic acid, the styrene, the butyl acrylate, the dibenzoyl peroxide and the aminated silica is 100:17:35:6.5:4:4:1:1, and stirring at reflux for 4h to obtain SiO2Grafting water-based acrylic acid epoxy resin emulsion;
(5) adding SiO into a reaction bottle2Grafting water-based acrylic epoxy resin emulsion, film-forming aid dipropylene glycol ethyl ether, defoaming agent Z-4933, flatting agent EFKA-3777 and curing agent triethylene tetramine, wherein the mass ratio of the five components is 100:3.5:0.5:0.3:10, fully stirring, spraying the mixture on a tin plate polished by abrasive paper, standing and culturing at room temperature for 4 days to obtain SiO2A composite anticorrosive material grafted with water-based acrylic epoxy resin.
Example 2
(1) Adding deionized water, concentrated ammonia water and isopropanol into a reaction bottle, placing the reaction bottle in a water bath device, wherein the water bath device comprises a main body, the bottom of the main body is movably connected with a motor, the top of the motor is movably connected with a connecting rod, the right side of the top of the connecting rod is movably connected with a first gear, the left side of the first gear is movably connected with a second gear, the left side of the second gear is movably connected with a third gear, the top of the third gear is movably connected with a magnet, the middle of the main body is movably connected with a partition plate, the top of the partition plate is movably connected with a beaker, stirring uniformly at 60 ℃, adding tetraethoxysilane, continuously stirring until complete precipitation, centrifugally washing with deionized water and absolute ethyl;
(2) adding thionyl chloride and silicon dioxide into a reaction bottle, and carrying out chlorination process, wherein the chlorination process is that stirring reaction is carried out for 24 hours at 70 ℃, thionyl chloride is removed by reduced pressure distillation at 30 ℃, tetrahydrofuran is used for washing and drying, and the chlorinated silicon dioxide is obtained;
(3) adding triethylene tetramine and chloro-silicon dioxide into a reaction bottle, and carrying out an amination process, wherein the amination process is to stir and react for 48 hours at the temperature of 100 ℃, cool the mixture to room temperature, wash the mixture clean with absolute ethyl alcohol, and carry out vacuum drying at the room temperature to obtain aminated silicon dioxide;
(4) adding epoxy resin into a reaction bottle, heating to 110 ℃, adding ethylene glycol monobutyl ether and N-butyl alcohol while stirring when the epoxy resin is in a molten state, fully stirring, introducing nitrogen, dropwise adding methacrylic acid, styrene, butyl acrylate and dibenzoyl peroxide within 1.5h, heating to 1220 ℃, reacting at constant temperature for 4h, cooling to 60 ℃, adding N, N-dimethylethanolamine while stirring, controlling the pH of the solution to be neutral, reacting at constant temperature for 60min, adding aminated silica, wherein the mass ratio of the epoxy resin, the ethylene glycol monobutyl ether, the N-butyl alcohol, the methacrylic acid, the styrene, the butyl acrylate, the dibenzoyl peroxide and the aminated silica is 100:18.5:37.5:7:4.4:5:1.5:2.5, and stirring at reflux for 6h to obtain SiO2Grafting water-based acrylic acid epoxy resin emulsion;
(5) adding SiO into a reaction bottle2Grafting water-based acrylic epoxy resin emulsion, film-forming aid dipropylene glycol ethyl ether, defoaming agent Z-4933, leveling agent EFKA-3777 and curing agent triethylene tetramine, wherein the mass ratio of the five components is 100:3.65:0.55:0.35:11.5, fully stirring, spraying the mixture on a sand-polished tin plate, standing and culturing at room temperature for 5 days to obtain SiO2A composite anticorrosive material grafted with water-based acrylic epoxy resin.
Example 3
(1) Adding deionized water, concentrated ammonia water and isopropanol into a reaction bottle, placing the reaction bottle in a water bath device, wherein the water bath device comprises a main body, the bottom of the main body is movably connected with a motor, the top of the motor is movably connected with a connecting rod, the right side of the top of the connecting rod is movably connected with a first gear, the left side of the first gear is movably connected with a second gear, the left side of the second gear is movably connected with a third gear, the top of the third gear is movably connected with a magnet, the middle of the main body is movably connected with a partition plate, the top of the partition plate is movably connected with a beaker, stirring is uniformly at 55 ℃, adding tetraethoxysilane, continuously stirring until complete precipitation, centrifugally washing with deionized water and absolute;
(2) adding thionyl chloride and silicon dioxide into a reaction bottle, and carrying out chlorination process, wherein the chlorination process is that stirring reaction is carried out for 12 hours at the temperature of 75 ℃, thionyl chloride is removed by reduced pressure distillation at the temperature of 35 ℃, tetrahydrofuran is used for washing and drying, and the chlorinated silicon dioxide is obtained;
(3) adding triethylene tetramine and chloro-silicon dioxide into a reaction bottle, and carrying out an amination process, wherein the amination process is to stir and react for 72 hours at 90 ℃, cool to room temperature, wash cleanly with absolute ethyl alcohol, and carry out vacuum drying at room temperature to obtain aminated silicon dioxide;
(4) adding epoxy resin into a reaction bottle, heating to 100 ℃, adding ethylene glycol monobutyl ether and N-butyl alcohol while stirring when the epoxy resin is in a molten state, fully stirring, introducing nitrogen, dropwise adding methacrylic acid, styrene, butyl acrylate and dibenzoyl peroxide within 2h, heating to 110 ℃, reacting at a constant temperature for 5h, cooling to 50 ℃, adding N, N-dimethylethanolamine while stirring, controlling the pH of the solution to be neutral, reacting at the constant temperature for 90min, adding aminated silica, wherein the mass ratio of the epoxy resin, the ethylene glycol monobutyl ether, the N-butyl alcohol, the methacrylic acid, the styrene, the butyl acrylate, the dibenzoyl peroxide and the aminated silica is 100:19:38:6.9:4.5:4.9:1.6:3, and stirring under reflux for 5h to obtain SiO2Grafting water-based acrylic acid epoxy resin emulsion;
(5) adding SiO into a reaction bottle2Grafting water-based acrylic epoxy resin emulsion, film-forming aid dipropylene glycol ethyl ether, defoaming agent Z-4933, flatting agent EFKA-3777 and curing agent triethylene tetramine, wherein the mass ratio of the five components is 100:3.7:0.6:0.4:12, fully stirring, spraying the mixture on a tin plate polished by abrasive paper, standing and culturing at room temperature for 6 days to obtain SiO2A composite anticorrosive material grafted with water-based acrylic epoxy resin.
Example 4
(1) Adding deionized water, concentrated ammonia water and isopropanol into a reaction bottle, placing the reaction bottle in a water bath device, wherein the water bath device comprises a main body, the bottom of the main body is movably connected with a motor, the top of the motor is movably connected with a connecting rod, the right side of the top of the connecting rod is movably connected with a first gear, the left side of the first gear is movably connected with a second gear, the left side of the second gear is movably connected with a third gear, the top of the third gear is movably connected with a magnet, the middle of the main body is movably connected with a partition plate, the top of the partition plate is movably connected with a beaker, stirring is uniformly at 65 ℃, adding tetraethoxysilane, continuously stirring until complete precipitation, centrifugally washing with deionized water and absolute;
(2) adding thionyl chloride and silicon dioxide into a reaction bottle, and carrying out chlorination process, wherein the chlorination process is that stirring reaction is carried out for 36 hours at the temperature of 75 ℃, thionyl chloride is removed by reduced pressure distillation at the temperature of 35 ℃, tetrahydrofuran is used for washing and drying, and the chlorinated silicon dioxide is obtained;
(3) adding triethylene tetramine and chloro-silicon dioxide into a reaction bottle, and carrying out an amination process, wherein the amination process is to stir and react for 72 hours at 110 ℃, cool to room temperature, wash cleanly with absolute ethyl alcohol, and carry out vacuum drying at room temperature to obtain aminated silicon dioxide;
(4) adding epoxy resin into a reaction bottle, heating to 120 ℃, adding ethylene glycol monobutyl ether and N-butyl alcohol while stirring when the epoxy resin is in a molten state, fully stirring, introducing nitrogen, dropwise adding methacrylic acid, styrene, butyl acrylate and dibenzoyl peroxide within 2h, heating to 130 ℃, reacting at constant temperature for 5h, cooling to 70 ℃, adding N, N-dimethylethanolamine while stirring, controlling the pH of the solution to be neutral, reacting at constant temperature for 90min, adding aminated silica, wherein the mass ratio of the epoxy resin, the ethylene glycol monobutyl ether, the N-butyl alcohol, the methacrylic acid, the styrene, the butyl acrylate, the dibenzoyl peroxide and the aminated silica is 100:20:40:7.5:4.8:6:2:4, and stirring at reflux for 8h to obtain SiO2Grafting water-based acrylic acid epoxy resin emulsion;
(5) adding SiO into a reaction bottle2Grafting water-based acrylic epoxy resin emulsion, film-forming aid dipropylene glycol ethyl ether, defoaming agent Z-4933, flatting agent EFKA-3777 and curing agent triethylene tetramine, wherein the mass ratio of the five components is 100:3.8:0.6:0.4:13, fully stirring, spraying the mixture on a tin plate polished by abrasive paper, standing and culturing at room temperature for 6 days to obtain SiO2Grafted aqueous acrylic acidEpoxy resin composite anticorrosive material.
Comparative example 1
(1) Adding deionized water, concentrated ammonia water and isopropanol into a reaction bottle, placing the reaction bottle in a water bath device, wherein the water bath device comprises a main body, the bottom of the main body is movably connected with a motor, the top of the motor is movably connected with a connecting rod, the right side of the top of the connecting rod is movably connected with a first gear, the left side of the first gear is movably connected with a second gear, the left side of the second gear is movably connected with a third gear, the top of the third gear is movably connected with a magnet, the middle of the main body is movably connected with a partition plate, the top of the partition plate is movably connected with a beaker, stirring is uniformly at 65 ℃, adding tetraethoxysilane, continuously stirring until complete precipitation, centrifugally washing with deionized water and absolute;
(2) adding thionyl chloride and silicon dioxide into a reaction bottle, and carrying out chlorination process, wherein the chlorination process is that stirring reaction is carried out for 36 hours at 65 ℃, thionyl chloride is removed by reduced pressure distillation at 25 ℃, tetrahydrofuran is used for washing and drying, and the chlorinated silicon dioxide is obtained;
(3) adding triethylene tetramine and chloro-silicon dioxide into a reaction bottle, and carrying out an amination process, wherein the amination process is to stir and react for 24 hours at 110 ℃, cool to room temperature, wash with absolute ethyl alcohol, and dry in vacuum at room temperature to obtain aminated silicon dioxide;
(4) adding epoxy resin into a reaction bottle, heating to 120 ℃, adding ethylene glycol monobutyl ether and N-butyl alcohol while stirring when the epoxy resin is in a molten state, fully stirring, introducing nitrogen, dropwise adding methacrylic acid, styrene, butyl acrylate and dibenzoyl peroxide within 1h, heating to 130 ℃, reacting at constant temperature for 3h, cooling to 70 ℃, adding N, N-dimethylethanolamine while stirring, controlling the pH of the solution to be neutral, reacting at constant temperature for 30min, adding aminated silica, wherein the mass ratio of the epoxy resin, the ethylene glycol monobutyl ether, the N-butyl alcohol, the methacrylic acid, the styrene, the butyl acrylate, the dibenzoyl peroxide and the aminated silica is 100:15:30:6:3.8:3:0.5:0.7, and stirring under reflux for 8h to obtain SiO2Grafting water-based acrylic acid epoxy resin emulsion;
(5) adding SiO into a reaction bottle2Grafting water-based acrylic epoxy resin emulsion, film-forming aid dipropylene glycol ethyl ether, defoaming agent Z-4933, flatting agent EFKA-3777 and curing agent triethylene tetramine, wherein the mass ratio of the five components is 100:3:0.4:0.2:8, fully stirring, spraying the mixture on a tin plate polished by abrasive paper, and standing and culturing at room temperature for 4 days to obtain SiO2A composite anticorrosive material grafted with water-based acrylic epoxy resin.
SiO-containing films obtained in examples and comparative examples2The tin plate of the composite anticorrosive material grafted with the water-based acrylic epoxy resin is placed in a salt spray experiment box for a salt spray resistance test, and the test standard is GB/T1771-2007.
Figure BDA0002675285880000111
SiO-containing films obtained in examples and comparative examples2A tin plate of the composite anticorrosive material grafted with the water-based acrylic epoxy resin is horizontally placed under a falling hammer of a QCJ-100 paint film impactor, the height of the falling hammer is adjusted to carry out an impact resistance experiment, and the impact strength of a coating is tested, wherein the test standard is GB/T1732-1993.
Figure BDA0002675285880000112

Claims (6)

1. SiO (silicon dioxide)2The composite anticorrosive material grafted with the water-based acrylic epoxy resin is characterized in that: the SiO2The preparation method of the composite anticorrosive material grafted with the water-based acrylic epoxy resin comprises the following steps:
(1) adding deionized water, strong ammonia water and isopropanol into a reaction bottle, placing the reaction bottle in a water bath device, uniformly stirring at 55-65 ℃, adding tetraethoxysilane, continuously stirring until the precipitate is completely precipitated, centrifugally washing the precipitate with deionized water and absolute ethyl alcohol, and drying the precipitate to obtain silicon dioxide;
(2) adding thionyl chloride and silicon dioxide into a reaction bottle, carrying out chlorination, distilling under reduced pressure at 25-35 ℃ to remove thionyl chloride, washing with tetrahydrofuran, and drying to obtain chlorinated silicon dioxide;
(3) adding triethylene tetramine and chloro-silicon dioxide into a reaction bottle, carrying out an amination process, cooling to room temperature, washing with absolute ethyl alcohol, and drying in vacuum at room temperature to obtain aminated silicon dioxide;
(4) adding epoxy resin into a reaction bottle, heating to 120 ℃ for 100-2Grafting water-based acrylic acid epoxy resin emulsion;
(5) adding SiO into a reaction bottle2Grafting water-based acrylic epoxy resin emulsion, film-forming additive dipropylene glycol ethyl ether, defoaming agent Z-4933, flatting agent EFKA-3777 and curing agent triethylene tetramine, fully stirring, spraying the mixture on a tin plate polished by sand paper, and standing and culturing at room temperature for 4-6 days to obtain SiO2A composite anticorrosive material grafted with water-based acrylic epoxy resin.
2. An SiO as claimed in claim 12The composite anticorrosive material grafted with the water-based acrylic epoxy resin is characterized in that: the water bath device in the step (1) comprises a main body, wherein the bottom of the main body is movably connected with a motor, the top of the motor is movably connected with a connecting rod, the right side of the top of the connecting rod is movably connected with a first gear, the left side of the first gear is movably connected with a second gear, the left side of the second gear is movably connected with a third gear, the top of the third gear is movably connected with a magnet, the middle of the main body is movably connected with a partition plate, and the top of the partition plate is movably.
3. An SiO as claimed in claim 12The composite anticorrosive material grafted with the water-based acrylic epoxy resin is characterized in that: the chlorination process in the step (2) is stirring reaction at 65-75 ℃ for 12-36 h.
4. An SiO as claimed in claim 12The composite anticorrosive material grafted with the water-based acrylic epoxy resin is characterized in that: the amination process in the step (3) is stirring reaction at 90-110 ℃ for 24-72 h.
5. An SiO as claimed in claim 12The composite anticorrosive material grafted with the water-based acrylic epoxy resin is characterized in that: in the step (4), the mass ratio of the epoxy resin, the ethylene glycol monobutyl ether, the n-butyl alcohol, the methacrylic acid, the styrene, the butyl acrylate, the dibenzoyl peroxide and the aminated silicon dioxide is 100:17-20:35-40:6.5-7.5:4-4.8:4-6:1-2: 1-4.
6. An SiO as claimed in claim 12The composite anticorrosive material grafted with the water-based acrylic epoxy resin is characterized in that: SiO in the step (5)2The mass ratio of the grafted waterborne acrylic epoxy resin emulsion to the film-forming additive dipropylene glycol ethyl ether to the defoaming agent Z-4933 to the leveling agent EFKA-3777 to the curing agent triethylene tetramine is 100:3.5-3.8:0.5-0.6:0.3-0.4: 10-13.
CN202010945912.1A 2020-09-10 2020-09-10 SiO (silicon dioxide)2Composite anticorrosive material of grafted water-based acrylic epoxy resin and preparation method thereof Withdrawn CN112029369A (en)

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Cited By (3)

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CN113249014A (en) * 2021-06-30 2021-08-13 启东海大聚龙新材料科技有限公司 Deep sea anticorrosive paint and preparation method thereof
CN113337186A (en) * 2021-06-07 2021-09-03 深圳福帝宝生物技术有限公司 Grave protection material and preparation method thereof
CN115851062A (en) * 2022-12-07 2023-03-28 雅图高新材料股份有限公司 Acrylic water-based high-adhesion primer and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113337186A (en) * 2021-06-07 2021-09-03 深圳福帝宝生物技术有限公司 Grave protection material and preparation method thereof
CN113249014A (en) * 2021-06-30 2021-08-13 启东海大聚龙新材料科技有限公司 Deep sea anticorrosive paint and preparation method thereof
CN115851062A (en) * 2022-12-07 2023-03-28 雅图高新材料股份有限公司 Acrylic water-based high-adhesion primer and preparation method thereof

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