CN112759715B - High-hydroxyl-content aqueous acrylic acid dispersion and preparation method thereof - Google Patents
High-hydroxyl-content aqueous acrylic acid dispersion and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- 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
Abstract
The invention discloses a high-hydroxyl-content aqueous acrylic acid dispersion and a preparation method thereof, belonging to the technical field of high-molecular coating. The aqueous acrylic acid dispersoid comprises 5-20wt% of soft monomer, 5-20wt% of hard monomer, 0.4-20wt% of modified silicone oil, 5-50wt% of reactive solvent, 5-40wt% of hydroxyl monomer, 0.5-10wt% of hydrophilic monomer, 1-10wt% of neutralizer, 30-70wt% of deionized water, and the balance of initiator and chain transfer agent; the invention provides a synthesis method which solves the problem of viscosity increase caused by high hydroxyl content in the prior art, and provides a water-based hydroxyl acrylic dispersion with high hydroxyl content, high solid content and low viscosity, wherein the hydroxyl content is up to 4-7%, and the solid content is up to 40-70%.
Description
Technical Field
The invention belongs to the technical field of high polymer coating, and particularly relates to a high-hydroxyl-content water-based acrylic acid dispersion and a preparation method thereof.
Background
The hydroxy acrylic resin aqueous dispersion is called as hydroxypropyl dispersion for short, and the preparation and research of the hydroxypropyl dispersion are more reported at home and abroad. And similar products are already on the market. However, the existing commercial hydroxypropyl dispersion resin has the problems of low viscosity, low hydroxyl value, low solid content, high solvent content and the like. This is because when the content of polar groups carboxyl and hydroxyl in the hydroxypropyl dispersion is too high, it is liable to cause abnormality in viscosity at the time of water dispersion, thus making it difficult to prepare a hydroxypropyl resin aqueous dispersion of high solids and low viscosity, which leads to difficulty in construction of the coating and insufficient fullness, leveling property and the like of the coating film. Therefore, in order to solve the above problems, a high boiling point solvent which is relatively expensive is often selected or the amount of the solvent is increased or the hydroxyl content is reduced in the process of preparing the hydroxypropyl dispersion resin with high solid content and low viscosity, but the VOC content and the production cost are increased although the high solid content and low viscosity of the dispersion resin are realized by the measures, and the coating film resistance is not up to standard due to insufficient crosslinking density caused by the reduction of the hydroxyl content, and particularly, the use requirements on salt spray resistance and weather resistance are difficult to meet.
The existing aqueous acrylic acid dispersoid is generally synthesized by adopting stepwise dripping to form a shell-core structure (CN 201811314199X, an aqueous acrylic acid dispersoid with a self-crosslinking core-shell structure, a preparation method and application thereof), and the molecular weight of a product is reduced by adopting a high-temperature reaction so as to achieve the purposes of low molecular weight and low viscosity of the product. However, the hydroxyl monomer is completely in the shell layer, and if the hydroxyl content is high enough, the viscosity of the product is high, so that the solid content is difficult to be high.
In some of the patents with high hydroxyl content (CN 2018112474986), some synthetic methods are simple, no mention is made of the treatment or protection of the hydroxyl monomers, and no mention is made of how much the final hydroxyl content is increased. Patent CN2017108247241 is a polyurethane dispersion with high hydroxyl content, although hydroxyl content can reach 3-6%, the molecular structure of polyurethane determines the final salt spray resistance and weather resistance of the product, and the liquid medium resistance is lower than that of acrylic dispersion. And the solid content of the synthesized dispersion is generally 40%, so that the viscosity of the product influences the improvement of the solid content.
CN2017111229713 is a water-based hydroxy acrylic acid dispersoid and a preparation method, wherein the patent uses polyol for priming, and adopts a mode of combining high-temperature polymerization and low-temperature polymerization to synthesize the water-based hydroxy acrylic acid dispersoid without organic solvent. In the method, a polyol is additionally introduced as a priming solvent, the polyol does not participate in the reaction, and the reaction is divided into high-temperature and low-temperature polymerization steps. Although it is mentioned that polyols react with curing agents, their effect on properties is not known. Second, the reaction process is cumbersome and does not mention how much of a specific hydroxyl content is.
CN2020106426554 the high solids aqueous hydroxyacrylic acid dispersion is obtained by a chain transfer polymerization process with a reactive polyol solvent. The method is simple to operate and has excellent paint film performance. However, the introduction of hydroxyl-containing acrylic monomers in one step increases the difficulty of dispersion when water is added to a large amount of hydroxyl groups, increases the viscosity of the dispersion, and decreases the solid content.
Disadvantages of the prior art: the increase in hydroxyl content requires the introduction of more hydroxyl monomers, how to protect these hydroxyl groups from affecting the hydration viscosity; increasing the hydroxyl content requires the introduction of high boiling solvents or increasing the amount of solvents that affect the VOC value.
Disclosure of Invention
In order to solve the problems, the invention provides a high hydroxyl content aqueous acrylic dispersion, which comprises the following components in percentage by mass:
the modified silicone oil comprises one or more of silicone oil products with methacrylic acid or mercapto functional groups at two ends or one end and silicone oil chains in branched chains.
The viscosity of the modified silicone oil at 25 ℃ is 90-1000mm 2 S, preferably 90-800mm 2 Preferably 10-800mm 2 /s。
The modified silicone oil specifically comprises KF-2001, KF-2004, X-22-174ASX, X-22-174BX, KF-2012, X-22-2426 and X-22-2404 of Xinyue silicone.
The solid content in the aqueous acrylic acid dispersion is 40-70%; hydroxyl content 4-8%; the molecular weight is 2-15 ten thousand.
The soft monomer comprises one or more of butyl acrylate, butyl methacrylate, ethyl acrylate, n-octyl acrylate, hexyl acrylate, isooctyl methacrylate, dodecyl methacrylate and vinyl versatate.
The hard monomer comprises one or more of methyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, propyl methacrylate, cyclohexyl methacrylate, vinyl acetate and styrene.
The reaction solvent comprises one or more of acrylic modified polyester polyol, tertiary glycidyl ester, tertiary vinyl ester, isobornyl methacrylate and glycidyl acrylate;
further, the acrylic modified polyester polyol comprises one or more of acrylic modified polycaprolactone polyol, polyether polyol and polycarbonate polyol;
further, the acrylic-modified polyester polyol has a molecular weight of 100 to 1000.
The hydroxyl monomer comprises one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate.
The hydrophilic monomer comprises one or more of methacrylic acid, acrylic acid, itaconic acid, maleic acid and maleic anhydride;
the neutralizing agent comprises one or more of triethylamine, triethanolamine, diethanolamine, N-dimethylacetamide, sodium hydroxide and potassium hydroxide;
the initiator comprises one or more of di-tert-butyl peroxide, di-tert-amyl peroxide, tert-butyl peroxybenzoate, benzoyl peroxide and azodiisobutyronitrile;
the chain transfer agent comprises one or more of dodecyl mercaptan and aliphatic mercaptan.
A method for preparing an aqueous acrylic dispersion comprising the steps of:
1) Preparing a nuclear layer mixed solution: mixing soft monomer, hydroxyl monomer, hydrophilic monomer, initiator, chain transfer agent and reaction solvent for 20 min for use;
the mass of the hydroxyl monomer and the hydrophilic monomer in the core layer mixed solution is respectively 50-90% and 5-20% of the mass of the hydroxyl monomer and the hydrophilic monomer in the aqueous acrylic acid dispersion;
the mass of the initiator and the chain transfer agent is respectively 0.5-10% and 0.1-8% of the total mass of the monomers in the core layer mixed solution; the total mass of the monomers in the core layer mixed solution is the total mass of the soft monomers, the hydroxyl monomers and the hydrophilic monomers in the core layer mixed solution;
the mass of the reactive solvent is 0-40% of the mass of the reactive solvent in the aqueous acrylic dispersion;
2) Preparing a shell layer mixed solution: mixing a hard monomer, a hydroxyl monomer, a hydrophilic monomer, an initiator, a chain transfer agent and a reaction solvent for 20 minutes for later use;
the mass of the hydroxyl monomer and the hydrophilic monomer in the shell layer mixed solution is respectively 10-50% and 80-95% of the mass of the hydroxyl monomer and the hydrophilic monomer in the aqueous acrylic acid dispersion;
the mass of the initiator and the chain transfer agent is respectively 0.5-10% and 0.1-8% of the total mass of the monomers in the shell mixed solution; the total mass of the monomers in the shell layer mixed solution is the total mass of the hard monomers, the hydroxyl monomers and the hydrophilic monomers in the shell layer mixed solution;
the mass of the reactive solvent is 0-20% of the mass of the reactive solvent in the aqueous acrylic dispersion;
3) Synthesizing a nuclear structure: adding 30-80% of the mass of the reactive solvent in the aqueous acrylic acid dispersion into a reaction kettle, and heating to 90-150 ℃; then adding 1-10wt% of the nuclear layer mixed solution into the reaction kettle, and respectively dripping the residual nuclear layer mixed solution and part of modified silicone oil after 10-60 minutes at the speed of 2-4 hours; after the dripping is finished, preserving the heat for 2-4 hours; the modified silicone oil is 50-90wt% of the modified silicone oil in the aqueous acrylic acid dispersoid;
4) And (3) synthesizing a shell structure: adding 20-40% of the mass of the reaction solvent and 1-10% of the mass of the shell mixed solution into the reaction kettle, and continuously dropwise adding the residual shell mixed solution and the residual modified silicone oil after 10-60 minutes at a dropwise adding speed of 2-4 hours; after the dripping is finished, preserving the heat for 2-4 hours;
5) Adding initiator accounting for 0.01-1% of the mass of all reaction monomers in the aqueous acrylic acid dispersion, and preserving heat for 3-6h;
6) Cooling to 50-90 ℃, adding a neutralizing agent, and neutralizing for 30-60 minutes;
7) Cooling to 20-80 ℃, adding a proper amount of deionized water, and stirring and dispersing at a high speed for 30-60 minutes to obtain the aqueous acrylic acid dispersoid.
The application of the aqueous acrylic acid dispersion is that the aqueous acrylic acid dispersion is compounded with isocyanate curing agent, and the aqueous acrylic acid dispersion is applied to the coating industry with the anti-corrosion and rust-proof requirements.
The main body of the aqueous acrylic acid dispersoid is a shell-core structure, soft monomers and most of hydroxyl monomers are introduced into a core layer, and meanwhile, branched silane and alkane with functional groups are introduced into the core layer to form a comb-shaped branched structure on a molecular chain. The branched structure of silane and alkane has two main roles:
1) The branched structure is equivalent to a protective layer, can protect a large number of hydroxyl groups of the core layer from being exposed during hydration, and does not influence the hydration viscosity; it is beneficial to obtain a dispersion with high hydroxyl content and high solid content. In particular silane branching, due to the hydrophobicity of silane, is distinguished by protecting and shielding the hydroxyl group from interactions with other functional groups (mainly water molecules) and hydroxyl groups. The shell layer hard monomer and a small amount of branched silane and alkane further play a role in protecting hydroxyl groups; both are beneficial in obtaining high hydroxyl content, high solids dispersions.
2) The branched structure also has a part of functions of diluting the reaction viscosity, so that the reaction process is controllable. The general acrylic acid usually uses some polar and nonpolar solvents to dilute the reaction viscosity, but the solvents need post-treatment, so that the operation is complicated, the production cost is increased, and therefore, the reactive solvents are introduced to dilute the reaction viscosity and participate in the reaction, so that a series of subsequent problems are avoided.
3) The branched chain structure of the silane can further endow the product with better water resistance, solvent resistance, salt mist resistance and the like due to the unique property of the silicone oil, so that the property of the final product can be better improved.
The invention has the beneficial effects that:
1. the invention provides a synthesis method which solves the problem of viscosity increase caused by high hydroxyl content in the prior art, and provides a water-based hydroxyl acrylic dispersion with high hydroxyl content, high solid content and low viscosity, wherein the hydroxyl content is up to 4-7%, and the solid content is up to 40-70%.
2. The preparation process of the invention does not use solvent and does not influence VOC value.
3. The synthesized aqueous acrylic acid dispersion can be used by being compounded with isocyanate curing agents; and has excellent salt fog resistance, weather resistance and liquid medium resistance; can be applied to occasions with high anti-corrosion and rust-proof requirements, such as industries of automobiles, high-speed rails, steel pipes and the like.
Drawings
FIG. 1 is a schematic core-shell structure of an aqueous acrylic dispersion;
Detailed Description
The invention is described in further detail below with reference to the attached drawings and specific examples:
example 1
1) Preparing a nuclear layer mixed solution: 5.00g of butyl acrylate, 4.00g of ethyl acrylate, 24.00g of hydroxyethyl methacrylate, 0.50g of methacrylic acid, 1.26g of di-tert-butyl peroxide, 0.63g of n-dodecyl mercaptan and 5.00g of isobornyl methacrylate are uniformly mixed for later use;
2) Preparing a shell layer mixed solution: methyl methacrylate 5.00g, styrene 4.00g, hydroxyethyl methacrylate 6.00g, methacrylic acid 4.00g, di-tert-butyl peroxide 0.68g, n-dodecyl mercaptan 0.34g and isobornyl methacrylate 5.00g are uniformly mixed for later use;
3) Synthesizing a nuclear structure: 10.00g of glycidyl methacrylate is added into a reaction kettle, and the temperature is raised to 110 ℃; then adding 4.00g of the nuclear layer mixed solution into the reaction kettle at one time, after stabilizing for 15 minutes, respectively dripping 15.00g of the rest nuclear layer mixed solution and methacrylic acid modified silicone oil (Xinyue organosilicon KF-2012), and dripping for 3 hours; after the dripping is finished, preserving the heat for 3 hours;
4) And (3) synthesizing a shell structure: adding 5.00g of glycidyl methacrylate and 2.00g of shell mixed solution into a reaction kettle, stabilizing for 15 minutes, and then continuously dropwise adding 5.00g of the rest shell mixed solution and methacrylic acid modified silicone oil (Xinyue organic silicon KF-2012) respectively at an acceleration of 2 hours; after the dripping is finished, preserving the heat for 2 hours;
5) Then 0.49g of di-tert-butyl peroxide is added, and the temperature is kept for 3 hours;
6) Cooling to 60 ℃, adding 8.00g of triethanolamine as a neutralizing agent, and neutralizing for 30 minutes;
7) Cooling to 40 ℃, adding 146.00g of deionized water, and stirring and dispersing at high speed for 60 minutes to obtain the aqueous acrylic acid dispersion.
The core-shell structure of the aqueous acrylic dispersion obtained is shown in FIG. 1, the theoretical hydroxyl content of the aqueous acrylic dispersion is 4.0%, the solid content of the aqueous acrylic dispersion is 40%, and the viscosity of the aqueous acrylic dispersion is 394 mPa.s.
Example 2
1) Preparing a nuclear layer mixed solution: 4.00g of butyl methacrylate, 6.00g of butyl acrylate, 18.00g of hydroxyethyl acrylate, 15.00g of hydroxypropyl acrylate, 0.30g of methacrylic acid, 2.77g of di-tert-amyl peroxide, 0.69g of n-dodecyl mercaptan and 5.00g of acrylic acid modified polycaprolactone, and mixing for 20 minutes for later use;
2) Preparing a shell layer mixed solution: 12.00g of ethyl methacrylate, 3.00g of styrene, 2.00g of hydroxyethyl acrylate, 1.20g of hydroxypropyl acrylate, 2.70g of methacrylic acid, 1.23g of di-tert-amyl peroxide, 0.31g of n-dodecyl mercaptan and 0.80g of acrylic acid modified polycaprolactone, and mixing for 20 minutes for later use;
3) Synthesizing a nuclear structure: adding 5.00g of isobornyl methacrylate into a reaction kettle, and heating to 140 ℃; then adding 2.50g of the nuclear layer mixed solution into the reaction kettle at one time, after stabilizing for 10 minutes, respectively dripping 16.00g of the rest nuclear layer mixed solution and methacrylic acid modified silicone oil (Xinyue organic silicon X-22-2426), and dripping acceleration for 2 hours; after the dripping is finished, preserving the heat for 3 hours;
4) And (3) synthesizing a shell structure: adding 5.00g of isobornyl methacrylate and 1.45g of shell mixed solution into a reaction kettle, stabilizing for 10 minutes, and then continuously dropwise adding 4.00g of the rest shell mixed solution and methacrylic acid modified silicone oil (Xinyue organic silicon X-22-2426) respectively at a dropwise acceleration rate of 1h; after the dripping is finished, preserving the heat for 2 hours;
5) Adding 0.30g of di-tert-amyl peroxide, and preserving heat for 2 hours;
6) Cooling to 50 ℃, adding 5.43g of neutralizing agent triethylamine, and neutralizing for 30 minutes;
7) Cooling to 40 ℃, adding 100.00g of deionized water, and stirring and dispersing at a high speed for 30 minutes to obtain the aqueous acrylic acid dispersion.
Theoretical hydroxyl content of the aqueous acrylic dispersion obtained theoretical hydroxyl content 5.0%, solids content 50%, dispersion viscosity 690mpa·s.
Example 3
1) Preparing a nuclear layer mixed solution: 2.00g of dodecyl methacrylate, 7.00g of hexyl acrylate, 30.00g of hydroxyethyl acrylate, 10.00g of hydroxypropyl methacrylate, 0.30g of methacrylic acid, 3.52g of tert-butyl peroxybenzoate and 1.41g of n-dodecyl mercaptan are mixed for 20 minutes for later use;
2) Preparing a shell layer mixed solution: 8.00g of methyl methacrylate, 2.00g of vinyl acetate, 7.00g of hydroxyethyl acrylate, 3.00g of hydroxypropyl methacrylate, 2.70g of methacrylic acid, 1.49g of tert-butyl peroxybenzoate and 0.59g of n-dodecyl mercaptan are mixed for 20 minutes for later use;
3) Synthesizing a nuclear structure: 7.00g of tertiary glycidyl ester is added into a reaction kettle, and the temperature is raised to 130 ℃; then adding 2.50g of the nuclear layer mixed solution into the reaction kettle at one time, and after stabilizing for 10 minutes, respectively dripping 14.00g of the residual nuclear layer mixed solution and mercapto-modified silicone oil (Xinyue organosilicon KF-2001) for 4 hours; after the dripping is finished, preserving the heat for 3 hours;
4) And (3) synthesizing a shell structure: adding 3.00g of tertiary glycidyl ester and 1.45g of shell mixed solution into a reaction kettle, stabilizing for 10 minutes, and then continuously dropwise adding 4.00g of residual shell mixed solution and mercapto-modified silicone oil (Xinyue organosilicon KF-2001) respectively, wherein the dropwise adding speed is 3 hours; after the dripping is finished, preserving the heat for 2 hours;
5) Adding 0.30g of tert-butyl peroxybenzoate, and preserving heat for 2h;
6) Cooling to 80 ℃, adding 4.67g of neutralizer N, N-dimethylacetamide, and neutralizing for 30 minutes;
7) Cooling to 40 ℃, adding 67.00g of deionized water, and stirring and dispersing at a high speed for 60 minutes to obtain the aqueous acrylic acid dispersion.
Theoretical hydroxyl content of the aqueous acrylic dispersion obtained theoretical hydroxyl content 7.0%, solids content 60%, dispersion viscosity 1080mpa·s.
Due to the increase of the hydroxyl content in the dispersion, more hydroxyl monomers are necessarily added in the synthesis process, and the increase of the hydroxyl functional groups can enhance the interaction between the hydroxyl functional groups and water molecules in the hydration process, so that the volume of the fluid is increased, and the final viscosity of the dispersion is increased; even the experiments failed due to excessive viscosity which prevented the hydration process from being completed.
Therefore, in order to examine the influence of the modified silicone oil on the reaction process and the final product properties in the present invention, the aqueous acrylic dispersion was synthesized without adding the modified silicone oil to the reaction monomer of example 1, by adjusting other reactive solvents, while maintaining the hydroxyl group content unchanged.
Comparative example 1
1) Preparing a nuclear layer mixed solution: 5.00g of butyl acrylate, 4.00g of ethyl acrylate, 24.00g of hydroxyethyl methacrylate, 0.50g of methacrylic acid, 0.80g of di-tert-butyl peroxide, 0.40g of n-dodecyl mercaptan and 5.00g of isobornyl methacrylate are uniformly mixed for later use;
2) Preparing a shell layer mixed solution: methyl methacrylate 5.00g, styrene 4.00g, hydroxyethyl methacrylate 6.00g, methacrylic acid 4.00g, di-tert-butyl peroxide 0.49g, n-dodecyl mercaptan 0.25g and isobornyl methacrylate 5.00g are uniformly mixed for later use;
3) Synthesizing a nuclear structure: 25.00g of glycidyl methacrylate is added into a reaction kettle and heated to 110 ℃; then adding 4.00g of the nuclear layer mixed solution into the reaction kettle at one time, and after stabilizing for 15 minutes, respectively dripping the residual nuclear layer mixed solution for 3 hours; after the dripping is finished, preserving the heat for 3 hours;
4) And (3) synthesizing a shell structure: adding 10.00g of glycidyl methacrylate and 2.00g of shell mixed solution into a reaction kettle, stabilizing for 15 minutes, and then continuously dropwise adding the rest shell mixed solution respectively at a dropwise speed of 2 hours; after the dripping is finished, preserving the heat for 2 hours;
5) Then 0.49g of di-tert-butyl peroxide is added, and the temperature is kept for 3 hours;
6) Cooling to 60 ℃, adding 8.00g of triethanolamine as a neutralizing agent, and neutralizing for 30 minutes;
7) Cooling to 40 ℃, adding 146.00g of deionized water, and stirring and dispersing at high speed for 60 minutes to obtain the aqueous acrylic acid dispersion.
Theoretical hydroxyl content of the aqueous acrylic dispersion obtained theoretical hydroxyl content 5.0%, solids content 50%, dispersion viscosity 1240 mpa.s.
From the results obtained in example 1 and comparative example 1, it can be seen that the aqueous acrylic dispersion had a very large increase in viscosity and poor flowability at the same hydroxyl group content without the protective effect of the modified silicone oil. This is because, although the amount of the alkane-based reactive solvent in the comparative example is increased, since the alkane does not have the hydrophobicity of the silane-based molecular chain, it does not function well to shield and protect the hydroxyl group, and thus the increase in viscosity of the final dispersion is very remarkable. The alkane reactive solvent plays a similar role in reducing the reaction viscosity, so that the molecular weight of the product is not excessively large and is difficult to be dispersed by hydration due to the explosion or excessive reaction.
Performance testing
The aqueous dispersion of the present invention can be used as the hydroxyl component of a two-component aqueous polyurethane, and the resulting product can advantageously be suitable as a high performance aqueous coating by compounding with a curing agent which is conventional in the art, such as the curing agent available from BayerXP2655. The aqueous hydroxyl dispersion and the curing agent are mixed in a conventional manner, for example, in a high-speed disperser, just before use, and then the resulting mixture is applied to a substrate according to a conventional method, for example, by brushing, spraying, dipping, roll coating, knife coating or the like, and the substrate is not particularly limited and may be, for example, a steel plate, wood, film, leather or the like.
The aqueous acrylic acid dispersoid obtained by the invention is compounded with the curing agent, the wetting agent is added after the mixture and the dispersion are uniformly mixed, and the viscosity is regulated to 800 mPa.s, so that the aqueous acrylic acid dispersoid can be directly coated and applied to the surface of a substrate.
The method comprises the following specific steps: the aqueous acrylic acid dispersoid and the curing agent of the inventionXP2655, available from Bayer of Kochia Polymer (China) Co., ltd.) was mixed and dispersed uniformly in a disperser (FLUKO FA25 type, available from Fruck fluid machinery Co., ltd.) at 16000rpm, a wetting agent (model YMT 245, available from Meter (Beijing) environmental materials science and technology Co.) was added and viscosity was adjusted, after the viscosity was adjusted to 800 mPas, the mixture was directly coated on a steel plate or an iron plate with a wire rod of 100. Mu.m, and dried in a blast oven at 70℃for 40 minutes.
1) Neutral salt spray resistance
According to national standard GB/T1771-91 (determination of neutral salt spray resistance of paint and varnish), continuously observing the rust condition of the surface of a steel plate in a salt spray box, and observing for 700-1000h; four sides of the steel plate are sealed by paraffin-rosin.
2) Resistance to liquid Medium
According to national standard GB 9274-88 (determination of liquid-resistant Medium for paint and varnish), an iron plate is soaked in a liquid medium to be tested, and the conditions of rust, damage and the like of a film surface are observed for 24-48h, and the time is recorded.
3) Water resistance
According to national standard GB 5209-85 "method for measuring water resistance of paint and varnish" an iron plate is soaked in a constant-temperature water tank, and the conditions of rust, damage and the like of a film surface are observed for 24-48h, and the time is recorded.
4) Mechanical properties
The impact property, hardness, bending property, adhesive force and plastic deformation property of the iron plate film surface coating are respectively measured according to national standard GB/T1732 paint film impact resistance measurement method, GB/T color paint and varnish pencil method measurement paint film hardness, GB/T color paint and varnish bending test (cylindrical shaft), GB/T9286 color paint and varnish cross-cut test and GB/T color paint and varnish cup test.
Table 1 results of liquid Medium resistance of samples
TABLE 2 results of mechanical Properties of samples
Table 3 results of salt spray resistance of samples
As can be seen from the detection results of the dispersion performance and the product performance, after the modified silicone oil is added, the modified silicone oil acts together with other active solvents, has obvious effects of protecting and shielding hydroxyl groups in the hydration stage, and obviously reduces the viscosity of the dispersion, thus being beneficial to mixing and reaction with a curing agent in the later stage. Otherwise, local unevenness or side reaction of the curing agent is liable to be caused to generate carbon dioxide gas, thereby deteriorating the performance of the paint film. Moreover, due to the unique property of the silicone oil, the addition of the silane chain is also greatly helpful for improving the solvent resistance and the water resistance of the product. The properties of the final product are compared, and after the modified silicone oil is added, the water resistance, acid and alkali resistance of the product are obviously improved, and the mechanical property and salt spray resistance of the product are also improved.
Claims (5)
1. The high-hydroxyl-content aqueous acrylic dispersion is characterized by comprising the following components in percentage by mass:
soft monomer 5-20wt%
Hard monomer 5-20wt%
0.4 to 20 percent of modified silicone oil wt percent
5-50% wt% of reactive solvent
Hydroxyl monomer 5-40wt%
Hydrophilic monomer 0.5-10wt%
Neutralizing agent 1-10wt%
30-70wt% of deionized water, and the balance of initiator and chain transfer agent;
the modified silicone oil comprises one or more of silicone oil products with methacrylic acid or mercapto functional groups at two ends or a single end and silicone oil chains in branched chains;
the soft monomer comprises one or more of butyl acrylate, butyl methacrylate, ethyl acrylate, n-octyl acrylate, hexyl acrylate, isooctyl methacrylate, dodecyl methacrylate and vinyl versatate;
the hard monomer comprises one or more of methyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, propyl methacrylate, cyclohexyl methacrylate, vinyl acetate and styrene;
the reaction solvent comprises one or more of acrylic modified polyester polyol, tertiary glycidyl ester, tertiary vinyl ester, isobornyl methacrylate and glycidyl acrylate;
the acrylic modified polyester polyol comprises one or more of acrylic modified polycaprolactone polyol, polyether polyol and polycarbonate polyol;
the molecular weight of the acrylic-modified polyester polyol is in the range of 100 to 1000;
the hydroxyl monomer comprises one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate;
the hydrophilic monomer comprises one or more of methacrylic acid, acrylic acid, itaconic acid, maleic acid and maleic anhydride;
the neutralizing agent comprises one or more of triethylamine, triethanolamine, diethanolamine, N-dimethylacetamide, sodium hydroxide and potassium hydroxide;
the initiator comprises one or more of di-tert-butyl peroxide, di-tert-amyl peroxide, tert-butyl peroxybenzoate, benzoyl peroxide and azodiisobutyronitrile;
the chain transfer agent comprises one or more of dodecyl mercaptan and aliphatic mercaptan.
2. The aqueous acrylic dispersion according to claim 1, characterized in that the modified silicone oil has a viscosity of 90-1000mm at 25 °c 2 /s。
3. The aqueous acrylic dispersion according to claim 1, characterized in that the solids content in the aqueous acrylic dispersion is 40-70%; hydroxyl content 4-8%; the molecular weight is 2-15 ten thousand.
4. A process for the preparation of an aqueous acrylic dispersion according to any one of claims 1 to 3, characterized by comprising the steps of:
1) Preparing a nuclear layer mixed solution: mixing soft monomer, hydroxyl monomer, hydrophilic monomer, initiator, chain transfer agent and reaction solvent for 20 min for use;
the mass of the hydroxyl monomer and the hydrophilic monomer in the core layer mixed solution is respectively 50-90% and 5-20% of the mass of the hydroxyl monomer and the hydrophilic monomer in the aqueous acrylic acid dispersion;
the mass of the initiator and the chain transfer agent is respectively 0.5-10% and 0.1-8% of the total mass of the monomers in the core layer mixed solution;
the mass of the reactive solvent is 0-40% of the mass of the reactive solvent in the aqueous acrylic dispersion;
2) Preparing a shell layer mixed solution: mixing a hard monomer, a hydroxyl monomer, a hydrophilic monomer, an initiator, a chain transfer agent and a reaction solvent for 20 minutes for later use;
the mass of the hydroxyl monomer and the hydrophilic monomer in the shell layer mixed solution is respectively 10-50% and 80-95% of the mass of the hydroxyl monomer and the hydrophilic monomer in the aqueous acrylic acid dispersion;
the mass of the initiator and the chain transfer agent is respectively 0.5-10% and 0.1-8% of the total mass of the monomers in the shell mixed solution;
the mass of the reactive solvent is 0-20% of the mass of the reactive solvent in the aqueous acrylic dispersion;
3) Synthesizing a nuclear structure: adding 30-80% of the mass of the reactive solvent in the aqueous acrylic acid dispersion into a reaction kettle, and heating to 90-150 ℃; then adding 1-10wt% of the nuclear layer mixed solution into the reaction kettle, and respectively dripping the residual nuclear layer mixed solution and part of modified silicone oil after 10-60 minutes at the speed of 2-4 hours; after the dripping is finished, preserving the heat for 2-4 hours; the modified silicone oil is 50-90wt% of the modified silicone oil in the aqueous acrylic acid dispersoid;
4) And (3) synthesizing a shell structure: adding 20-40% of the mass of the reaction solvent and 1-10% of the mass of the shell mixed solution into the reaction kettle, and continuously dropwise adding the residual shell mixed solution and the residual modified silicone oil after 10-60 minutes at a dropwise adding speed of 2-4 hours; after the dripping is finished, preserving the heat for 2-4 hours;
5) Adding initiator accounting for 0.01-1% of the mass of all reaction monomers in the aqueous acrylic acid dispersion, and preserving heat for 3-6h;
6) Cooling to 50-90 ℃, adding a neutralizing agent, and neutralizing for 30-60 minutes;
7) Cooling to 20-80 ℃, adding a proper amount of deionized water, and stirring and dispersing at a high speed for 30-60 minutes to obtain the aqueous acrylic acid dispersoid.
5. The use of the aqueous acrylic dispersion according to any one of claims 1 to 3, wherein the aqueous acrylic dispersion is compounded with an isocyanate curing agent for use in the coating industry with anti-corrosive and rust-preventing requirements.
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