CN114316160A - Acrylic emulsion polymer and preparation method of water-based paint based on polymer - Google Patents
Acrylic emulsion polymer and preparation method of water-based paint based on polymer Download PDFInfo
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- CN114316160A CN114316160A CN202111364727.4A CN202111364727A CN114316160A CN 114316160 A CN114316160 A CN 114316160A CN 202111364727 A CN202111364727 A CN 202111364727A CN 114316160 A CN114316160 A CN 114316160A
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Abstract
The invention relates to an acrylic emulsion polymer and a preparation method of a water-based paint based on the acrylic emulsion polymer, wherein the acrylic emulsion polymer comprises an acrylic emulsion synthesized by a polymerizable emulsifier with a certain structure and hydroxyl-terminated polydimethylsiloxane, and is matched with an aziridine crosslinking agent to form a water-based paint composition when the water-based paint is used. The water-based paint composition has the advantages of simple preparation method, convenient operation, simple and environment-friendly process, suitability for industrial production, and capability of producing a paint with good water-soaking resistance and high hardness.
Description
The technical field is as follows:
the invention relates to an acrylic emulsion polymer and a preparation method of a water-based paint based on the acrylic emulsion polymer, which have good hardness and water resistance and can keep better weather resistance.
Technical background:
in recent years, with the continuous and rapid development of Chinese economy, the urban process and the industrialization process are continuously increased, the environmental pollution is increasingly serious, and the national attention on environmental protection is higher and higher.
Most of the wood paints in the current market are still oily paints, and the oily paints contain a large amount of organic solvents and have large pollution to the environment. Compared with oil paint, the water-based wood paint takes water as a solvent, is nontoxic and tasteless, and greatly reduces the use of organic solvents. The development of aqueous wood lacquer is a necessary trend when environmental protection is concerned.
The conventional water-based wood lacquer is prepared by adding an auxiliary agent, a pigment filler, water and the like into an emulsion, uniformly stirring the mixture, and then adjusting the mixture to a proper viscosity by using a thickening agent. The emulsion is the main determining factor of the performance of the waterborne wood lacquer after film forming, the film forming mechanism of the waterborne emulsion is different from solvent-based resin, the waterborne wood lacquer is finally formed by fusing and extruding emulsion particles, and the loss of the performance of the waterborne wood lacquer after film forming is bound to be brought by the emulsifier and the inorganic salt in the emulsion. Therefore, the performance of the water-based paint after film formation is often not equal to that of oil-based paint, and the problems of low paint film hardness, poor water resistance and the like exist.
To increase the hardness of aqueous paint films, it is common practice in the market to use two-component emulsions, emulsions with hydroxyl groups, which generally achieve higher hardness by reaction with polyurethane curing agents. However, the two-component resin needs to be added with a curing agent during use, so that the use is inconvenient, the pot life is short, the ageing resistance is generally poor, and the yellowing is easy to occur. This also limits the use of two-component emulsions.
For example, the invention patent of patent No. CN 101481581A relates to a nano modified silicone acrylic polyurethane coating and a preparation method thereof, which belongs to the field of fine chemical engineering, in particular to a nano modified silicone acrylic polyurethane coating for automobiles or motorcycles and a preparation method thereof, the nano modified silicone acrylic polyurethane coating is mainly coated on the surface of primer and paint of automobiles or motorcycles, and can improve multiple properties of the coating, such as acid rain resistance, scratch resistance and the like, and the nano modified silicone acrylic polyurethane coating is characterized in that nano particles are fully dispersed, then the nano modified silicone high-solid hydroxyl acrylic resin is prepared by in-situ polymerization and copolymerization of the nano modified silicone high-solid hydroxyl acrylic resin and high-solid hydroxyl acrylic resin, and then a proper amount of diisocyanate is added to obtain the nano modified silicone acrylic polyurethane coating.
For example, patent No. CN 1178997C discloses an abrasion resistant aqueous coating composition and a method for producing an abrasion resistant coating. To aqueous coating compositions comprising a polycarbodiimide, an emulsion polymer having a plurality of functional groups reactive with the carbodiimide moiety, and an alkoxysilane. The emulsion synthesis disclosed in this patent uses, in part, a non-reactive emulsifier and is therefore still deficient in water resistance.
Therefore, there is a need for the development of an acrylic emulsion polymer for use in an aqueous coating composition that has good storage stability, high hardness, good water resistance without sacrificing weatherability.
Disclosure of Invention
The invention provides an acrylic emulsion polymer which is different from the traditional two-component coating and realizes high hardness and high water resistance, and a preparation method of a water-based coating based on the acrylic emulsion polymer.
An acrylic emulsion polymer comprising an acrylic emulsion polymer, wherein said acrylic emulsion polymer comprises as polymerized units a polymerizable emulsifier and a hydroxy terminated polydimethylsiloxane and an aziridine-based crosslinking agent.
The amount of the hydroxyl-terminated polydimethylsiloxane is 0.1 to 10 percent of the dry weight of the emulsion polymer, and the amount of the aziridine-based crosslinking agent is 0.1 to 5 percent based on the total weight of the aqueous coating composition.
The amount of the polymerizable emulsifier is 0.1-3% of the dry weight of the acrylic polymer emulsion.
The surfactant of the polymerizable emulsifier has the structure of formula (I):
wherein R1 is hydrogen or C1-C20 alkyl,
r2 is hydrogen or a methyl group,
r3 is hydrogen or C1-C20 alkyl,
a represents an alkylene group or a substituted alkylene group having 2 to 4 carbon atoms;
n is an integer ranging from 0 to 1, 00; and is
X represents hydrogen or an anionic hydrophilic group selected from: - (CH2) a-SO3M, - (CH2) b-COOM, -PO3M2, -P (Z) O2M or-CO-CH 2-CH (SO3M) -COOM, wherein a and b are each independently an integer of 0 to 4, Z represents a residue obtained by removing X from the general formula (I), and M each represents hydrogen, an alkali metal atom, an alkaline earth metal atom, an ammonium residue or an alkanolamine residue.
The molecular weight of the hydroxyl-terminated polydimethylsilane is 200-100,000 g/mol.
The particle size of the acrylic emulsion polymer is 40nm-300 nm.
The acrylic emulsion polymer may comprise, as polymerized units, one or more ethylenically unsaturated nonionic monomers.
The acrylic emulsion polymer comprises, as polymerized units, one or more ethylenically unsaturated monomers having one or more functional groups.
The acrylic emulsion polymer comprises as polymerized units one or more polyethylenically unsaturated monomers, including di-, tri-, tetra-or higher polyfunctional ethylenically unsaturated monomers.
A preparation method of the acrylic emulsion polymer is characterized in that: the preparation method comprises the following steps:
a) measuring a monomer pre-emulsion raw material containing the components;
b) mixing the measured monomer pre-emulsion raw materials to obtain monomer pre-emulsion,
c) then in a 3 liter four-necked round bottom flask equipped with paddle stirrer bar, thermometer, nitrogen inlet and reflux condenser, deionized water was added and heated to 82 ℃ under nitrogen atmosphere with stirring;
d) then adding an emulsifier and a certain amount of monomer pre-emulsion into a flask, and then adding an initiator at a constant speed within three minutes;
e) keeping the reaction solution for 1 minute under stirring, and then dropwise adding the rest monomer pre-emulsion and the rest initiator into the reactor in two ways for 120 minutes;
f) after the completion of the feed, the reactor was kept at 82 ℃ for 1 hour of reaction, followed by cooling to 70 ℃ to start the work-up reaction to eliminate residual monomers, cooling to neutralize, adjusting the pH to 7.5-8.5, and then dropping the ADH suspension over 20 minutes. A polymer emulsion with a solids content of about 40% was obtained.
The raw materials of the monomer pre-emulsion comprise deionized water, 0.1-3% of polymerizable emulsifier, 0.1-3% of 1, 6-hexanediol diacrylate, 0-30% of butyl acrylate, 0-30% of 2-ethylhexyl acrylate, 0-80% of methyl methacrylate, 0-80% of styrene, 0.1-10% of hydroxyl-terminated polydimethylsiloxane, 0-4% of acrylic acid and 0-4% of methacrylic acid.
The preparation method of the water-based paint composition is characterized by comprising the following steps:
s1, preparing raw materials of 0.1-5% of aziridine cross-linking agent, 2-10% of film-forming additive, 0.1-1% of wetting agent, 0.3-1% of defoaming agent, 0.5-1% of thickening agent, 5-12% of water and 75-85% of emulsion polymer.
S2, adding the emulsion polymer into a 150mL round-bottom flask, and sequentially adding various auxiliary agent components of an aziridine crosslinking agent under the stirring of a low-shear mixer at 500rpm to finally obtain the uniform water-based coating composition.
The invention has the beneficial effects that:
the invention relates to an acrylic emulsion polymer, which comprises an acrylic emulsion synthesized by a polymerizable emulsifier with a certain structure and hydroxyl-terminated polydimethylsiloxane, and is matched with an aziridine crosslinking agent to form a water-based coating composition when a water-based coating is used.
Compared with the traditional emulsifier, the polymerizable emulsifier with a certain structure and active structure is polymerized on the high molecular chain segment in the polymerization reaction process, so that the problem of film forming defects caused by the migration of a free emulsifier in the film forming dehydration process is avoided, meanwhile, the hydroxyl-terminated polydimethylsiloxane forms partial covalent bond combination with the acrylic chain segment in the polymerization process, and due to the hydrophobicity of silicon oxygen bonds, moisture and harmful ions can be prevented from permeating into a paint film, and the purpose of waterproof protection is achieved. In addition, the aziridine crosslinking agent with multiple functionality can react with carboxyl in the acrylic emulsion polymer at room temperature, so that the crosslinking density of the polymer is improved, better water resistance is obtained, and the surface anti-adhesion property, the adhesion on a special substrate and the like can be improved.
2) The preparation method of the acrylic emulsion polymer-based water-based paint composition is simple, convenient to operate, simple in process, environment-friendly, suitable for industrial production, and capable of preparing a paint with good water-soaking resistance and high hardness.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Each feature disclosed in this specification may be replaced by an alternative feature serving the same, equivalent, or similar purpose. Not to be reiterated herein, but to the extent of space.
Detailed Description
"acrylic acid" in the present invention includes (meth) acrylic acid, alkyl (meth) acrylates, (meth) acrylamides, (meth) acrylonitrile and modified forms thereof, such as (meth) hydroxyalkyl acrylates. Throughout this document, the word fragment "(meth) acryl" refers to both "methacryl" and "acryl". For example, (meth) acrylic acid refers to methacrylic acid and acrylic acid, and methyl (meth) acrylate refers to methyl methacrylate and methyl acrylate.
The "glass transition temperature" or "Tg" in the present invention can be measured by various techniques including, for example, differential scanning calorimetry ("DSC") or calculated by using the fox equation. Specific values of Tg reported herein are those calculated using the fox equation (t.g.fox, american society of physics, inc., vol., No. 1, No. 3, page 123 (1956)).
The aqueous coating composition of the present invention may comprise one or more acrylic emulsion polymers. By "acrylic emulsion polymer" herein is meant an emulsion polymer comprising as polymerized units one or more acrylic monomers or mixtures thereof with other monomers including, for example, styrene or substituted styrenes.
Acrylic emulsion polymers suitable for use in the present invention may comprise as polymerized units one or more ethylenically unsaturated nonionic monomers. By "nonionic monomer" herein is meant a monomer that does not have an ionic charge between pH l-14. Examples of suitable ethylenically unsaturated nonionic monomers include (meth) acrylate monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, nonyl methacrylate, isodecyl methacrylate, dodecyl methacrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; (meth) acrylonitrile; styrene and substituted styrenes such as alpha-methylstyrene, p-methylstyrene, tert-butylstyrene, vinyltoluene; butadiene; ethylene, propylene and 1-decene; vinyl acetate, vinyl butyrate, vinyl versatate and other vinyl esters; vinyl monomers such as vinyl chloride and vinylidene chloride; or mixtures thereof. Preferred ethylenically unsaturated nonionic monomers are selected from styrene, butyl acrylate or mixtures thereof. The acrylic emulsion polymer may comprise, as polymerized units, 60 weight percent or more, 80 weight percent or more, or even 90 weight percent or more, and at the same time 99.9 weight percent or less, 97 weight percent or less, or even 95 weight percent or less of the ethylenically unsaturated nonionic monomer, based on the dry weight of the acrylic emulsion polymer.
The acrylic emulsion polymer suitable for use in the present invention may further comprise, as polymerized units, one or more ethylenically unsaturated monomers having one or more functional groups. The functional group may be selected from carbonyl, acetoacetate, alkoxysilane, ureido, amide, imide, amino, carboxyl, phosphorus groups, or combinations thereof. Examples of such functional group-containing ethylenically unsaturated monomers may include α, β -ethylenically unsaturated carboxylic acids, including acid-bearing monomers such as methacrylic acid, acrylic acid, itaconic acid, maleic acid, or fumaric acid; or monomers bearing acid-forming groups which generate or can subsequently be converted into such acid groups (such as anhydrides, (meth) acrylic anhydrides or maleic anhydride); vinylphosphonic acid, allylphosphonic acid, phosphoalkyl (meth) acrylates, such as phosphoethyl (meth) acrylate, phosphopropyl (meth) acrylate, phosphobutyl (meth) acrylate or salts thereof; 2-acrylamido-2-methyl-1-propanesulfonic acid; sodium salt of 2-acrylamido-2-methyl-1-propanesulfonic acid; ammonium salts of 2-acrylamido-2-methyl-1-propanesulfonic acid; sodium vinyl sulfonate; allyl ether sulfonic acid sodium salt; and the like; diacetone acrylamide (DAAM), acetoacetoxyethyl (meth) acrylate, acetoacetoxypropyl (meth) acrylate, acetoacetoxybutyl (meth) acrylate, propyl 2, 3-di (acetoacetoxy) (meth) acrylate, allyl acetoacetate, or vinyl acetoacetate; monosubstituted (meth) acrylamide, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-butylacrylamide, N-tert-butylacrylamide, N-2-ethylhexylacrylamide, N-dimethylacrylamide, N-diethylacrylamide or a mixture thereof. Preferred functional group-containing ethylenically unsaturated monomers include arylamides, methacrylamides, diacetone acrylamide, methacrylamidoethylene urea, acetoacetoxyethyl methacrylate, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, acrylic acid, methacrylic acid, or mixtures thereof. The acrylic emulsion polymer may comprise, as polymerized units, from 0% to 5%, from 0.1% to 3%, from 0.3% to 2.5%, or from 0.5% to 2.0% of such functional group-containing ethylenically unsaturated monomers, by dry weight of the acrylic emulsion polymer.
The acrylic emulsion polymer suitable for use in the present invention may further comprise as polymerized units one or more polyethylenically unsaturated monomers, including di-, tri-, tetra-or higher polyfunctional ethylenically unsaturated monomers. Examples of suitable multi-ethylenically unsaturated monomers include butadiene, allyl (meth) acrylate, divinyl benzene, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, or mixtures thereof. The acrylic emulsion polymer may comprise, as polymerized units, from 0 wt% to 1 wt%, from 0 wt% to 0.6 wt%, or from 0 wt% to 0.2 wt% of the polyethylenically unsaturated monomer, based on dry weight of the acrylic emulsion polymer. Preferably, the acrylic emulsion polymer is substantially free (e.g., less than 0.1 weight percent) of polymerized units of the polyethylenically unsaturated monomer.
The glass transition temperature of the acrylic emulsion polymer suitable for use in the present invention may be from-20 ℃ to 80 ℃.
Examples of the invention
Some examples of the invention will now be described in the following examples, in which all parts and percentages are by weight unless otherwise indicated. The following materials were used in the examples:
diacetone acrylamide ("DAAM"), a hydroxy terminated polydimethylsiloxane ("PDMS"), is available from Shanghai Rujie chemical Co.
REASOAP SR-1025 anionically polymerizable emulsifier ("SR-1025"), available from Adeca (ADEKA), is poly (oxy-1, 2-ethanediyl), α -sulfo- Ω - [1- (hydroxymethyl) -2- (2-propenoxyethoxy ] -, C11-C10-14-rich branched alkyl ether, ammonium salt.
Butyl acrylate ("BA"), 2-ethylhexyl acrylate ("2-EHA"), methyl methacrylate ("MMA"), styrene ("ST"), butyl methacrylate ("BMA"), acrylic acid ("AA") and methacrylic acid ("MAA") are all available from BASF corporation.
1, 6-hexanediol diacrylate ("HDDA") is available from Michael chemical reagent, Inc.
Tert-butyl hydroperoxide and isoascorbic acid are available from Shanghai Rujie chemical Co.
Adipic acid dihydrazide ("ADH") is available from Shanghai Rujie chemical Co.
The aziridine crosslinking agent CX-100 is available from Corcission polymers, Inc.
Dipropylene glycol monomethyl ether ("DPM") is available from shanghai rude chemicals, inc.
Texanol is available from Islam chemical.
Wetting agent BYK349, defoamer BYK024, thickener BYK-Optiflo L1400 and thickener BYK-Optiflo H3300 are all available from Bick chemical company.
Pencil hardness test
The drawing is carried out according to the regulations of GB/T6739-2006, and the pencil is a drawing pencil for the Chinese card 101.
Water soaking test
The prepared coating composition is scraped on a tin plate by a wire rod to prepare a wet film with the thickness of 100 microns, and the wet film is dried for seven days at the temperature of 25 ℃ and the humidity of 65 ℃ to obtain a dried coating film. The tinplate was dipped in deionized water for 168 hours, and the paint film was observed and scored according to the following criteria.
The present invention is further illustrated in detail by the following examples, which are provided only for illustrating the present invention and are not intended to limit the scope of the present invention.
Synthesis of Polymer emulsion 1:
a monomer pre-emulsion was prepared by mixing 270.0g of Deionized (DI) water, 35.28g of SR-1025, 44.12g of DAAM, 97.07g of BA, 97.07g of 2-EHA, 604.46g of MMA, 8.82g of HDDA, 8.82g of PDMS and 22.06g of MAA.
In a 3 liter four-necked round bottom flask equipped with paddle stirrer bar, thermometer, nitrogen inlet and reflux condenser, 875.0g of deionized water were added and heated to 82 ℃ under nitrogen atmosphere with stirring. 35.28g of SR-1025 and 59.39g of the monomer pre-emulsion were then added to the flask, followed by a constant addition of a solution of 0.96g of ammonium persulfate dissolved in 16.0g of deionized water over three minutes. After being held for 1 minute with stirring, the remaining monomer pre-emulsion and a solution of 2.09g of ammonium persulfate dissolved in 58.0g of deionized water were initially added dropwise in two passes to the reactor over a period of 120 minutes. After the completion of the feeding, the reactor was kept at 82 ℃ for 1 hour of reaction, followed by cooling to 70 ℃ to start dropping a solution of 1.71g of t-butyl hydroperoxide dissolved in 6.4g of deionized water and a solution of 0.78g of erythorbic acid dissolved in 16.8g of deionized water over 60 minutes, after cooling to 50 ℃ to drop 24.86g of 25% aqueous ammonia solution over 20 minutes to adjust the pH to 7.5-8.5, and then dropping 18.76g of ADH suspension dispersed in 24.93g of deionized water over 20 minutes. Finally, a polymer emulsion with a solids content of about 40% was obtained.
Synthesis of Polymer emulsion 2:
a monomer pre-emulsion was prepared by mixing 270.0g of Deionized (DI) water, 35.28g of SR-1025, 44.12g of DAAM, 97.07g of BA, 97.07g of 2-EHA, 569.18g of ST, 8.82g of HDDA, 44.1g of PDMS and 22.06g of AA.
In a 3 liter four-necked round bottom flask equipped with paddle stirrer bar, thermometer, nitrogen inlet and reflux condenser, 875.0g of deionized water were added and heated to 82 ℃ under nitrogen atmosphere with stirring. 35.28g of SR-1025 and 59.39g of the monomer pre-emulsion were then added to the flask, followed by a constant addition of a solution of 0.96g of ammonium persulfate dissolved in 16.0g of deionized water over three minutes. After being held for 1 minute with stirring, the remaining monomer pre-emulsion and a solution of 2.09g of ammonium persulfate dissolved in 58.0g of deionized water were initially added dropwise in two passes to the reactor over a period of 120 minutes. After the completion of the feeding, the reactor was kept at 82 ℃ for 1 hour of reaction, followed by cooling to 70 ℃ to start dropping a solution of 1.71g of t-butyl hydroperoxide dissolved in 6.4g of deionized water and a solution of 0.78g of erythorbic acid dissolved in 16.8g of deionized water over 60 minutes, after cooling to 50 ℃ to drop 24.86g of 25% aqueous ammonia solution over 20 minutes to adjust the pH to 7.5-8.5, and then dropping 18.76g of ADH suspension dispersed in 24.93g of deionized water over 20 minutes. Finally, a polymer emulsion with a solids content of about 40% was obtained.
Synthesis of Polymer emulsion 3:
a monomer pre-emulsion was prepared by mixing 270.0g of Deionized (DI) water, 35.28g of SR-1025, 44.12g of DAAM, 97.07g of BMA, 97.07g of 2-EHA, 525.08g of MMA, 8.82g of HDDA, 88.2g of PDMS and 22.06g of MAA.
In a 3 liter four-necked round bottom flask equipped with paddle stirrer bar, thermometer, nitrogen inlet and reflux condenser, 875.0g of deionized water were added and heated to 82 ℃ under nitrogen atmosphere with stirring. 35.28g of SR-1025 and 59.39g of the monomer pre-emulsion were then added to the flask, followed by a constant addition of a solution of 0.96g of ammonium persulfate dissolved in 16.0g of deionized water over three minutes. After being held for 1 minute with stirring, the remaining monomer pre-emulsion and a solution of 2.09g of ammonium persulfate dissolved in 58.0g of deionized water were initially added dropwise in two passes to the reactor over a period of 120 minutes. After the completion of the feeding, the reactor was kept at 82 ℃ for 1 hour of reaction, followed by cooling to 70 ℃ to start dropping a solution of 1.71g of t-butyl hydroperoxide dissolved in 6.4g of deionized water and a solution of 0.78g of erythorbic acid dissolved in 16.8g of deionized water over 60 minutes, after cooling to 50 ℃ to drop 24.86g of 25% aqueous ammonia solution over 20 minutes to adjust the pH to 7.5-8.5, and then dropping 18.76g of ADH suspension dispersed in 24.93g of deionized water over 20 minutes. Finally, a polymer emulsion with a solids content of about 40% was obtained.
Synthesis of Polymer emulsion 4:
a monomer pre-emulsion was prepared by mixing 270.0g of Deionized (DI) water, 35.28g of SR-1025, 44.12g of DAAM, 97.07g of BA, 97.07g of 2-EHA, 613.28g of MMA, 8.82g of HDDA and 22.06g of MAA.
In a 3 liter four-necked round bottom flask equipped with paddle stirrer bar, thermometer, nitrogen inlet and reflux condenser, 875.0g of deionized water were added and heated to 82 ℃ under nitrogen atmosphere with stirring. 35.28g of SR-1025 and 59.39g of the monomer pre-emulsion were then added to the flask, followed by a constant addition of a solution of 0.96g of ammonium persulfate dissolved in 16.0g of deionized water over three minutes. After being held for 1 minute with stirring, the remaining monomer pre-emulsion and a solution of 2.09g of ammonium persulfate dissolved in 58.0g of deionized water were initially added dropwise in two passes to the reactor over a period of 120 minutes. After the completion of the feeding, the reactor was kept at 82 ℃ for 1 hour of reaction, followed by cooling to 70 ℃ to start dropping a solution of 1.71g of t-butyl hydroperoxide dissolved in 6.4g of deionized water and a solution of 0.78g of erythorbic acid dissolved in 16.8g of deionized water over 60 minutes, after cooling to 50 ℃ to drop 24.86g of 25% aqueous ammonia solution over 20 minutes to adjust the pH to 7.5-8.5, and then dropping 18.76g of ADH suspension dispersed in 24.93g of deionized water over 20 minutes. Finally, a polymer emulsion with a solids content of about 40% was obtained.
Synthesis of Polymer emulsion 5:
a monomer pre-emulsion was prepared by mixing 270.0g of Deionized (DI) water, 35.28g of SLS, 44.12g of DAAM, 97.07g of BA, 97.07g of 2-EHA, 604.46g of MMA, 8.82g of HDDA, 8.82g of PDMS and 22.06g of MAA.
In a 3 liter four-necked round bottom flask equipped with paddle stirrer bar, thermometer, nitrogen inlet and reflux condenser, 875.0g of deionized water were added and heated to 82 ℃ under nitrogen atmosphere with stirring. Then 35.28g of SLS and 59.39g of the monomer pre-emulsion were added to the flask followed by a uniform addition of a solution of 0.96g of ammonium persulfate dissolved in 16.0g of deionized water over three minutes. After being held for 1 minute with stirring, the remaining monomer pre-emulsion and a solution of 2.09g of ammonium persulfate dissolved in 58.0g of deionized water were initially added dropwise in two passes to the reactor over a period of 120 minutes. After the completion of the feeding, the reactor was kept at 82 ℃ for 1 hour of reaction, followed by cooling to 70 ℃ to start dropping a solution of 1.71g of t-butyl hydroperoxide dissolved in 6.4g of deionized water and a solution of 0.78g of erythorbic acid dissolved in 16.8g of deionized water over 60 minutes, after cooling to 50 ℃ to drop 24.86g of 25% aqueous ammonia solution over 20 minutes to adjust the pH to 7.5-8.5, and then dropping 18.76g of ADH suspension dispersed in 24.93g of deionized water over 20 minutes. Finally, a polymer emulsion with a solids content of about 40% was obtained.
Coating composition EX1
Example coating compositions Ex1-4 and comparative example coating compositions Comp Ex1-4 were prepared according to the formulations listed in table 1. 80g of emulsion polymer 1 was added to a 150mL round bottom flask, and the various adjuvant components were added sequentially with stirring from a low shear mixer at 500rpm to finally obtain a homogeneous coating composition EX 1.
TABLE 1
Coating composition EX2
The coating composition of EX2 was prepared according to the same procedure described above in EX1, using the emulsion polymer 2.
Coating composition EX3
The coating composition of EX3 was prepared according to the same procedure described above in EX1, using the emulsion polymer 3.
Coating composition EX4
The coating composition of EX4 was prepared according to the same procedure described above in EX1, except that the additive was 5 wt% CX-100, based on the total weight of the coating composition.
Coating composition Comp EX1
The coating composition of Comp EX1 was prepared according to the same procedure as described above in EX1, using emulsion polymer 4.
Coating composition Comp EX2
The coating composition of Comp EX2 was prepared according to the same procedure described above for EX1, using emulsion polymer 5.
Coating composition Comp EX3
The coating composition of Comp EX3 was prepared according to the same procedure described above in EX1, except that no CX-100 was added.
Coating composition Comp EX4
The coating composition of Comp EX4 was prepared according to the same procedure described above in EX1, except that the emulsion polymer used was emulsion polymer 5 and CX-100 was added in an amount of 5% of the total weight of the coating composition.
Table 2 gives the properties of the above coating compositions and coatings prepared therefrom. As shown in table 2, the coating composition without the hydroxyl-terminated dimethoxysilane (Comp EX 1) exhibited poor bubble water performance, and the emulsion polymer made without the polymerizable emulsifier produced a coating composition that was relatively poor in both hardness and bubble water resistance.
In contrast, the coating compositions of the present invention (Ex 1-4) exhibit good resistance to water-soaking and provide high hardness coatings of HB or higher as measured by the GB/T6739-2006 method.
TABLE 2
Claims (9)
1. An acrylic emulsion polymer comprising a polymerizable emulsifier as a polymerization unit and a hydroxyl-terminated polydimethylsiloxane, wherein the acrylic emulsion polymer further comprises an aziridine-based crosslinking agent when used in an aqueous coating composition.
2. The aqueous coating composition of claim 1, wherein the amount of the hydroxy-terminated polydimethylsiloxane is from 0.1 to 10% by dry weight of the emulsion polymer, and the amount of the aziridine-based crosslinking agent is from 0.1 to 5% by total weight of the aqueous coating composition.
3. The aqueous coating composition of claim 1, wherein the amount of polymerizable emulsifier is 0.1-3% by dry weight of the acrylic polymer emulsion.
4. An aqueous coating composition according to claim 3, characterized in that the surfactant of the polymerizable emulsifier has the structure of formula (I):
wherein R1 is hydrogen or C1-C20 alkyl,
r2 is hydrogen or a methyl group,
r3 is hydrogen or C1-C20 alkyl,
a represents an alkylene group or a substituted alkylene group having 2 to 4 carbon atoms;
n is an integer ranging from 0 to 1, 00; and is
X represents hydrogen or an anionic hydrophilic group selected from: - (CH2) a-SO3M, - (CH2) b-COOM, -PO3M2, -P (Z) O2M or-CO-CH 2-CH (SO3M) -COOM, wherein a and b are each independently an integer of 0 to 4, Z represents a residue obtained by removing X from the general formula (I), and M each represents hydrogen, an alkali metal atom, an alkaline earth metal atom, an ammonium residue or an alkanolamine residue.
5. The acrylic emulsion polymer as claimed in claim 4, wherein the molecular weight of said hydroxyl terminated polydimethylsilane is 200-100,000 g/mol, and the particle size of said acrylic emulsion polymer is from 40nm to 300 nm.
6. The acrylic emulsion polymer of claim 4 wherein said acrylic emulsion polymer comprises as polymerized units one or more ethylenically unsaturated nonionic monomers, said acrylic emulsion polymer comprises as polymerized units one or more ethylenically unsaturated monomers having one or more functional groups, said acrylic emulsion polymer comprises as polymerized units one or more polyethylenically unsaturated monomers, including di-, tri-, tetra-or higher polyethylenically unsaturated monomers.
7. A method for preparing an acrylic emulsion polymer as claimed in any one of claims 1 to 6, wherein: the preparation method comprises the following steps:
a) measuring a monomer pre-emulsion raw material containing the components;
b) mixing the measured monomer pre-emulsion raw materials to obtain monomer pre-emulsion,
c) then in a 3 liter four-necked round bottom flask equipped with paddle stirrer bar, thermometer, nitrogen inlet and reflux condenser, deionized water was added and heated to 82 ℃ under nitrogen atmosphere with stirring;
d) then adding an emulsifier and a certain amount of monomer pre-emulsion into a flask, and then adding an initiator at a constant speed within three minutes;
e) keeping the reaction solution for 1 minute under stirring, and then dropwise adding the rest monomer pre-emulsion and the rest initiator into the reactor in two ways for 120 minutes;
f) after the completion of the feed, the reactor was kept at 82 ℃ for 1 hour of reaction, followed by cooling to 70 ℃ to start the work-up reaction to eliminate residual monomers, cooling to neutralize, adjusting the pH to 7.5-8.5, and then dropping the ADH suspension over 20 minutes. A polymer emulsion with a solids content of about 40% was obtained.
8. The method of claim 7, wherein the acrylic emulsion polymer comprises: the raw materials of the monomer pre-emulsion comprise deionized water, 0.1-3% of polymerizable emulsifier, 0.1-3% of 1, 6-hexanediol diacrylate, 0-30% of butyl acrylate, 0-30% of 2-ethylhexyl acrylate, 0-80% of methyl methacrylate, 0-80% of styrene, 0.1-10% of hydroxyl-terminated polydimethylsiloxane, 0-4% of acrylic acid and 0-4% of methacrylic acid.
9. A method for preparing an aqueous coating composition according to claim 8, comprising the steps of:
s1, preparing raw materials of 0.1-5% of aziridine cross-linking agent, 2-10% of film-forming additive, 0.1-1% of wetting agent, 0.3-1% of defoaming agent, 0.5-1% of thickening agent, 5-12% of water and 75-85% of emulsion polymer.
S2, adding the emulsion polymer into a 150mL round-bottom flask, and sequentially adding various auxiliary agent components of an aziridine crosslinking agent under the stirring of a low-shear mixer at 500rpm to finally obtain the uniform water-based coating composition.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010847A (en) * | 2022-07-15 | 2022-09-06 | 亚士创能科技(上海)股份有限公司 | Emulsion for sand-in-water continuous phase and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04202388A (en) * | 1990-11-29 | 1992-07-23 | Nippon Shokubai Co Ltd | Weather-resistant coating material composition |
| US20040266935A1 (en) * | 2003-06-30 | 2004-12-30 | Harukazu Okuda | Emulsion composition for building materials |
| CN1922228A (en) * | 2004-02-24 | 2007-02-28 | 株式会社钟化 | Graft copolymer, flame retardant composed of such copolymer and resin composition containing such flame retardant |
| CN102311692A (en) * | 2010-07-06 | 2012-01-11 | 张铮 | Organic silicon acrylic coating |
| AU2011363044A1 (en) * | 2011-03-21 | 2013-09-26 | Momentive Performance Materials Inc. | Siloxane monomers containing hydrolysis resistance carbosiloxane linkage, process for their preparation and thin films containing the same for contact lens application |
| CN103382236A (en) * | 2013-05-12 | 2013-11-06 | 北京化工大学 | Silicone-acrylate emulsion with high organosilicon content and preparation method thereof |
| WO2021046673A1 (en) * | 2019-09-09 | 2021-03-18 | Dow Global Technologies Llc | Aqueous dispersion of polymeric particles |
-
2021
- 2021-11-17 CN CN202111364727.4A patent/CN114316160A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04202388A (en) * | 1990-11-29 | 1992-07-23 | Nippon Shokubai Co Ltd | Weather-resistant coating material composition |
| US20040266935A1 (en) * | 2003-06-30 | 2004-12-30 | Harukazu Okuda | Emulsion composition for building materials |
| CN1922228A (en) * | 2004-02-24 | 2007-02-28 | 株式会社钟化 | Graft copolymer, flame retardant composed of such copolymer and resin composition containing such flame retardant |
| CN102311692A (en) * | 2010-07-06 | 2012-01-11 | 张铮 | Organic silicon acrylic coating |
| AU2011363044A1 (en) * | 2011-03-21 | 2013-09-26 | Momentive Performance Materials Inc. | Siloxane monomers containing hydrolysis resistance carbosiloxane linkage, process for their preparation and thin films containing the same for contact lens application |
| CN103382236A (en) * | 2013-05-12 | 2013-11-06 | 北京化工大学 | Silicone-acrylate emulsion with high organosilicon content and preparation method thereof |
| WO2021046673A1 (en) * | 2019-09-09 | 2021-03-18 | Dow Global Technologies Llc | Aqueous dispersion of polymeric particles |
Non-Patent Citations (4)
| Title |
|---|
| LIN, HN,等: "Effects of the methacrylate monomers with different end groups on the morphologies, electro-optical and mechanical properties of polymer dispersed liquid crystals composite films", LIQUID CRYSTALS, vol. 48, no. 5, pages 722 - 734 * |
| 朱艳虹，等: "反应性乳化剂对丙烯酸酯乳液及涂膜性能的影响", 化工新型材料, vol. 41, no. 12, pages 137 - 139 * |
| 苏奎: "聚硅氧烷-(甲基)丙烯酸酯共聚乳液的制备与性能", 精细化工, vol. 31, no. 05, pages 643 - 648 * |
| 谭文丽: "核壳型有机硅改性丙烯酸酯涂料印花黏合剂", 印染, vol. 12, pages 5 - 8 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010847A (en) * | 2022-07-15 | 2022-09-06 | 亚士创能科技(上海)股份有限公司 | Emulsion for sand-in-water continuous phase and preparation method and application thereof |
| CN115010847B (en) * | 2022-07-15 | 2023-12-15 | 亚士创能科技(上海)股份有限公司 | Emulsion for sand-in-water continuous phase and preparation method and application thereof |
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