CN109761834B - Preparation method and application of water-dispersible polyaspartic ester resin and water-based polyurea coating - Google Patents
Preparation method and application of water-dispersible polyaspartic ester resin and water-based polyurea coating Download PDFInfo
- Publication number
- CN109761834B CN109761834B CN201910161992.9A CN201910161992A CN109761834B CN 109761834 B CN109761834 B CN 109761834B CN 201910161992 A CN201910161992 A CN 201910161992A CN 109761834 B CN109761834 B CN 109761834B
- Authority
- CN
- China
- Prior art keywords
- water
- resin
- acid ester
- aqueous
- component
- 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.)
- Active
Links
Images
Abstract
The invention relates to polyaspartic ester resin, in particular to a preparation method and application of water dispersible polyaspartic ester resin and aqueous polyurea coating, wherein the water dispersible polyaspartic ester is obtained by carrying out Michael addition reaction on unsaturated dicarboxylic ester, unsaturated monocarboxylic acid and primary amino compound under the action of catalyst and neutralizer; the performance of a coating film of the two-component water-based polyurea coating obtained by utilizing the water dispersion of the water dispersible polyaspartic ester keeps the main characteristics of a solvent-based polyurea coating, including fast curing at room temperature, high glossiness, high transparency, excellent water resistance, corrosion resistance, ultraviolet resistance, aging resistance and the like.
Description
Technical Field
The invention relates to an aspartate resin, in particular to an aspartate resin with a new structure and a preparation method thereof, and a polyurea coating prepared by the aspartate resin with the new structure
Background
The use of polyaspartic acid esters for the preparation of polyurea coatings has been known for nearly a decade. The polyurea coating has excellent ageing resistance, ultraviolet light resistance and excellent wear resistance and waterproof performance, and is mainly applied to industrial terraces, outdoor road pavement and waterproof surface coating of swimming pools and water orchards in the early stage. In recent years, polyaspartic ester polyurea coatings have also begun to be used in the field of industrial coatings, on the one hand, because such polyurea coatings can be rapidly cured at low temperatures, even at room temperature, and because the optical properties, mechanical properties and chemical resistance of the paint film exceed or are equivalent to those of conventional high-temperature baking paints, they are high-performance coatings that can be baked free; on the other hand, the solvent content of polyaspartate polyurea coating systems varies depending on the application. As an industrial coating, the construction solid content of the polyurea coating is generally higher than 60 percent and far higher than 35-45 percent of the construction solid content of the traditional high-temperature baking paint, and the used solvent does not contain benzene and other harmful solvents, so the polyurea industrial coating taking polyaspartic acid ester as a raw material is an energy-saving and environment-friendly coating.
However, in view of the current tightening of environmental legislation, the development of aqueous coatings in the traditional world is still high, and the trend of "oil to water" is becoming more and more a consensus in the coatings world. In this context, the art of making polyurea coatings aqueous has also gradually begun.
EP-A0849301 reports a technique for waterborne polyaspartic ester coatings, but the polyaspartic esters used are not hydrophilic per se, but only hydrophilic isocyanate curing agents are added to the non-hydrophilic polyaspartic esters before use and are then mixed with water, so that the entire coating system is not water-stable.
US200614922a1 reports a process for the preparation of an aqueous polyaspartic ester. It is prepared through the first ester exchange reaction between hydrophilic polyglycol monoether and maleic acid ester or esterification reaction with maleic anhydride and the subsequent Michael addition reaction between the hydrophilic monomer-bearing maleic acid ester and the primary amino compound to obtain hydrophilic polyaspartic acid ester. However, the method has two defects, namely, ester exchange reaction or esterification reaction can be completed only through a violent reaction process, so that the color of the product is usually darker, and the color of the polyaspartic ester prepared by the product cannot meet the requirements of most industrial paints on transparency and gloss; secondly, catalysts are used in the ester exchange and esterification reaction processes, the removal treatment of the catalysts after the reaction is finished is very troublesome, but if the removal treatment is not carried out, the residual catalysts are brought into the final coating product, and the construction performance and the final product performance of the coating are damaged.
Another process for the preparation of aqueous polyaspartic esters is reported in EP290398a 1. The hydrophilic polyaspartic acid ester is prepared by preparing a hydrophilic monofunctional isocyanate prepolymer and grafting the prepolymer to polyaspartic acid ester. However, this method has the disadvantage that the preparation of the prepolymer requires a several-fold excess of isocyanate and the excess is finally separated off. This adds a number of difficulties and costs to the actual production process.
Therefore, a new hydrophilic polyaspartic acid ester and a preparation method thereof are developed, so that the novel hydrophilic polyaspartic acid ester not only can meet the use requirement of industrial coatings, but also has a simple, convenient and low-cost production process route, and becomes a main task for developing the water-based technology of polyurea coatings.
The invention provides a water dispersible polyaspartic ester and a synthesis method thereof, and also provides a method for preparing a two-component water-based polyurea coating by using the water dispersible polyaspartic ester. The aqueous polyurea coating provided by the invention not only keeps the main characteristics of the solvent polyurea coating in performance, but also has the operable time of more than 5 hours, thereby greatly simplifying the construction difficulty of the traditional polyurea coating.
Disclosure of Invention
The purpose of the invention is as follows: the present invention provides a water dispersible polyaspartic ester and a method for its synthesis, the water dispersible polyaspartic ester being represented by formula I:
in the formula R1And R2May be an alkyl group having the same or different carbon atoms, R3May be H or-CH3. Wherein Y may be an alkylene group, a cycloalkylene group, an arylene group, or a combination thereof.
The polyaspartate ester is any one of the following structural formulas:
the present invention discloses a method for neutralizing water dispersible polyaspartic acid ester with organic amine aqueous solution and dispersing at high speed to obtain aqueous polyaspartic acid ester dispersion.
The invention also provides a method for preparing the two-component water-based polyurea coating by using the aqueous dispersion of polyaspartic ester.
The two-component water-based polyurea coating prepared by the invention has the operable time of more than 5 hours, and simultaneously keeps the main characteristics of a solvent-based coating in performance.
The invention discloses a synthesis method of water dispersible polyaspartic ester, which is obtained by carrying out Michael addition reaction on unsaturated dicarboxylic ester, unsaturated monocarboxylic acid and primary amino compound under the action of a catalyst and a neutralizing agent. The reaction scheme can be represented by the following reaction scheme 1:
reaction scheme 1
In the formula R1And R2May be an alkyl group having the same or different carbon atoms, R3May be H or-CH3. Wherein Y may be an alkylene group (e.g.:
wherein n ≧ 0, or n ≧ 1), a cycloalkylene group (e.g.:
) Arylene (e.g.:
) Or a combination thereof.
The unsaturated dicarboxylic acid ester can be dialkyl maleate, including but not limited to diethyl maleate, dipropyl maleate, dibutyl maleate, methyl propyl maleate, mixtures thereof, and the like;
the unsaturated dicarboxylic acid ester may also be a dialkyl fumarate, including but not limited to diethyl fumarate, dipropyl fumarate, dibutyl fumarate, and methylpropyl fumarate, mixtures thereof, and the like.
The unsaturated monocarboxylic acid may be acrylic acid or methacrylic acid.
The primary amino compound reacted with the unsaturated dicarboxylic acid ester and the unsaturated carboxylic acid as described above includes, but is not limited to, ethylenediamine, 1, 2-propylenediamine, 2, 5-dimethyl-2, 5-hexamethylenediamine, 1, 11-undecylenediamine, 1, 12-dodecyldiamine, 2,4 ' -diamino-dicyclohexylmethane, 1-amino-3, 3, 5-trimethyl-5-aminomethylcyclohexane, 2, 4-toluenediamine or 2, 6-toluenediamine, 2,4 ' -diaminodiphenylmethane or 4,4 ' -diaminodiphenylmethane, and mixtures thereof, and the like. The primary amino compounds reacted with the unsaturated dicarboxylic acid ester and the unsaturated carboxylic acid further include, but are not limited to, 1, 4-butanediamine, 1, 6-hexanediamine, 2,4, 4-trimethyl-1, 6-hexanediamine, 1-amino-3, 3, 5-trimethyl-5-aminomethylcyclohexane, 4,4 ' -diamino-dicyclohexylmethane, 3 ' -dimethyl-4, 4 ' -diamino-dicyclohexylmethane, mixtures thereof, and the like. The primary amino compounds reacted with the unsaturated dicarboxylic acid ester and the unsaturated carboxylic acid as described above may also include, but are not limited to, terminal amino compounds of polypropylene oxide, polyethylene oxide, or copolymers of ethylene oxide and propylene oxide, such as Jeffamine D230, D2000, T403, T5000, ED600, ED900, etc., from the company HUNTSMAN.
The dialkyl maleates mentioned above are preferably diethyl maleate and dipropyl maleate, and most preferably diethyl maleate.
The dialkyl fumarates mentioned above are preferably diethyl fumarate and dipropyl fumarate, and most preferably diethyl fumarate.
The above-mentioned unsaturated monocarboxylic acid ester is preferably acrylic acid or methacrylic acid, and acrylic acid is more preferred.
The primary amino compound is preferably 1, 6-hexamethylenediamine, 4 '-diamino-dicyclohexylmethane, 3' -dimethyl-4, 4 '-diamino-dicyclohexylmethane, and most preferably 1, 6-hexamethylenediamine and 4, 4' -diamino-dicyclohexylmethane are used.
The above unsaturated dicarboxylic acid ester and unsaturated monocarboxylic acid are suitably in a molar ratio of 0.80:0.20 to 0.40:0.60, preferably in a molar ratio of 0.80:0.20 to 0.50:0.50, and most preferably in a molar ratio of 0.75:0.25 to 0.65: 0.35.
The molar ratio of the sum of the above-mentioned moles of unsaturated dicarboxylic acid ester and unsaturated monocarboxylic acid to primary amino compound is suitably from 2:1.10 to 2:1.00, preferably from 2:1.08 to 2:1.05, most preferably from 2:1.03 to 2: 1.00.
The Michael addition reaction of the above-mentioned unsaturated carboxylic acid ester and unsaturated monocarboxylic acid with a primary amino compound is desirably carried out in the presence of a catalyst. As the catalyst, sodium methoxide, sodium hydroxide, dibutyltin dilaurate, dibutyltin oxide, 2,4,6-3 (dimethylaminomethyl) phenol, etc. can be mentioned. 2,4,6-3 (dimethylaminomethyl) phenol is preferred. The amount of the catalyst is 0.05-1 wt%, preferably 0.1-0.5 wt% of the total reactant.
The neutralizing agent may be an organic basic compound including, but not limited to, ethylenediamine, ethanolamine, dimethylformamide, dimethylethanolamine, and the like. Dimethylformamide and dimethylethanolamine are preferably used. The amount of neutralizing agent used is such as to adjust the initial pH of the reaction mixture to a value in the range of 6 to 7.
In the synthesis of a water-dispersible polyaspartic ester disclosed in the present invention, the Michael addition reaction between an unsaturated dicarboxylic acid and an unsaturated monocarboxylic acid with a primary amino compound is suitably carried out at a reaction temperature of 45 ℃ to 80 ℃, preferably at a reaction temperature of 55 ℃ to 70 ℃, and most preferably at a reaction temperature of 60 ℃ to 65 ℃.
In the synthesis of a water-dispersible polyaspartic ester disclosed in the present patent application, the reaction time of the unsaturated dicarboxylic acid with the Michael addition reaction between the saturated monocarboxylic acid and the primary amino compound is suitably 6 to 24 hours, preferably 8 to 18 hours, and most preferably 10 to 16 hours.
The method for preparing the aqueous dispersion of water-dispersible polyaspartic acid ester according to the present invention, which is prepared by the present invention, comprises:
a preparing 20% -30% concentration organic amine aqueous solution, suitable organic amine including but not limited to ethylenediamine, ethanolamine, dimethylformamide, dimethylethanolamine and so on. Dimethylformamide and dimethylethanolamine are preferably used.
b slowly adding the organic amine aqueous solution into the water dispersible polyaspartic acid ester prepared by the Ming patent under stirring, wherein the adding amount of the organic amine aqueous solution can be calculated according to the equivalent of carboxylic acid in the resin, and the equivalent of alkali and acid is kept. The stirring speed is kept at 300-500 r/min, and the stirring time is kept at 20-30 min
And c, adding deionized water under the stirring state to ensure that the final solid content of the polyaspartic acid ester water dispersion is 50 percent, and then increasing the stirring rotating speed to 3000 revolutions per minute for 20-30 minutes. Before the high-speed dispersion is finished, the pH value of the dispersion is adjusted to be between 8 and 9 by using an organic amine aqueous solution. Finally obtaining the water dispersion of the polyaspartic acid ester with stable storage.
The two-component water-based polyurea coating prepared by the aqueous dispersion of polyaspartic ester provided by the invention comprises a resin component (component B) and a curing agent component (component A), wherein:
the resin component comprises the polyaspartic ester aqueous dispersion prepared by the invention, film forming auxiliary agents, water, defoaming agents, flatting agents, thickening agents, wetting agents, pigments and fillers, and other needed coating auxiliary agents including antirust agents, mildew inhibitors, bactericides and the like. For some purposes of use, the resin component may also be supplemented with other suitable aqueous dispersions or emulsions of hydroxyl-containing resins, including but not limited to polyurethane resins, acrylic resins, or epoxy resins. The amount of the additive is preferably 10-50% of the total amount of the resin.
b the above curing agent component consists of hydrophilic aliphatic polyisocyanate including but not limited to trimer or biuret form of Hexamethylene Diisocyanate (HDI), trimer or biuret form of isophorone diisocyanate (IPDI), and other isocyanate-based curing agents suitable for water-borne coatings. Such as Bayhydur304, Bayhydur305, Bayhydur3100, Bayhydur XP2487, Bayhydur XP2655, and Bayhydur401-70, all of which are created by kojic.
The mixing ratio of the resin component (B component) and the curing agent component (A component) of the two-component aqueous polyurea coating prepared by the polyaspartic acid ester aqueous dispersion prepared by the invention can be calculated according to the ratio of active hydrogen equivalent in the resin component to isocyanate equivalent in the curing agent component, and the ratio of H/NCO can be in the range of 1:1.0-1:2.0, preferably 1:1.0-1:1.5, and most preferably 1:1.0-1: 1.2.
The forming construction of the water-based polyurea coating prepared by the invention can adopt any one of the traditional coating construction methods, including spraying, brushing, dipping, roller coating and the like, and can be single-layer coating or multi-layer coating. The coated base material can be metal, plastic, wood, glass or concrete. The base surfaces of all these materials need to be cleaned and polished before coating, and if necessary, primer application can be performed first.
The aqueous polyurea coating prepared by the invention can be planned at room temperature (25 ℃) usually, and the curing time is 20-30 minutes. Alternatively, the curing may be carried out at a temperature of between 40 ℃ and 80 ℃ for a corresponding curing time of between 15 and 20 minutes.
Has the advantages that:
the water-dispersible polyaspartic acid ester prepared by the method is light in color, and the color (Pt-Co standard) is 20-30 #.
The polyaspartic ester aqueous dispersion prepared by the invention is small in particle size (the average particle size is 90-120nm), low in viscosity (2000 +/-500 mPa.s) and high in storage stability.
The polyaspartic ester aqueous dispersion prepared by the invention has good compatibility with aqueous dispersions or emulsions of other resins. Therefore, the resin component (B component) of the two-component water-based polyurea coating prepared by the invention can be used alone as the only resin, and can also be matched with other suitable water dispersions or emulsions of hydroxyl-containing polyurethane resin, acrylic resin, epoxy resin and the like. Thereby improving certain performances of the two-component water-based polyurea coating prepared by the invention and reducing the cost.
The main characteristics of the solvent-type polyurea coating are kept by the film performance of the two-component water-based polyurea coating prepared by the invention, including fast curing at room temperature, high glossiness, high transparency, excellent water resistance, corrosion resistance, ultraviolet light resistance, aging resistance and the like.
The operable time of the double-component water-based polyurea coating prepared by the invention is more than 5 hours, and meanwhile, the coating film can be quickly planned at room temperature. Sufficient operating time is available so that the two-component aqueous polyurea coating can be applied by the one-component coating method without the need for a special two-component spray machine.
Drawings
FIG. 1 is an infrared spectrum of diethyl maleate;
FIG. 2 is an acrylic acid IR spectrum;
FIG. 3 is an infrared spectrum of product E1.
Detailed Description
EXAMPLE 1 Synthesis of resin E1
In a 500ml four-necked flask equipped with an electric stirrer, a thermometer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, 0.8mol (137.7g) of diethyl maleate and 0.2mol (14.4g) of acrylic acid were added, and after mixing uniformly, an appropriate amount of Dimethylformamide (DMF) was added to adjust the pH of the mixture to 6 to 7. 0.26g of 2,4, 6-tris (dimethylaminomethyl) phenol was additionally added. Stirring, introducing nitrogen, slowly heating to 45-50 deg.C, adding 0.5mol (105.2g) of 4, 4-diamino-dicyclohexylmethane, controlling the temperature not to exceed 60 deg.C, maintaining for 40-60 min, and reacting at 60-65 deg.C for 12 hr. Cooling to 40 ℃ and discharging to obtain the product E1. The product was a pale yellow transparent liquid with a 23# hue (Pt-Co), at which point the conversion was 86% as measured by the "iodination method" and 97% after 48 hours. The theoretical calculated amino equivalent weight is 257.3.
The infrared spectra of diethyl maleate and acrylic acid are shown in FIG. 1 and FIG. 2, respectively. Wherein the absorption peaks at 1640.29 and 1636.47 are the absorption peaks of diethyl maleate and the double bond of acrylic acid, respectively. Fig. 3 is an infrared image of product E1. It can be seen from the figure that the absorption peaks at 1640.29 and 1636.47 have disappeared, indicating that diethyl maleate and acrylic acid have reacted to form product E1;
structural formula of E1:
example 2 Synthesis of resin E2
In a 500ml four-necked flask equipped with an electric stirrer, a thermometer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, 0.8mol (137.7g) of diethyl maleate and 0.2mol (14.4g) of acrylic acid were added, and after mixing uniformly, an appropriate amount of Dimethylformamide (DMF) was added to adjust the pH of the mixture to 6 to 7. 0.27g of 2,4, 6-tris (dimethylaminomethyl) phenol was additionally added. Stirring is started, nitrogen is introduced, the temperature is slowly raised to 45-50 ℃, 0.5mol (119g) of 3,3 '-dimethyl-4, 4' -diamino-dicyclohexyl methane l is added dropwise, the temperature is controlled not to exceed 60 ℃, the dropwise addition is finished within 40-60 minutes, and then the reaction is carried out for 12 hours within the range of 60-65 ℃. Cooling to 40 ℃ and discharging to obtain the product E2. The product was a pale yellow clear liquid with a color number (Pt-Co) of 25#, at which point the conversion was 87% as determined by the "iodination method" and 96% after 48 hours. The theoretical calculated amino equivalent weight is 271.1;
structural formula of E2
Example 3 Synthesis of resin E3
In a 500ml four-necked flask equipped with an electric stirrer, a thermometer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, 0.8mol (137.7g) of diethyl maleate and 0.2mol (17.2g) of methacrylic acid were added, and after mixing them well, an appropriate amount of Dimethylformamide (DMF) was added to adjust the pH of the mixture to 6 to 7. 0.26g of 2,4, 6-tris (dimethylaminomethyl) phenol was additionally added. Stirring, introducing nitrogen, slowly heating to 45-50 deg.C, adding 0.5mol (105.2g) of 4, 4-diamino-dicyclohexylmethane, controlling the temperature not to exceed 60 deg.C, maintaining for 40-60 min, and reacting at 60-65 deg.C for 12 hr. Cooling to 40 ℃ and discharging to obtain the product E3. The product was a pale yellow clear liquid with a color number (Pt-Co) of 25#, at which time the conversion was 85% by "iodination" and 96% after 48 hours. The theoretical calculated amino equivalent weight is 260.1;
structural formula of E3
Example 4 Synthesis of resin E4
In a 500ml four-necked flask equipped with an electric stirrer, a thermometer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, 0.8mol (137.7g) of diethyl maleate and 0.2mol (17.2g) of methacrylic acid were added, and after mixing them well, an appropriate amount of Dimethylformamide (DMF) was added to adjust the pH of the mixture to 6 to 7. 0.27g of 2,4, 6-tris (dimethylaminomethyl) phenol was additionally added. Stirring is started, nitrogen is introduced, the temperature is slowly raised to 45-50 ℃, 0.5mol (119g) of 3,3 '-dimethyl-4, 4' -diamino-dicyclohexyl methane is added dropwise, the temperature is controlled not to exceed 60 ℃, the dropwise addition is finished within 40-60 minutes, and then the reaction is carried out for 12 hours within the range of 60-65 ℃. Cooling to 40 ℃ and discharging to obtain the product E4. The product was a pale yellow transparent liquid with a color number (Pt-Co) of 26#, at which point the conversion was 85% by "iodination" and 95% after 48 hours. The theoretical calculated amino equivalent weight is 273.9.
Structural formula of E4
EXAMPLE 5 preparation of aqueous polyaspartic ester Dispersion 1
100g of the water-dispersible polyaspartic ester resin (E1) obtained in example 1 was stirred
Under this condition (400rpm), 22g of a 25% aqueous solution of Dimethylformamide (DMF) was slowly added thereto, and the rotation speed was kept constant (300 revolutions per minute and 500 revolutions per minute) for 25 minutes. Then, 83.5g of deionized water is slowly added, the rotating speed is increased to 3000rpm, and the mixture is kept for 15 minutes; and regulating the pH value to be within the range of 8.5-9.0 by using a DMF aqueous solution with the concentration of 25% to obtain the polyaspartic acid ester aqueous dispersion 1 with the solid content of 50%.
Example 6 (preparation of aqueous dispersions 2-4)
Aqueous dispersions of resins E2, E3, and E4 of examples 2-4, respectively, were prepared according to the same procedure as in example 5, and the corresponding formulation data are shown in Table 1. The index data relating to the individual dispersions are also given in Table 1 (in g by weight).
TABLE 1 recipe and index data sheet for each dispersion
Note: the nanometer particle size analyzer is Winner800 (Jinan micro-nano particle instrument Co., Ltd.) and the high-speed centrifuge is LG10-2.4A (Beijing Leiboer)
Example 7 waterborne coating preparation
The aqueous polyurea coatings were formulated according to the formulas of component B (resin component) and component a (curing agent component) in table 2, wherein:
a2233 is Shiquanheng hydroxyl acrylic acid aqueous dispersion with a solid content of 45% and a hydroxyl content (pure resin) of 3.3%;
the component A (curing agent) is a compound of Desmodur X2655 and propylene glycol methyl ether acetate 8:2(w/w) which are created by Costa, and the average NCO is 16.8 percent.
The A, B components are fully and uniformly mixed according to the respective given proportion, then the viscosity is adjusted to 25-30s (coating-4 cups) by using a proper amount of deionized water, and then the mixture is sprayed on a test board by using an air spray gun, and the wet film is controlled at 50-60 mu m. The surface can be dried in 25 minutes under the environment of room temperature and humidity of 40-75%. If necessary, the mixture can be flashed (leveled) at room temperature for 10min and then placed into a container for baking for 20 min to be dried. Other performance indexes of the respective coating films are also shown in Table 2 (in g, weight units).
TABLE 2 formulation and Performance Table of the aqueous polyurea coatings
As can be seen from Table 2, the samples No. 1 to No. 4 each used E1 to E4 resin alone as a resin component, and the adhesion of their coating films to aluminum alloy substrates was rated 1 to 2 (one hundred grid method). Because the E1 resin and the hydroxy acrylic resin aqueous dispersion 2233 have good compatibility, the adhesion of the coating on the aluminum alloy substrate can reach 0-1 grade (one hundred lattice method) by matching.
Claims (6)
1. A water-dispersible polyaspartate characterized in that the polyaspartate is of any one of the following structural formulas:
2. the process of claim 1, wherein the water-dispersible polyaspartic acid ester is obtained by Michael addition reaction of an unsaturated dicarboxylic acid ester and an unsaturated monocarboxylic acid with a primary amino compound under the action of a catalyst and a neutralizing agent;
the unsaturated dicarboxylic acid ester is diethyl maleate, diethyl fumarate or a mixture of the two;
the unsaturated monocarboxylic acid is acrylic acid or methacrylic acid;
the primary amino compound is 2,4，Diamino-dicyclohexylmethane or 3,3，-dimethyl-4, 4，-diamino-dicyclohexylmethane;
the catalyst is sodium methoxide, sodium hydroxide, dibutyltin dilaurate, dibutyltin oxide or 2,4, 6-tri (dimethylamino methyl) phenol;
the molar ratio of the unsaturated dicarboxylic acid ester to the unsaturated monocarboxylic acid is 0.80:0.20-0.40: 0.60;
the molar ratio of the sum of the moles of the unsaturated dicarboxylic acid ester and the unsaturated monocarboxylic acid to the primary amino compound is 2:1.10-2: 1.00;
the reaction temperature between the unsaturated dicarboxylic ester and the unsaturated monocarboxylic acid and the primary amino compound is 45-80 ℃;
the reaction time between the unsaturated dicarboxylic ester and the unsaturated monocarboxylic acid and the primary amino compound is 6-24 hours.
3. A method for preparing an aqueous dispersion of a water-dispersible polyaspartic acid ester, comprising the steps of:
preparing an organic amine aqueous solution with the volume percentage of 20-30%, wherein the organic amine is ethylenediamine, ethanolamine, dimethylformamide or dimethylethanolamine;
b. slowly adding an aqueous solution of an organic amine to the water-dispersible polyaspartic acid ester prepared according to claim 2 while stirring, wherein the amount of the aqueous solution of the organic amine added is calculated according to the equivalents of carboxylic acid in the resin, and the equivalents of base and acid are maintained; the stirring speed is kept at 300-500 r/min, and the stirring time is kept at 20-30 min;
c. adding deionized water under stirring to make the final solid content of the polyaspartic acid ester water dispersion be 50%, then increasing the stirring speed to 2000-3000 r/min, and keeping for 20-30 min; before the high-speed dispersion is finished, the pH value of the dispersion is adjusted to be between 8 and 9 by using an organic amine aqueous solution, and the water-dispersible polyaspartic acid ester aqueous dispersion is obtained.
4. A two-component aqueous polyurea coating prepared from an aqueous dispersion of polyaspartic acid ester is characterized by consisting of a resin component and a curing agent component, wherein:
a. the resin component comprises the aqueous polyaspartic ester dispersion prepared according to claim 3, film-forming auxiliary agents, water, defoaming agents, leveling agents, thickening agents, wetting agents, pigments and fillers, and other required coating auxiliary agents;
b. the curing agent component is composed of a hydrophilic aliphatic polyisocyanate selected from the trimer or biuret form of hexamethylene diisocyanate or the trimer or biuret form of isophorone diisocyanate.
5. The two-component aqueous polyurea coating prepared from an aqueous dispersion of polyaspartic acid ester according to claim 4, wherein the other desired coating aids are selected from the group consisting of rust inhibitors, mold inhibitors, bactericides, emulsions, dispersions or aqueous solutions of resin A; the resin A is polyurethane resin, acrylic resin or epoxy resin, and the addition amount of the resin A is 30-50% of the total amount of the resin.
6. The two-component aqueous polyurea coating material prepared from the aqueous dispersion of polyaspartic acid ester according to claim 4 or 5, wherein the mixing ratio of the resin component and the curing agent component is: calculated according to the ratio of active hydrogen equivalent in the resin component to isocyanate equivalent in the curing agent component, [ H ]/[ NCO ] is 1:1.0-1: 2.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910161992.9A CN109761834B (en) | 2019-03-05 | 2019-03-05 | Preparation method and application of water-dispersible polyaspartic ester resin and water-based polyurea coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910161992.9A CN109761834B (en) | 2019-03-05 | 2019-03-05 | Preparation method and application of water-dispersible polyaspartic ester resin and water-based polyurea coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109761834A CN109761834A (en) | 2019-05-17 |
| CN109761834B true CN109761834B (en) | 2021-10-22 |
Family
ID=66456650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910161992.9A Active CN109761834B (en) | 2019-03-05 | 2019-03-05 | Preparation method and application of water-dispersible polyaspartic ester resin and water-based polyurea coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109761834B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183335B (en) * | 2019-06-10 | 2022-07-12 | 万华化学集团股份有限公司 | Method for preparing polyaspartic acid ester |
| US11673997B2 (en) * | 2019-07-31 | 2023-06-13 | Covestro Llc | Work time to walk-on time ratio by adding a phenolic catalyst to polyaspartic flooring formulations |
| CN111019496B (en) * | 2019-12-16 | 2021-06-11 | 东南大学 | Water-dispersible two-component polyurea coating composition with excellent weather resistance and elasticity, preparation method and application thereof |
| CN111019497B (en) * | 2019-12-23 | 2021-05-07 | 复旦大学 | High-adhesion water-based polyurea colored paint and preparation method thereof |
| CN111635498B (en) * | 2020-05-11 | 2021-12-28 | 上海嘉宝莉涂料有限公司 | Modified polyurea and application thereof |
| CN111848921B (en) * | 2020-07-23 | 2022-05-27 | 深圳飞扬兴业科技有限公司 | Waterborne polyurethane resin for coating and preparation method thereof |
| CN111826066A (en) * | 2020-08-19 | 2020-10-27 | 陕西邦希化工有限公司 | Anticorrosive paint for petroleum pipeline and preparation method thereof |
| CN112079740B (en) * | 2020-09-18 | 2022-05-27 | 深圳飞扬兴业科技有限公司 | Synthesis method and application of asparagus resin and aqueous asparagus polyurea |
| CN112250817B (en) * | 2020-09-27 | 2022-09-23 | 深圳飞扬骏研新材料股份有限公司 | Synthesis method of water-based asparagus polyurea and application of water-based asparagus polyurea in seam beautifying agent |
| CN112778886B (en) * | 2021-01-06 | 2022-04-01 | 江苏凯伦建材股份有限公司 | Photo-curing two-component polyurea waterproof coating and preparation method thereof |
| CN112831263A (en) * | 2021-02-22 | 2021-05-25 | 郁维铭 | Double-component water-based automobile finishing varnish and application thereof |
| CN113150662B (en) * | 2021-04-02 | 2022-02-18 | 浙江艾特普科技有限公司 | PAE polyurea foaming flame-retardant heat-preservation high-strength coating |
| CN114133513A (en) * | 2021-11-11 | 2022-03-04 | 武汉工程大学 | Water-based polyaspartic acid ester dispersoid, preparation method thereof and water-based polyurea coating resin |
| CN113999598B (en) * | 2021-11-21 | 2022-06-17 | 江苏朗越环保科技有限公司 | Preparation method of bi-component water-based paint |
| CN113845826B (en) * | 2021-11-21 | 2022-03-15 | 常州威斯敦粘合材料有限责任公司 | Two-component water-based paint |
| CN113913095B (en) * | 2021-11-21 | 2022-04-22 | 大美泰康（天津）生态科技有限公司 | Environment-friendly antibacterial coating and preparation method thereof |
| CN114315621A (en) * | 2021-12-30 | 2022-04-12 | 深圳飞扬骏研新材料股份有限公司 | Aliphatic secondary amino ester resin and preparation method thereof |
| CN115141524A (en) * | 2022-08-09 | 2022-10-04 | 江苏海晟涂料有限公司 | Oil-resistant insulating water-based paint for metal surface |
| CN116855165A (en) * | 2023-07-14 | 2023-10-10 | 河北金坤工程材料有限公司 | High-performance polyurethane waterproof paint |
| CN117362587A (en) * | 2023-11-01 | 2024-01-09 | 张望清 | Single-component polyurethane modified epoxy resin emulsion and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5552516A (en) * | 1994-06-22 | 1996-09-03 | Donlar Corporation | Soluble, crosslinked polyaspartates |
| EP0826716A2 (en) * | 1996-08-23 | 1998-03-04 | Mitsubishi Chemical Corporation | Amine-modified polyaspartic acid or salt thereof and process for preparing the same |
| CN101589084A (en) * | 2006-12-18 | 2009-11-25 | Ppg工业俄亥俄公司 | (Meth)acrylate/aspartate amine curatives and coatings and articles comprising the same |
| CN109251643A (en) * | 2018-08-16 | 2019-01-22 | 游代华 | A kind of Polyaspartic Polyurea coating and its application |
| CN109320681A (en) * | 2018-11-05 | 2019-02-12 | 深圳飞扬兴业科技有限公司 | A kind of preparation method of polyaspartic ester resin |
-
2019
- 2019-03-05 CN CN201910161992.9A patent/CN109761834B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5552516A (en) * | 1994-06-22 | 1996-09-03 | Donlar Corporation | Soluble, crosslinked polyaspartates |
| EP0826716A2 (en) * | 1996-08-23 | 1998-03-04 | Mitsubishi Chemical Corporation | Amine-modified polyaspartic acid or salt thereof and process for preparing the same |
| CN101589084A (en) * | 2006-12-18 | 2009-11-25 | Ppg工业俄亥俄公司 | (Meth)acrylate/aspartate amine curatives and coatings and articles comprising the same |
| CN109251643A (en) * | 2018-08-16 | 2019-01-22 | 游代华 | A kind of Polyaspartic Polyurea coating and its application |
| CN109320681A (en) * | 2018-11-05 | 2019-02-12 | 深圳飞扬兴业科技有限公司 | A kind of preparation method of polyaspartic ester resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109761834A (en) | 2019-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109761834B (en) | Preparation method and application of water-dispersible polyaspartic ester resin and water-based polyurea coating | |
| CN109824555B (en) | Sulfamic acid and preparation method and application thereof | |
| KR101962054B1 (en) | Aqueous polyurethane-polyurea dispersion and aqueous base paint containing said dispersion | |
| CA2163544A1 (en) | Process for the preparation of polyurethane resins and their use and the use of ethoxyethyl propionate for the preparation of polyurethane resins | |
| US9416295B2 (en) | Aqueous autoxidisable coating composition | |
| JPH02103276A (en) | Method of using polyurethane resin for aqueous filler composition | |
| AU2012298508B2 (en) | Coating composition and use thereof | |
| US5589535A (en) | Air-drying polyurethane resins, their preparation and use | |
| KR20190047134A (en) | Aqueous polyurethane-polyurea dispersion and aqueous base paint containing said dispersion | |
| JP2003531258A (en) | Branched hydroxyl-functional polyester resins and their use in aqueous crosslinkable binder compositions | |
| JPH09241348A (en) | Aqueous polyurethane dispersion based on 1-methyl-2,4-and/or-2,6-diisocyanatocyclohexane and its use as glass fiber size | |
| KR101326338B1 (en) | Aqueous hydroxy-functional polyester dispersions containing urethane groups | |
| EP0654052A1 (en) | Polyol and polyisocyanate-based water-dilutable coating agent, process for preparing the same and its use | |
| CA2313373A1 (en) | Curable polyurethane polymer | |
| EP2121801A1 (en) | Water-dispersible, air-drying uralkyd resins | |
| KR100940452B1 (en) | Coating composition | |
| KR100446672B1 (en) | New Polyamines and Their Use in Coating Compositions | |
| US8337955B2 (en) | Aqueous coating composition comprising an autoxidisable amide group containing resin | |
| CN110862763A (en) | Quick-drying waterborne polyurethane color modifier and preparation method thereof | |
| CN101161747B (en) | Preparation method of polycaprolactone siloxane aqueous polyurethane paint for woodenware | |
| CN114716898B (en) | Interpenetrating network structure polyurethane modified acrylate self-cleaning strippable coating | |
| EP2744840B1 (en) | Coating composition and use thereof | |
| CN117925078A (en) | Coating suitable for compact coating and application thereof | |
| KR19980057237A (en) | Process for producing water-dispersible resin of acrylic-urethane-acrylic block copolymer and water-soluble coating composition containing same | |
| CN117510831A (en) | Water-dispersible polyaspartic acid ester resin, water-based automobile finishing varnish, and preparation methods and applications thereof |
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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190618 Address after: 215011 Room 1128 Building, Building A, 16 Hanjiang Road, Gulou District, Nanjing City, Jiangsu Province Applicant after: Yu Weiming Applicant after: Nanjing Blue Wind New Material Technology Co., Ltd. Address before: Room 1128, Building A, 16 Hanjiang Road, Gulou District, Nanjing City, Jiangsu Province Applicant before: Yu Weiming |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |