CN115124900B - IBOA modified long-acting anti-corrosion aqueous acrylic paint and preparation method thereof - Google Patents
IBOA modified long-acting anti-corrosion aqueous acrylic paint and preparation method thereof Download PDFInfo
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- CN115124900B CN115124900B CN202210893363.7A CN202210893363A CN115124900B CN 115124900 B CN115124900 B CN 115124900B CN 202210893363 A CN202210893363 A CN 202210893363A CN 115124900 B CN115124900 B CN 115124900B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D151/003—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 by reactions only involving unsaturated carbon-to-carbon bonds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to the technical field of coatings, in particular to an IBOA modified long-acting anti-corrosion aqueous acrylic coating and a preparation method thereof. The coating comprises the following components: 30-50 parts of IBOA modified aqueous acrylic emulsion, 17-25 parts of water, 1-5 parts of film forming additive, 10-20 parts of rust-proof pigment, 10-30 parts of physical shielding filler and 5-15 parts of physical shielding filler; after methyl methacrylate and butyl acrylate are subjected to a first polymerization reaction to obtain a polymerization product, the polymerization product is continuously subjected to a second polymerization reaction with isobornyl acrylate, butyl acrylate and vinyl tri- (beta-methoxyethoxy) silane monomer to obtain the IBOA modified aqueous acrylic emulsion. The paint provided by the invention has good wettability, no shrinkage cavity or edge shrinkage in the construction process, and excellent corrosion resistance and weather resistance; the paint can be combined with the bottom surface in a C1-C3 corrosion environment, so that the construction procedure can be reduced, and the construction efficiency can be improved.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to an IBOA modified long-acting anti-corrosion aqueous acrylic coating and a preparation method thereof.
Background
The water-based acrylic acid paint has the characteristics of low price, safety, environmental protection, excellent aging resistance, simple synthesis and processing and the like, and has important application in the functions of water resistance, fire resistance, corrosion resistance, pollution resistance, heat insulation, heat preservation and the like. The paint in the anticorrosion field is generally applied in medium and light corrosion environments, and the modified resin is mainly used in the preparation of the paint because the self-anticorrosion property of the acrylic resin is insufficient.
In the existing water-based acrylic paint, ZHONGZ et al introduce hydroxy phosphate monomer with anti-flash corrosion function into acrylic resin molecules to prepare water-based acrylic paint with water resistance of 300h and salt fog resistance of 240 h; li Shuhua et al modified acrylic resin by functional phosphate monomer, the paint film of the prepared water-based acrylic paint can resist 5% NaCl solution for 30d, the impact strength reaches 50cm, the adhesive force is 0 grade, and the flexibility is 3mm; fuC and the like, and preparing the coating with salt fog resistance of more than 250 hours by introducing vinylidene chloride monomers; zhang Aili the self-made organosilicon modified epoxy acrylic emulsion is used as a base material to prepare the water-based anticorrosive paint with salt fog resistance of 600h and water resistance of 1440 h.
Although the water-based acrylic acid antirust paint has a great breakthrough in research, compared with solvent antirust paint which is still dominant in the market, the performance of the water-based acrylic acid antirust paint is still to be improved, and the main reason is that the linear structural molecular chain of the water-based acrylic acid antirust paint lacks crosslinking points and cannot form an effective network structure after film formation, and the water resistance, mechanical property and corrosion resistance have certain defects; the residual hydrophilic groups cause the problems of poor water resistance, easy flash erosion, poor heat resistance, poor hot-sticking cold-embrittlement cracking resistance, easy shrinkage cavity and edge shrinkage and the like.
Disclosure of Invention
To solve the above-mentioned shortcomings of the prior art in the background art: the existing aqueous acrylic antirust coating has the problems of poor water resistance, poor corrosion resistance, easiness in shrinkage cavity and edge shrinkage and the like. The paint provided by the invention has good wettability, no shrinkage cavity or edge shrinkage in the construction process, and excellent corrosion resistance and weather resistance; the paint can be combined with the bottom surface in a C1-C3 corrosion environment, so that the construction procedure can be reduced, and the construction efficiency can be improved.
The invention provides an IBOA modified long-acting anti-corrosion water-based acrylic paint, which comprises the following components: 30-50 parts of IBOA modified aqueous acrylic emulsion, 17-25 parts of water, 1-5 parts of film forming additive, 10-20 parts of rust-proof pigment, 10-30 parts of physical shielding filler and 5-15 parts of physical shielding filler;
after methyl methacrylate and butyl acrylate are subjected to a first polymerization reaction to obtain a polymerization product, the polymerization product is continuously subjected to a second polymerization reaction with isobornyl acrylate, butyl acrylate and vinyl tri- (beta-methoxyethoxy) silane monomers to obtain the IBOA modified aqueous acrylic emulsion.
Wherein, the molecular structure of isobornyl acrylate (IBOA) is as follows:
according to the invention, the preparation of the modified acrylic resin increases the resin network structure and crosslinking points, so that the crosslinking density of the water-based acrylic coating is improved, and the adhesive strength, the water resistance and the salt fog resistance of the water-based acrylic coating are improved; the modification of the resin by the isobornyl acrylate (IBOA) increases the hardness of the water-based acrylic resin, reduces the surface tension of the water-based acrylic resin, improves the self wettability of the water-based acrylic resin, solves the problems of shrinkage cavity and edge shrinkage of the water-based acrylic coating, and simultaneously improves the weather resistance and the hydrophobicity of the water-based acrylic resin by introducing certain siloxane groups so as to achieve the purpose of integrating the bottom surfaces. Specifically, the present invention includes at least the following inventive concepts:
(1) The common acrylic resin is modified through the double five-membered ring and single six-membered ring structure with the common carbon chain introduced into the structure, so that the problems of shrinkage cavity and edge shrinkage easily occurring in construction of the water-based acrylic coating due to high water tension are solved.
(2) Through the synergistic effect of several soft and hard monomers, the modified resin makes the flexibility and physical and mechanical strength of the coating harmonious and unified. The acrylic resin has the common problems of poor hot-sticking and cold-embrittlement cracking resistance and large curing shrinkage, and is easy to crack when the thickness of a coating film is large; the methyl methacrylate and vinyl tri- (beta-methoxyethoxy) silane structure endows the coating with certain hardness, wherein the vinyl tri- (beta-methoxyethoxy) silane has higher hardness, the glass transition temperature of the coating is improved, the problem of hot adhesion of the coating is solved, and meanwhile, the monomer has certain hydrophobicity after being solidified, so that the anti-fouling performance of the water-based acrylic coating is improved. The butyl acrylate structure endows the resin with excellent flexibility, the whole resin structure forms an effective hard-soft interphase structure through reasonable control of the proportion of a plurality of monomers and modification of a special structure, and the soft resin can effectively absorb energy when the coating is subjected to external force, so that the stress concentration and absorption effect are achieved, the impact resistance and flexibility of the coating are improved, and the problems of cold brittleness and poor cracking resistance of the coating are solved.
(3) The modification of the resin structure increases the resin network structure and the crosslinking point, and improves the crosslinking density, adhesion strength, water resistance, anti-pollution property, salt fog resistance and other properties of the water-based acrylic coating. IBOA modified aqueous acrylic resin and anti-theftThe synergistic effect of the rust pigment, the physical shielding filler and the volume concentration (PVC) of the formula pigment effectively improves the comprehensive anti-corrosion performance, especially the medium resistance and the salt spray resistance of the water-based acrylic paint. The traditional water-based acrylic resin structure is mostly of a linear structure, and is lack of crosslinking points, and an effective net structure cannot be formed after film formation, so that certain defects exist in water resistance, mechanical property and corrosion resistance. The side chain of the modified aqueous acrylic resin contains Si-OCH 3 、Si-OC 2 H 5 The groups can absorb moisture in air to generate hydrolysis and polycondensation reaction to form polysiloxane, so that crosslinking points are increased, a crosslinked network structure is effectively improved, structures such as coupling type, interpenetrating network type, firm crosslinking and the like can be formed among polymer molecules and among polymers and base materials, a coating film has excellent water resistance, salt spray resistance, adhesion strength and the like, and the anti-rust pigment and physical shielding filler further prevent and delay the contact time of a corrosive medium and the base materials, so that the comprehensive corrosion resistance of the coating is greatly improved. Si-OCH 3 、Si-OC 2 H 5 The polysiloxane structure formed by polymerization has excellent hydrophobicity, and can effectively improve the water resistance and the anti-staining performance of the coating.
(4) The coating has excellent corrosion resistance and weather resistance through the resin structural design and the formula design, can be used as a primer-topcoat coating under the condition of medium and low corrosion environments, and is convenient to construct. The water-based acrylic acid coating has a C-C bond structure, the coating has poor weather resistance, is easy to degrade and age due to chain segment degradation under the condition of sunlight irradiation, further influences the corrosion resistance, and simultaneously has poor water resistance due to the hydrophilic effect of the water-based auxiliary agent. The acrylic resin synthesized by the invention contains a certain amount of Si-O bonds, and can effectively absorb ultraviolet energy to improve the weather resistance and corrosion resistance of the coating. Meanwhile, the special structures of the double five-membered ring and the single six-membered ring of the common carbon chain of the IBOA polymer in the side chain can form an interaction electron with the ester bond and the Si-O bond in the carbon chain, so that the polarity and the reactivity of carbonyl groups are reduced, the stability of the resin is improved, and the structure of a resin chain segment can be damaged by a higher energy method, so that the weather resistance and the dielectric resistance (corrosion resistance) of the coating are improved. The hydrolysis of the side chain Si-O and the hydrophobic property thereof effectively improve the defect of poor water resistance of the coating caused by the existence of hydrophilic substances.
In some embodiments, in the first polymerization reaction, the weight ratio of the methyl methacrylate to the butyl acrylate is (7 to 9): (3-5);
in the second polymerization reaction, the weight ratio of the isobornyl acrylate, butyl acrylate and vinyl tri- (beta-methoxyethoxy) silane monomer is (3.5-4.5): (2-4): (1.0-1.5).
In some embodiments, the composition comprises, in parts by weight:
30-50 parts of IBOA modified aqueous acrylic emulsion, 17-25 parts of water, 1-5 parts of film forming additive, 10-20 parts of antirust pigment, 10-30 parts of physical filler, 5-15 parts of physical shielding filler, 0.1-0.5 part of wetting agent, 0.3-1.0 part of dispersing agent, 0.1-0.7 part of defoaming agent, 0.1-1.0 part of anti-flash rust agent, 0.1-0.5 part of pH regulator and 0.5-1.5 part of thickening agent.
In some embodiments, the IBOA modified aqueous acrylic emulsion is prepared by:
adding methyl methacrylate, butyl acrylate, water, an emulsifier and an alkaline aqueous solution into a reactor, and uniformly mixing; after a certain period of time of protective gas is introduced, the system starts to heat up to 55-60 ℃, and initiator aqueous solution is added dropwise, and after all initiator aqueous solution is added dropwise, the system is heated up to 70-80 ℃ for a first polymerization reaction for 7-8 h; wherein the weight ratio of the methyl methacrylate to the butyl acrylate is (7-9): (3-5);
then, dropwise adding isobornyl acrylate into the reactor, and carrying out heat preservation reaction for 3-3.5 h after the dropwise adding is finished; butyl acrylate is dripped, and the reaction is carried out for 7 to 8 hours after the dripping is finished; dripping vinyl tri- (beta-methoxyethoxy) silane monomer and organic mixed solution, and reacting for 4-5 h after finishing dripping; the weight ratio of the isobornyl acrylate, butyl acrylate, vinyl tri- (beta-methoxyethoxy) silane monomer and the organic mixed solution is (3.5-4.5): (2-4): (1.0-1.5): (4-6).
In some embodiments, the initiator comprises an aqueous ammonium persulfate solution and an aqueous sodium bisulfite solution,
the emulsifier comprises sodium dodecyl sulfate and Tween-80.
In some embodiments, the organic mixed solution consists of isopropyl alcohol and deionized water.
In some embodiments, the rust inhibitive pigment is one or more combinations of iron oxide red, zinc phosphate, nanocomposite iron titanium powder;
the physical filler is one or a combination of more of titanium dioxide, talcum powder, barium deposition and mica powder;
the physical shielding filler is one or a combination of a plurality of mica powder and sericite powder.
In some embodiments, the coalescent is one or more of alcohol ester twelve, dalprad C, dalprad D;
the flash rust inhibitor is one or a combination of more of Halox515, raybo60, sodium nitrite and composite flash rust inhibitor;
the thickener is one or more of BR-125P, WT-204 and WT-105A, COAPUR-2025.
In some embodiments, the pH adjustor comprises one or more of DMEA, AMP-95, codibuffer G3, aqueous ammonia;
the wetting agent comprises one or more of X-405, BYK-348, enviroGem 360 and H-140;
the dispersing agent comprises one or more of BYK-190, disper5040, TS200 and ED 3060;
the defoamer comprises one or more of NXZ, tego800 and Tego 8030.
The invention also provides a preparation method of the IBOA modified long-acting anti-corrosion aqueous acrylic paint, which comprises the following steps:
s100, uniformly dispersing a first part of water, a first part of IBOA modified aqueous acrylic emulsion, a film forming auxiliary agent, a wetting agent, a dispersing agent, a defoaming agent, an anti-flash rust agent and a pH regulator in a container at a low speed to obtain a mixture M;
s200, adding an anti-rust pigment, an extender filler and a physical shielding filler into the mixture M obtained in the S100, and uniformly dispersing at a high speed to obtain a mixture N;
s300, adding a thickening agent into the mixture N obtained in the step S200, and dispersing at a high speed until the fineness of the paint is less than or equal to 60 mu m;
s400, adding water of the second part and IBOA modified aqueous acrylic emulsion of the second part, and dispersing uniformly at a low speed to obtain the IBOA modified long-acting anti-corrosion aqueous acrylic coating;
wherein the sum of the amounts of the IBOA modified aqueous acrylic emulsion of the first part and the IBOA modified aqueous acrylic emulsion of the second part is the total amount of the IBOA modified aqueous acrylic emulsion; the weight ratio of the IBOA modified aqueous acrylic emulsion of the first part to the IBOA modified aqueous acrylic emulsion of the second part is (15-25): (15-25);
the sum of the amounts of water of the first part and the second part is the total amount of said water; the weight ratio of the water in the first part to the water in the second part is (15-20): (2-5).
Based on the above, compared with the prior art, the IBOA modified long-acting anti-corrosion aqueous acrylic paint provided by the invention has the following beneficial effects:
the coating prepared from the IBOA modified long-acting anti-corrosion aqueous acrylic coating provided by the invention has excellent adhesion strength, water resistance and salt spray resistance; the coating has good wettability, and solves the problems of shrinkage cavity and shrinkage edge existing in the existing water-based acrylic coating; the defects of hot adhesion, cold brittleness, easy cracking and easy staining of the existing acrylic coating are overcome; meanwhile, the coating has excellent corrosion resistance and weather resistance, and can be used as primer-topcoat coating.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure and/or components pointed out in the written description and claims.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the following description will be made in conjunction with the technical solutions in the embodiments of the present invention, and it is apparent that the described embodiments are some, but not all, embodiments of the present invention; the technical features designed in the different embodiments of the invention described below can be combined with each other as long as they do not conflict with each other; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that all terms used in the present invention (including technical terms and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs and are not to be construed as limiting the present invention; it will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The invention also provides a preparation method of the IBOA modified long-acting anti-corrosion aqueous acrylic paint, which comprises the following steps:
(1) Adding the deionized water of the first part and the IBOA modified aqueous acrylic emulsion of the second part, adding a film forming additive, a wetting agent, a dispersing agent, a defoaming agent, an anti-flash rust agent and a pH regulator into a dispersing cylinder under low-speed stirring at 300-700 rpm, and dispersing for 5-10 min at low speed at 300-700 rpm;
(2) Adding antirust pigment, extender filler and physical shielding filler, and dispersing uniformly at a high speed of 1000-1500 rpm;
(3) Adding a thickening agent, and dispersing at high speed at 1000-1500 rpm until the fineness of the paint is less than or equal to 60 mu m;
(4) Adding the deionized water of the second part and the IBOA modified aqueous acrylic emulsion of the second part, and dispersing for 5-10 min at a low speed of 300-700 rpm;
(5) Filtering and packaging to obtain the finished product.
Wherein, the liquid crystal display device comprises a liquid crystal display device,
(1) The specific formula of the paint is as follows:
30-50 parts of IBOA modified aqueous acrylic emulsion, 17-25 parts of water, 1-5 parts of film forming additive, 10-20 parts of antirust pigment, 10-30 parts of physical filler, 5-15 parts of physical shielding filler, 0.1-0.5 part of wetting agent, 0.3-1.0 part of dispersing agent, 0.1-0.7 part of defoaming agent, 0.1-1.0 part of anti-flash rust agent, 0.1-0.5 part of pH regulator and 0.5-1.5 part of thickening agent. Wherein the sum of the amounts of the IBOA modified aqueous acrylic emulsion of the first part and the IBOA modified aqueous acrylic emulsion of the second part is the total amount of the IBOA modified aqueous acrylic emulsion; the weight ratio of the IBOA modified aqueous acrylic emulsion of the first part to the IBOA modified aqueous acrylic emulsion of the second part is (15-25): (15-25); the sum of the amounts of water of the first part and the second part is the total amount of said water; the weight ratio of the water in the first part to the water in the second part is (15-20): (2-5).
Wherein, regarding the IBOA modified aqueous acrylic emulsion:
after methyl methacrylate and butyl acrylate are subjected to a first polymerization reaction to obtain a polymerization product, the polymerization product is continuously subjected to a second polymerization reaction with isobornyl acrylate, butyl acrylate and vinyl tri- (beta-methoxyethoxy) silane monomer to obtain the IBOA modified aqueous acrylic emulsion.
The invention also provides a preparation method of the IBOA modified aqueous acrylic emulsion, which comprises the following steps:
(1) 7-9 g of methyl Methacrylate (MA), 3-5 g of Butyl Acrylate (BA), 90-110 g of deionized water, 0.5-0.7 g of Sodium Dodecyl Sulfate (SDS), 0.2-0.3 g of Tween-80 and 5-6 g of sodium bicarbonate aqueous solution with the mass fraction of wt% = 1.5-2% are added into a 250ml four-neck flask and stirred uniformly. After 20-30 min of protective gas is introduced, heating to 55-60 ℃, slowly dripping 10.5-11.5 g of ammonium persulfate aqueous solution (initiator) with the mass fraction of wt% = 4.5-5.0% and 9.5-10.5 g of sodium bisulfite (initiator) with the mass fraction of wt% = 2.0-2.5% respectively by using a constant pressure dropping funnel, and dripping for 40-60 min; after the initiator aqueous solution is completely dripped, heating to 70-80 ℃ for carrying out first polymerization reaction for 7-8 hours; wherein, the protective gas is preferably nitrogen.
(2) Slowly adding 3.5-4.5 g of isobornyl acrylate (IBOA) monomer into the system by using a constant pressure dropping funnel, keeping the dropping speed at a proper level that the system keeps a blue phase, and carrying out heat preservation reaction for 3-3.5 hours after the dropping is finished; slowly adding 2-4 g butyl acrylate into the system by using a constant pressure dropping funnel, wherein the dropping speed is proper to keep the system in a blue phase, and preserving heat for reaction for 7-8 hours after the dropping is finished; slowly adding 1.0-1.5 g of vinyl tri- (beta-methoxyethoxy) silane monomer and 4-6 g of organic mixed solution into the system by using a constant pressure dropping funnel, wherein the dropping speed is proper that the system keeps a blue phase, and preserving heat for reaction for 4-5 hours after the dropping is finished. Wherein the organic mixed solution consists of isopropanol and deionized water, and the mass ratio of the isopropanol to the deionized water is (8-10): (0.8-1.5).
The invention also provides the following examples and comparative examples of formulations (unit: parts by weight) as shown in tables 1-2 below:
TABLE 1
TABLE 2
Specifically, for the raw material components in examples and comparative examples:
example 1
The film forming auxiliary agent is alcohol ester twelve, the wetting agent is X-405, the dispersing agent is BYK-190, the defoaming agent is NXZ, the flash rust inhibitor is Halox515, the pH regulator is DMEA, the thickening agent is BR-125P, the rust-proof pigment is ferric oxide red, the constitution filler is 800-mesh talcum powder, rutile-type titanium white and 800-mesh wollastonite powder, the mass ratio is 3:1:2, and the physical shielding filler is 800-mesh mica powder.
The self-made IBOA modified aqueous acrylic emulsion is self-made, and comprises the following specific processes:
(1) Into a 250ml four-necked flask, 7.0g of methyl Methacrylate (MA), 3.5g of Butyl Acrylate (BA), 90.5g of deionized water, 0.50g of Sodium Dodecyl Sulfate (SDS), 0.30g of Tween-80 and 5.0g of sodium bicarbonate aqueous solution with mass fraction wt% = 2% were added, and the mixture was stirred uniformly. After the protective gas is introduced for 20min, heating to 55 ℃, and respectively slowly dropwise adding 10.50g of ammonium persulfate aqueous solution (initiator) with the mass fraction of wt% = 5% and 9.50g of sodium bisulfite aqueous solution (initiator) with the mass fraction of wt% = 2.5% by using a constant pressure dropping funnel for 45min; after all the initiator aqueous solution is added dropwise, heating to 75 ℃ for carrying out a first polymerization reaction for 7.5 hours; wherein the protective gas is nitrogen.
(2) Slowly adding 3.5g of isobornyl acrylate (IBOA) monomer into the system by using a constant pressure dropping funnel, wherein the dropping speed is proper to keep the blue phase of the system, and preserving heat for reaction for 3.5 hours after the addition is finished; slowly adding 2.0g butyl acrylate into the system by using a constant pressure dropping funnel, wherein the dropping speed is proper to keep the system in a blue phase, and preserving heat for reaction for 7.0 hours after the dropping is finished; 1.0g of vinyl tri- (beta-methoxyethoxy) silane monomer and 4.0g of organic mixed solution are slowly added into the system by using a constant pressure dropping funnel, the dropping speed is proper to keep the system in a blue phase, and the reaction is kept for 4.5 hours after the addition is finished. The organic mixed solution consists of isopropanol and deionized water, wherein the mass ratio of the isopropanol to the deionized water is 9:1.
Example 2
The film forming additive is DALPAD C, the wetting agent is EnviroGem 360, the dispersing agent is Disper5040, the defoaming agent is Tego800, the flash rust inhibitor is Raybo60, the pH regulator is AMP-95, the thickening agent is WT-204, the rust-proof pigment is composite nano ferrotitanium powder, the constitution filler is rutile type titanium white, 800-mesh wollastonite powder and 800-mesh barium deposition, the mass ratio is 1:2:1, and the physical shielding filler is GA-2 sericite powder.
The self-made IBOA modified aqueous acrylic emulsion is self-made, and comprises the following specific processes:
(1) Into a 250ml four-necked flask, 8.0g of methyl Methacrylate (MA), 4.0g of Butyl Acrylate (BA), 95.0g of deionized water, 0.60g of Sodium Dodecyl Sulfate (SDS), 0.20g of Tween-80 and 5.5g of sodium bicarbonate aqueous solution with mass fraction wt% = 2% were added, and the mixture was stirred uniformly. After 25min of protective gas is introduced, heating to 60 ℃, and respectively and slowly dropwise adding 10.5g of ammonium persulfate aqueous solution (initiator) with the mass fraction of wt% = 5% and 10.0g of sodium bisulfite aqueous solution (initiator) with the mass fraction of wt% = 2.5% by using a constant pressure dropping funnel for 50min; heating to 70 ℃ after the initiator aqueous solution is completely dripped for first polymerization reaction for 8 hours; wherein the protective gas is nitrogen.
(2) Slowly adding 4.0g of isobornyl acrylate (IBOA) monomer into the system by using a constant pressure dropping funnel, wherein the dropping speed is proper to keep the blue phase of the system, and preserving the heat for reaction for 3.5 hours after the dropping is finished; slowly adding 2.5g butyl acrylate into the system by using a constant pressure dropping funnel, wherein the dropping speed is proper to keep the system in a blue phase, and preserving heat for reaction for 7.5 hours after the dropping is finished; 1.2g of vinyl tri- (beta-methoxyethoxy) silane monomer and 5.0g of organic mixed solution are slowly added into the system by using a constant pressure dropping funnel, the dropping speed is proper to keep the system in a blue phase, and the reaction is kept for 4.0 hours after the addition is finished. The organic mixed solution consists of isopropanol and deionized water, wherein the mass ratio of the isopropanol to the deionized water is 9:1.
Example 3
The IBOA modified aqueous acrylic emulsion is self-made, the film forming additive is DALPAD D, the wetting agent is H-140, the dispersing agent is TS200, the defoaming agent is Tego8030, the anti-flash rust agent is a composite anti-flash rust agent consisting of benzotriazole, ammonium molybdate and ammonium benzoate (mass ratio of 1:3:3), the pH regulator is Codistuffer G3, and the thickening agent is WT-105A: the composite thickener for coapsur-2025=1:1, wherein the rust-proof pigment is zinc phosphate, the extender filler is rutile type titanium white and 800-mesh talcum powder, the mass ratio is 1:3, and the physical shielding filler is 200-mesh glass flake.
The self-made IBOA modified aqueous acrylic emulsion is self-made, and comprises the following specific processes:
(1) Into a 250ml four-necked flask, 9.0g of methyl Methacrylate (MA), 5.0g of Butyl Acrylate (BA), 110g of deionized water, 0.65g of Sodium Dodecyl Sulfate (SDS), 0.15g of Tween-80 and 6.0g of sodium bicarbonate aqueous solution with the mass fraction of wt% = 2% were added, and the mixture was stirred uniformly. After the protective gas is introduced for 30min, heating to 60 ℃, slowly dropwise adding 11.5g of ammonium persulfate aqueous solution (initiator) with the mass fraction of wt% = 5% and 9.5g of sodium bisulfite aqueous solution (initiator) with the mass fraction of wt% = 2.5% respectively by using a constant pressure dropping funnel for 60min; heating to 80 ℃ after the initiator aqueous solution is completely dripped for 7.0 hours in a first polymerization reaction; wherein the protective gas is nitrogen.
(2) Slowly adding 4.5g of isobornyl acrylate (IBOA) monomer into the system by using a constant pressure dropping funnel, wherein the dropping speed is proper to keep the blue phase of the system, and preserving heat for reaction for 3.5 hours after the dropping is finished; slowly adding 2.0g butyl acrylate into the system by using a constant pressure dropping funnel, wherein the dropping speed is proper to keep the system in a blue phase, and preserving the heat for reaction for 8.0 hours after the dropping is finished; 1.5g of vinyl tri- (beta-methoxyethoxy) silane monomer and 6.0g of organic mixed solution are slowly added into the system by using a constant pressure dropping funnel, the dropping speed is proper to keep the system in a blue phase, and the reaction is kept for 5.0 hours after the addition is finished. The organic mixed solution consists of isopropanol and deionized water, wherein the mass ratio of the isopropanol to the deionized water is 9:1.
Comparative examples 1 to 6:
the choice of raw material types for comparative examples 1-6 was consistent with example 1; the IBOA modified aqueous acrylic emulsion a differs from the IBOA modified aqueous acrylic emulsion prepared in example 1 only in that: in the preparation process of the IBOA modified aqueous acrylic emulsion a, a monomer butyl acrylate BA is not added in the first polymerization reaction process;
IBOA modified aqueous acrylic emulsion b differs from the IBOA modified aqueous acrylic emulsion made in example 1 only in that: in the preparation process of the IBOA modified aqueous acrylic emulsion b, no monomer IBOA is added to participate in the reaction;
IBOA modified aqueous acrylic emulsion c differs from the IBOA modified aqueous acrylic emulsion made in example 1 only in that: in the preparation process of the IBOA modified aqueous acrylic emulsion c, monomer vinyl tri- (beta-methoxyethoxy) silane is not added to participate in the reaction;
the commercial aqueous acrylic emulsion is HG-54C.
The specific preparation processes of examples 1-3 and comparative examples 1-6 were as follows according to the formulations in Table 1:
(1) Adding a first part of deionized water and a second part of acrylic emulsion (self-made IBOA modified aqueous acrylic emulsion or IBOA modified aqueous acrylic emulsion a or IBOA modified aqueous acrylic emulsion b or IBOA modified aqueous acrylic emulsion c or commercial acrylic emulsion is selected according to the formula of tables 1-2), adding a film forming auxiliary agent, a wetting agent, a dispersing agent, a defoaming agent, an anti-flash rust agent and a pH regulator into a dispersing cylinder under low-speed stirring at 500rpm, and dispersing for 8min at low speed at 500 rpm;
(2) Adding antirust pigment, extender filler and physical shielding filler, and dispersing uniformly at a high speed at 1300 rpm;
(3) Adding a thickener, and dispersing at a high speed at 1300rpm until the fineness of the paint is less than or equal to 60 mu m;
(4) Adding a second part of deionized water and a second part of acrylic emulsion (self-made IBOA modified aqueous acrylic emulsion or IBOA modified aqueous acrylic emulsion a or IBOA modified aqueous acrylic emulsion b or IBOA modified aqueous acrylic emulsion c or commercial acrylic emulsion is selected according to the formula of tables 1-2), and dispersing at a low speed for 8min at 500 rpm;
(5) Filtering and packaging to obtain the finished product.
Comparative example 7:
the existing commercial waterborne polyurethane coating produced by Guangzhou Jitai corporation has the brand JT-433M waterborne aliphatic polyurethane finish paint.
The products obtained in the above examples and those obtained in the comparative examples were subjected to the following performance tests and the test results thereof were obtained as shown in the following tables 3 to 4:
table 3 example and comparative example performance data
Table 4 example and comparative example performance data
Wherein, the smaller the adhesion grade value, the stronger the adhesion thereof.
Analysis of the above test results revealed that:
it can be seen from examples 1 to 3 and comparative example 4 that: the IBOA modified water-based acrylic paint prepared by the invention has excellent adhesive force, water resistance and salt fog resistance; the paint has the advantages of high hardness, sufficient flexibility, cracking resistance, good wettability (no obvious shrinkage cavity and edge shrinkage after thin coating), good stain resistance and good weather resistance.
It can be seen from examples 1 to 3 and comparative example 7 that: the coating of the coating prepared by the invention has weather resistance equivalent to that of the existing aqueous polyurethane coating, and can be used as primer-topcoat coating;
it can be seen from examples 1 to 3 and comparative example 1 that: the butyl acrylate BA polymer chain segment is introduced into the coating prepared by the invention, so that the flexibility and cracking resistance of the coating can be effectively improved, and the comprehensive performance of the coating is improved;
from examples 1 to 3 and comparative example 2, it can be seen that: the IBOA polymer chain segment is introduced into the coating prepared by the invention, so that the wettability, hardness, anti-staining property, adhesive force and corrosion resistance of the coating can be effectively improved, meanwhile, the weather resistance of the coating is improved to a certain extent, and the synergistic effect of the IBOA and BA can ensure that the coating has both flexibility and hardness and the corrosion resistance and the workability of the coating are improved;
it can be seen from examples 1 to 3 and comparative example 3 that: the vinyl tri- (beta-methoxyethoxy) silane polymer chain segment is introduced into the coating prepared by the invention, so that the weather resistance, corrosion resistance and stain resistance of the coating can be obviously improved, and meanwhile, the adhesive force and hardness of the coating are improved to a certain extent;
it can be seen from examples 1 to 3 and comparative examples 5 to 6 that: the synergistic effect of the IBOA modified aqueous acrylic resin and the antirust pigment and the physical shielding filler in the coating prepared by the invention can effectively improve the comprehensive performance of the coating.
In summary, under the synergistic effects of the monomer copolymerization with different structural characteristics and the prepared IBOA modified aqueous acrylic resin emulsion, filler and the like, the coating can have excellent comprehensive properties, and the lack of a certain component in the coating can obviously reduce a certain performance in the comprehensive properties, so that the effect of the invention is realized under the synergistic effect of the raw materials, rather than the simple superposition of the raw materials, and the invention is creative.
Summarizing the performance results of the IBOA modified long-acting anti-corrosion water-based acrylic paint provided by the invention, the IBOA modified long-acting anti-corrosion water-based acrylic paint has the following beneficial effects:
(1) In the IBOA modified long-acting anti-corrosion aqueous acrylic coating provided by the invention, the coating network structure and the crosslinking point are increased through resin modification, so that the crosslinking density is high, and the coating adhesion strength, the water resistance, the salt mist resistance and other performances are excellent;
(2) In the IBOA modified long-acting corrosion-resistant water-based acrylic paint provided by the invention, the double five-membered rings with the carbon chain structure are shared, but six-membered rings enable the coating to have high hardness and low surface tension, so that the wettability of the coating is good, and the problems of shrinkage cavity and shrinkage edge existing in the existing water-based acrylic paint are solved;
(3) In the IBOA modified long-acting corrosion-resistant water-based acrylic paint, the IBOA and vinyl tri- (beta-methoxyethoxy) silane side chain structure provides excellent hardness, high glass ring transition temperature, good hydrophobicity and extremely low curing shrinkage rate of the coating, and butyl acrylate provides excellent stress absorption effect of the coating, and the synergistic effect of the IBOA and the vinyl tri- (beta-methoxyethoxy) silane side chain structure solves the problems of hot adhesion, cold brittleness, easy cracking and easy pollution of the existing acrylic paint;
(4) In the IBOA modified long-acting anti-corrosion aqueous acrylic coating provided by the invention, the synergistic effect of the resin structural design and the formula design ensures that the coating has excellent anti-corrosion property and weather resistance at the same time, and can be used as a primer-topcoat coating.
It should be noted that:
in addition to the actual selection of the specific embodiment, the components of the aqueous acrylic paint provided by the invention comprise 30-50 parts of IBOA modified aqueous acrylic emulsion, 17-25 parts of water, 1-5 parts of film forming additive, 10-20 parts of rust-proof pigment, 10-30 parts of physical shielding filler, 5-15 parts of wetting agent, 0.1-0.5 part of dispersing agent, 0.3-1.0 part of defoaming agent, 0.1-0.7 part of flash rust inhibitor, 0.1-0.5 part of pH regulator and 0.5-1.5 part of thickener. The inventive arrangements are possible within the above formulations, including but not limited to the embodiment arrangements described above;
in addition to the practical choices embodied in the specific embodiments described above, preferably, the rust inhibitive pigment may be selected from one or more of iron oxide red, zinc phosphate, nanocomposite iron titanium powder, including but not limited to the embodiment solutions described above;
in addition to the practical choices presented in the above specific embodiments, preferably, the physical filler may be one or more of titanium dioxide, talcum powder, barium deposit, mica powder, including but not limited to the embodiments described above;
in addition to the practical choices embodied in the specific embodiments described above, preferably, the physical shielding filler may be selected from one or more of mica powder, sericite powder, or a combination thereof, including but not limited to the embodiment solutions described above;
in addition to the practical choices presented in the specific embodiments above, preferably, the film-forming aid may be one or more of alcohol ester twelve, DALPADC (with tripropylene glycol n-butyl ether as the main component), DALPAD D (with dipropylene glycol n-butyl ether as the main component), including but not limited to the embodiments above;
in addition to the practical choices embodied in the specific embodiments described above, preferably, the flash rust inhibitor may be selected from one or more of Halox515, raybo60, sodium nitrite, and complex flash rust inhibitors (e.g., a combination of benzotriazole, ammonium molybdate and ammonium benzoate), including but not limited to the embodiments described above;
in addition to the actual choices embodied in the specific embodiments described above, preferably, the thickener may be selected from one or more of BR-125P, WT-204, WT-105A, COAPUR-2025, including but not limited to the embodiment versions described above;
in addition to the practical choices embodied in the specific embodiments described above, preferably, the pH adjustor can be one or more of DMEA, AMP-95, codistuffer G3, ammonia, including but not limited to the embodiment solutions described above;
in addition to the practical choices embodied in the specific embodiments described above, preferably, the wetting agent may be selected from one or more of X-405, BYK-348, enviroGem 360, H-140, including but not limited to the embodiment schemes described above;
in addition to the actual choices embodied in the specific embodiments described above, preferably, the dispersant may be selected from one or more of BYK-190, disper5040, TS200, ED3060, including but not limited to the embodiment schemes described above;
in addition to the practical choices embodied in the specific embodiments described above, preferably, the defoamer may be selected from one or more of NXZ, tego800, tego8030, including but not limited to the embodiment described above.
The specific parameters or reagents commonly used in the above embodiments are specific embodiments or preferred embodiments contemplated by the present invention, and are not limiting thereof; and can be adaptively adjusted by those skilled in the art within the concept and the protection scope of the invention.
In addition, unless otherwise specified, the starting materials employed may also be commercially available products conventionally used in the art or may be prepared by methods conventionally used in the art.
In addition, it should be understood by those skilled in the art that although many problems exist in the prior art, each embodiment or technical solution of the present invention may be modified in only one or several respects, without having to solve all technical problems listed in the prior art or the background art at the same time. Those skilled in the art will understand that nothing in one claim should be taken as a limitation on that claim.
Although terms such as IBOA modified aqueous acrylic emulsion, film forming aids, physical fillers, etc. are more used herein, the possibility of using other terms is not precluded. These terms are used merely for convenience in describing and explaining the nature of the invention; they are to be interpreted as any additional limitation that is not inconsistent with the spirit of the present invention; the terms first, second, and the like in the description and in the claims, if any, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (7)
1. The IBOA modified long-acting anti-corrosion aqueous acrylic paint is characterized by comprising the following components in parts by weight:
30-50 parts of IBOA modified aqueous acrylic emulsion, 17-25 parts of water, 1-5 parts of film forming additive, 10-20 parts of rust-proof pigment, 10-30 parts of physical filler, 5-15 parts of physical shielding filler, 0.1-0.5 part of wetting agent, 0.3-1.0 part of dispersing agent, 0.1-0.7 part of defoaming agent, 0.1-1.0 part of flash rust inhibitor, 0.1-0.5 part of pH regulator and 0.5-1.5 part of thickener, wherein after a polymerization product is obtained by a first polymerization reaction of methyl methacrylate and butyl acrylate, the polymerization product is continuously subjected to a second polymerization reaction with isobornyl acrylate, butyl acrylate and vinyl tri- (beta-methoxyethoxy) silane monomer to obtain the IBOA modified aqueous acrylic emulsion;
the preparation process of the IBOA modified aqueous acrylic emulsion comprises the following steps:
adding methyl methacrylate, butyl acrylate, water, an emulsifier and an alkaline aqueous solution into a reactor, and uniformly mixing; after a certain period of time of protective gas is introduced, the system starts to heat up to 55-60 ℃, and initiator aqueous solution is added dropwise, after all initiator aqueous solution is added dropwise, the system is heated up to 70-80 ℃ to perform first polymerization reaction 7-8 h; wherein the weight ratio of the methyl methacrylate to the butyl acrylate is (7-9): (3-5);
then, dropwise adding isobornyl acrylate into the reactor, and carrying out heat preservation reaction for 3-3.5 h after the dropwise adding is finished; butyl acrylate is dripped, and the temperature is kept for reaction after the dripping is finished for 7 to 8h; dripping vinyl tri- (beta-methoxyethoxy) silane monomer and organic mixed solution, and reacting at a temperature of 4-5 h after dripping; the weight ratio of the isobornyl acrylate, butyl acrylate, vinyl tri- (beta-methoxyethoxy) silane monomer and the organic mixed solution is (3.5-4.5): (2-4): (1.0-1.5): (4-6).
2. The IBOA modified long-acting corrosion resistant aqueous acrylic paint of claim 1 wherein: the initiator aqueous solution comprises ammonium persulfate aqueous solution and sodium bisulphite aqueous solution,
the emulsifier comprises sodium dodecyl sulfate and Tween-80.
3. The IBOA modified long-acting corrosion resistant aqueous acrylic paint of claim 1 wherein: the organic mixed solution consists of isopropanol and deionized water.
4. The IBOA modified long-acting corrosion resistant aqueous acrylic paint of claim 1 wherein: the antirust pigment is one or a combination of more of iron oxide red, zinc phosphate and nano composite iron-titanium powder;
the physical filler is one or a combination of more of titanium dioxide, talcum powder, barium deposition and mica powder;
the physical shielding filler is mica powder.
5. The IBOA modified long-acting corrosion resistant aqueous acrylic paint of claim 1 wherein: the film forming auxiliary agent is one or a combination of more of alcohol ester twelve, DALPAD C and DALPAD D;
the flash rust inhibitor is one or a combination of more of Halox515, raybo60 and sodium nitrite;
the thickener is one or more of BR-125P, WT-204 and WT-105A, COAPUR-2025.
6. The IBOA modified long-acting corrosion resistant aqueous acrylic paint of claim 1 wherein: the pH regulator comprises one or more of DMEA, AMP-95, codistuffer G3 and ammonia water;
the wetting agent comprises one or more of X-405, BYK-348, enviroGem 360 and H-140;
the dispersing agent comprises one or more of BYK-190, disper5040, TS200 and ED 3060;
the defoamer comprises one or more of NXZ, tego800 and Tego 8030.
7. A method for preparing an IBOA modified long-acting corrosion resistant aqueous acrylic paint according to any one of claims 1 to 6, comprising the steps of:
s100, uniformly dispersing a first part of water, a first part of IBOA modified aqueous acrylic emulsion, a film forming auxiliary agent, a wetting agent, a dispersing agent, a defoaming agent, an anti-flash rust agent and a pH regulator in a container at a low speed to obtain a mixture M;
s200, adding an anti-rust pigment, an extender filler and a physical shielding filler into the mixture M obtained in the S100, and uniformly dispersing at a high speed to obtain a mixture N;
s300, adding a thickening agent into the mixture N obtained in the step S200, and dispersing at a high speed until the fineness of the paint is less than or equal to 60 mu m;
s400, adding water of the second part and IBOA modified aqueous acrylic emulsion of the second part, and dispersing uniformly at a low speed to obtain the IBOA modified long-acting anti-corrosion aqueous acrylic coating;
wherein the sum of the amounts of the IBOA modified aqueous acrylic emulsion of the first part and the IBOA modified aqueous acrylic emulsion of the second part is the total amount of the IBOA modified aqueous acrylic emulsion; the weight ratio of the IBOA modified aqueous acrylic emulsion of the first part to the IBOA modified aqueous acrylic emulsion of the second part is (15-25): (15-25);
the sum of the amounts of water of the first part and the second part is the total amount of said water; the weight ratio of the water in the first part to the water in the second part is (15-20): (2-5).
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| CN111607030A (en) * | 2019-02-22 | 2020-09-01 | 长兴化学工业(中国)有限公司 | Water-based acrylate composition, coating thereof and preparation method thereof |
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