CN111138598A - Small-particle-size acrylic acid aqueous dispersion and preparation method thereof - Google Patents

Small-particle-size acrylic acid aqueous dispersion and preparation method thereof Download PDF

Info

Publication number
CN111138598A
CN111138598A CN201911391581.5A CN201911391581A CN111138598A CN 111138598 A CN111138598 A CN 111138598A CN 201911391581 A CN201911391581 A CN 201911391581A CN 111138598 A CN111138598 A CN 111138598A
Authority
CN
China
Prior art keywords
polymer
monomer
acrylic acid
acrylic
acrylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201911391581.5A
Other languages
Chinese (zh)
Inventor
冯是军
尹浩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Resins Foshan Co Ltd
Original Assignee
DSM Syntech Synthetic Resin Foshan Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DSM Syntech Synthetic Resin Foshan Co Ltd filed Critical DSM Syntech Synthetic Resin Foshan Co Ltd
Priority to CN201911391581.5A priority Critical patent/CN111138598A/en
Publication of CN111138598A publication Critical patent/CN111138598A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Abstract

The invention relates to a small-particle-size high-hardness acrylic acid aqueous dispersion and a preparation method thereof, and is characterized in that a shell polymer contained in the acrylic acid aqueous dispersion has the following characteristics: a glass transition temperature (Tg) of 50 to 150 ℃, an acid value of 30 to 70mgKOH/g, an acrylate monomer as a polymerization unit in an amount of 60 to 100% by weight based on the weight of the shell polymer, and a self-crosslinking monomer in an amount of 0 to 40%; the core polymer comprises a polymer having a glass transition temperature (Tg) of-20 to 80 ℃, an acid value of 0 to 20mgKOH/g, 30 to 80% of a styrenic monomer, and has a hydrophobicity characterized by a Hansch parameter of at least 3.0. The preparation method is obtained by the free radical initiated aqueous emulsion polymerization, the particle size of the emulsion can be controlled according to the required size, the particle size can reach less than 50nm, the light transmittance of the finished product reaches more than 15, and the emulsion can be used for coating wood, concrete, terraces, paper and the like.

Description

Small-particle-size acrylic acid aqueous dispersion and preparation method thereof
Technical Field
The invention relates to a method for producing an aqueous acrylate dispersion with a very small particle size and high hardness, and to the use of the dispersion for coating wood, concrete, terraces and paper. The aqueous acrylate dispersion is obtained by free-radical-initiated aqueous emulsion polymerization.
Background
Environmental regulations have prompted the transformation of current solvent-based coatings to water-based coatings, which is particularly evident in wood coating. However, the prior water-based coating resin has obvious differences from solvent-based coating resin in the aspects of in-can transparency, wet film transparency and dry film transparency. This is because most aqueous coating resins exist in the aqueous phase as a "dispersion" rather than as a solution, and light is scattered at the interface of the aqueous phase and the dispersion particles, resulting in an opaque appearance of the resin. The transparency of the in-tank and wet film is greatly related to the particle size of the resin, and the finer the particle size, the smaller the light scattering ratio, and the more excellent the transparency of the in-tank and wet film of the resin. The color mixing and the aesthetic feeling of the paint are improved for the paint user.
On the other hand, the wood grain wettability of resin is also an important index for aqueous wood coating. Resin dispersions with large particle sizes are difficult to penetrate into wood grain resulting in poor wood grain wetting and a paint film with poor aesthetic appeal. The dispersion particles of small particle size can penetrate relatively easily into the wood grain, giving the paint film a penetrating, moist appearance.
For cost reasons, acrylic dispersions are the most used waterborne resins in wood coatings. In the prior art, the interfacial tension between dispersion particles and water is reduced and the particle size is reduced mainly by increasing the dosage of an emulsifier, introducing sulfonate into a monomer, increasing the acid value of resin and the like. EP2697267 discloses a technique for preparing aqueous dispersions of multiphase vinyl polymer particles by phase inversion using a water-plasticizable high acid number first stage polymer of low molecular weight as a second stage polymeric emulsifier to achieve low particle size and good film formation of acrylic emulsions. However, high acid number first stage oligomers inevitably lead to water sensitivity problems, which are undesirable in wood finishing. And the transparency in the dispersion tank prepared by the technology does not achieve the optimal effect, and further room for improvement is provided.
Patent EP 24576797 discloses another process for preparing an aqueous acrylic dispersion of fine particle size by core-shell emulsion polymerization with the introduction of the sulfonic acid monomer 2-acrylamido-2-methylpropanesulfonic acid at the stage of seed polymerization for the purpose of providing the latex particles with a stronger hydrophilicity, to prepare a colorant having a particle size of < 60nm which is transparent in the wet state. However, the introduction of sulfonic acid groups also causes the problem of reduced water resistance of paint films, so that the prepared dispersion is difficult to be used for solid-color finishing paints for woodware coating.
Disclosure of Invention
The object of the present invention is to provide an aqueous acrylic dispersion, more specifically an adhesive and a coating composition for one-component woodware coating, which exhibits a fine particle size (achievable < 50nm), excellent in-can and wet film transparency, excellent water resistance and high hardness.
An acrylic acid aqueous dispersion with small particle size and high hardness is characterized in that the components comprise a shell polymer and a core-shell structure of a core polymer,
wherein the shell polymers as protective colloids have the following characteristics: a glass transition temperature (Tg) of 50 to 150 ℃, an acid value of 30 to 70mgKOH/g, an acrylate monomer as a polymerization unit in an amount of 60 to 100% by weight based on the weight of the shell polymer, and a self-crosslinking monomer in an amount of 0 to 40%;
wherein the core polymer has a glass transition temperature (Tg) of-20 to 80 ℃, an acid value of 0 to 20mgKOH/g, 30 to 80% of styrene monomers, and has a hydrophobicity characterized by a Hansch parameter of at least 3.0.
The styrene monomer is selected from styrene, methyl styrene, vinyl toluene, methoxy styrene, butyl styrene or chlorostyrene and a mixture set thereof;
the acrylic monomer is selected from alkyl (methyl) acrylate of C1-C10 alkyl, methyl methacrylate, methyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, tert-butyl methacrylate and isodecyl methacrylate; (meth) acrylic acid; (meth) acrylamide; (meth) acrylonitrile and mixtures thereof.
The mass fraction of the core polymer is 20-80% of the total mass of the shell polymer and the core polymer.
A process for preparing the above-mentioned aqueous acrylic dispersion having a small particle diameter and a high hardness, which is obtained by radical-initiated aqueous emulsion polymerization, comprising the steps of:
s1, under the condition of emulsion polymerization, carrying out contact polymerization on 60-100% of acrylate monomers and 0-40% of self-crosslinking monomers in a reactor;
s2, neutralizing the shell acrylic acid polymer by using an alkali solution;
s3, adding a core polymer monomer containing 30-80% of styrene monomers in the second stage, and carrying out emulsion polymerization by a batch method under the action of a thermal initiation system or an oxidation-reduction initiation system to form high-hardness acrylic acid aqueous dispersion with the particle size of less than 50 nm;
wherein the self-crosslinking monomer is entirely distributed on the shell polymer and the core polymer is substantially free of the crosslinking monomer; the (meth) acrylic monomer is distributed throughout the shell polymer, and the core polymer is substantially free of (meth) acrylic monomer.
In step S1, a chain transfer agent is used to reduce the molecular weight of the polymer.
The use of the small-particle-size high-hardness acrylic acid aqueous dispersion is characterized by being used for coating wood, concrete, terraces and paper.
The invention has the beneficial effects that: the acrylic acid aqueous dispersion can realize excellent in-tank transparency and dry-wet film transparency, and can obtain a completely transparent polymer wet film;
the preparation method of the acrylic acid aqueous dispersion is obtained by aqueous emulsion polymerization initiated by free radicals, the particle size of the finished acrylic acid aqueous dispersion can be controlled according to the required size, the particle size can be less than 50nm, the light transmittance of the finished product is more than 15, and the shell polymer in the acrylic acid aqueous dispersion has the following characteristics: a glass transition temperature (Tg) of 50 to 150 ℃, an acid value of 30 to 70mgKOH/g, an acrylate monomer as a polymerization unit in an amount of 60 to 100% by weight based on the weight of the shell polymer, and a self-crosslinking monomer in an amount of 0 to 40%; wherein the core polymer has a glass transition temperature (Tg) of-20 to 80 ℃, an acid value of 0 to 20mgKOH/g, 30 to 80% of styrene monomers, and has a hydrophobicity characterized by a Hansch parameter of at least 3.0.
The acrylic acid aqueous dispersion has wide application, and can be used for coating wood, concrete, terraces, paper and the like.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The Tg values used herein were calculated using the Fox formula (t.g. Fox, fill.am. physics, vol.1, phase 3, page 123 (1956)), i.e. for calculating the Tg values of copolymers of monomers M1 and M2:
1/Tg (calculated) w (M1)/Tg (M1) + w (M2)/Tg (M2)
Wherein, Tg (calculated): the calculated glass transition temperature of the copolymer; w (M1): the mass fraction of monomer M1 in the copolymer; w (M2): the mass fraction of monomer M2 in the copolymer; tg (M1): the glass transition temperature of homopolymer of monomer M1; tg (M2): the glass transition temperature of homopolymer of monomer M2; all temperatures are in kelvin temperature ° K, and the glass transition temperature of the homopolymer can be found, for example, in the Polymer Handbook (edited by j.
The light transmission coefficient (LT) is generally determined by the following method: the aqueous polymer dispersion was adjusted to a solids content of 40% with deionized water and measured with a DR/2010 spectrometer from Hach, Germany. The measurements were performed relative to water, with the LT of water designated as 100%.
The acid number is defined according to DIN EN ISO 3682(DIN 53402) as the ratio of the mass mKOH of potassium hydroxide required for neutralization of the test sample to the mass of this sample or, in the case of solutions or dispersions, the mass mB of the solids in the sample. The customary units are mgKOH/g or mg/g.
An acrylic acid aqueous dispersion with small particle size and high hardness is characterized in that the components comprise a shell polymer and a core-shell structure of a core polymer,
wherein the shell polymers as protective colloids have the following characteristics: a glass transition temperature (Tg) of 50 to 150 ℃, an acid value of 30 to 70mgKOH/g, an acrylate monomer as a polymerization unit in an amount of 60 to 100% by weight based on the weight of the shell polymer, and a self-crosslinking monomer in an amount of 0 to 40%;
wherein the core is partially polymerized, has a glass transition temperature (Tg) of-20 to 80 ℃, an acid value of 0 to 20mgKOH/g, has 30 to 80 percent of styrene monomers, and has hydrophobicity characterized by a Hansch parameter of at least 3.0.
The styrene monomer is selected from styrene, methyl styrene, vinyl toluene, methoxy styrene, butyl styrene or chlorostyrene and a mixture set thereof;
the acrylic monomer is selected from alkyl (methyl) acrylate of C1-C10 alkyl, methyl methacrylate, methyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, tert-butyl methacrylate and isodecyl methacrylate; (meth) acrylic acid; (meth) acrylamide; (meth) acrylonitrile and mixtures thereof.
The mass fraction of the core polymer is 20-80% of the total mass of the shell polymer and the core polymer.
A process for preparing the above-mentioned aqueous acrylic dispersion having a small particle diameter and a high hardness by radical-initiated aqueous emulsion polymerization, which comprises the following steps:
s1, under the condition of emulsion polymerization, carrying out contact polymerization on 60-100% of acrylate monomers and 0-40% of self-crosslinking monomers in a reactor;
s2, neutralizing the shell acrylic acid polymer by using an alkali solution;
s3, adding a core polymer monomer containing 30-80% of styrene monomers in the second stage, and carrying out emulsion polymerization by a batch method under the action of a thermal initiation system or an oxidation-reduction initiation system to form high-hardness acrylic acid aqueous dispersion with the particle size of less than 50 nm;
wherein the self-crosslinking monomer is entirely distributed on the shell polymer and the core polymer is substantially free of the crosslinking monomer; the (meth) acrylic monomer is distributed throughout the shell polymer, and the core polymer is substantially free of (meth) acrylic monomer.
Examples of suitable acrylate monomers include acrylates and methacrylates such as methyl methacrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, n-butyl methacrylate, t-butyl methacrylate, isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, and the like. More preferred combinations of acrylate monomers include methyl methacrylate and n-butyl acrylate; methyl methacrylate and 2-ethylhexyl acrylate.
Additional acid functional monomers may be included in the shell polymer, suitable acid functional monomers include acrylic acid, methacrylic acid and itaconic acid; sulfur acid-containing functional monomers including sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, styrene sulfonic acid, vinyl sulfonic acid, and 2- (meth) acrylamido-2-methylpropane sulfonic acid and salts thereof.
Suitable self-crosslinking monomers include N-methylol (meth) acrylamide, diacetone acrylamide, acetoacetoxyethyl (meth) acrylate, acetoacetoxymethylethyl acrylate, acetoacetoxypropyl acrylate, allyl acetoacetate, acetoacetamidoethyl (meth) acrylate and acetoacetoxybutyl acrylate, preferably diacetone acrylamide.
Examples of the styrene-based monomer preferred in the core polymerization stage include styrene, vinyltoluene, methylstyrene, methoxystyrene, butylstyrene or chlorostyrene, etc.
Exemplary chain transfer agents include mercaptoethanol, 1-octanethiol, n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptopropionic acid, n-butyl mercaptopropionate, isooctyl mercaptopropionate, allyl thioglycolate, crotyl mercaptopropionate, crotyl thioglycolate, α -methylstyrene dimer, and the like, with preferred chain transfer agents including n-dodecyl mercaptan, 1-octanethiol.
In a preferred embodiment of step S2, the prepared shell emulsion polymer is neutralized with a solution of a basic substance. Exemplary bases include ammonia, dimethylethanolamine, triethylamine, 2-methyl-2-amino-1-propanol, sodium hydroxide, potassium hydroxide, and the like, and neutralization with ammonia or sodium hydroxide is preferred.
The shell polymer in the emulsion polymer particles has a high glass transition temperature (Tg) of 50 to 150 ℃, preferably 60 to 130 ℃, more preferably 70 to 120 ℃.
The core polymer has a glass transition temperature (Tg) of-20 to 80 deg.C, preferably-20 to 50 deg.C, more preferably-10 to 30 deg.C.
In order to obtain the desired excellent properties of fine particle diameter and moldability, the mass percentage of the shell polymer to the total monomer mass is advantageously in the range of more than 20% to 80%, preferably 30% to 80%, more preferably 40% to 70%.
The monomer mixture for the shell polymer preferably has an acid value of 30 to 70mgKOH/g, more preferably 40 to 70mgKOH/g, still more preferably 40 to 60 mgKOH/g; the core polymer preferably has an acid value of 0 to 20mgKOH/g, more preferably 0 to 10mgKOH/g, and still more preferably 0 to 5 mgKOH/g.
In step S3, the monomer preferably has a hydrophobicity as defined by a Hansch parameter of at least 3.0, preferably a Hansch parameter of greater than 3.3, more preferably greater than 3.5. The Hansch parameter of the polymer was calculated using the group contribution method, with the central idea that each polymerized unit was assigned a hydrophobicity contribution value and the hydrophobicity of the whole monomer was quantitatively calculated based on the average mass fraction of the monomer in the polymer (Hansch, Fujita, j.amer.chem.soc, 86, 1616-. Monomers having a Hansch parameter of greater than 3 are generally referred to as "hydrophobic monomers".
For the shell and core stage emulsion polymerization, thermal initiation systems such as sodium persulfate, potassium persulfate, and ammonium persulfate may be employed. Or by a redox initiation system, typical oxidizing agents for redox systems include hydrogen peroxide, dibenzoyl peroxide, lauryl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, benzoyl peroxide and the like.
Suitable reducing agents include sodium bisulfite, sodium dithionite, formaldehyde and sodium sulfoxylate, disodium-2-hydroxy-2-sulfinic acid acetic acid, ascorbic acid, erythorbic acid, and mixtures thereof.
The use of the small-particle-size high-hardness acrylic acid aqueous dispersion is characterized by being used for coating wood, concrete, terraces and paper.
Raw material name abbreviation table:
Figure BDA0002345112990000051
Figure BDA0002345112990000061
example 1
S1:
To a reactor equipped with a stirrer, liquid addition port, reflux condenser and nitrogen purge line was added 550g of deionized water and 1.3g of SLS, and the initial charge was heated to 85 ℃ with stirring to fully dissolve the emulsifier. 22g of feed 1 (mixture as in Table one below) were added for emulsification for 1 minute, and then a solution of 0.3g of SPS in 10g of deionized water was added while maintaining the temperature for seed emulsion polymerization;
after 15min, 85 ℃ was maintained and the remainder of feed 1 was added dropwise simultaneously with a solution of 0.6g SPS in 50g of deionized water. Feeding 1 into the reaction kettle for 90min, and adding the SPS solution into the reaction kettle for 100 min. After the addition, the feed 1 and the SPS solution container and pipeline were rinsed with 8g of deionized water, respectively, and the temperature was maintained at 85 ℃ for 20 min.
S2:
A solution of 11.7g of NaOH in 60g of deionized water was then added dropwise to the reactor over 30min to neutralize the polymer emulsion.
After the dropwise addition, the temperature is kept for 1h.
S3:
The system was cooled to 75 ℃, the solution of feed 2 (mixture in table two below) was added and the vessel was rinsed with 10g of deionized water, mixed and emulsified for 30 min. 0.85g of TBHP (70%) was added in one portion, and a mixture of 0.358g of IAA and 6g of deionized water was added to the reactor, and the mixture was stirred well to polymerize the system for 15 min. And heating to 80 ℃, and dropwise adding a mixed solution of 0.3g of IAA and 6g of deionized water for 30 min. And after the dropwise addition, keeping the temperature at 70 ℃ for 30min, adding 11.2g of ADH, putting the mixture into a reactor, keeping the temperature for 30min, cooling to 40 ℃, and filtering by using 50-micron filter cloth, wherein the final product is a small-particle-size high-hardness acrylic acid aqueous dispersion with the pH of 8.36, the particle size of 36nm, the solid content of 40.50% and the Brookfield viscosity of 327 mPa.s.
Watch 1
Charge 1 (homogeneous mixture of the following)
Figure BDA0002345112990000071
Watch two
Charge 2 (homogeneous solution of the following)
170g St
145g BA
Example 2
An aqueous composition was prepared as described in example 1, except that the monomer mixed solution in feed 2 was replaced with 100g St, 190g BMA, and 25g EHA.
Example 3
An aqueous composition was prepared as described in example 1, except that the monomer mixed solution in feed 2 was replaced with 70g of St, 175g of MMA, and 70g of EHA.
Comparative example 1
An aqueous composition was prepared as described in example 1, except that the monomer mixed solution in feed 2 was replaced with 16g of St, 145g of BA and 154g of MMA.
The dispersion parameters obtained in the above examples are summarized in the following table:
example 1 Example 2 Example 3 Comparative example 1
Solid content (%) 40.50 40.77 40.41 40.32
PH 8.36 8.20 8.44 8.58
Particle size (nm) 36 31 52 61
Viscosity (mPa.s) 327 406 275 203
Hansch value of nuclear monomer 3.78 3.89 3.16 2.61
Light transmittance (%) 22 27 18 11
In summary, the above results show that an aqueous acrylic dispersion having high transparency and excellent in-can clarity can be prepared by finely adjusting the hydrophobicity (Hansch value) of the core monomer, and that the obtained aqueous acrylic dispersion has a wide range of applications, and can be used for coating wood, concrete, flooring, paper, and the like.

Claims (7)

1. An acrylic acid aqueous dispersion with small particle size and high hardness is characterized in that the components comprise a shell polymer and a core-shell structure of a core polymer,
wherein the shell polymers as protective colloids have the following characteristics: a glass transition temperature (Tg) of 50 to 150 ℃, an acid value of 30 to 70mgKOH/g, an acrylate monomer as a polymerization unit in an amount of 60 to 100% by weight based on the weight of the shell polymer, and a self-crosslinking monomer in an amount of 0 to 40%;
wherein the core polymer has a glass transition temperature (Tg) of-20 to 80 ℃, an acid value of 0 to 20mgKOH/g, 30 to 80% of styrene monomers, and a hydrophobicity characterized by a Hansch parameter of at least 3.0.
2. The small particle size, high hardness aqueous acrylic dispersion of claim 1 wherein said styrenic monomer is selected from the group consisting of styrene, methyl styrene, vinyl toluene, methoxy styrene, butyl styrene or chlorostyrene and mixtures thereof;
the acrylic monomer is selected from alkyl (methyl) acrylate of C1-C10 alkyl, methyl methacrylate, methyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, tert-butyl methacrylate and isodecyl methacrylate; (meth) acrylic acid; (meth) acrylamide; (meth) acrylonitrile and mixtures thereof.
3. The small-particle-size high-hardness acrylic aqueous dispersion according to claim 1, wherein the mass fraction of the core polymer is 20 to 80% of the total mass of the shell polymer and the core polymer.
4. A method for preparing the small-particle-size high-hardness acrylic acid aqueous dispersion according to any one of claims 1 to 3, wherein the method is obtained by radical-initiated aqueous emulsion polymerization, and comprises the following steps:
s1, under the condition of emulsion polymerization, carrying out contact polymerization on 60-100% of acrylate monomers and 0-40% of self-crosslinking monomers in a reactor;
s2, neutralizing the shell acrylic acid polymer by using an alkali solution;
s3, adding a core polymer monomer containing 30-80% of styrene monomers in the second stage, and carrying out emulsion polymerization by a batch method under the action of a thermal initiation system or an oxidation-reduction initiation system to form high-hardness acrylic acid aqueous dispersion with the particle size of less than 50 nm;
wherein the self-crosslinking monomer is entirely distributed on the shell polymer and the core polymer is substantially free of the crosslinking monomer; the (meth) acrylic monomer is distributed throughout the shell polymer, and the core polymer is substantially free of (meth) acrylic monomer.
5. The method for preparing a small-particle-size and high-hardness acrylic acid aqueous dispersion according to claim 4, wherein a chain transfer agent is used to reduce the polymer molecular weight in step S1.
6. The process for preparing an aqueous acrylic dispersion having a small particle size and a high hardness as claimed in claim 4, wherein the reactor is a reactor equipped with a stirrer, a liquid feeding port, a reflux condenser and a nitrogen purge line.
7. Use of the small-particle-size high-hardness acrylic aqueous dispersion according to any one of claims 1 to 3 for coating wood, concrete, flooring and paper.
CN201911391581.5A 2019-12-30 2019-12-30 Small-particle-size acrylic acid aqueous dispersion and preparation method thereof Pending CN111138598A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911391581.5A CN111138598A (en) 2019-12-30 2019-12-30 Small-particle-size acrylic acid aqueous dispersion and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911391581.5A CN111138598A (en) 2019-12-30 2019-12-30 Small-particle-size acrylic acid aqueous dispersion and preparation method thereof

Publications (1)

Publication Number Publication Date
CN111138598A true CN111138598A (en) 2020-05-12

Family

ID=70521723

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911391581.5A Pending CN111138598A (en) 2019-12-30 2019-12-30 Small-particle-size acrylic acid aqueous dispersion and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111138598A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023108831A1 (en) * 2021-12-17 2023-06-22 深圳市裕同包装科技股份有限公司 Aqueous base oil and preparation method therefor, and printed product

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102199239A (en) * 2010-03-24 2011-09-28 东莞大宝化工制品有限公司 Preparation method for acrylic acid microemulsion with self-crosslinking core-shell structure
WO2012130712A1 (en) * 2011-03-30 2012-10-04 Basf Se Aqueous multistage polymer dispersion, process for its preparation and use thereof as binder for coating substrates

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102199239A (en) * 2010-03-24 2011-09-28 东莞大宝化工制品有限公司 Preparation method for acrylic acid microemulsion with self-crosslinking core-shell structure
WO2012130712A1 (en) * 2011-03-30 2012-10-04 Basf Se Aqueous multistage polymer dispersion, process for its preparation and use thereof as binder for coating substrates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王沛等: "《高分子材料科学实验》", 31 March 2019, 大连海事大学出版社 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023108831A1 (en) * 2021-12-17 2023-06-22 深圳市裕同包装科技股份有限公司 Aqueous base oil and preparation method therefor, and printed product

Similar Documents

Publication Publication Date Title
EP1710284B1 (en) Aqueous polymer dispersions
TWI401262B (en) Process for preparing emulsion polymers
US8975332B2 (en) Process for preparing aqueous vinyl polymer dispersions
US9499680B2 (en) Hydroxyethyl cellulose grafted acrylic latex
CN109400815B (en) Chlorinated polypropylene modified acrylic resin with excellent interlayer adhesion and preparation method thereof
JPH09328502A (en) Water-base polymer dispersion as binder for nonblocking, scratch-resistant elastic coating material
CN111138598A (en) Small-particle-size acrylic acid aqueous dispersion and preparation method thereof
JPH01306453A (en) Polymer composition for flexible sheet
TWI498390B (en) Process for the synthesis of improved binders and modified tacticity
CN112513113B (en) Graft copolymer, thermoplastic resin composition, and molded article thereof
WO2018015169A1 (en) Process for preparing an aqueous polymer dispersion having high chemical resistance
CN101538347B (en) Maleimide copolymer and synthetic method thereof
CN108779318A (en) The method for preparing aqueous adhesive composition and the protective coating made of the aqueous adhesive composition
JPH044323B2 (en)
JPWO2012036173A1 (en) Processing aid for thermoplastic resin and thermoplastic resin composition containing the same
KR101057532B1 (en) Manufacturing method of water-soluble topcoat for automobile
CN115701438A (en) Water-based acrylic resin and manufacturing method thereof
CN115667395A (en) Thermoplastic resin composition and molded article thereof
US20210179884A1 (en) Redox chased suspension bead additives for paints and stains
EP3898711A1 (en) Water-borne core-shell polymers, a method for making the same and the applications thereof
CA2987223A1 (en) Aqueous dispersion of polymer particles with acorn morphology
MXPA99007403A (en) Water-based emulsion polymers which resist blocking
MXPA98002668A (en) Polymerized latex polymerized seed that has a gradient polymeric morphology and process to prepare my

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB03 Change of inventor or designer information
CB03 Change of inventor or designer information

Inventor after: Feng Shijun

Inventor after: Yin Hao

Inventor before: Feng Shijun

Inventor before: Yin Hao

RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200512