CN109232912B - High-storage-stability water-based acrylic acid secondary dispersion - Google Patents
High-storage-stability water-based acrylic acid secondary dispersion Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
Abstract
The invention discloses a high-storage-stability type water-based acrylic acid secondary dispersion, which comprises low-surface-tension deionized water and at least two polyacrylate polymers containing hydrophilic groups, wherein the two polyacrylate polymers are dispersed in the low-surface-tension deionized water. The preparation method comprises the following steps: preparing at least two polyacrylate polymers containing hydrophilic groups, and dispersing the neutralized mixture of the polymers in deionized water with the surface tension not more than 40dyn/cm to obtain the high-storage-stability type water-based acrylic secondary dispersion. Compared with the conventional dispersion, the secondary dispersion prepared by the invention has a storage stability period of more than one year, maintains the inherent quality of the excellent secondary dispersion, and has wide application value in the field of high-end coating.
Description
Technical Field
The invention relates to the field of organic polymer synthesis, in particular to a high-storage-stability type water-based acrylic acid secondary dispersion.
Background
In recent years, excellent properties exhibited by polyurethanes and amino resins applied to the field of coatings have been recognized in the industry. With the improvement of environmental protection requirements, the development and application of waterborne polyurethane and waterborne amino resin coatings are mature day by day, and the two-component environmental protection coating mainly comprises a resin base material and a waterborne curing agent. The aqueous secondary dispersion as the base material of the two-component aqueous polyurethane and aqueous amino resin paint is a new favorite for replacing the base material of solvent type resin due to the advantages of high gloss, high resistance and the like. However, the aqueous acrylic secondary dispersions as high-end two-component aqueous polyurethanes and amino resin binders currently suffer from a number of defects in stability, most of which are stored for less than half a year or even less than a few months, i.e. gelation, delamination, which severely affects the formulation, storage and final properties of the coating.
The Chinese invention patent is a patent which relates to the improvement of the storage stability of the aqueous acrylic acid secondary dispersion.
U.S. Pat. No. 6,63, 691 discloses that a special hydrophobic polymer is added to the bottom of the kettle, and on this basis, polymerization of vinyl monomers such as hydroxy acrylate, carboxylic acid monomer and methyl hydroxy acrylate is carried out, and finally dispersion is carried out in water to obtain a stable secondary dispersion, wherein the preparation of the special hydrophobic polymer is more complex and the use effect is not obvious;
U.S. patent US2003/0050385 discloses a method for preparing an acrylic secondary dispersion in which a hydrophilic polymer is added to the bottom of the tank to improve the storage stability of the final dispersion, with insignificant effect;
US6586521 discloses a method for preparing an acrylic secondary dispersion in which two hydrophilic polymers are prepared to improve storage stability, the process is cumbersome and it is difficult to achieve 1 year storage stability.
The invention prepares the high-storage-stability type water-based acrylic acid secondary dispersion by combining the characteristic that the primary dispersion (the dispersion prepared by adopting an emulsion polymerization process) has high storage stability, is characterized by having the thermal storage stability of more than one year, is prepared by dispersing an acrylate polymer with a specific structure in deionized water with low surface tension, and is suitable for the high-end coating fields of water-based polyurethane, water-based amino resin and the like.
Disclosure of Invention
The invention aims to provide a high-storage-stability water-based acrylic secondary dispersion and a preparation method thereof, so as to solve the defects in the prior art.
The primary dispersion is prepared by adopting an emulsion polymerization process, and because a large amount of surfactant is contained, the water resistance of a final paint film is poor, and meanwhile, the gloss of the paint film is obviously inferior to that of a paint film taking solvent type resin as a base material; the conventional secondary dispersion adopts bulk or solution polymerization to form resin, and the resin is dispersed in water to form aqueous dispersion, so that the paint film has good water resistance, and the gloss and comprehensive performance of the paint film can be comparable to those of a paint film using solvent-based resin as a base material. It is generally accepted in the industry that secondary dispersions should avoid surfactants to reduce water resistance. However, the invention finds that the high-storage-stability water-based acrylic secondary dispersion can be prepared by scientifically designing the structure and the composition of the polymer and scientifically adding a very small amount of surfactant in the dispersion process, and has no influence on the water resistance and other properties of a paint film.
The invention is realized by the following technical scheme:
a high storage stability aqueous acrylic secondary dispersion comprising a low surface tension deionized water and at least two hydrophilic group-containing polyacrylate polymers dispersed in said low surface tension deionized water.
Preferably, the high storage stability aqueous acrylic secondary dispersion comprises the following components:
a polyacrylate polymer containing not more than 10% by weight of hydrophilic groups, i.e. polymer (I);
one or two polyacrylate polymers containing 5 to 25 wt.% of hydrophilic groups, i.e.polymer (II) or/and polymer (III);
deionized water having a surface tension of not more than 40 dyn/cm.
The polymer (I) is prepared by polymerizing at least two vinyl monomers, wherein the vinyl monomers at least contain one hydrophilic monomer, and the mass content of hydrophilic groups accounts for 0-10 wt% of the mass of the polymer (I).
The polymer (II) or the polymer (III) is prepared by polymerizing at least two vinyl monomers, wherein the vinyl monomers at least contain one carboxylic acid type or sulfonic acid type hydrophilic monomer, and the mass content of hydrophilic groups accounts for 5-25 wt% of the mass of the polymer (II) or the polymer (III).
The vinyl monomer is selected from at least two of acrylic acid and ester monomers thereof, methacrylic acid and ester monomers thereof, acrylic acid hydroxy ester, methacrylic acid hydroxy ester, maleic acid, fumaric acid, itaconic acid, vinyl acetate, styrene, methyl styrene, acrylonitrile and methacrylonitrile; the hydrophilic monomer is at least one selected from acrylic acid, methacrylic acid, acrylic acid hydroxy ester, methacrylic acid hydroxy ester, maleic acid, fumaric acid, itaconic acid, vinyl sulfonic acid and styrene sulfonic acid.
The polymers (I), (II) and (III) can be prepared by radical polymerization or ionic polymerization, which are well known in the art, and the reaction temperature is suitably 80 to 160 ℃ and the reaction time for each polymer is 2 to 5 hours.
The deionized water with the surface tension not more than 40dyn/cm is prepared by adding a trace amount of surfactant into the deionized water. The amount of the surfactant added is generally 0.01 to 0.1 wt% of the amount of the deionized water, and the specific amount is limited to the extent that the surface tension of the deionized water after the addition is not more than 40 dyn/cm. In addition, the conductivity of the deionized water should be no greater than 10 us/cm.
Preferably, the surfactant is a compound containing no alkylphenol ethoxylates.
Further preferably, the surfactant is selected from at least one of fatty alcohol ethoxylate surfactants (e.g., Rhodacure BC610\ L4\ LA9\ L790 from Solvay), sulfonate surfactants (e.g., Rhodacal A256L \ DS4\ DS10\ DSB from Rhodia), sulfate surfactants (e.g., Rhodapon BOS \ L22EP \ UBWX \ TDS from Rhodia), and sulfosuccinate surfactants (e.g., Geropon ACR3\ 4\ ACR9N from Rhodia).
As a preferred technical scheme, the high storage stability type water-based acrylic acid secondary dispersion comprises the following components in parts by weight:
10-55 parts of a polymer (I);
5-50 parts of polymer (II) or/and (III);
40-60 parts of deionized water with the surface tension not more than 40 dyn/cm;
the total amount of the components is 100 parts.
Preferably, the high-storage-stability type water-based acrylic acid secondary dispersion has an acid value of 5-20mgKOH/g, a solid content of 40-60 wt%, no delamination after 12 months of storage at 0-50 ℃ and no more than 30% of viscosity change.
As a further preferred embodiment, the high storage stability aqueous acrylic secondary dispersion of the present invention further comprises a neutralizing agent.
The neutralizer is used for neutralizing carboxylic acid groups or sulfonic acid groups in the polyacrylate polymer, and ammonia water and organic amine compounds can be used, and are specifically but not limited to at least one selected from ammonia water, diethylamine, triethylamine, diethylenetriamine, triethylenediamine, triethanolamine, N-dimethylethanolamine, N-dimethylisopropanolamine, N-diethylethanolamine, N-diethylisopropanolamine, morpholine and N-methylmorpholine.
Preferably, the neutralizing agent is used in an amount of 0.3 to 5 parts by weight.
The invention also discloses a preparation method of the high-storage-stability type water-based acrylic acid secondary dispersion, which comprises the following steps:
step one, preparing a polymer (I);
step two, preparing a polymer (II) or/and a polymer (III);
and step three, dispersing the mixture of the polymers in deionized water with the surface tension not more than 40dyn/cm to prepare the high-storage-stability type water-based acrylic acid secondary dispersion.
Preferably, the mixture of the polymers is neutralized by a neutralizing agent and then redispersed in deionized water with the surface tension of not more than 40dyn/cm to prepare the high-storage-stability type water-based acrylic acid secondary dispersion.
The polymers (I), (II) and (III) can be prepared by radical polymerization or ionic polymerization, which are well known in the art, and the reaction temperature is suitably 80 to 160 ℃ and the reaction time for each polymer is 2 to 5 hours.
The polymer (I), the polymer (II), and the polymer (III) may be prepared separately and then mixed, or may be prepared sequentially in the same reactor, wherein at least one of the polymer (II) and the polymer (III) is present.
Preferably, the polymer (I), the polymer (II) and the polymer (III) are respectively prepared by adding an initiator into the vinyl monomer in the presence of a reactive diluent, a cosolvent and a chain transfer agent to carry out polymerization reaction, wherein at least one of the reactive diluent and the cosolvent is used.
More preferably, the reactive diluent is at least one selected from the group consisting of glycerol acrylate, glycerol methacrylate, isobornyl acrylate, isobornyl methacrylate, glycidyl versatate, epsilon-caprolactone and trimethylolpropane;
the cosolvent is at least one selected from ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, propylene glycol methyl ether acetate and an aromatic solvent solvesso100\150\200, and a dearomatized hydrocarbon solvent Exxsol D30\ D40\ D60\ D80;
the chain transfer agent is selected from at least one of dodecyl mercaptan, dodecyl tertiary mercaptan, carbon tetrachloride, thioglycolic acid, mercaptopropionic acid and ethyl mercaptopropionate;
the initiator is at least one selected from 2, 2-azobisisobutyronitrile, azobisisovaleronitrile, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butyl peroxyvalerate, di-tert-butyl peroxide, di-tert-amyl peroxide, cumyl hydroperoxide, isopropyl hydroperoxide, butyl lithium and allyl sodium.
Preferably, the amount of each additive is specifically as follows based on the total amount of the vinyl monomers: 0-10 wt% of reactive diluent, 1-10 wt% of cosolvent, 0.05-0.5 wt% of chain transfer agent and 0.5-5 wt% of initiator. The amounts of the above-mentioned auxiliaries used in the polymerization can, of course, be adjusted appropriately according to the requirements of the actual reaction, and the selection of these amounts is readily and well known to the person skilled in the art.
Compared with the similar water-based acrylic acid secondary dispersion, the high-storage-stability water-based acrylic acid secondary dispersion has the following advantages:
1. due to the creative use of a very small amount of surfactant and the synergistic effect of the surfactant and the high-molecular hydrophilic group in the dispersion polymer, the acid value can be lower on the premise of ensuring the stability of the dispersion, so that the water resistance of the final paint film is better;
2. the low acid value ensures that the acrylic acid secondary dispersion with low viscosity and high solid content is prepared due to the creative use of a very small amount of surfactant and the synergistic effect of the surfactant and the high molecular hydrophilic group in the dispersion polymer;
3. the extremely small amount of surfactant and the high molecular hydrophilic group in the invention have synergistic effect, so that the storage stability of the dispersion is excellent, the dispersion is stored for more than 12 months at 50 ℃, the viscosity change is slight, and the dispersion state is uniform;
4. the extremely small amount of surfactant and the high molecular hydrophilic group in the invention have synergistic effect, so that the dispersion has more excellent dispersibility and compatibility to isocyanate curing agent or amino resin, and the final paint film has more excellent comprehensive performance;
5. the cosolvent content of the water-based acrylic acid secondary dispersion can be as low as 1 wt%, meets the strict requirements of water-based environment-friendly coatings, and is particularly suitable for the fields of industrial coatings, automobile coatings, transportation tool coatings and wood coatings.
Detailed Description
The invention is illustrated below by means of specific examples, without being restricted thereto.
In the following examples, the high storage stability aqueous acrylic secondary dispersions according to the invention were prepared essentially as follows:
1. performing nitrogen substitution on a pressurized reactor provided with a condenser;
2. adding at least one of a cosolvent and an active diluent into the reaction kettle;
3. heating to a specified temperature, simultaneously dropwise adding an initiator and a mixed monomer (containing a chain transfer agent), wherein the dropwise adding time of the mixed monomer is 2-5 hours, the dropwise adding time of the initiator is 0.5 hour longer than that of the monomer, and keeping the temperature for 2 hours. The polymers (I), (II) and (III) can be prepared separately and then mixed, or can be prepared in sequence;
4. cooling to below 75 deg.C, adding neutralizer, and homogenizing for more than 30 min.
5. And strongly dispersing the neutralized polymer in water with the surface tension not higher than 40dyn/cm for 1-2 hours to obtain the milky white blue-light high-storage-stability type water-based acrylic acid secondary dispersion.
It is to be understood that the method of making the high storage stability aqueous acrylic secondary dispersions and the specific examples below are exemplary of preferred embodiments only and are not intended to limit the invention. Other suitable methods of preparation will be readily apparent to those skilled in the art based on the present disclosure.
In all the following examples and comparative examples, the relevant parameter measuring instruments were as follows:
the surface tension is measured by an ITOH surface tension meter 514B;
the viscosity measurement is carried out by adopting a Brookfield viscometer;
detecting pH value with METTLER TOLEDO FE28 type PH meter;
the particle size of the dispersion is detected by a Zetasizer Nano type laser particle size analyzer manufactured by Malvern company;
the solid content is detected by drying a sample of about 1g at 125 ℃ for 1 hour;
the OH content and acid number are calculated according to methods accepted in the industry.
The reactors used in the examples were each equipped with a condenser, and nitrogen was introduced both at the start of the feed and during the reaction.
Example 1
52g Solvesso 150 and 58g dipropylene glycol methyl ether were added to the reactor, stirred and heated with the condenser on. When the temperature rises to 128 ℃, the mixture I-1(120g of styrene, 80g of methyl methacrylate, 40g of tert-butyl methacrylate, 80g of 2-ethylhexyl acrylate, 124g of hydroxypropyl acrylate and 0.44g of dodecyl mercaptan) and the mixture I-2(17.2g of tert-butyl peroxy-2-ethylhexanoate mixed with 6g of Solvesso 150 and 4g of dipropylene glycol methyl ether) are simultaneously added dropwise over 150 minutes and 160 minutes, respectively, to obtain the polymer (I). Wherein the mass content of hydrophilic groups is 3.5% by weight based on the mass of the polymer (I).
Subsequently, blend II-1(40g of methyl methacrylate, 36.8g of butyl methacrylate, 21g of methacrylic acid, 30g of 2-ethylhexyl acrylate, 50g of hydroxypropyl acrylate, 0.1g of dodecyl mercaptan) and blend II-2 (a mixture of 7.2g of t-butyl peroxy-2-ethylhexanoate with 3g of Solvesso 150 and 2g of dipropylene glycol methyl ether) were simultaneously added dropwise over 70 minutes and 80 minutes, respectively, to complete the addition, thereby obtaining polymer (II). Wherein the mass content of hydrophilic groups was 9.5% by weight based on the mass of the polymer (II).
The temperature is maintained at 128 ℃ and 130 ℃ for 120 minutes. The temperature is reduced to 74 ℃, 34.2g of triethanolamine is added, and the mixture is homogenized for 30 minutes, thus obtaining the mixed polymer. A milky-white, blue-colored aqueous dispersion was prepared by formulating 0.06 wt% Rhodasurf L4 (surface tension 30dyn/cm) with 696g of deionized water having an electric conductivity of 5. mu.S/cm and then dispersing the above mixed polymer therein under vigorous stirring. The physical properties of the dispersion are shown in Table 1:
TABLE 1
Example 2
108g of dipropylene glycol methyl ether were added to the reactor, stirred and heated with the condenser on. When the temperature rises to 129 ℃, the mixture I-1(116g of styrene, 80g of methyl methacrylate, 20g of tert-butyl methacrylate, 70g of 2-ethylhexyl methacrylate, 118g of hydroxypropyl methacrylate, 40g of hydroxypropyl acrylate and 0.40g of ethyl mercaptopropionate) and the mixture I-2 (a mixed solution of 17.5g of tert-butyl peroxy-2-ethylhexanoate and 10g of dipropylene glycol methyl ether) were simultaneously added dropwise over 150 minutes and 160 minutes, respectively, to obtain a polymer (I). Wherein the mass content of hydrophilic groups is 4.1 wt% based on the mass of the polymer (I).
Subsequently, mixture II-1(40g of methyl methacrylate, 36.8g of butyl methacrylate, 16.4g of acrylic acid, 30g of 2-ethylhexyl methacrylate, 50g of hydroxypropyl acrylate, 0.1g of ethyl mercaptopropionate) and mixture II-2 (a mixture of 7.2g of t-butyl peroxy-2-ethylhexanoate and 5g of dipropylene glycol methyl ether) were simultaneously added dropwise over 70 minutes and 80 minutes, respectively, to complete the dropwise addition, thereby obtaining polymer (II). Wherein the mass content of hydrophilic groups was 9.3% by weight based on the mass of the polymer (II).
Then, the mixture III (10g of methyl methacrylate, 10g of butyl methacrylate, 20g of hydroxypropyl acrylate and 3g of tert-butyl peroxy-2-ethylhexanoate) was immediately added dropwise over 30 minutes to obtain the polymer (III). Wherein the mass content of hydrophilic groups is 6.1% by weight based on the mass of the polymer (III).
The temperature is maintained at 128 ℃ and 130 ℃ for 120 minutes. The temperature is reduced to 73 ℃, 21.8g of N, N-dimethylethanolamine is added, and the mixture is homogenized for 30 minutes to obtain a mixed polymer. An aqueous milky-blue dispersion was prepared by formulating 0.06 wt% of Rhodacal A256L (surface tension: 32dyn/cm) with 701g of deionized water having an electric conductivity of 5. mu.S/cm and then dispersing the above mixed polymer therein under vigorous stirring. The physical properties of the dispersion are shown in Table 2:
TABLE 2
Example 3
108g of dipropylene glycol methyl ether were added to the reactor, stirred and heated with the condenser on. When the temperature was raised to 126 ℃, simultaneously dropwise addition of blend I-1(60g of styrene, 67.8g of methyl methacrylate, 40g of isobornyl methacrylate, 80g of 2-ethylhexyl acrylate, 196.2g of hydroxybutyl acrylate, 0.40g of ethyl mercaptopropionate) and blend I-2 (a mixture of 16.8g of tert-butyl peroxydiethylacetate and 10g of dipropylene glycol methyl ether) was started, and the dropwise addition was completed in 150 minutes and 160 minutes, respectively, to obtain polymer (I). Wherein the mass content of the hydrophilic group accounts for 5.0 wt% of the mass of the polymer (I).
Subsequently, mixture II-1(20g of methyl methacrylate, 20.6g of butyl methacrylate, 23.2g of methacrylic acid, 16g of 2-ethylhexyl acrylate, 98.1g of hydroxybutyl acrylate, 0.10g of ethyl mercaptopropionate) and mixture II-2 (a mixture of 6.2g of tert-butyl peroxydiethylacetate and 5g of dipropylene glycol methyl ether) were simultaneously added dropwise over 70 minutes and 80 minutes, respectively, to complete the dropwise addition, thereby obtaining polymer (II). Wherein the mass content of hydrophilic groups was 6.3% by weight based on the mass of the polymer (II).
The temperature is maintained at 126 ℃ and 130 ℃ for 120 minutes. The temperature is reduced to 74 ℃, 36.2g of triethanolamine is added, and the mixture is homogenized for 30 minutes to obtain the mixed polymer. A milky-white, blue-colored aqueous dispersion was prepared by formulating 0.05% by weight of Geropon ACR9N (surface tension 28dyn/cm) with 765g of deionized water having an electric conductivity of 9. mu.S/cm and then dispersing the above mixed polymer therein under vigorous stirring. The physical properties of the dispersion are shown in Table 3:
TABLE 3
Example 4
70g of CARDURA E10P (glycidyl versatate from HEXION) were added to the reactor, stirred and heated with the condenser on. The temperature was raised to 129 ℃ and simultaneously dropwise addition of blend I-1(81g of styrene, 60g of methyl methacrylate, 25g of methacrylic acid, 80g of 2-ethylhexyl methacrylate, 88g of hydroxypropyl methacrylate, 40g of hydroxypropyl acrylate, 0.40g of ethyl mercaptopropionate) and blend I-2 (a mixture of 15.6g of tert-butyl peroxy-2-ethylhexanoate and 10g of dipropylene glycol methyl ether) was started, and the dropwise addition was completed in 150 minutes and 160 minutes, respectively, to obtain polymer (I). Wherein the mass content of hydrophilic groups was 4.7% by weight based on the mass of the polymer (I).
Subsequently, mixture II-1(38g of methyl methacrylate, 36.1g of butyl methacrylate, 19.1g of acrylic acid, 30g of 2-ethylhexyl methacrylate, 50g of hydroxypropyl acrylate, 0.10g of ethyl mercaptopropionate) and mixture II-2 (a mixture of 7.2g of t-butyl peroxy-2-ethylhexanoate and 4.4g of dipropylene glycol methyl ether) were simultaneously added dropwise over 70 minutes and 80 minutes, respectively, to complete the dropwise addition, thereby obtaining polymer (II). Wherein the mass content of hydrophilic groups was 12.3% by weight based on the mass of the polymer (II).
Then, the mixture III (10g of methyl methacrylate, 10g of butyl methacrylate, 20g of hydroxypropyl acrylate and 3g of tert-butyl peroxy-2-ethylhexanoate) was immediately added dropwise over 30 minutes to obtain the polymer (III). Wherein the mass content of hydrophilic groups is 6.1% by weight based on the mass of the polymer (III).
The temperature is maintained at 128 ℃ and 130 ℃ for 120 minutes. The temperature is reduced to 73 ℃, 21.3g of N, N-dimethylethanolamine is added, and the mixture is homogenized for 30 minutes to obtain a mixed polymer. A water dispersion of milky blue was prepared by formulating 0.06% by weight of Rhodapon UBWX (surface tension: 29dyn/cm) with 718g of deionized water having an electric conductivity of 7. mu.S/cm and then dispersing the above mixed polymer therein under vigorous stirring. The physical properties of the dispersion are shown in Table 4:
TABLE 4
Comparative example
Polymer blends were prepared as in example 1, except that 696g of deionized water having a conductivity of 5. mu.S/cm (surface tension 72dyn/cm) were used to disperse the polymer blends with vigorous stirring to give an aqueous milky-white dispersion with blue light. The physical properties of the dispersion are shown in Table 5:
TABLE 5
Application examples
This example is intended to compare the thermal storage stability at 50 ℃ of two-component polyurethane coatings based on aqueous acrylic secondary dispersions of the invention of examples 1 to 4 and comparative example, respectively, and on polyisocyanate curing agents, which were allowed to stand for 160 days.
TABLE 6 thermal storage stability at 50 ℃ of the aqueous secondary dispersions prepared in the examples and comparative examples
Remarking: data of 160 days at 50 ℃ and data of 180 days at 50 ℃
As can be seen from the data in Table 6, the aqueous dispersions prepared in the examples have significantly better storage stability at 50 ℃ than the comparative examples, storage at 50 ℃ for more than 12 months, small viscosity change and uniform dispersion state.
The example and comparative dispersions were used to formulate two-component coatings, the specific formulations are shown in table 7:
TABLE 7
The performance indexes of the water-based two-component coating are shown in Table 8:
TABLE 8
As can be seen from the data in Table 8, the paint films of the coatings formulated in the examples have significantly better properties than the comparative examples.
Claims (5)
1. A high storage stability aqueous acrylic secondary dispersion comprising a low surface tension deionized water and at least two hydrophilic group-containing polyacrylate polymers dispersed in said low surface tension deionized water; the paint specifically comprises the following components:
a polyacrylate polymer containing not more than 10% by weight of hydrophilic groups, i.e. polymer (I);
one or two polyacrylate polymers containing 5 to 25 wt.% of hydrophilic groups, i.e.polymer (II) or/and polymer (III);
deionized water having a surface tension of no more than 40 dyn/cm;
a neutralizing agent;
the dosage of each component is respectively as follows according to the parts by weight:
10-55 parts of a polymer (I);
5-50 parts of polymer (II) or/and (III);
40-60 parts of deionized water with the surface tension not more than 40 dyn/cm;
the total amount of the components is 100 parts;
the polymer (I) is prepared by polymerizing at least two vinyl monomers, wherein the vinyl monomers at least contain one hydrophilic monomer, and the mass content of hydrophilic groups accounts for 0-10 wt% of the mass of the polymer (I); the polymer (II) or the polymer (III) is prepared by polymerizing at least two vinyl monomers, wherein the vinyl monomers at least contain a carboxylic acid type or sulfonic acid type hydrophilic monomer, and the mass content of hydrophilic groups accounts for 5-25 wt% of the mass of the polymer (II) or the polymer (III);
the deionized water with low surface tension is prepared by adding a small amount of surfactant into the deionized water, wherein the surfactant is a compound without alkylphenol ethoxylates.
2. The high storage stability aqueous acrylic secondary dispersion according to claim 1, wherein the vinyl monomer is selected from at least two of acrylic acid and its ester monomers, methacrylic acid and its ester monomers, hydroxy acrylate, hydroxy methacrylate, maleic acid, fumaric acid, itaconic acid, vinyl acetate, styrene, methyl styrene, acrylonitrile, methacrylonitrile; the hydrophilic monomer is at least one selected from acrylic acid, methacrylic acid, acrylic acid hydroxy ester, methacrylic acid hydroxy ester, maleic acid, fumaric acid, itaconic acid, vinyl sulfonic acid and styrene sulfonic acid.
3. The high storage stable aqueous acrylic secondary dispersion according to claim 1 or 2, wherein the high storage stable aqueous acrylic secondary dispersion has an acid value of 5 to 20mgKOH/g, a solid content of 40 to 60 wt%, no delamination and no more than 30% viscosity change upon storage at 0 to 50 ℃ for 12 months.
4. A process for preparing the high storage stability aqueous acrylic secondary dispersion according to any of claims 1 to 3, comprising the steps of:
step one, preparing a polymer (I);
step two, preparing a polymer (II) or/and a polymer (III);
and step three, neutralizing the mixture of the polymers by using a neutralizing agent, and dispersing the neutralized mixture into deionized water with the surface tension not more than 40dyn/cm to prepare the high-storage-stability type water-based acrylic acid secondary dispersion.
5. The method of claim 4, wherein each of the polymer (I), the polymer (II) and the polymer (III) is prepared by polymerizing at least two vinyl monomers in the presence of a reactive diluent, a cosolvent and a chain transfer agent by adding an initiator, wherein at least one of the reactive diluent and the cosolvent is used.
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