CN108690174B - Preparation process of acrylic polymer emulsion with flash rust resistance function - Google Patents
Preparation process of acrylic polymer emulsion with flash rust resistance function 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
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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
A preparation process of acrylic polymer emulsion with flash rust resistance belongs to the technical field of acrylic polymer emulsion, and comprises the following steps: A. preparing a core layer pre-emulsion; B. preparing a shell layer pre-emulsion; C. preparation of an initiator: seed initiator, nuclear layer initiator and shell layer initiator; D. adding 350 parts of water 250-plus and 0.1-1.5 parts of sodium dodecyl benzene sulfonate into a reaction kettle, stirring and heating to 80 ℃, adding 5% of nuclear layer pre-emulsion, adding a seed initiator, and reacting for 25 min; and then, dropwise adding the rest of the nuclear layer pre-emulsion and the nuclear layer initiator, preserving heat for 20-40min after dropwise adding is completed within 2-2.5h, dropwise adding the rest of the nuclear layer pre-emulsion and the shell layer initiator, preserving heat for 2-2.5h after dropwise adding is completed within 1-1.5h, cooling to below 40 ℃, adjusting the pH to 7.5-8, adding an antifoaming agent and a bactericide, and filtering to obtain the product. After the emulsion prepared by the invention is applied to industrial protective primer, the early flash rust resistance, the impact resistance, the adhesive force and the salt spray resistance are greatly improved.
Description
Technical Field
The invention belongs to the technical field of acrylic polymer emulsion, and particularly relates to a preparation process of acrylic polymer emulsion with flash rust resistance. The acrylic polymer emulsion with the flash rust resistance function prepared by the preparation process is of a nuclear layer two-layer structure, and after the acrylic polymer emulsion is applied to industrial protective primer, the flash rust resistance, the impact resistance, the adhesive force and the salt spray resistance in the early stage are greatly improved, and the performance is excellent.
Background
Currently, in order to realize the strategic goal of 'green development', various environmental protection policies are continuously issued by countries and places to guide enterprises to reduce the emission of VOC in the production process and when users use terminal products. The coating taking water as a diluent becomes an important development direction in the coating industry of China, the current water-based industrial paint has opportunities and also faces great challenges, and a plurality of performances can not reach the effect of solvent-based coatings. One of the problems which plague aqueous industrial paints is the tendency of flash rust to occur during the drying of the metal surface.
The flash rust occurs mainly due to the formation of an oxygen concentration cell, where an electrochemical reaction occurs on the metal surface, a cathode is formed in an oxygen-rich region, an anode is formed in an oxygen-poor region, and when water is adsorbed on the metal surface in a thin film state, the reaction speed of the electrochemical reaction is extremely high because the transfer rate of oxygen is high. Therefore, flash rust in aqueous industrial paints tends to appear in the late stage of drying before the water is substantially evaporated, and the time is short, and a large amount of rust spots tend to appear in 1 to 2 minutes.
In aqueous industrial paints, anti-flash rust agents are generally used to eliminate the appearance of flash rust, the most commonly used NaNO2The flash rust inhibitor can prevent flash rust by rapidly adsorbing organic substances on the metal surface and blocking the ion transfer process of the battery, but the adhesion between the polymer and the substrate is weakened. The existing flash rust inhibitor solves the problem that the flash rust of the early water-based flash rust cannot be eliminated by forming an oxygen concentration battery and blocking the ion transmission of the battery, and no research report aiming at solving the problem of the early water-based flash rust exists at present.
Disclosure of Invention
The invention designs a preparation process of acrylic polymer emulsion with flash rust resistance function for radically solving flash rust and solving the problem of early water-based flash rust. The invention adopts special monomers of polyoxyalkylene ether (alkyl polyoxyethylene acrylate) containing polar side chains, tert-butylaminoethyl methacrylate (2- (tert-butylamino) ethyl methacrylate, TBAEMA (CAS: 3775-90-4), acrylic acid polyoxypropylene ester and hydroxyethyl caprolactone acrylate monomer (HECLA, CAS: 110489-05-9), adopts a two-stage polymerization process to prepare the acrylic polymer particles with the core-shell structure, and polar long-chain polymers at the periphery of the particles are quickly attached to the surface of a metal base material, thereby avoiding the formation of an oxygen concentration difference battery in the early film forming process of the aqueous polymer, eliminating the flash rust of early water and simultaneously improving the adhesive force on the metal base material.
The technical scheme adopted by the invention for realizing the purpose is as follows: the preparation process of the acrylic polymer emulsion with the flash rust resistance function comprises the following steps:
A. preparation of core layer pre-emulsion: sequentially adding 150 parts of water 100, 1-4 parts of emulsifier, 80-150 parts of styrene, 30-100 parts of isooctyl acrylate and 1-5 parts of methacrylic acid into an emulsion reaction kettle I according to parts by weight, and stirring for 1-1.5 hours to obtain a core layer pre-emulsion;
B. preparing a shell layer pre-emulsion, sequentially adding 150 parts of 100-one water, 0.2-1.5 parts of emulsifier, 50-120 parts of styrene, 10-20 parts of methyl methacrylate, 2-8 parts of 2- (tert-butylamino) ethyl methacrylate, 3-10 parts of hydroxyethyl caprolactone acrylate, 30-60 parts of alkyl polyoxyethylene acrylate, 5-15 parts of n-butyl acrylate, 30-80 parts of isooctyl acrylate and 5-15 parts of polyoxypropylene acrylate into an emulsion reaction kettle II according to parts by weight, and stirring for 1-1.5 hours to obtain a shell layer pre-emulsion;
C. preparation of an initiator:
seed initiator: dissolving 0.5-1.5 parts of initiator in 3-5 parts of water to obtain a seed initiator;
nuclear layer initiator: dissolving 0.2-1 part of initiator in 3-5 parts of water to obtain a nuclear layer initiator;
shell initiator: dissolving 0.1-0.6 part of initiator in 3-5 parts of water to obtain a shell initiator;
D. preparation of acrylic polymer emulsion having flash rust resistance: adding 350 parts of water 250 and 0.1-1.5 parts of emulsifier into a reaction kettle, stirring, heating to 80 ℃, adding 5% of nuclear layer pre-emulsion, then adding a seed initiator, and reacting for 20-30 min; and then, dropwise adding the rest of the nuclear layer pre-emulsion and the nuclear layer initiator, preserving heat for 20-40min after dropwise adding is completed within 2-2.5h, dropwise adding the rest of the nuclear layer pre-emulsion and the shell layer initiator, preserving heat for 2-2.5h after dropwise adding is completed within 1-1.5h, cooling to below 40 ℃, adjusting the pH to 7.5-8 by using ammonia water, adding a defoaming agent and a bactericide, and filtering to obtain the acrylic polymer emulsion with the flash rust resistance function.
The initiator is one or two of ammonium persulfate, sodium persulfate and potassium persulfate.
The emulsifier is one or two of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
The defoaming agent is defoaming agent NXZ.
The bactericide is a bactericide BIT 20.
The invention has the beneficial effects that:
1. the final emulsion has fine particle size of 50-70nm, and adopts core-shell structure to control the distribution of polar functional monomer in the outer layer of emulsion particle.
2. The shell layer uses polyoxyalkylene ether containing reactive groups as a main raw material to form a water-soluble surface layer with a non-ionic structure, which is beneficial to the rapid adhesion of polymers in polymer particles on a metal substrate, improves the adhesive force of the polymers on the substrate, avoids the contact of water and the substrate in the later drying period and avoids the occurrence of oxygen concentration electrochemical corrosion.
3. 2- (tertiary butyl amino) ethyl methacrylate, acrylic acid polyoxypropylene ester and hydroxyethyl caprolactone acrylate monomers are adopted in the shell layer to assist and further enhance the adhesion of the polymer on the surface layer of the polymer particle to the base material.
4. The water paint for metal surface prepared by the emulsion can use little or no flash rust inhibitor, can obtain good flash rust resistant effect, and obviously improves the performances of adhesive force, salt mist resistance and the like.
5. According to the invention, the acrylic polymer emulsion with a core-shell two-layer structure is prepared by reasonably controlling the emulsion components and the preparation process, so that the overall performance of the emulsion is balanced, and the comprehensive performances such as compactness, adhesive force, impact resistance, salt mist resistance and the like of a paint film are improved on the basis of ensuring full film formation. On the other hand, the invention introduces special monomers of polyoxyalkylene ether (alkyl polyoxyethylene acrylate) containing polar side chain, 2- (tert-butylamino) ethyl methacrylate, hydroxyethyl caprolactone acrylate, acrylic acid polyoxypropylene ester and other monomers into the emulsion according to the proportion to prepare the acrylic polymer particles with the core-shell structure, so that the polar long-chain polymer at the periphery of the particles is quickly attached to the surface of the metal base material, and the formation of an oxygen concentration cell in the early film forming process of the aqueous polymer is avoided, thereby eliminating the flash rust of the early water, and improving the early flash rust resistance, adhesive force, impact resistance and salt fog resistance of the film forming.
6. The emulsion product synthesized by the invention does not contain APEO, has low formaldehyde, no benzene series and other pollution emissions, and has good product stability. Compared with the main competitors at home and abroad, the anti-flash rust paint has excellent early-stage anti-flash rust, adhesive force, impact resistance, salt mist resistance and the like on the key performance, and the final product has excellent performance and is environment-friendly.
Detailed Description
The present invention will be further described with reference to the following examples.
Detailed description of the preferred embodiments
Example 1
A. Preparation of core layer pre-emulsion: sequentially adding 100 parts of water, 1 part of sodium dodecyl benzene sulfonate, 80 parts of styrene, 30 parts of isooctyl acrylate and 1 part of methacrylic acid into an emulsion reaction kettle I according to the parts by weight, and stirring for 1h to obtain a core layer pre-emulsion;
B. preparing a shell layer pre-emulsion, namely sequentially adding 150 parts of water, 1.5 parts of sodium dodecyl benzene sulfonate, 120 parts of styrene, 20 parts of methyl methacrylate, 8 parts of 2- (tert-butylamino) ethyl methacrylate, 10 parts of hydroxyethyl caprolactone acrylate, 60 parts of alkyl polyoxyethylene acrylate, 15 parts of n-butyl acrylate, 80 parts of isooctyl acrylate and 15 parts of polyoxypropylene acrylate into an emulsion reaction kettle II according to parts by weight, and stirring for 1.5 hours to obtain the shell layer pre-emulsion;
C. preparation of an initiator:
seed initiator: dissolving 0.5 part of ammonium persulfate in 3 parts of water to obtain a seed initiator;
nuclear layer initiator: dissolving 0.2 part of ammonium persulfate in 3 parts of water to obtain a nuclear layer initiator;
shell initiator: dissolving 0.1 part of ammonium persulfate in 3 parts of water to obtain a shell initiator;
D. preparation of acrylic polymer emulsion having flash rust resistance: adding 250 parts of water and 0.1 part of sodium dodecyl benzene sulfonate into a reaction kettle, stirring and heating to 80 ℃, adding 5% of nuclear layer pre-emulsion, then adding a seed initiator, and reacting for 25 min; and then, dropwise adding the rest of the nuclear layer pre-emulsion and the nuclear layer initiator, keeping the temperature for 20min after dropwise adding is finished within 2h, then dropwise adding the rest of the nuclear layer pre-emulsion and the shell layer initiator, keeping the temperature for 2h after dropwise adding is finished within 1h, cooling to 35 ℃, adjusting the pH to 7.5 by using ammonia water, adding an antifoaming agent NXZ and a bactericide BIT20, and filtering to obtain the acrylic polymer emulsion with the flash rust resistance.
Example 2
The preparation process of the acrylic polymer emulsion with the flash rust resistance function is characterized by comprising the following steps:
A. preparation of core layer pre-emulsion: sequentially adding 150 parts of water, 4 parts of sodium dodecyl benzene sulfonate, 150 parts of styrene, 100 parts of isooctyl acrylate and 5 parts of methacrylic acid into an emulsion reaction kettle I according to the parts by weight, and stirring for 1.5 hours to obtain a core layer pre-emulsion;
B. preparing a shell-layer pre-emulsion, namely sequentially adding 100 parts of water, 0.2 part of sodium dodecyl benzene sulfonate, 50 parts of styrene, 10 parts of methyl methacrylate, 2 parts of 2- (tert-butylamino) ethyl methacrylate, 3 parts of hydroxyethyl caprolactone acrylate, 30 parts of alkyl polyoxyethylene acrylate, 5 parts of n-butyl acrylate, 30 parts of isooctyl acrylate and 5 parts of polyoxypropylene acrylate into an emulsion reaction kettle II according to parts by weight, and stirring for 1 hour to obtain the shell-layer pre-emulsion;
C. preparation of ammonium persulfate:
seed initiator: dissolving 1.5 parts of ammonium persulfate in 3 parts of water to obtain a seed initiator ammonium;
nuclear layer initiator: dissolving 1 part of ammonium persulfate in 5 parts of water to obtain a nuclear layer initiator;
shell initiator: dissolving 0.6 part of ammonium persulfate in 5 parts of water to obtain a shell initiator;
D. preparation of acrylic polymer emulsion having flash rust resistance: adding 350 parts of water and 1.5 parts of sodium dodecyl benzene sulfonate into a reaction kettle, stirring and heating to 80 ℃, adding 5% of nuclear layer pre-emulsion, then adding a seed initiator, and reacting for 25 min; and then, dropwise adding the rest of the nuclear layer pre-emulsion and the nuclear layer initiator, preserving heat for 40min after dropwise adding is finished within 2.5h, then dropwise adding the rest of the nuclear layer pre-emulsion and the shell layer initiator, preserving heat for 2.5h after dropwise adding is finished within 1.5h, cooling to 38 ℃, adjusting the pH to 8 with ammonia water, adding a defoaming agent and a bactericide, and filtering to obtain the acrylic polymer emulsion with the flash rust resistance function.
Example 3
The preparation process of the acrylic polymer emulsion with the flash rust resistance function is characterized by comprising the following steps:
A. preparation of core layer pre-emulsion: according to the weight parts, 120 parts of water, 3 parts of sodium dodecyl benzene sulfonate, 100 parts of styrene, 50 parts of isooctyl acrylate and 3 parts of methacrylic acid are sequentially added into an emulsion reaction kettle I, and stirred for 1.2 hours to obtain a core layer pre-emulsion;
B. preparing a shell-layer pre-emulsion, namely sequentially adding 120 parts of water, 0.8 part of sodium dodecyl benzene sulfonate, 70 parts of styrene, 15 parts of methyl methacrylate, 5 parts of 2- (tert-butylamino) ethyl methacrylate, 7 parts of hydroxyethyl caprolactone acrylate, 50 parts of alkyl polyoxyethylene acrylate, 10 parts of n-butyl acrylate, 50 parts of isooctyl acrylate and 10 parts of polyoxypropylene acrylate into an emulsion reaction kettle II according to parts by weight, and stirring for 1.2 hours to obtain the shell-layer pre-emulsion;
C. preparation of ammonium persulfate:
seed initiator: dissolving 1 part of ammonium persulfate in 4 parts of water to obtain a seed initiator;
nuclear layer initiator: dissolving 0.5 part of ammonium persulfate in 4 parts of water to obtain a nuclear layer initiator;
shell initiator: dissolving 0.3 part of ammonium persulfate in 4 parts of water to obtain a shell initiator;
D. preparation of acrylic polymer emulsion having flash rust resistance: adding 300 parts of water and 0.8 part of sodium dodecyl benzene sulfonate into a reaction kettle, stirring and heating to 80 ℃, adding 5% of nuclear layer pre-emulsion, then adding a seed initiator, and reacting for 25 min; and then, dropwise adding the rest of the nuclear layer pre-emulsion and the nuclear layer initiator, preserving the heat for 30min after the dropwise adding is finished within 2.2h, then dropwise adding the rest of the nuclear layer pre-emulsion and the shell layer initiator, preserving the heat for 2.2h after the dropwise adding is finished within 1.2h, cooling to 37 ℃, adjusting the pH to 7.8 by using ammonia water, adding a defoaming agent and a bactericide, and filtering to obtain the acrylic polymer emulsion with the flash rust resistance.
Example 4
The preparation process of the acrylic polymer emulsion with the flash rust resistance function is characterized by comprising the following steps:
A. preparation of core layer pre-emulsion: adding 130 parts of water, 2 parts of sodium dodecyl benzene sulfonate, 120 parts of styrene, 70 parts of isooctyl acrylate and 4 parts of methacrylic acid into an emulsion reaction kettle I in sequence according to the parts by weight, and stirring for 1.3 hours to obtain a core layer pre-emulsion;
B. preparing a shell-layer pre-emulsion, namely sequentially adding 130 parts of water, 1 part of sodium dodecyl benzene sulfonate, 100 parts of styrene, 13 parts of methyl methacrylate, 7 parts of 2- (tert-butylamino) ethyl methacrylate, 5 parts of hydroxyethyl caprolactone acrylate, 45 parts of alkyl polyoxyethylene acrylate, 8 parts of n-butyl acrylate, 70 parts of isooctyl acrylate and 8 parts of polyoxypropylene acrylate into an emulsion reaction kettle II according to parts by weight, and stirring for 1.3 hours to obtain a shell-layer pre-emulsion;
C. preparation of ammonium persulfate:
seed initiator: dissolving 1.2 parts of ammonium persulfate in 3.5 parts of water to obtain a seed initiator;
nuclear layer initiator: dissolving 0.4 part of ammonium persulfate in 4.5 parts of water to obtain a nuclear layer initiator;
shell initiator: dissolving 0.5 part of ammonium persulfate in 3.5 parts of water to obtain a shell initiator;
D. preparation of acrylic polymer emulsion having flash rust resistance: adding 280 parts of water and 1.2 parts of sodium dodecyl benzene sulfonate into a reaction kettle, stirring and heating to 80 ℃, adding 5% of nuclear layer pre-emulsion, then adding a seed initiator, and reacting for 25 min; and then, dropwise adding the rest of the nuclear layer pre-emulsion and the nuclear layer initiator, preserving heat for 25min after dropwise adding is finished within 2.4h, dropwise adding the rest of the nuclear layer pre-emulsion and the shell layer initiator, preserving heat for 2h after dropwise adding is finished within 1.4h, cooling to 33 ℃, adjusting the pH to 7.7 by using ammonia water, adding a defoaming agent and a bactericide, and filtering to obtain the acrylic polymer emulsion with the flash rust resistance.
Example 5
The preparation process of the acrylic polymer emulsion with the flash rust resistance function is characterized by comprising the following steps:
A. preparation of core layer pre-emulsion: according to the weight parts, 110 parts of water, 2.5 parts of sodium dodecyl benzene sulfonate, 90 parts of styrene, 90 parts of isooctyl acrylate and 2.5 parts of methacrylic acid are sequentially added into an emulsion reaction kettle I and stirred for 1.1h to obtain a core layer pre-emulsion;
B. preparing a shell-layer pre-emulsion, namely sequentially adding 140 parts of water, 0.5 part of sodium dodecyl benzene sulfonate, 90 parts of styrene, 18 parts of methyl methacrylate, 4 parts of 2- (tert-butylamino) ethyl methacrylate, 9 parts of hydroxyethyl caprolactone acrylate, 55 parts of alkyl polyoxyethylene acrylate, 12 parts of n-butyl acrylate, 40 parts of isooctyl acrylate and 12 parts of polyoxypropylene acrylate into an emulsion reaction kettle II according to parts by weight, and stirring for 1.4 hours to obtain the shell-layer pre-emulsion;
C. preparation of ammonium persulfate:
seed initiator: dissolving 1.1 parts of ammonium persulfate in 4.5 parts of water to obtain a seed initiator;
nuclear layer initiator: dissolving 0.7 part of ammonium persulfate in 3.5 parts of water to obtain a nuclear layer initiator;
shell initiator: dissolving 0.2 part of ammonium persulfate in 4 parts of water to obtain a shell initiator;
D. preparation of acrylic polymer emulsion having flash rust resistance: adding 320 parts of water and 0.6 part of sodium dodecyl benzene sulfonate into a reaction kettle, stirring and heating to 80 ℃, adding 5% of nuclear layer pre-emulsion, then adding a seed initiator, and reacting for 25 min; and then, dropwise adding the rest of the nuclear layer pre-emulsion and the nuclear layer initiator, keeping the temperature for 20min after the dropwise adding is finished within 2h, then dropwise adding the rest of the shell layer pre-emulsion and the shell layer initiator, keeping the temperature for 2h after the dropwise adding is finished within 1h, cooling to 39 ℃, adjusting the pH to 7.9 by using ammonia water, adding a defoaming agent and a bactericide, and filtering to obtain the acrylic polymer emulsion with the flash rust resistance.
Second, experimental data and analysis
The acrylic polymer emulsion having flash rust resistance prepared as described above was compared with commercially available product emulsions for testing application properties.
1. Flash rust resistance of emulsion film
Coating the emulsion on the surface of the treated carbon steel substrate, and drying in a constant temperature and humidity cabinet to obtain a wet film thickness of 80-100 microns. The drying temperature of the constant temperature and humidity cabinet is 25 ℃, and the relative humidity conditions of 40% and 85% are compared with the flash rust condition when the acrylic polymer emulsion, the commercially available product HG-54C (resin for the aqueous metal protective paint of the Dow HG-54C) and the commercially available product 719F (Badufu RS-719F) are dried; in run Nos. 4, 5, 9, and 10, 0.2% sodium nitrite was added to HG-54C and 719F.
TABLE 1
| Experiment number | Emulsion sample | Sodium nitrite | Drying temperature C | Relative humidity% | Flash rust rating |
| 1 | The invention | - | 25 | 40 | Is free of |
| 2 | HG-54C | - | 25 | 40 | In |
| 3 | 719F | - | 25 | 40 | In |
| 4 | HG-54C | 0.2％ | 25 | 40 | Is free of |
| 5 | 719F | 0.2％ | 25 | 40 | Is free of |
| 6 | The invention | - | 25 | 85 | Is free of |
| 7 | HG-54C | - | 25 | 85 | Severe severity of disease |
| 8 | 719F | - | 25 | 85 | Severe severity of disease |
| 9 | HG-54C | 0.2％ | 25 | 85 | Light and slight |
| 10 | 719F | 0.2％ | 25 | 85 | Light and slight |
Under the conditions of 25 ℃ and 40% relative humidity, the drying time of the polymer emulsion is relatively short, the polymer emulsion is transparent after about 15min, most of moisture is volatilized, flash rust appears in experiment numbers 2 and 3 to which sodium nitrite is not added, and flash rust does not appear in experiment numbers 4 and 5 to which sodium nitrite is added. At 25 ℃ and a relative humidity of 85%, the drying time is obviously prolonged, the retention time of partial micro water drops is prolonged, the condition time for flash rust generation is prolonged, and flash rust is more likely to occur. The flash rust grades of experiment numbers 7 and 8 were severe, and slight flash rust also appeared in experiment numbers 9 and 10 to which sodium nitrite was added.
The faster the dry zone progresses, the shorter the corrosion process of the oxygen concentration cell, the less corrosion products are produced and the less flash rust occurs. Under the condition of low humidity, the drying process is fast, flash rust does not appear in experiment numbers 4 and 5 in which sodium nitrite is added, and the sodium nitrite prevents the corrosion process through anode passivation reaction. However, the corrosion time was prolonged after the humidity was increased, and sodium nitrite was gradually consumed, and the occurrence of corrosion could not be prevented, and in the high humidity condition, the corrosion process occurred in experiment nos. 9 and 10 in spite of the addition of sodium nitrite, and slight flash rust occurred. No flash rust occurred in the home-made emulsion under both of these drying conditions.
2. Flash rust resistance of coating
The following coating formulations were used as examples to test the coating properties: the paint comprises, by weight, 45-55 parts of emulsion, 13-19 parts of deionized water, 0.1-0.2 part of a wetting agent TO-8 (100%), 0.6-1.0 part of a dispersant SN-5040 (44%), 0.2-0.3 part of a pH regulator AMP-95 (95%), 6-10 parts of titanium dioxide, 3-9 parts of heavy calcium carbonate, 1-3 parts of dipropylene glycol monobutyl ether (99%), 0.4-0.8 part of a thickener RM8W (17%), 0.1-0.2 part of a defoaming agent NXZ, 200.05-0.1 part of preservative BIT and 0.1-0.3 part of a flatting agent RM2020 (20%). The emulsion is respectively selected from the acrylic polymer emulsion prepared by the invention, HG-54C and 719F for testing, and when the emulsion is selected from HG-54C or 719F, 2% of flash rust resistant agent (0.2% of sodium nitrite) is added into 100 parts by weight of the coating formula.
It can be seen from Table 2 that the coatings exhibited excellent flash rust resistance under low humidity conditions after the addition of the flash rust inhibitor, but slight flash rust was observed in test Nos. 5 and 6 in which the flash rust inhibitor was added at high humidity. This is a problem that the current aqueous industrial paints are used under low temperature and high humidity conditions, and under such conditions, the problem can only be solved by using a large amount of the anti-flash rust agent, but the water resistance of the paint is reduced. The coatings prepared from the acrylic polymer emulsion of the present invention exhibit good flash rust resistance under both conditions.
TABLE 2 coating film formation conditions on non-rust substrates
| Experiment number | Emulsion sample | Flash rust inhibitor | Drying temperature C | Relative humidity% | Flash rust rating |
| 11 | The invention | - | 25 | 40 | Is free of |
| 12 | HG-54C | 2％ | 25 | 40 | Is free of |
| 13 | 719F | 2％ | 25 | 40 | Is free of |
| 14 | The invention | - | 25 | 85 | Is free of |
| 15 | HG-54C | 2％ | 25 | 85 | Light and slight |
| 16 | 719F | 2％ | 25 | 85 | Light and slight |
The steel plates used in the laboratory were carefully ground, taking into account only the influence of the drying conditions. However, in actual construction, the base material is not treated completely, and rust still remains, so that the occurrence probability of flash rust increases. Table 3 shows the selection of substrates bearing rust versus flash rust. Flash rust occurs under high humidity conditions, but the acrylic polymer emulsion of the present invention produces much better coatings. This is because the iron oxide deposition structure in the rusty substrate rust spot region has various forms, and the polymer of the outer layer of the polymer does not effectively adhere to the entire rust surface, and the region where no polymer adheres is likely to suffer from the oxygen concentration corrosion phenomenon.
TABLE 3 film Forming conditions for coating on rusty substrates
| Experiment number | Emulsion sample | Flash rust inhibitor | Drying temperature C | Relative humidity% | Flash rust rating |
| 17 | The invention | - | 25 | 80 | Light and slight |
| 18 | HG-54C | 2％ | 25 | 80 | Severe severity of disease |
| 19 | 719F | 2％ | 25 | 80 | Severe severity of disease |
3. Coating performance
The following coating formulations were used as examples to test the coating properties: the paint comprises, by weight, 45-55 parts of emulsion, 13-19 parts of deionized water, 0.1-0.2 part of a wetting agent TO-8 (100%), 0.6-1.0 part of a dispersant SN-5040 (44%), 0.2-0.3 part of a pH regulator AMP-95 (95%), 6-10 parts of titanium dioxide, 3-9 parts of heavy calcium carbonate, 1-3 parts of dipropylene glycol monobutyl ether (99%), 0.4-0.8 part of a thickener RM8W (17%), 0.1-0.2 part of a defoaming agent NXZ, 200.05-0.1 part of preservative BIT and 0.1-0.3 part of a flatting agent RM2020 (20%). The emulsion is respectively selected from the acrylic polymer emulsion prepared by the invention, HG-54C and 719F for testing, and when the emulsion is selected from HG-54C or 719F, 2% of flash rust resistant agent (0.2% of sodium nitrite) is added into 100 parts by weight of the coating formula.
From the results of the paint performance, the paint using HG-54C, 719F showed slight blistering, possibly related to the amount of anti-flash rust agent. The acrylic polymer emulsion has excellent paint performance, water resistance, adhesion and the like.
TABLE 4 paint Performance test results
In conclusion, the overall performance of the acrylic polymer emulsion with the flash rust resistance and the finished paint prepared from the acrylic polymer emulsion are superior to that of a competitive product emulsion, and the acrylic polymer emulsion has a good application prospect in the industrial protective paint market.
Claims (5)
1. The preparation process of the acrylic polymer emulsion with the flash rust resistance function is characterized by comprising the following steps:
A. preparation of core layer pre-emulsion: sequentially adding 150 parts of water 100, 1-4 parts of emulsifier, 80-150 parts of styrene, 30-100 parts of isooctyl acrylate and 1-5 parts of methacrylic acid into an emulsion reaction kettle I according to parts by weight, and stirring for 1-1.5 hours to obtain a core layer pre-emulsion;
B. preparing a shell layer pre-emulsion, sequentially adding 150 parts of 100-one water, 0.2-1.5 parts of emulsifier, 50-120 parts of styrene, 10-20 parts of methyl methacrylate, 2-8 parts of 2- (tert-butylamino) ethyl methacrylate, 3-10 parts of hydroxyethyl caprolactone acrylate, 30-60 parts of alkyl polyoxyethylene acrylate, 5-15 parts of n-butyl acrylate, 30-80 parts of isooctyl acrylate and 5-15 parts of polyoxypropylene acrylate into an emulsion reaction kettle II according to parts by weight, and stirring for 1-1.5 hours to obtain a shell layer pre-emulsion;
C. preparation of an initiator:
seed initiator: dissolving 0.5-1.5 parts of initiator in 3-5 parts of water to obtain a seed initiator;
nuclear layer initiator: dissolving 0.2-1 part of initiator in 3-5 parts of water to obtain a nuclear layer initiator;
shell initiator: dissolving 0.1-0.6 part of initiator in 3-5 parts of water to obtain a shell initiator;
D. preparation of acrylic polymer emulsion having flash rust resistance: adding 350 parts of water 250 and 0.1-1.5 parts of emulsifier into a reaction kettle, stirring, heating to 80 ℃, adding 5% of nuclear layer pre-emulsion, then adding a seed initiator, and reacting for 20-30 min; and then, dropwise adding the rest of the nuclear layer pre-emulsion and the nuclear layer initiator, preserving heat for 20-40min after dropwise adding is completed within 2-2.5h, dropwise adding the rest of the nuclear layer pre-emulsion and the shell layer initiator, preserving heat for 2-2.5h after dropwise adding is completed within 1-1.5h, cooling to below 40 ℃, adjusting the pH to 7.5-8 by using ammonia water, adding a defoaming agent and a bactericide, and filtering to obtain the acrylic polymer emulsion with the flash rust resistance function.
2. The process for preparing acrylic polymer emulsion with flash rust resisting function according to claim 1, wherein the initiator is one or two selected from ammonium persulfate, sodium persulfate and potassium persulfate.
3. The process for preparing an acrylic polymer emulsion with flash rust resistance according to claim 1, wherein the emulsifier is one or two selected from sodium dodecylbenzene sulfonate and sodium dodecylsulfate.
4. The process for preparing an acrylic polymer emulsion with flash rust resistance according to claim 1, wherein the defoaming agent is NXZ defoaming agent.
5. The process for preparing acrylic polymer emulsion with flash rust resisting function according to claim 1, wherein the bactericide is bactericide BIT 20.
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Denomination of invention: Preparation of acrylic polymer lotion with flash rust resistance Effective date of registration: 20230713 Granted publication date: 20200428 Pledgee: Renmin sub branch of Hengshui Bank Co.,Ltd. Pledgor: HENGSHUI XINGUANG NEW MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2023980048488 |