CN111892692B - Asparagus polyurea prepolymer, preparation method thereof and water-based paint - Google Patents

Asparagus polyurea prepolymer, preparation method thereof and water-based paint Download PDF

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CN111892692B
CN111892692B CN202010802224.XA CN202010802224A CN111892692B CN 111892692 B CN111892692 B CN 111892692B CN 202010802224 A CN202010802224 A CN 202010802224A CN 111892692 B CN111892692 B CN 111892692B
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water
polyurea prepolymer
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asparagus
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CN111892692A (en
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徐涛
杨轩
鲁晓东
李斌仁
龙绪俭
熊东路
肖增钧
陈林生
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Shenzhen Feiyang Junyan New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/6795—Unsaturated polyethers
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Abstract

The invention provides an asparagus polyurea prepolymer, a preparation method thereof and a waterproof water-based paint. The aspartic polyurea prepolymer is a reaction product formed by the reaction of polyfunctional acrylate, alicyclic diamine and maleic diester, has a plurality of reaction active sites, can improve the crosslinking density of a water-based aspartic polyurea system, and is matched with aspartic resin and a water-based isocyanate curing agent to form a water-resistant water-based coating film, and the cured film has good water resistance, high hardness, good flexibility and adhesive force.

Description

Asparagus polyurea prepolymer, preparation method thereof and water-based paint
Technical Field
The invention relates to the technical field of water-based paint, in particular to an asparagus polyurea prepolymer, a preparation method thereof and a water-resistant water-based paint.
Background
The polyaspartic acid ester polyurea is called third-generation polyurea, has excellent corrosion resistance, ultraviolet light resistance, acid and alkali resistance and good mechanical property, is slightly influenced by temperature, can be cured at low temperature, and has continuous and compact coating. The polyaspartic ester has low viscosity, so the polyaspartic ester polyurea coating has high construction solid content which is generally more than 70 percent, and is an energy-saving and environment-friendly coating.
With the development of the technology, the use of organic solvents can be further reduced by the water-based paint, the water-based paint is more environment-friendly, and construction equipment of the water-based paint is easy to clean. However, water-based paints also have their disadvantages, such as insufficient wetting and water resistance.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the water resistance of the water-based polyaspartic ester polyurea coating is improved.
In order to solve the technical problems, the invention adopts the technical scheme that:
an aspartyl polyurea prepolymer is a reaction product formed by reacting polyfunctional acrylate, alicyclic diamine and maleic diester.
Further, the multifunctional acrylate is
Figure BDA0002627823400000011
Wherein R is one or more of
Figure BDA0002627823400000021
Figure BDA0002627823400000022
N ranges from 2 to 20, n 1 Has a value range of 1 to 30,n 2 Has a value in the range of 1 to 30,n 3 Has a value in the range of 1 to 30 0 Is H or Me, R 1 Is H or Me; r is 2 Is composed of
Figure BDA0002627823400000023
One of (1), R 3 Is composed of
Figure BDA0002627823400000024
Wherein m is in the range of 1-30 6 Is H or Me; r is 4 Is composed of
Figure BDA0002627823400000025
P ranges from 1 to 30; r 5 Is composed of
Figure BDA0002627823400000026
Figure BDA0002627823400000027
One of (1), p 1 The value of (a) is in the range of 1 to 30.
Further, the alicyclic diamine is
Figure BDA0002627823400000028
Wherein R is 7 Is H or Me.
Further, the maleic acid diester is
Figure BDA0002627823400000029
Wherein R is 8 Is a straight chain or branched alkyl chain with 1-20 carbon atoms.
A preparation method of an aspartic polyurea prepolymer comprises the following steps:
the method comprises the following steps: under the condition of keeping out of the sun, controlling the temperature to be within the range of 40-50 ℃, slowly dripping polyfunctional acrylate into the alicyclic diamine for reaction, and obtaining an intermediate after the reaction is finished.
Step two: under the protection of inert gas, controlling the temperature within the range of 60-80 ℃, dripping the maleic diester into the intermediate for reaction, and obtaining the asparagus polyurea prepolymer after the reaction is finished.
Further, the molar amount of the multifunctional acrylate is n (A) The functionality is T; the molar weight of the alicyclic diamine is Z T n (A) The mole amount of the maleic acid diester is (2Z-1) T n (A) Wherein the value range of Z is 1-1.5.
Further, in the step one, before the multifunctional acrylate is dripped, a solvent for preventing reaction gelation is mixed into the alicyclic diamine, wherein the solvent is one or more of absolute ethyl alcohol, toluene, acetone or N, N-dimethylformamide.
Further, whether the reaction is finished or not is judged by detecting the primary amine value of the reaction solution: when the primary amine value of the reaction liquid in the step one reaches the theoretical residual primary amine value, judging that the reaction in the step one is finished; when the primary amine value of the reaction solution in the second step is 0, judging that the reaction in the second step is finished; after the reaction of step one was completed, the solvent was removed by evaporation under reduced pressure.
A waterproof water-based paint, which comprises the asparagus polyurea prepolymer, the asparagus polyurea resin and a water-based isocyanate curing agent; the weight ratio of the asparagus polyurea resin to the asparagus polyurea prepolymer is 1:0.1 to 2; the molar weight of-NCO in the water-based isocyanate curing agent is n (NCO) The total molar amount of-NH in the asparagus polyurea resin and the asparagus polyurea prepolymer is n (NH) Wherein n is (NCO) ：n (NH) ＝1.05-1.2。
Further, deionized water is added during mixing and stirred to form emulsion.
The invention has the beneficial effects that: the aspartic polyurea prepolymer formed by the reaction of polyfunctional acrylate, alicyclic diamine and maleic diester has a plurality of reactive sites, can improve the crosslinking density of a water-based aspartic polyurea system, is matched with aspartic resin and a water-based isocyanate curing agent to prepare a film, and the cured film has good water resistance, high hardness, good flexibility and good adhesive force.
Detailed Description
The most key concept of the invention is as follows: the crosslinking density of the two-component system is improved, so that the water resistance of a cured product is improved.
In order to further discuss the feasibility of the inventive concept, the detailed description of the technical contents, the construction characteristics, the objects and the effects according to the invention are explained in detail.
Example 1
An aspartic polyurea prepolymer is a reaction product formed by reacting a polyfunctional acrylate, a cycloaliphatic diamine and a maleic diester.
The multifunctional acrylate is
Figure BDA0002627823400000041
Wherein R is one or more of
Figure BDA0002627823400000042
Figure BDA0002627823400000043
N ranges from 2 to 20, n 1 Has a value range of 1 to 30,n 2 Has a value range of 1 to 30,n 3 Has a value in the range of 1 to 30 0 Is H or Me, R 1 Is H or Me; r 2 Is composed of
Figure BDA0002627823400000044
One of (1), R 3 Is composed of
Figure BDA0002627823400000045
Wherein m is in the range of 1-30 6 Is H or Me; r 4 Is composed of
Figure BDA0002627823400000046
P ranges from 1 to 30; r 5 Is composed of
Figure BDA0002627823400000047
Figure BDA0002627823400000048
One of (1), p 1 The value range of (A) is 1-30.
The alicyclic diamine is
Figure BDA0002627823400000049
Wherein R is 7 Is H or Me.
The maleic acid diester is
Figure BDA0002627823400000051
Wherein R is 8 Is a straight chain or branched alkyl chain with 1-20 carbon atoms. When used, the polymer can contain different chain lengths (R) 8 Chain) are used in combination.
Example 2
A preparation method of an aspartic polyurea prepolymer comprises the following steps:
the method comprises the following steps: under the condition of keeping out of the sun, controlling the temperature to be within the range of 40-50 ℃, slowly dripping the multifunctional acrylate into the alicyclic diamine for reaction, and obtaining an intermediate after the reaction is finished.
Step two: under the protection of inert gas, controlling the temperature within the range of 60-80 ℃, dripping the maleic diester into the intermediate for reaction, and obtaining the asparagus polyurea prepolymer after the reaction is finished.
The molar amount of the multifunctional acrylate is n (A) The functionality is T; the molar quantity of the alicyclic diamine is Z x T x n (A) The mole amount of the maleic acid diester is (2Z-1) T n (A) Wherein the value range of Z is 1-1.5. The dosage of the alicyclic diamine and the maleic diester is adjusted according to the functionality and the molar weight of the selected multifunctional acrylate.
In the first step, before the multifunctional acrylate is dripped, a solvent for preventing reaction gelation is further mixed into the alicyclic diamine, wherein the solvent is one or more of absolute ethyl alcohol, toluene, acetone or N, N-dimethylformamide. Observing the reaction process in the reaction process, and if the reaction still has a gelling tendency, continuously adding a proper amount of solvent.
Judging whether the reaction is finished or not by detecting the primary amine value of the reaction solution: when the primary amine value of the reaction liquid in the step one reaches the theoretical residual primary amine value, judging that the reaction in the step one is finished; when the primary amine value of the reaction solution in the second step is 0, judging that the reaction in the second step is finished; after the reaction of step one was completed, the solvent was removed by evaporation under reduced pressure. The theoretical residual primary amine value is the residual primary amine value after the reaction of the active sites of the multifunctional acrylate is completed.
Example 3
A waterproof water-based paint, which comprises the aspartic polyurea prepolymer, the aspartic polyurea resin and a water-based isocyanate curing agent; the weight ratio of the asparagus polyurea resin to the asparagus polyurea prepolymer is 1:0.1 to 2; the aqueous isocyanateThe molar amount of-NCO in the curing agent is n (NCO) The total molar amount of-NH in the asparagus polyurea resin and the asparagus polyurea prepolymer is n (NH) Wherein n is (NCO) ：n (NH) 1.05-1.2. When mixing, deionized water is also added and stirred to form emulsion.
To further discuss the beneficial effects of the present invention, the following test examples and test results are used for illustration:
test example 1
Synthesis of an aspartic polyurea prepolymer 1:
the method comprises the following steps: under the condition of keeping out of the sun, controlling the temperature to be 40-50 ℃, adding 200g of absolute ethyl alcohol into 1-methyl-2, 4-cyclohexanediamine, slowly dripping 198g of ethylene glycol dimethacrylate into 256.4g of 1-methyl-2, 4-cyclohexanediamine for reaction, stopping the reaction when the primary amine value of the reaction solution reaches the theoretical residual primary amine value of 171.2mg KOH/g, and evaporating under reduced pressure to remove the absolute ethyl alcohol to obtain an intermediate M1.
Step two: and under the protection of inert gas, controlling the temperature to be 60-80 ℃, dripping 172g of diethyl maleate into 227.2g of the intermediate M1 for reaction for 2-3 days, measuring the primary amine value of the reaction solution to be 0, stopping the reaction, and cooling to obtain the asparagus polyurea prepolymer 1.
The preparation method comprises the steps of mixing the asparagus polyurea prepolymer 1, the asparagus polyurea resin F520 and the self-made water-based isocyanate curing agent (NCO = 13%) according to the proportion of formulas (formulas 1 and 2) in the table 1, adding a certain amount of deionized water, stirring to form an emulsion, adjusting the solid content of the coating to 65%, coating the emulsion on tinplate, standing at room temperature to cure and form a film, and the performance result of the film is shown in the table 2.
Test example 2
Synthesis of an aspartic polyurea prepolymer 2:
the method comprises the following steps: under the condition of keeping out of the sun, controlling the temperature to be between 40 and 50 ℃, adding 100g of toluene into 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane, slowly dripping 198g of ethylene glycol dimethacrylate into 476.8g of 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane for reaction, stopping the reaction when the primary amine value of the reaction liquid reaches the theoretical residual primary amine value of 144.6mg KOH/g, and evaporating and removing the toluene by reduced pressure evaporation to obtain an intermediate M2.
Step two: and (3) under the protection of inert gas, controlling the temperature to be 60-80 ℃, dripping 172g of diethyl maleate into 337.4g of the intermediate M2 for reaction for 2-3 days, measuring the primary amine value of the reaction solution to be 0, stopping the reaction, and cooling to obtain the asparagus polyurea prepolymer 2.
The preparation method comprises the steps of matching an asparagus polyurea prepolymer 2, an asparagus polyurea resin F520 and a self-made water-based isocyanate curing agent (NCO = 13%) according to the proportion of formulas (formulas 3 and 4) in the table 1, adding a certain amount of deionized water, stirring to form an emulsion, adjusting the solid content of the coating to 65%, coating the emulsion on a tinplate, standing at room temperature, curing to form a film, and obtaining the performance result of the film shown in the table 2.
Test example 3
Synthesis of an aspartic polyurea prepolymer 3:
the method comprises the following steps: under the condition of keeping out of the sun, controlling the temperature to be between 40 and 50 ℃, adding 150g of acetone into the 1-methyl-2, 4-cyclohexanediamine, slowly dripping 300.3g of tripropylene glycol diacrylate into 256.4g of the 1-methyl-2, 4-cyclohexanediamine for reaction, stopping the reaction when the primary amine value of the reaction solution reaches the theoretical residual primary amine value of 158.5mg KOH/g, and evaporating the acetone under reduced pressure to obtain an intermediate M3.
Step two: and (3) under the protection of inert gas, controlling the temperature to be 60-80 ℃, dripping 172g of diethyl maleate into 278.3g of the intermediate M3 for reaction for 2-3 days, measuring the primary amine value of the reaction solution to be 0, stopping the reaction, and cooling to obtain the asparagus polyurea prepolymer 3.
The preparation method comprises the steps of matching an asparagus polyurea prepolymer 3, an asparagus polyurea resin F520 and a self-made water-based isocyanate curing agent (NCO = 13%) according to the proportion of formulas (formulas 5 and 6) in the table 1, adding a certain amount of deionized water, stirring to form an emulsion, adjusting the solid content of the coating to 65%, coating the emulsion on tinplate, standing at room temperature to cure and form a film, and the performance result of the film is shown in the table 2.
Test example 4
Synthesis of an aspartic polyurea prepolymer 4:
the method comprises the following steps: under the dark condition, controlling the temperature to be 40-50 ℃, adding 100gN, N-dimethylformamide into 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane, slowly dripping 300.3g of tripropylene glycol diacrylate into 476.8g of 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane for reaction, measuring that the primary amine value of the reaction liquid reaches the theoretical residual primary amine value of 127.7mg KOH/g, stopping the reaction, and evaporating under reduced pressure to remove the N, N-dimethylformamide to obtain an intermediate M4.
Step two: and (3) under the protection of inert gas, controlling the temperature to be 60-80 ℃, dripping 172g of diethyl maleate into 388.5g of the intermediate M4 for reaction for 2-3 days, measuring the primary amine value of the reaction solution to be 0, stopping the reaction, and cooling to obtain the asparagus polyurea prepolymer 4.
The preparation method comprises the steps of matching an asparagus polyurea prepolymer 4, an asparagus polyurea resin F520 and a self-made water-based isocyanate curing agent (NCO = 13%) according to the proportion of formulas (formulas 7 and 8) in the table 1, adding a certain amount of deionized water, stirring to form an emulsion, adjusting the solid content of the coating to 65%, coating the emulsion on a tinplate, standing at room temperature, curing to form a film, and obtaining the performance result of the film shown in the table 2.
Test example 5
Synthesis of an aspartic polyurea prepolymer 5:
the method comprises the following steps: and (2) under the condition of keeping out of the sun, controlling the temperature to be between 40 and 50 ℃, adding 100g of absolute ethyl alcohol into the 1-methyl-2, 4-cyclohexanediamine, slowly dripping 296.3g of trimethylolpropane triacrylate into 384.6g of the 1-methyl-2, 4-cyclohexanediamine for reaction, stopping the reaction when the primary amine value of the reaction solution reaches the theoretical residual primary amine value of 215.2mg KOH/g, and evaporating under reduced pressure to remove the absolute ethyl alcohol to obtain an intermediate M5.
Step two: and (3) under the protection of inert gas, controlling the temperature to be 60-80 ℃, dripping 172g of diethyl maleate into 227g of the intermediate M5 for reaction for 2-3 days, measuring the primary amine value of the reaction solution to be 0, stopping the reaction, and cooling to obtain the asparagus polyurea prepolymer 5.
The preparation method comprises the steps of matching an asparagus polyurea prepolymer 5, an asparagus polyurea resin F520 and a self-made water-based isocyanate curing agent (NCO = 13%) according to the proportion of formulas (formulas 9 and 10) in the table 1, adding a certain amount of deionized water, stirring to form an emulsion, adjusting the solid content of the coating to 65%, coating the emulsion on a tinplate, standing at room temperature, curing to form a film, and obtaining the performance result of the film shown in the table 2.
Test example 6
Synthesis of an aspartic polyurea prepolymer 6:
the method comprises the following steps: under the dark condition, the temperature is controlled to be 40-50 ℃, 150g of absolute ethyl alcohol is added into 3, 3-dimethyl-4, 4-diaminodicyclohexyl methane, 296.3g of trimethylolpropane triacrylate is slowly dropped into 715.2g of 3, 3-dimethyl-4, 4-diaminodicyclohexyl methane for reaction, the reaction is stopped when the primary amine value of the reaction solution reaches the theoretical residual primary amine value of 144.6mg KOH/g, and the absolute ethyl alcohol is evaporated under reduced pressure to obtain an intermediate M6.
Step two: and (3) controlling the temperature to be 60-80 ℃ under the protection of inert gas, dripping 172g of diethyl maleate into 337.1g of the intermediate M6 for reaction for 2-3 days, measuring the primary amine value of the reaction solution to be 0, stopping the reaction, and cooling to obtain the asparagus polyurea prepolymer 6.
The preparation method comprises the steps of matching an asparagus polyurea prepolymer 6, an asparagus polyurea resin F520 and a self-made water-based isocyanate curing agent (NCO = 13%) according to the proportion of formulas (formulas 11 and 12) in the table 1, adding a certain amount of deionized water, stirring to form an emulsion, adjusting the solid content of the coating to 65%, coating the emulsion on a tinplate, standing at room temperature, curing to form a film, and obtaining the performance result of the film shown in the table 2.
Comparative example
The preparation method comprises the steps of matching the asparagus polyurea resin F520 and the self-made water-based isocyanate curing agent (NCO = 13%) according to the proportion of the formula (formula 13) in the table 1, adding a certain amount of deionized water, stirring to form emulsion, adjusting the solid content of the coating to 65%, coating the emulsion on tinplate, standing at room temperature, curing and forming a film, wherein the performance result of the film is shown in the table 2.
Formulations in Table 1, according to n (NCO) :n (NH) And (5) blending the mixture until the ratio is 1.05. In addition to the aspartic polyurea resin F520 and the self-made aqueous isocyanate curing agent (NCO = 13%) used in the above test examples 1-6, other aspartic polyurea resins and aqueous isocyanate curing agents may be used according to the weight ratio of the aspartic polyurea resin to the aspartic polyurea prepolymer of 1:0.1-2, n in the coating (NCO) ：n (NH) The ratio of =1.05-1.2.
Table 1 test water-based paint formula table
Figure BDA0002627823400000091
TABLE 2 film Performance test results of water-based paint after film coating
Figure BDA0002627823400000101
As is clear from the results in tables 1 and 2, the aspartyl polyurea prepolymer formed by the reaction of polyfunctional acrylate, cycloaliphatic diamine and maleic diester according to the present invention has a plurality of reactive sites, and can increase the crosslinking density of the aqueous aspartyl polyurea two-component system, reduce the activation time, and improve the water resistance of the cured film. The water-based paint prepared by mixing the asparaguese polyurea prepolymer, the asparaguese polyurea resin and the water-based isocyanate curing agent film has better water resistance, higher hardness, better flexibility and better adhesive force.
The above description is only an embodiment of the present invention, and is not intended to limit the scope of the present invention, and all equivalent structures or equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are also included in the scope of the present invention.

Claims (5)

1. An aspartic polyurea prepolymer is characterized by being a reaction product formed by reacting multifunctional acrylate, a dibasic alicyclic amine and a maleic diester;
the multifunctional acrylate is
Figure FDA0003801366500000011
Wherein R is one or more of
Figure FDA0003801366500000012
Figure FDA0003801366500000013
N is in the range of 2-20, and n1 is in the range of1-30, n2 ranges from 1-30, n3 ranges from 1-30, R0 is H or Me, and R1 is Me; r2 is
Figure FDA0003801366500000014
One of (1), R 3 Is composed of
Figure FDA0003801366500000015
Wherein m ranges from 1 to 30, R 6 Is H or Me; r 4 Is composed of
Figure FDA0003801366500000016
P ranges from 1 to 30; r 5 Is composed of
Figure FDA0003801366500000017
Figure FDA0003801366500000018
One of (1), p 1 The value range of (1) to (30);
the alicyclic diamine is
Figure FDA0003801366500000019
Figure FDA0003801366500000021
Wherein R is 7 Is H or Me;
the maleic acid diester is
Figure FDA0003801366500000022
Wherein R is 8 Is a straight chain or branched alkyl chain with 1-20 carbon atoms;
the preparation method of the aspartic polyurea prepolymer comprises the following steps:
the method comprises the following steps: under the condition of keeping out of the sun, controlling the temperature to be within the range of 40-50 ℃, slowly dripping polyfunctional acrylate into the alicyclic diamine for reaction, and obtaining an intermediate after the reaction is finished;
step two: under the protection of inert gas, controlling the temperature within the range of 60-80 ℃, dripping the maleic diester into an intermediate to react, and obtaining an asparagus polyurea prepolymer after the reaction is finished;
the molar amount of the multifunctional acrylate is n (A) The functionality is T; the molar weight of the alicyclic diamine is Z T n (A) The mole amount of the maleic acid diester is (2Z-1) T n (A) Wherein the value range of Z is 1-1.5;
in the first step, before the multifunctional acrylate is dripped, a solvent for preventing reaction gelation is also mixed into the alicyclic diamine, wherein the solvent is one or more of absolute ethyl alcohol, toluene, acetone or N, N-dimethylformamide.
2. The method of preparing an aspartyl polyurea prepolymer according to claim 1, comprising the step of:
the method comprises the following steps: under the condition of keeping out of the sun, controlling the temperature to be within the range of 40-50 ℃, slowly dripping polyfunctional acrylate into the alicyclic diamine for reaction, and obtaining an intermediate after the reaction is finished;
step two: under the protection of inert gas, controlling the temperature within the range of 60-80 ℃, dripping the maleic diester into the intermediate for reaction, and obtaining an aspartic polyurea prepolymer after the reaction is finished;
the molar amount of the multifunctional acrylate is n (A) And a functionality of T; the molar quantity of the alicyclic diamine is Z x T x n (A) The mole amount of the maleic acid diester is (2Z-1) T n (A) Wherein the value range of Z is 1-1.5;
in the first step, before the multifunctional acrylate is dripped, a solvent for preventing reaction gelation is also mixed into the alicyclic diamine, wherein the solvent is one or more of absolute ethyl alcohol, toluene, acetone or N, N-dimethylformamide.
3. The method of preparing an aspartyl polyurea prepolymer as claimed in claim 2, wherein the reaction is judged to be completed by detecting the primary amine value of the reaction solution: when the primary amine value of the reaction liquid in the step one reaches the theoretical residual primary amine value, judging that the reaction in the step one is finished; when the primary amine value of the reaction solution in the second step is 0, judging that the reaction in the second step is finished; after the reaction of step one was completed, the solvent was removed by evaporation under reduced pressure.
4. A water-resistant water-based paint, which is characterized by comprising the aspartic polyurea prepolymer, the aspartic polyurea resin and a water-based isocyanate curing agent according to claim 1; the weight ratio of the asparagus polyurea resin to the asparagus polyurea prepolymer is 1:0.1-2; the molar weight of-NCO in the water-based isocyanate curing agent is n (NCO) The total molar amount of-NH in the asparagus polyurea resin and the asparagus polyurea prepolymer is n (NH) Wherein n is (NCO) ：n (NH) ＝1.05-1.2。
5. The water-resistant waterborne coating of claim 4, wherein deionized water is further added and stirred into an emulsion during mixing.
CN202010802224.XA 2020-08-11 2020-08-11 Asparagus polyurea prepolymer, preparation method thereof and water-based paint Active CN111892692B (en)

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