CN115109200B - Inert acrylic ester aqueous emulsion, preparation method thereof and aqueous multicolor paint - Google Patents
Inert acrylic ester aqueous emulsion, preparation method thereof and aqueous multicolor paint Download PDFInfo
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- CN115109200B CN115109200B CN202210759898.5A CN202210759898A CN115109200B CN 115109200 B CN115109200 B CN 115109200B CN 202210759898 A CN202210759898 A CN 202210759898A CN 115109200 B CN115109200 B CN 115109200B
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
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Abstract
The invention belongs to the technical field of aqueous emulsion, and particularly relates to an inert acrylic ester aqueous emulsion, a preparation method thereof and an aqueous multicolor paint, wherein the inert acrylic ester aqueous emulsion is prepared from the following raw materials: acrylate hard monomer, acrylate soft monomer, hydrophilic monomer, functional monomer, initiator, mixed emulsifier, strong ammonia water and water; the functional monomer has double bonds, bisphosphonate groups and polyoxyethylene ether chain segments. The aqueous multicolor paint prepared from the inert acrylic ester aqueous emulsion provided by the invention has small viscosity change in one month of storage process and excellent water resistance and water-white resistance.
Description
Technical Field
The invention belongs to the technical field of aqueous emulsion, and particularly relates to an inert acrylic ester aqueous emulsion, a preparation method thereof and an aqueous multicolor paint.
Background
With advances in technology and improvements in aesthetic levels, people are no longer satisfied with white or monochrome residential facades. Therefore, various color wall surfaces are developed in a dispute. In recent years, the water-based multicolor paint is widely favored in the market due to the advantages of various colors, similar lines with natural stone blocks, easy construction and the like. The aqueous colorful paint is formed by suspending two or more aqueous colorful particles in an aqueous medium, wherein the aqueous colorful particles are dispersed phase, and the aqueous medium is composed of continuous phase, protective gum solution and other auxiliary agents. The disperse phase is usually formed by mixing pigment, filler, emulsion, gel system and the like, and has certain strength, flexibility, contrast and color impermeability; the continuous phase is a mixture of emulsion and auxiliary agent, and the protective colloid solution is generally prepared by dispersing protective colloid with magnesium lithium silicate as a main component in water at high speed.
As a main component of the protective paste, lithium magnesium silicate plays an extremely important role in multicolor paints. The magnesium lithium silicate is a sheet-shaped nano-structure inorganic substance, the layers of the sheet layer are negatively charged, and the edges of the sheet layer are positively charged, so that in the magnesium lithium silicate aqueous solution, the magnesium lithium silicate sheet layer is separated due to hydration, and the edges of the sheet layer are in a stacked state due to mutual attraction of positive and negative charges, namely, a card house structure is formed, so that the magnesium lithium silicate aqueous solution becomes jelly-shaped transparent solution, and the viscosity is extremely high. Therefore, those skilled in the art generally need to add a viscosity reducer into the lithium magnesium silicate and prepare a protective adhesive to reduce the viscosity of the aqueous solution of the lithium magnesium silicate, so that the aqueous multicolor paint has good fluidity after being prepared, is convenient for operators to construct, and does not lose the functionality and ornamental value of the aqueous multicolor paint.
The viscosity of the aqueous multicolor paint is mainly determined by the aqueous medium. In aqueous media, the compatibility of the emulsion in the continuous phase with the protective gum is often the main factor determining the viscosity change of the multicolor paint. If the emulsion of the continuous phase is incompatible with the protective adhesive, after part of the continuous phase is mixed with the protective adhesive solution, the additional adsorption and isolation effects are generated, the viscosity reducer concentration between the magnesium lithium silicate sheets is reduced, so that the clamping house structure of the magnesium lithium silicate is reestablished, the viscosity of the aqueous medium is rapidly increased in a short time to be in gel form, the production of the aqueous multicolor paint is brought into serious production problems, the construction is more difficult, the efficiency is reduced, the wall protection capability is reduced, even serious quality problems are possibly generated, and the aesthetic property is greatly reduced. To this end, many efforts have been made by those skilled in the art:
CN109988275a discloses a colorful carrying phase emulsion, a preparation method thereof and a colorful paint, by introducing acid anhydrides and carboxylic acid monomers, when carboxyl groups on a polymer chain encounter alkaline protective glue, ionization occurs to form carboxylate ions with negative charges, so that electrostatic repulsion of carboxylate anions on the same main chain occurs, directional and cation protective glue quantitatively thicken, and emulsion with good self-thickening effect and excellent water-white resistance is obtained. However, the carboxylic acid is unevenly distributed in the emulsion and greatly influenced by the pH of the system, and the viscosity of products in different batches is unstable due to the fact that the reaction rate is delayed, the reaction duration is long and the industrial production period is possibly influenced due to the fact that the viscosity is increased after the pH is increased, steric hindrance and other factors.
CN109504207B discloses a water-based multicolor paint and a preparation method thereof. In the invention, different continuous phases A and B are mixed to be used as continuous phases, so that the water-based multicolor paint with small viscosity change (less than or equal to 5 KU) and good water-white resistance can be obtained. However, the invention also has obvious defects: the continuous phase A and the continuous phase B are two completely different emulsions, the process and the technical parameters may be greatly different, the tiny parameter changes can cause great differences in the properties of the mixture, the paint is a metastable product of a multicomponent mixture, more than ten components are contained, the batch change of the emulsion can cause serious influence on the final state of the paint, so that stability tests after the continuous phase A and the continuous phase B of different batches are mixed need to be verified one by one, and the production can be amplified after the continuous phase A and the continuous phase B are stable, thereby greatly increasing the workload of paint engineers.
Meanwhile, CN109504207B discloses the use of emulsion Archsol8087 is used as a continuous matched water-based multicolor paint, the storage can reach one month, the viscosity of the paint changes to 5KU, the spraying effect is good, but the defect is obvious, namely, the water-white resistance is poor, and the use requirement of customers cannot be met.
Disclosure of Invention
In order to overcome the defects in the prior art, the technical problems to be solved by the invention are as follows: provides an inert acrylic ester aqueous emulsion with small viscosity change and excellent water resistance and water whitening resistance, a preparation method thereof and an aqueous multicolor paint comprising the inert acrylic ester aqueous emulsion.
In order to solve the technical problems, the invention provides an inert acrylic ester aqueous emulsion which is prepared from the following raw materials:
acrylate hard monomer, acrylate soft monomer, hydrophilic monomer, functional monomer, initiator, mixed emulsifier, strong ammonia water and water;
the functional monomer has double bonds, bisphosphonate groups and polyoxyethylene ether chain segments.
And a preparation method of the inert acrylic ester aqueous emulsion is provided, which comprises the following steps:
s1, mixing 225-285 parts of the hard acrylate monomer, 92-156 parts of the soft acrylate monomer and 2.3-7.7 parts of the hydrophilic monomer by weight to obtain a monomer composition;
s2, 3.5-3.7 parts of the mixed emulsifier are dissolved in 100 parts of deionized water according to parts by weight, so as to obtain a mixed emulsifier solution;
s3, mixing and dispersing 340-350 parts by weight of the monomer composition, 50 parts by weight of the mixed emulsifier solution and 170-190 parts by weight of deionized water to obtain acrylate monomer pre-emulsion;
s4, mixing and dispersing 38-40 parts by weight of the monomer composition, 12-20 parts by weight of the functional monomer, 0.5-1 part by weight of concentrated ammonia water, 10 parts by weight of the mixed emulsifier solution and 30-40 parts by weight of deionized water to obtain a functional monomer mixed emulsion;
s5, mixing 220-240 parts of deionized water, the rest of mixed emulsifier solution and 0.6 part of initiator, adding 75 parts of acrylate monomer pre-emulsion at one time, stirring and heating to 75-85 ℃, reacting for 0.5-1 h until the system presents blue light, dropwise adding the rest of acrylate monomer pre-emulsion at a set temperature within 2-2.5 hours, and meanwhile dropwise adding the initiator; and then continuously dripping the functional monomer mixed emulsion for 0.5-1 h, simultaneously dripping the initiator, preserving heat for 3-5 h after dripping, cooling to 30-40 ℃, regulating the pH value of the solution to be 6-8 by using concentrated ammonia water, and adding proper amount of water to regulate the solid content to 39-41%, thus obtaining the inert acrylic ester aqueous emulsion.
Further provided is an aqueous multicolor paint comprising the inert acrylic ester aqueous emulsion prepared by the preparation method of the inert acrylic ester aqueous emulsion.
The invention has the beneficial effects that: according to the invention, functional monomers with amino groups, bisphosphonate groups and polyoxyethylene ether chain segments are introduced into the inert acrylic ester aqueous emulsion, and the functional monomers have double bonds, so that the functional monomers can be connected to the main chain of the acrylic ester polymer in a free radical polymerization mode to form a stable structure. The biphosphonate in the functional monomer can be neutralized by ammonia water to form dissociated phosphonate, and the molecular chain of the biphosphonate is negatively charged, so that when the inert acrylic ester aqueous emulsion is mixed with the magnesium lithium silicate, the negative charge on the molecular chain of the biphosphonate can react with the positive charge at the edge of the magnesium lithium silicate sheet layer and prevent the establishment of a clamping structure of the magnesium lithium silicate, and the viscosity of the aqueous multicolor paint is basically unchanged after one month of storage. And because the functional monomer has a polyoxyethylene chain segment with the polymerization degree of about 10, the polyoxyethylene chain segment has better flexibility and hydrophilicity, so that the functional monomer can be stretched in aqueous emulsion, and the terminal biphosphonate group can move in a larger range, thereby allowing the functional monomer to better contact and combine with a sheet layer of lithium magnesium silicate, and further better avoiding the excessive viscosity change of the aqueous multicolor paint. Meanwhile, after the construction of the finished product prepared from the inert acrylic ester aqueous emulsion, the polyoxyethylene chain segment is regular, so that crystallization is easy to occur in the film forming process, a regular and compact structure is formed, and a paint film is not easy to be corroded by water, namely the water resistance and the water whitening resistance are obviously improved.
The functional monomer is mainly distributed outside emulsion latex particles during polymerization, and because phosphonic acid groups have good hydrophilicity, the stability of the inert acrylic ester aqueous emulsion is enhanced, the dosage of the emulsifier can be effectively reduced, and the water resistance and the water whitening resistance of the product are improved. And a more perfect and compact paint film can be formed in the subsequent construction process, so that the protection effect of the paint film can be better exerted.
The latex particle size of the inert acrylic ester aqueous emulsion provided by the invention is fine, the emulsion is transparent, the transparency after film formation is high, the glossiness is good, the inert acrylic ester aqueous emulsion does not contain aromatic raw materials, the weather resistance is good, and the inert acrylic ester aqueous emulsion is suitable for a continuous phase of an aqueous multicolor coating.
Detailed Description
In order to describe the technical contents, the achieved objects and effects of the present invention in detail, the following description will be made with reference to the embodiments.
An inert acrylic ester aqueous emulsion is prepared from the following raw materials: acrylate hard monomer, acrylate soft monomer, hydrophilic monomer, functional monomer, initiator, mixed emulsifier, strong ammonia water and water; the functional monomer has double bonds, bisphosphonate groups and polyoxyethylene ether chain segments.
Wherein the inert property is that the emulsion and the protective colloid solution do not interact.
Specifically, the acrylate hard monomer, the acrylate soft monomer, the hydrophilic monomer, the functional monomer and the like are polymerized by a specific process in the presence of an initiator to form an inert acrylate aqueous emulsion. Since the functional monomer has a double bond, it can be attached to the main chain of the acrylate polymer in a radical polymerization manner, thereby forming a stable structure. The biphosphonate in the functional monomer can be neutralized by ammonia water to form dissociated phosphonate, and the molecular chain of the biphosphonate is negatively charged, so that when the inert acrylic ester aqueous emulsion is mixed with the magnesium lithium silicate, the negative charge on the molecular chain of the biphosphonate can react with the positive charge at the edge of the magnesium lithium silicate sheet layer and prevent the establishment of a clamping structure of the magnesium lithium silicate, and the viscosity of the aqueous multicolor paint is basically unchanged after one month of storage. And the functional monomer has a polyoxyethylene chain segment with the polymerization degree of about 10, and the polyoxyethylene chain segment has better flexibility and hydrophilicity, so that the functional monomer can be stretched in aqueous emulsion, and the biphosphonate group at the tail end can move in a larger range, thereby allowing the functional monomer to better contact and combine with a sheet layer of lithium magnesium silicate, and further better avoiding the overlarge viscosity change of the aqueous multicolor paint. Meanwhile, after the construction of the finished product prepared from the inert acrylic ester aqueous emulsion, the polyoxyethylene chain segment is regular, so that crystallization is easy to occur in the film forming process, a regular and compact structure is formed, and a paint film is not easy to be corroded by water, namely the water resistance and the water whitening resistance are obviously improved.
In one embodiment, the functional monomer is prepared by the following method:
s1, mixing 1.0 part of allyl alcohol polyether, 3.0-5.0 parts of epoxy chloropropane and 0.04-0.06 part of catalyst in mol part, stirring and heating to 50-60 ℃, removing excessive epoxy chloropropane after reacting for 2-4 hours, cooling to 25-35 ℃, adding 1.1-1.3 parts of sodium hydroxide, and reacting for 1-2 hours to obtain an epoxy modified allyl polyether solution;
s2, neutralizing 1-1.25 parts of an amino-containing bisphosphonic acid compound with 4-5 parts of sodium hydroxide, slowly dripping the bisphosphonic acid compound into the epoxy modified allyl polyether solution, heating to 40-50 ℃ after dripping, cooling to 10-20 ℃ after keeping for 3-5 hours, and regulating the pH to 4-6 by using 10% hydrochloric acid; adding sodium chloride into the solution, stirring until the lower layer solution is supersaturated, and extracting to obtain the functional monomer.
Among them, the extraction is preferably performed by shaking. In a more preferred embodiment, ethyl acetate is added to the supersaturated solution in an amount of 2 times the volume, the mixture is extracted by shaking, the upper layer solution is collected after standing, and the ethyl acetate is distilled off under reduced pressure at 50 ℃ to obtain a pale yellow transparent liquid, namely the functional monomer.
In the synthetic route of the functional monomer, hydroxyl at one end of the allyl alcohol polyoxyethylene ether reacts with epoxy chloropropane under the condition of taking NaH as a catalyst to generate an allyl alcohol polyoxyethylene chlorohydrin ether intermediate, then the allyl alcohol polyoxyethylene ether reacts with alkali in a ring closure way to generate glycidyl ether group allyl alcohol polyoxyethylene ether, and finally the functional monomer is obtained by utilizing the reaction of the active epoxy group of the glycidyl ether group and the amino group in the amino bisphosphonic acid.
Further, the allyl alcohol polyether is propanol polyoxyethylene ether, and the hydroxyl value of the allyl alcohol polyether is 101-123 mgKOH/g.
Further, the catalyst is sodium hydride.
Further, the amine group-containing bisphosphonic acid compound is represented by the following general formula (a);
where b=3 or 4. Namely, when b takes a value of 3, the bisphosphonic acid compound containing an amino group is 3-amino-1-hydroxypropionyl group-1, 1-biphosphoric acid (CAS: 40391-99-9); and when b takes a value of 4, the amine group-containing bisphosphonic acid compound is 4-amino-1-hydroxybutanylidene-1, 1-bisphosphoric acid (CAS: 66376-36-1).
Further, the acrylate hard monomer is at least one selected from methyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate.
Further, the acrylic ester soft monomer is at least one selected from ethyl acrylate, butyl acrylate, isobutyl acrylate and (2-ethylhexyl) acrylate.
Further, the hydrophilic monomer is selected from acrylic acid or methacrylic acid.
The hydrophilic monomer may provide physical stability to the emulsion, but may cause insufficient water resistance of the product when it is used in an excessive amount due to its hydrophilicity, so that it is preferably used in an amount of 0.6 to 2.0% by weight based on the total weight of the acrylate hard monomer, the acrylate soft monomer and the hydrophilic monomer.
Further, the mixed emulsifier is a combination of an anionic non-complex emulsifier and an anionic emulsifier. The emulsifier is used in the amount of the active matter contained in the emulsifier. Wherein the negative non-composite emulsifier is selected from one of DisponilFES77 (effective content 32-34%), ABEX8018R (effective content 31-33%) and EmulphorFAS30 (effective content 29-31%). The anionic emulsifier is selected from one of sodium dodecyl benzene sulfonate (effective content 100%), sodium dodecyl sulfate (effective content 100%) and Dowfax2A1 (effective content 44-46%).
Further, the initiator is potassium persulfate or ammonium persulfate.
The preparation method of the inert acrylic ester aqueous emulsion comprises the following steps:
s1, mixing 225-285 parts of the hard acrylate monomer, 92-156 parts of the soft acrylate monomer and 2.3-7.7 parts of the hydrophilic monomer by weight to obtain a monomer composition;
s2, 3.5-3.7 parts of the mixed emulsifier are dissolved in 100 parts of deionized water according to parts by weight, so as to obtain a mixed emulsifier solution;
s3, mixing 340-350 parts by weight of the monomer composition, 50 parts by weight of the mixed emulsifier solution and 170-190 parts by weight of deionized water, and dispersing at 800rpm for 0.5 hour to obtain acrylate monomer pre-emulsion;
s4, mixing 38-40 parts by weight of the monomer composition, 12-20 parts by weight of the functional monomer, 0.5-1 part by weight of concentrated ammonia water, 10 parts by weight of the mixed emulsifier solution and 30-40 parts by weight of deionized water, and dispersing for 0.5 hour at 800rpm to obtain a functional monomer mixed emulsion;
s5, mixing 220-240 parts of deionized water, the rest of mixed emulsifier solution and 0.6 part of initiator, adding 75 parts of acrylate monomer pre-emulsion at one time, stirring and heating to 75-85 ℃ at 200rpm, reacting for 0.5-1 h until the system presents blue light, dropwise adding the rest of acrylate monomer pre-emulsion at 75-85 ℃ within 2-2.5 h, and dropwise adding 0.6g of initiator dissolved in 20g of deionized water; and then continuing to dropwise add the functional monomer mixed emulsion for 0.5-1 h, simultaneously dropwise adding 0.2 part of the initiator dissolved in 10 parts of deionized water, preserving heat for 3-5 h after the completion of dropwise adding, cooling to 30-40 ℃, regulating the pH value of the solution to be between 6 and 8 by using concentrated ammonia water, and adding a proper amount of water to regulate the solid content to be between 39 and 41 percent to obtain the inert acrylic ester aqueous emulsion.
The aqueous multicolor paint comprises the inert acrylic ester aqueous emulsion prepared by the preparation method of the inert acrylic ester aqueous emulsion.
Example 1
A preparation method of an inert acrylic ester aqueous emulsion comprises the following steps:
s1, adding 1mol of allyl alcohol polyoxyethylene ether (hydroxyl value 102 mgKOH/g) and 5.0mol of epichlorohydrin into a reaction kettle, adding 0.06mol of NaH, heating to 60 ℃ under stirring, reacting for 2 hours, and distilling under reduced pressure at 60 ℃ to remove excessive epichlorohydrin; cooling to 25 ℃, adding 130ml of 10mol/LNaOH solution, and reacting for 2 hours to obtain an epoxy modified allyl polyether solution 1A;
s2, dispersing 1mol of 4-amino-1-hydroxybutanylidene-1, 1-diphosphonic acid in water, and neutralizing with 10 mol/400 ml of LNaOH to obtain colorless transparent aqueous solution; slowly dripping the obtained aqueous solution into the epoxy modified allyl alcohol polyether solution 1A, heating to 50 ℃ after the dripping is finished, and keeping for 3 hours; cooling to 10deg.C, and adjusting pH to=4 with 10% hydrochloric acid; adding sodium chloride into the solution in batches, stirring until the lower layer solution is saturated, and leaving a small amount of undissolved sodium chloride, adding ethyl acetate with the volume of 2 times, and shaking for extraction; standing, collecting upper solution, and distilling at 50deg.C under reduced pressure to remove ethyl acetate to obtain yellowish transparent liquid, namely functional monomer allyl polyether bisphosphonic acid 1B;
s3, uniformly stirring and mixing 174.6g of methyl methacrylate, 98.6g of ethyl methacrylate, 46.5g of butyl acrylate, 66g of (2-ethylhexyl) acrylate and 2.3g of acrylic acid to obtain a monomer composition; 6.36g of DisponilFES77 and 1.4g of sodium dodecyl benzene sulfonate are dissolved in 100g of deionized water to obtain a mixed emulsifier solution; 350g of the monomer composition, 50g of the mixed emulsifier solution, 170g of deionized water, and adding the mixture into the aqueous solution of the mixed emulsifier, and dispersing at 800rpm for 0.5 hour to obtain stable acrylate monomer pre-emulsion; 38g of monomer composition, 12g of allyl polyether bisphosphonic acid 1B,0.5g of concentrated ammonia water, 10g of mixed emulsifier solution and 30g of deionized water are mixed, and dispersed at 800rpm for 0.5 hour to obtain functional monomer mixed emulsion; adding 230g of deionized water, the rest of mixed emulsifier solution and 0.6g of initiator potassium persulfate into a reaction bottle, adding 75g of acrylate monomer pre-emulsion at one time, stirring and heating to 85 ℃ at 200rpm, reacting for 0.5 hour, enabling the system to display blue light, dropwise adding the rest of acrylate monomer pre-emulsion at 85 ℃ within 2 hours, and dropwise adding 0.6g of initiator potassium persulfate dissolved in 20g of deionized water; and then continuously dripping the functional monomer mixed emulsion for 0.5 hour, simultaneously dripping 0.2g of initiator potassium persulfate dissolved in 10g of deionized water, preserving heat for 3 hours after dripping, cooling to 40 ℃, regulating pH=6 by using strong ammonia water, and adding a proper amount of water to regulate the solid content to 41%, thus obtaining the inert acrylic ester aqueous emulsion 1C.
Example 2:
a preparation method of an inert acrylic ester aqueous emulsion comprises the following steps:
s1, adding 1mol of allyl alcohol polyoxyethylene ether (hydroxyl value 120 mgKOH/g) and 3.0mol of epichlorohydrin into a reaction kettle, adding 0.04mol of NaH, heating to 50 ℃ under stirring, reacting for 4 hours, and distilling under reduced pressure at 50 ℃ to remove excessive epichlorohydrin; cooling to 35 ℃, adding 110ml of 10mol/LNaOH solution, and reacting for 1 hour to obtain epoxy modified allyl polyether solution 2A;
s2, dispersing 1.1mol of 3-amino-1-hydroxypropyl-1, 1-diphosphonic acid in water, and neutralizing with 10 mol/440 ml of LNaOH to obtain colorless transparent aqueous solution; slowly dripping the obtained aqueous solution into an epoxy modified allyl alcohol polyether solution 2A, heating to 40 ℃ after the dripping is finished, and keeping for 5 hours; cooling to 20 ℃, and adjusting the pH to be=6 with 10% hydrochloric acid; adding sodium chloride into the solution in batches, stirring until the lower layer solution is saturated, and leaving a small amount of undissolved sodium chloride, adding ethyl acetate with the volume of 2 times, and shaking for extraction; standing, collecting the upper solution, and distilling at 50deg.C under reduced pressure to remove ethyl acetate to obtain yellowish transparent liquid, namely functional monomer allyl polyether bisphosphonic acid 2B;
s3, uniformly stirring and mixing 168g of methyl methacrylate, 80.2g of ethyl methacrylate, 34.5g of methyl acrylate, 49.7g of butyl acrylate, 43.5g of (2-ethylhexyl) acrylate and 6.1g of methacrylic acid to obtain a monomer composition; 7.12g ABEX8018R and 1.42g sodium dodecyl sulfate are dissolved in 100g deionized water to obtain a mixed emulsifier solution; 342g of the monomer composition, 50g of the mixed emulsifier solution, 170g of deionized water are added into a reaction kettle, and dispersed for 0.5 hour at 800rpm, so as to obtain stable acrylate monomer pre-emulsion; mixing 40g of monomer composition, 18g of allyl polyether bisphosphonic acid 2B,0.8g of concentrated ammonia water, 10g of mixed emulsifier solution and 40g of deionized water, and dispersing at 800rpm for 0.5 hour to obtain functional monomer mixed emulsion; adding 240g of deionized water, the rest of mixed emulsifier solution and 0.6g of initiator ammonium persulfate into a reaction bottle, adding 75g of acrylate monomer pre-emulsion at one time, stirring and heating to 75 ℃ at 200rpm, reacting for 1 hour until the system presents blue light, dripping the rest of acrylate monomer pre-emulsion at 75 ℃ within 2.5 hours, and dripping 0.6g of initiator potassium persulfate dissolved in 20g of deionized water; and then continuously dripping the functional monomer mixed emulsion for 1 hour, simultaneously dripping 0.2g of initiator ammonium persulfate dissolved in 10g of deionized water, preserving heat for 5 hours after dripping, reducing to 30 ℃, regulating pH=6 by using concentrated ammonia water, and adding a proper amount of water to regulate the solid content to 40%, thereby obtaining the inert acrylic ester aqueous emulsion 2C.
Example 3:
a preparation method of an inert acrylic ester aqueous emulsion comprises the following steps:
s1, adding 1mol of allyl alcohol polyoxyethylene ether (hydroxyl value 106 mgKOH/g) and 4.5mol of epichlorohydrin into a reaction kettle, adding 0.05mol of NaH, heating to 55 ℃ under stirring, reacting for 3 hours, and distilling under reduced pressure at a set temperature to remove excessive epichlorohydrin; cooling to 28 ℃, adding 125ml of 10mol/LNaOH solution, and reacting for 1 hour to obtain an epoxy modified allyl polyether solution 3A;
s2, dispersing 1.25mol of 3-amino-1-hydroxy propylene-1, 1-diphosphonic acid in water, and neutralizing with 10mol/LNaOH (10 mol/LNaOH) 500ml to obtain colorless transparent aqueous solution; slowly dripping the obtained aqueous solution into an epoxy modified allyl alcohol polyether solution 3A, heating to 45 ℃ after the dripping is finished, and keeping for 4.5 hours; cooling to 16 ℃, and adjusting the pH to be=5 with 10% hydrochloric acid; adding sodium chloride into the solution in batches, stirring until the lower layer solution is saturated, and leaving a small amount of undissolved sodium chloride, adding ethyl acetate with the volume of 2 times, and shaking for extraction; standing, collecting the upper solution, and distilling at 50deg.C under reduced pressure to remove ethyl acetate to obtain yellowish transparent liquid, namely functional monomer allyl polyether bisphosphonic acid 3B;
s3, stirring and uniformly mixing 98.8g of methyl methacrylate, 114g of ethyl methacrylate, 34.4g of methyl acrylate, 45.6g of ethyl acrylate, 76g of butyl acrylate and 7.7g of methacrylic acid to obtain a monomer composition; 7.2g Emulphos FAS30 and 3.2g Dow fax2A1 were dissolved in 100g deionized water to give a mixed emulsifier solution; 340g of a monomer composition, 50g of a mixed emulsifier solution, 190g of deionized water are added into a reaction kettle, and dispersed at 800rpm for 0.5 hour, so as to obtain a stable acrylate monomer pre-emulsion; mixing 40g of monomer composition, 20g of allyl polyether bisphosphonic acid 3B,1g of concentrated ammonia water, 10g of mixed emulsifier solution, 40g of deionized water, and dispersing at 800rpm for 0.5 hour to obtain functional monomer mixed emulsion; adding 240g of deionized water, the rest of mixed emulsifier solution and 0.6g of initiator potassium persulfate into a reaction bottle, adding 75g of acrylate monomer pre-emulsion at one time, stirring and heating to 80 ℃ at 200rpm, reacting for 0.5 hour until the system presents blue light, dropwise adding the rest of acrylate monomer pre-emulsion at 80 ℃ within 2 hours, and simultaneously dropwise adding 0.6g of initiator potassium persulfate dissolved in 20g of deionized water; and then continuously dripping the functional monomer mixed emulsion for 0.5 hour, simultaneously dripping 0.2g of initiator potassium persulfate dissolved in 10g of deionized water, preserving heat for 4 hours after dripping, reducing the temperature to 35 ℃, regulating the pH to be 7 by using strong ammonia water, and adding a proper amount of water to regulate the solid content to be 39%, thus obtaining the inert acrylic ester aqueous emulsion 3C.
Example 4:
a preparation method of an inert acrylic ester aqueous emulsion comprises the following steps:
s1, adding 1mol of allyl alcohol polyoxyethylene ether (hydroxyl value 117 mgKOH/g) and 3.5mol of epoxy chloropropane into a reaction kettle, adding 0.04mol of NaH, heating to 52 ℃ under stirring, reacting for 3.5 hours, and then distilling under reduced pressure at a set temperature to remove excessive epoxy chloropropane; cooling to 30 ℃, adding 120ml of 10mol/LNaOH solution, and reacting for 1.5 hours to obtain an epoxy modified allyl polyether solution 4A;
s2, dispersing 1.15mol of 3-amino-1-hydroxy propylene-1, 1-diphosphonic acid in water, and neutralizing with 10mol/LNaOH460ml to obtain a colorless transparent aqueous solution; slowly dripping the obtained aqueous solution into an epoxy modified allyl alcohol polyether solution 4A, heating to 48 ℃ after the dripping is finished, and keeping for 3.5 hours; cooling to 20 ℃, and adjusting the pH to be 4 by 10% hydrochloric acid; adding sodium chloride into the solution in batches, stirring until the lower layer solution is saturated, and leaving a small amount of undissolved sodium chloride, adding ethyl acetate with the volume of 2 times, and shaking for extraction; standing, collecting upper solution, and distilling at 50deg.C under reduced pressure to remove ethyl acetate to obtain yellowish transparent liquid, namely functional monomer allyl polyether bisphosphonic acid 4B;
s3, stirring and uniformly mixing 180g of methyl methacrylate, 46g of butyl methacrylate, 69g of ethyl acrylate, 84.3g of butyl acrylate and 3.8g of methacrylic acid to obtain a monomer composition; 7.37gDisponil FES77 and 2.7g of Dowfax2A1 were dissolved in 100g of deionized water to obtain a mixed emulsifier solution; 344g of the monomer composition, 50g of the mixed emulsifier solution, 180g of deionized water are added into a reaction kettle, and dispersed for 0.5 hour at 800rpm, so as to obtain stable acrylate monomer pre-emulsion; 39g of the monomer composition, 17g of allyl polyether bisphosphonic acid 4B,0.9g of concentrated ammonia water, 10g of mixed emulsifier solution and 30g of deionized water are mixed, and dispersed at 800rpm for 0.5 hour to obtain a functional monomer mixed emulsion; adding 230g of deionized water, the rest of mixed emulsifier solution and 0.6g of initiator ammonium persulfate into a reaction bottle, adding 75g of acrylate monomer pre-emulsion at one time, stirring and heating to 82 ℃ at 200rpm, reacting for 1 hour until the system presents blue light, dripping the rest of acrylate monomer pre-emulsion at 82 ℃ within 2.5 hours, and dripping 0.6g of initiator potassium persulfate dissolved in 20g of deionized water; and then continuously dripping the functional monomer mixed emulsion for 1 hour, simultaneously dripping 0.2g of initiator ammonium persulfate dissolved in 10g of deionized water, preserving heat for 4.5 hours after dripping, reducing the temperature to 34 ℃, regulating the pH value to be 7 by using strong ammonia water, and adding a proper amount of water to regulate the solid content to be 40%, thereby obtaining the inert acrylic ester aqueous emulsion 4C.
Example 5:
a preparation method of an inert acrylic ester aqueous emulsion comprises the following steps:
s1, adding 1mol of allyl alcohol polyoxyethylene ether (hydroxyl value 113 mgKOH/g) and 4.0mol of epichlorohydrin into a reaction kettle, adding 0.06mol of NaH, heating to 57 ℃ under stirring, reacting for 3 hours, and distilling under reduced pressure at a set temperature to remove excessive epichlorohydrin; cooling to 25 ℃, adding 115ml of 10mol/LNaOH solution, and reacting for 2 hours to obtain epoxy modified allyl polyether solution 5A;
s2, dispersing 1.2mol of 4-amino-1-hydroxybutyryl-1, 1-diphosphonic acid in water, and neutralizing with 10mol/LNaOH480ml to obtain a colorless transparent aqueous solution; slowly dripping the obtained aqueous solution into an epoxy modified allyl alcohol polyether solution 5A, heating to 44 ℃ after the dripping is finished, and keeping for 4 hours; cooling to 20 ℃, and adjusting the pH to be=5 with 10% hydrochloric acid; adding sodium chloride into the solution in batches, stirring until the lower layer solution is saturated, and leaving a small amount of undissolved sodium chloride, adding ethyl acetate with the volume of 2 times, and shaking for extraction; standing, collecting upper solution, and distilling at 50deg.C under reduced pressure to remove ethyl acetate to obtain yellowish transparent liquid, namely functional monomer allyl polyether bisphosphonic acid 5B;
s3, uniformly stirring and mixing 184.8g of methyl methacrylate, 81.6g of butyl methacrylate, 48.1g of isobutyl acrylate, 67.4g of (2-ethylhexyl) acrylate and 3.1g of methacrylic acid to obtain a monomer composition; 6.87g of ABEX8018R and 1.37g of sodium dodecyl sulfate are dissolved in 100g of deionized water to obtain a mixed emulsifier solution; 345g of the monomer composition, 50g of the mixed emulsifier solution, 170g of deionized water are added into a reaction kettle, and dispersed for 0.5 hour at 800rpm, so as to obtain stable acrylate monomer pre-emulsion; mixing 40g of monomer composition, 15g of allyl polyether bisphosphonic acid 5B,0.7g of concentrated ammonia water, 10g of mixed emulsifier solution and 40g of deionized water, and dispersing at 800rpm for 0.5 hour to obtain functional monomer mixed emulsion; adding 240g of deionized water, the rest of mixed emulsifier solution and 0.6g of initiator potassium persulfate into a reaction bottle, adding 75g of acrylate monomer pre-emulsion at one time, stirring and heating to 78 ℃ at 200rpm, reacting for 1 hour, enabling the system to display blue light, dropwise adding the rest of acrylate monomer pre-emulsion at 78 ℃ within 2 hours, and dropwise adding 0.6g of initiator potassium persulfate dissolved in 20g of deionized water; and then continuously dripping the functional monomer mixed emulsion for 1 hour, simultaneously dripping 0.2g of initiator potassium persulfate dissolved in 10g of deionized water, preserving heat for 4 hours after dripping, reducing the temperature to 40 ℃, regulating the pH value to be 6 by using strong ammonia water, and adding a proper amount of water to regulate the solid content to be 40 percent to obtain the inert acrylic ester aqueous emulsion 5C.
Comparative example 1:
a process for the preparation of an inert aqueous acrylate emulsion, based on example 1, which keeps the Tg of the polymer substantially unchanged, replaces only 12g of allyl polyether bisphosphonic acid 1B and 0.5g of concentrated aqueous ammonia with 8.6g of methyl methacrylate and 3.4g of (2-ethylhexyl) acrylate. The synthesis process is described as follows:
174.6g of methyl methacrylate, 98.6g of ethyl methacrylate, 46.5g of butyl acrylate, 66g of (2-ethylhexyl) acrylate and 2.3g of acrylic acid are stirred and mixed uniformly to obtain a monomer composition; 6.36g of DisponilFES77 and 1.4g of sodium dodecyl benzene sulfonate are dissolved in 100g of deionized water to obtain a mixed emulsifier solution; 350g of the monomer composition, 50g of the mixed emulsifier solution, 170g of deionized water, and adding the mixture into the aqueous solution of the mixed emulsifier, and dispersing at 800rpm for 0.5 hour to obtain stable acrylate monomer pre-emulsion; 38g of the monomer composition, 8.6g of methyl methacrylate, 3.4g of (2-ethylhexyl) acrylate, 10g of mixed emulsifier solution, 30g of deionized water are mixed, and dispersed at 800rpm for 0.5 hour to obtain a functional monomer mixed emulsion; adding 230g of deionized water, the rest of mixed emulsifier solution and 0.6g of initiator potassium persulfate into a reaction bottle, adding 75g of acrylate monomer pre-emulsion at one time, stirring and heating to 85 ℃ at 200rpm, reacting for 0.5 hour, enabling the system to display blue light, dropwise adding the rest of acrylate monomer pre-emulsion at 85 ℃ within 2 hours, and dropwise adding 0.6g of initiator potassium persulfate dissolved in 20g of deionized water; and then continuously dripping the functional monomer mixed emulsion for 0.5 hour, simultaneously dripping 0.2g of initiator potassium persulfate dissolved in 10g of deionized water, preserving heat for 3 hours after dripping, cooling to 40 ℃, regulating pH=6 by using strong ammonia water, and adding a proper amount of water to regulate the solid content to 41%, thus obtaining the acrylic ester aqueous emulsion 6C.
Comparative example 2:
the preparation process of the inert acrylic ester water emulsion is based on the embodiment 1, and the amount of the mixed emulsifier is increased by 0.5 times. The synthesis process is described as follows:
174.6g of methyl methacrylate, 98.6g of ethyl methacrylate, 46.5g of butyl acrylate, 66g of (2-ethylhexyl) acrylate and 2.3g of acrylic acid are stirred and mixed uniformly to obtain a monomer composition; 9.54g of DisponilFES77 and 2.1g of sodium dodecyl benzene sulfonate are dissolved in 100g of deionized water to obtain a mixed emulsifier solution; 350g of the monomer composition, 50g of the mixed emulsifier solution, 170g of deionized water, and adding the mixture into the aqueous solution of the mixed emulsifier, and dispersing at 800rpm for 0.5 hour to obtain stable acrylate monomer pre-emulsion; 38g of the monomer composition, 8.6g of methyl methacrylate, 3.4g of (2-ethylhexyl) acrylate, 10g of mixed emulsifier solution, 30g of deionized water are mixed, and dispersed at 800rpm for 0.5 hour to obtain a functional monomer mixed emulsion; adding 230g of deionized water, the rest of mixed emulsifier solution and 0.6g of initiator potassium persulfate into a reaction bottle, adding 75g of acrylate monomer pre-emulsion at one time, stirring and heating to 85 ℃ at 200rpm, reacting for 0.5 hour, enabling the system to display blue light, dropwise adding the rest of acrylate monomer pre-emulsion at 85 ℃ within 2 hours, and dropwise adding 0.6g of initiator potassium persulfate dissolved in 20g of deionized water; and then continuously dripping the functional monomer mixed emulsion for 0.5 hour, simultaneously dripping 0.2g of initiator potassium persulfate dissolved in 10g of deionized water, preserving heat for 3 hours after dripping, cooling to 40 ℃, regulating pH=6 by using strong ammonia water, and adding a proper amount of water to regulate the solid content to 41%, thus obtaining the acrylic ester aqueous emulsion 7C.
Detection example 1
The appearance, stability at rest for one month, and viscosity of the inert aqueous acrylate emulsions obtained in examples 1 to 5 and the acrylate emulsions 6C and 7C obtained in comparative examples 1 to 2 were measured, and the measurement results are shown in Table 1.
TABLE 1
The normal indication in Table 1 is that the inert acrylate aqueous emulsion has no significant flocculation.
As can be seen from Table 1, the appearance of 1C-5C and 7C are similar, the emulsion stability after standing for one month is good, the bottom is free from sedimentation, flocculation and the like, and the emulsion viscosity is low. The emulsion 6C has obviously different appearance, is milky opaque, has fine particles, has obvious flocculation precipitation after standing for one month, and has lower viscosity than other emulsions. A comparison of the emulsions 6C and 7C shows that the emulsion 6C has insufficient amount of the emulsifier, poor emulsion stability and obviously improved emulsion stability by increasing the amount of the emulsifier. Meanwhile, the function monomer allyl polyether bisphosphonic acid has the function of stabilizing emulsion.
Detection example 2
The aqueous acrylic ester emulsions prepared in examples 1 to 5 and comparative examples 1 to 2 were prepared into aqueous multicolor paints according to the formulation of table 2, and the aqueous multicolor paints were subjected to viscosity detection within 5 minutes, 24 hours, one week and one month, respectively, and the detection results are shown in table 3.
The preparation method of the protective adhesive solution is described as follows: the protective gum powder S482 was added to deionized water and dispersed at 2000rpm for 30 minutes until the protective gum solution was completely transparent.
The preparation method of the color-mixing base paint is described as follows:
1) Sequentially adding the raw materials 1-5 of Table 2 into a clean container, and stirring at 800rpm for 10 minutes;
2) Sequentially adding the raw materials 6-7 and stirring at 1500rpm for 30 minutes;
3) Sequentially adding the raw materials 8-9, stirring at 1500rpm for 30 minutes, and testing the fineness of the mixture with a fineness gauge to be lower than 30 mu m;
4) The rotation speed is regulated to 800rpm, the raw materials are added in sequence for 10-14, and the stirring is carried out for 10 minutes;
5) Adding the raw material 15, stirring for 15 minutes, adding the raw material 16, and continuing stirring for 20 minutes to obtain the base paint.
6) And taking a certain amount of base paint, adding a small amount of pigment (iron oxide red, iron oxide black and medium yellow), and stirring uniformly at 800rpm to obtain the color-mixing base paint.
The continuous phase matching method is described as follows:
1) Sequentially adding the continuous phase raw materials 1-4, and stirring at 800rpm for 15 minutes;
2) Diluting the raw materials 5-6 with 3 times of the raw materials 9, adding, and stirring for 15 minutes;
3) Raw materials 7 to 8 are added in sequence, raw material 9 is added after stirring for 15 minutes, and stirring is continued for 15 minutes, so that a continuous phase is obtained.
The preparation method of the multicolor paint is described as follows:
1) 200g of protective adhesive solution is taken, 150g of red color mixing base paint is poured into the protective adhesive solution, and the mixture is slowly stirred at 50 rpm; 200g of yellow toning base paint is poured into the protective glue solution and stirred slowly at 50 rpm; 250g of black base paint is poured into the protective gum solution and stirred slowly at 50 rpm;
2) The stirring speed is increased to 150rpm, and stirring is carried out for 10 minutes, so that the particle size of the color-mixing base paint in the protective glue is suitable;
3) The continuous phase was added and stirred at 200rpm for 15 minutes to obtain an aqueous multicolor paint.
TABLE 2
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TABLE 3 Table 3
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As can be seen from Table 3, the inert aqueous acrylate emulsion 1C-5C has small viscosity change and good compatibility with the protective gum during storage for up to 1 month; the viscosity of the acrylic ester emulsions 6C and 7C after uniform mixing is slightly higher than that of the inert acrylic ester aqueous emulsion, after 24 hours, the viscosity of the acrylic ester emulsions 6C and 7C is rapidly increased to be more than 130KU, the fluidity is reduced, the fluidity is continuously increased, and after one week, the two aqueous multicolor coatings are both beyond the upper limit of the Stokes viscometer. It is considered that 6C and 7C continuously interact with the protective paste, which causes the viscosity to continuously rise, and finally become gel-like, and thus the paste cannot be used normally.
Detection example 3
The continuous phase of the acrylic aqueous emulsion prepared in examples 1 to 5 and comparative examples 1 to 2 was uniformly blade coated with a coating layer of about 200 μm thickness on a black plate according to the continuous phase prepared in Table 2, and after the coating layer was completely dried, about half the area of the coating layer was immersed in water, and after 24 hours, the water resistance and water whitening resistance of the coating layer were observed and rated. The rating criteria were: the score was 5, the highest score of 5 and the lowest score of 1. A score of 5 indicates that the film was not attacked by water and was substantially indistinguishable from the dried film after removal from water; the 4-point shows that the coating film is less corroded by water, and the coating film is better kept after being taken out of the water and has slight blushing; the 3-degree indicates that the coating film is obviously corroded by water, has obvious blushing phenomenon and has slight strength; the 2-point indicates that the coating film has obvious bubbling phenomenon, the coating film is whitish, the strength of the coating film is obviously reduced, and the coating film is slightly turbid in emulsion; a score 1 indicates that the coating film was peeled off from the substrate, the coating film was whitish, the coating film was not strong, and the coating film was broken upon light touch. The rating results are shown in Table 4.
TABLE 4 Table 4
As can be seen from Table 4, the inert aqueous acrylate emulsions 1C-5C had good water and water whitening resistance, whereas the aqueous acrylate emulsions 6C and 7C had very poor water and water whitening resistance, especially 7C.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent modifications made by the teachings of the present invention, or direct or indirect application in the relevant art, are intended to be included within the scope of the present invention.
Claims (8)
1. The inert acrylic ester aqueous emulsion is characterized by being prepared from the following raw materials:
acrylate hard monomer, acrylate soft monomer, hydrophilic monomer, functional monomer, initiator, mixed emulsifier, strong ammonia water and water;
the functional monomer is provided with a double bond, a bisphosphonate and a polyoxyethylene ether chain segment; the functional monomer is prepared by the following method:
s1, in terms of mole parts, mixing 1.0 part of allyl alcohol polyether, 3.0-5.0 parts of epoxy chloropropane and 0.04-0.06 parts of catalyst, stirring and heating to 50-60 ℃, removing excessive epoxy chloropropane after reacting for 2-4 hours, cooling to 25-35 ℃, adding 1.1-1.3 parts of sodium hydroxide, and reacting for 1-2 hours to obtain epoxy modified allyl polyether solution;
s2, neutralizing 1 to 1.25 parts of biphosphonic acid compound containing amino groups with 4 to 5 parts of sodium hydroxide, slowly dripping the biphosphonic acid compound into the epoxy modified allyl polyether solution, heating to 40 to 50 ℃ after dripping, keeping for 3 to 5 hours, cooling to 10 to 20 ℃, and regulating the pH to 4 to 6 by hydrochloric acid; adding sodium chloride into the solution, stirring until the lower layer solution is supersaturated, and extracting to obtain the functional monomer;
the allyl alcohol polyether is allyl alcohol polyoxyethylene ether, and the hydroxyl value of the allyl alcohol polyether is 101-123 mgKOH/g; the catalyst is sodium hydride; the amine group-containing bisphosphonic acid compound is represented by the following general formula (A);
where b=3 or 4.
2. The inert aqueous acrylate emulsion of claim 1 wherein the hard acrylate monomer is selected from at least one of methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate.
3. The inert aqueous acrylate emulsion of claim 1 wherein said soft acrylate monomer is selected from at least one of ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate.
4. The inert aqueous acrylate emulsion according to claim 1 wherein said hydrophilic monomer is selected from acrylic acid or methacrylic acid; the dosage of the hydrophilic monomer is 0.6-2.0% of the total weight of the acrylate hard monomer, the acrylate soft monomer and the hydrophilic monomer.
5. The inert, acrylate aqueous emulsion of claim 1 wherein said mixed emulsifier is a combination of an anionic non-complex emulsifier and an anionic emulsifier; the negative non-composite emulsifier is selected from one of Disponil FES77, ABEX8018R and Emulphor FAS 30; the anionic emulsifier is selected from one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and Dowfax2A 1.
6. The inert aqueous acrylate emulsion according to claim 1 wherein the initiator is potassium persulfate or ammonium persulfate.
7. A process for the preparation of an inert aqueous acrylate emulsion according to any one of claims 1 to 6 comprising the steps of:
s1, mixing 225-285 parts of the hard acrylate monomer, 92-156 parts of the soft acrylate monomer and 2.3-7.7 parts of the hydrophilic monomer by weight to obtain a monomer composition;
s2, 3.5-3.7 parts of the mixed emulsifier are dissolved in 100 parts of deionized water according to parts by weight, so as to obtain a mixed emulsifier solution;
s3, mixing and dispersing 340-350 parts by weight of the monomer composition, 50 parts by weight of the mixed emulsifier solution and 170-190 parts by weight of deionized water to obtain acrylate monomer pre-emulsion;
s4, mixing and dispersing 38-40 parts by weight of the monomer composition, 12-20 parts by weight of the functional monomer, 0.5-1 part by weight of concentrated ammonia water, 10 parts by weight of the mixed emulsifier solution and 30-40 parts by weight of deionized water to obtain a functional monomer mixed emulsion;
s5, mixing 220-240 parts of deionized water, the rest of mixed emulsifier solution and 0.6 part of initiator, adding 75 parts of acrylate monomer pre-emulsion at one time, stirring and heating to 75-85 ℃, reacting for 0.5-1 h until the system presents blue light, and dripping the rest of acrylate monomer pre-emulsion at a set temperature, and dripping the initiator at the same time; and then continuously dripping the functional monomer mixed emulsion, simultaneously dripping the initiator, preserving heat for 3-5 hours after dripping, cooling to 30-40 ℃, regulating the pH value of the solution to be 6-8 by using concentrated ammonia water, and adding a proper amount of water to regulate the solid content to be 39-41%, thus obtaining the inert acrylic ester aqueous emulsion.
8. An aqueous multicolor paint comprising the inert acrylic ester aqueous emulsion prepared by the method for preparing the inert acrylic ester aqueous emulsion of claim 7.
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