Root-puncture-resistant radix asparagi polyurea coating resin, preparation method thereof and coating prepared from root-puncture-resistant radix asparagi polyurea coating resin

Abstract

The invention discloses root puncture resistant radix asparagi polyurea coating resin, a preparation method thereof and a prepared coating, and relates to the field of coatings. The root-puncture-resistant radix asparagi polyurea coating resin is obtained by performing esterification reaction on (R)-2-(4-chloro-2-methyl phenoxy) propionic acid and an acrylate monomer containing hydroxyl to obtain an intermediate and then performing Michael reaction on the intermediate and fatty amine, and the molecular structure of the root-puncture-resistant radix asparagi polyurea coating resin contains (R)-2-(4-chloro-2-methyl phenoxy) propionic acid group and at least one imino group. According to the invention, the active group (R)-2-(4-chloro-2-methyl phenoxy) propionic acid in the root inhibitor is grafted to the asparagine polyurea coating resin through a chemical reaction mode, so that the problems of compatibility and dispersity of the root inhibitor (R)-2-(4-chloro-2-methyl phenoxy) propionic acid and the asparagine polyurea coating resin are solved; the root puncture resistant radix asparagi polyurea coating resin has stable root puncture resistance.

Description

Technical Field

[0001] The present application relates to the field of coatings, and in particular to a root-penetration-resistant asparagine polyurea coating resin, a preparation method thereof, and the resulting coating. Background Art

[0002] With the development of the construction industry and the continuous improvement of waterproofing requirements, waterproofing projects occupy a vital position in many fields. Asparagus polyurea, as a new type of two-component polyurea material, has been widely used in the waterproofing field because of its superior properties such as weather resistance, aging resistance, convenient construction, strong adhesion, high elasticity and toughness, low temperature resistance, acid and alkali resistance, etc.

[0003] However, in some specific occasions, such as dams, ponds and other environments with vegetation, it is not enough to have only waterproof function, and the material is also required to have root penetration resistance function. At present, root penetration-resistant waterproof materials are mainly divided into two categories: root penetration-resistant waterproof membranes and root penetration-resistant waterproof coatings. These materials usually achieve root barrier properties by adding chemical root inhibitors. Among them, the main component of the chemical root inhibitor is 2-(4-chloro-2-methylphenoxy) propionic acid ester derivatives, and its root barrier active group is mainly (R)-2-(4-chloro-2-methylphenoxy) propionic acid part. When the plant root system comes into contact with the active group, the active group interacts with the plant cell wall, inhibiting the main root system from absorbing surrounding nutrients and water, thereby inhibiting the growth of the main root.

[0004] However, the existing method of achieving root barrier performance by adding chemical root barrier agents has the following problems: the chemical root barrier agent exists in the material in the form of a physical mixture, which makes it difficult to ensure the uniformity of the mixture. Uneven mixing may result in good root barrier effects in some areas and poor effects in other areas, affecting the overall root puncture prevention performance. Summary of the invention

[0005] In order to improve the problem in the related art that when the root inhibitor is directly added to the asparagus resin coating, the root inhibitor is difficult to mix evenly and good root inhibition performance cannot be achieved, the present application provides a root penetration resistant asparagus polyurea coating resin, a preparation method thereof and the resulting coating.

[0006] In the first aspect, the present application provides a root penetration resistant asparagus polyurea coating resin adopts the following technical solution: A root-penetration-resistant asparagine polyurea coating resin is obtained by esterifying (R)-2-(4-chloro-2-methylphenoxy)propionic acid and a hydroxyl-containing acrylate monomer under the action of a catalyst to obtain an intermediate, and then reacting the intermediate with a fatty amine to obtain the intermediate through Michael reaction. The molecular structure of the root-penetration-resistant asparagine polyurea coating resin contains a (R)-2-(4-chloro-2-methylphenoxy)propionic acid group and at least one imine group.

[0007] The root penetration resistant asparagine polyurea coating resin in the present application grafts the active group (R)-2-(4-chloro-2-methylphenoxy)propionic acid in the root inhibitor onto the asparagine polyurea coating resin by chemical reaction, thereby solving the compatibility and dispersibility problems of the root inhibitor (R)-2-(4-chloro-2-methylphenoxy)propionic acid and the asparagine polyurea coating resin, so that the root penetration resistant asparagine polyurea coating resin has stable root penetration resistance and will not migrate or fail with environmental changes.

[0008] Preferably, the molar ratio of (R)-2-(4-chloro-2-methylphenoxy)propionic acid to hydroxyalkyl acrylate is 1:(1-3).

[0009] More preferably, the molar ratio of (R)-2-(4-chloro-2-methylphenoxy)propionic acid to hydroxyalkyl acrylate is 1:(1-2).

[0010] Taking the cost into consideration, it is further preferred that the molar ratio of the (R)-2-(4-chloro-2-methylphenoxy)propionic acid to the hydroxyalkyl acrylate is 1:(1-1.5).

[0011] In some specific embodiments, the hydroxyl group-containing acrylic acid ester monomer is at least one of a hydroxyalkyl acrylate monomer or a hydroxyalkyl methacrylate monomer.

[0012] The hydroxyalkyl acrylate monomers include but are not limited to hydroxyethyl acrylate and hydroxypropyl acrylate, and the hydroxyalkyl methacrylate monomers include but are not limited to hydroxyethyl methacrylate and hydroxypropyl methacrylate.

[0013] In some specific embodiments, the catalyst is at least one of sulfuric acid, trifluoromethanesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, and dibutyltin dilaurate.

[0014] Preferably, the catalyst is p-toluenesulfonic acid, which has a good catalytic effect and causes little corrosion to equipment.

[0015] In some specific embodiments, the amount of the catalyst used is 0.05 to 1% (by weight) of the sum of the amounts of (R)-2-(4-chloro-2-methylphenoxy)propionic acid and the hydroxyl-containing acrylate monomer.

[0016] Preferably, the amount of the catalyst used is 0.05 to 0.5% (by weight) of the sum of the amounts of (R)-2-(4-chloro-2-methylphenoxy)propionic acid and the hydroxyl-containing acrylate monomer.

[0017] Taking the cost into consideration, more preferably, the amount of the catalyst used is 0.05-0.3% (by weight) of the sum of the amounts of (R)-2-(4-chloro-2-methylphenoxy)propionic acid and the hydroxyl-containing acrylate monomer.

[0018] Preferably, the molar ratio of the unsaturated double bonds in the intermediate to the amino groups in the fatty amine is (1-1.05):1, and more preferably, the molar ratio of the unsaturated double bonds in the intermediate to the amino groups in the fatty amine is (1.01-1.05):1, so as to reduce the residual fatty amine.

[0019] In some specific embodiments, the fatty amine is at least one of monobasic fatty amine, dibasic fatty amine, and tribasic fatty amine.

[0020] Preferably, the fatty amine is a dibasic fatty amine.

[0021] The dibasic fatty amine is at least one of HMDA (1,6-hexanediol), DMDC (dimethyl diethyl ammonium chloride), polyetheramine D230 and polyetheramine D400.

[0022] In the second aspect, the present application provides a method for preparing a root puncture resistant asparagus polyurea coating resin using the following technical scheme: A method for preparing a root-penetration-resistant asparagine polyurea coating resin, which is used to prepare any of the above-mentioned root-penetration-resistant asparagine polyurea coating resins, comprises the following steps: (R)-2-(4-chloro-2-methylphenoxy)propionic acid, a hydroxyl-containing acrylic acid ester monomer, a catalyst and a polymerization inhibitor are added to a solvent, the temperature is raised to 60-120° C., and the heated reflux is performed to perform an esterification reaction, and the generated water is discharged during the reaction. After the reaction is completed, an organic phase is extracted and separated, and then the organic phase is washed and dried, and finally concentrated under reduced pressure to obtain an intermediate; The intermediate is added to a fatty amine, and under nitrogen protection, the temperature is raised to 90-140° C. to carry out Michael reaction to obtain a root penetration resistant asparagine polyurea coating resin.

[0023] In the present application, the carboxylic acid group in (R)-2-(4-chloro-2-methylphenoxy)propionic acid and the hydroxyl group in the hydroxyl-containing acrylate monomer undergo an esterification reaction under the action of a catalyst to generate an intermediate containing a (R)-2-(4-chloro-2-methylphenoxy)propionic acid group and an unsaturated double bond. The intermediate then undergoes a Michael reaction with a fatty amine to obtain an asparagine polyurea resin containing a root-blocking active group in its structure, i.e., a root-penetration-resistant asparagine polyurea coating resin. The root-penetration-resistant asparagine polyurea coating resin grafts the root-blocking active group (R)-2-(4-chloro-2-methylphenoxy)propionic acid in the root inhibitor onto the asparagine polyurea coating resin by chemical reaction, thereby solving the compatibility and dispersibility problems of the root inhibitor (R)-2-(4-chloro-2-methylphenoxy)propionic acid and the asparagine polyurea coating resin, and making the root-penetration-resistant asparagine polyurea coating resin have stable root-penetration-resistant performance.

[0024] Preferably, the temperature of the esterification reaction is 80-100°C; more preferably, the temperature of the esterification reaction is 80-90°C.

[0025] Preferably, the esterification reaction time is 6-16 h; more preferably, the esterification reaction time is 8-12 h; further preferably, the esterification reaction time is 8-10 h.

[0026] Preferably, the reaction temperature of the Michael reaction is 90-120°C.

[0027] Preferably, the Michael reaction lasts for 3-6 days; more preferably, the Michael reaction lasts for 4-5 days.

[0028] In the third aspect, the root penetration resistant asparagus polyurea coating provided in the present application adopts the following technical solution: A root penetration resistant asparagus polyurea coating comprises a main agent and an isocyanate curing agent, wherein the main agent is a composition of any one of the above root penetration resistant asparagus polyurea coating resins and a conventional asparagus resin on the market in a weight ratio of 1:(0-5), and the molar ratio of the imino group in the main agent to the isocyanate group in the isocyanate curing agent is 1:(1-1.05).

[0029] In the present application, the root penetration resistant asparagus polyurea coating is a two-component coating comprising a main agent and an isocyanate curing agent, wherein the root penetration resistant asparagus polyurea coating resin can be directly used as the main agent of the root penetration resistant asparagus polyurea coating, or a composition of a specific ratio of the root penetration resistant asparagus polyurea coating resin and conventional asparagus resin on the market can be used as the main agent according to the different root systems of plants to adjust the root penetration resistance effect of the coating while taking into account the cost of the root penetration resistant asparagus polyurea coating.

[0030] In summary, this application at least includes the following beneficial technical effects: (1) The root penetration resistant asparagine polyurea coating resin in the present application grafts the active group (R)-2-(4-chloro-2-methylphenoxy)propionic acid in the root inhibitor onto the asparagine polyurea coating resin by chemical reaction, thereby solving the compatibility and dispersibility problems between the root inhibitor (R)-2-(4-chloro-2-methylphenoxy)propionic acid and the asparagine polyurea coating resin, making the root penetration resistant asparagine polyurea coating resin have stable root penetration resistance and will not migrate or fail with environmental changes, thereby increasing the function of the asparagine polyurea resin and broadening the application field of the asparagine polyurea resin.

[0031] (2) The preparation method of the root penetration resistant asparagus polyurea coating resin in the present application is simple, the reaction conditions are mild, and it can be used directly without additional special post-treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 It is the molecular formula of the intermediate (R)-2-(4-chloro-2-methylphenoxy)propionic acid methacrylate of Example 1.

[0033] Figure 2 is the hydrogen nuclear magnetic resonance spectrum of the intermediate (R)-2-(4-chloro-2-methylphenoxy)propionic acid-methylacrylate of Example 1, wherein: δ7.19-7.12(m,2H), Figure 1 The H near the chlorine element on the benzene ring at positions 1 and 3; δ6.87 (d, J = 8.3 Hz, 1H), Figure 1 H on the benzene ring at position 2; δ5.96 (dq, J = 2.0, 1.3 Hz, 1H), Figure 1 At position 10, H on the double bond; δ5.65 (dt, J = 2.2, 1.4 Hz, 1H), Figure 1 At position 10, H on the double bond; δ4.86 (q, J = 6.6 Hz, 1H), Figure 1 H at position 6; δ4.49-4.37(m,2H), Figure 1 2 Hs at position 7; δ4.35-4.29(m,2H), Figure 1 2 Hs at position 8; δ 2.25 (d, J = 0.6 Hz, 3H), Figure 1 At position 4, 3 H on the methyl group of the benzene ring; δ1.92 (t, J = 1.5 Hz, 3H), Figure 1At position 9, 3 H on the acrylic acid methyl group; δ1.53 (d, J=6.6 Hz, 3H), Figure 1 At position 19, 3 Hs on the methyl group. DETAILED DESCRIPTION

[0034] The present application is further described below in conjunction with specific experiments. Example

[0035] [Example 1] A root penetration resistant asparagine polyurea coating resin, the preparation method of which comprises the following steps: S1. Add 42.9 g (0.2 mol) (R)-2-(4-chloro-2-methylphenoxy) propionic acid, 32.5 g (0.25 mol) hydroxyethyl methacrylate, 0.4 g inhibitor HQ, and 0.5 g p-toluenesulfonic acid into 100 mL solvent toluene, heat to 80°C and reflux to carry out esterification reaction. During the reaction, the generated water is discharged to allow the reaction to proceed in the direction of the product. Then, the reaction progress was tracked by gas chromatography every hour. When the amount of (R)-2-(4-chloro-2-methylphenoxy)propionic acid no longer changed (about 6h), the temperature of the reaction system was lowered to room temperature, water was added and stirred for 25min, and extracted with dichloromethane 3 times. The organic phases were combined, and the organic phases were backwashed 3 times with a 5% aqueous NaOH solution and a 20% aqueous NaCl solution. Then, anhydrous sodium sulfate was added to absorb the residual water in the organic phase, and finally filtered and concentrated under reduced pressure to obtain 60.0g (theoretical 68.9g) of a light yellow oily intermediate. In this embodiment, the intermediate is specifically (R)-2-(4-chloro-2-methylphenoxy)propionic acid-methylacrylate.

[0036] S2. 18.0 g of dibasic fatty amine HMDA was added to the above-mentioned (R)-2-(4-chloro-2-methylphenoxy) propionic acid-methyl acrylate, and the temperature was raised to 80° C. under nitrogen protection, and the reaction was carried out for 3 days, and then the temperature was raised to 90° C. and the reaction was carried out for 1 day, and finally the temperature was cooled to room temperature to obtain a root penetration-resistant asparagus polyurea coating resin.

[0037] [Example 2] A root penetration resistant asparagine polyurea coating resin, the preparation method of which comprises the following steps: S1. Add 42.9 g (0.2 mol) (R)-2-(4-chloro-2-methylphenoxy) propionic acid, 29.0 g (0.25 mol) hydroxyethyl acrylate, 0.4 g inhibitor HQ, and 0.5 g p-toluenesulfonic acid into 100 mL solvent toluene, heat to 80°C and reflux to carry out esterification reaction. During the reaction, the generated water is discharged to allow the reaction to proceed in the direction of the product. Then, the reaction progress was tracked by gas chromatography every hour. When the amount of (R)-2-(4-chloro-2-methylphenoxy)propionic acid no longer changed (about 6 hours), the temperature of the reaction system was lowered to room temperature, water was added and stirred for 25 minutes, and extracted with dichloromethane three times. The organic phases were combined, and the organic phases were backwashed three times with a 5% aqueous NaOH solution and a 20% aqueous NaCl solution. Then, anhydrous sodium sulfate was added to absorb the residual water in the organic phase, and finally filtered and concentrated under reduced pressure to obtain 58.8 g (theoretical 66.1 g) of a light yellow oily intermediate. In this embodiment, the intermediate is specifically (R)-2-(4-chloro-2-methylphenoxy)propionic acid acrylate.

[0038] S2. 18.4 g of dibasic fatty amine HMDA was added to the above-mentioned (R)-2-(4-chloro-2-methylphenoxy) propionic acid acrylate, and the temperature was raised to 80° C. under nitrogen protection, and the reaction was carried out for 3 days, and then the temperature was raised to 90° C. and the reaction was carried out for 1 day, and finally the temperature was cooled to room temperature to obtain a root penetration resistant asparagus polyurea coating resin.

[0039] [Example 3] A root penetration resistant asparagus polyurea coating resin, which differs from [Example 1] in that: S1. Add 42.9 g (0.2 mol) (R)-2-(4-chloro-2-methylphenoxy) propionic acid, 32.5 g (0.25 mol) hydroxyethyl methacrylate, 0.4 g inhibitor HQ, and 0.5 g p-toluenesulfonic acid into 100 mL solvent toluene, heat to 80°C and reflux to carry out esterification reaction. During the reaction, the generated water is discharged to allow the reaction to proceed in the direction of the product. Then, the reaction progress was tracked by gas chromatography every hour. When the amount of (R)-2-(4-chloro-2-methylphenoxy)propionic acid no longer changed (about 6h), the temperature of the reaction system was lowered to room temperature, water was added and stirred for 25min, and extracted with dichloromethane 3 times. The organic phases were combined, and the organic phases were backwashed 3 times with a 5% aqueous NaOH solution and a 20% aqueous NaCl solution. Then, anhydrous sodium sulfate was added to absorb the residual water in the organic phase, and finally filtered and concentrated under reduced pressure to obtain 58.5g (theoretical 68.9g) of a light yellow oily intermediate. In this embodiment, the intermediate is specifically (R)-2-(4-chloro-2-methylphenoxy)propionic acid-methylacrylate.

[0040] S2. 17.5 g of dibasic fatty amine HMDA was added to the above-mentioned (R)-2-(4-chloro-2-methylphenoxy) propionic acid-methyl acrylate, and the temperature was raised to 80° C. under nitrogen protection, and the reaction was carried out for 3 days, and then the temperature was raised to 90° C. and the reaction was carried out for 1 day, and finally the temperature was cooled to room temperature to obtain a root-penetration-resistant asparagus polyurea coating resin.

[0041] [Example 4] A root penetration resistant asparagine polyurea coating resin, the preparation method of which comprises the following steps: S1. Add 42.9 g (0.2 mol) (R)-2-(4-chloro-2-methylphenoxy) propionic acid, 32.5 g (0.25 mol) hydroxyethyl methacrylate, 0.4 g polymerization inhibitor HQ and 0.4 g sulfuric acid into 100 mL toluene solvent, heat to 80°C and reflux to carry out esterification reaction. During the reaction, the generated water is discharged to make the reaction proceed in the direction of product. Then, the reaction progress was tracked by gas chromatography every hour. When the amount of (R)-2-(4-chloro-2-methylphenoxy)propionic acid no longer changed (about 6 hours), the temperature of the reaction system was lowered to room temperature, water was added and stirred for 25 minutes, and the mixture was extracted with dichloromethane for 3 times. The organic phases were combined, and the organic phases were backwashed 3 times with a 5% aqueous NaOH solution and a 20% aqueous NaCl solution. Then, anhydrous sodium sulfate was added to absorb the residual water in the organic phase, and the mixture was filtered and concentrated under reduced pressure to obtain 60.6 g (theoretical 68.9 g) of a light yellow oily intermediate. In this embodiment, the intermediate is specifically (R)-2-(4-chloro-2-methylphenoxy)propionic acid-methylacrylate.

[0042] S2. 18.3 g of dibasic fatty amine HMDA was added to the above-mentioned (R)-2-(4-chloro-2-methylphenoxy) propionic acid-methyl acrylate, and the temperature was raised to 80° C. under nitrogen protection, and the reaction was carried out for 3 days, and then the temperature was raised to 90° C. and the reaction was carried out for 1 day, and finally the temperature was cooled to room temperature to obtain a root penetration-resistant asparagus polyurea coating resin.

[0043] [Example 5] A root penetration resistant asparagine polyurea coating resin, the preparation method of which comprises the following steps: S1. Add 42.9 g (0.2 mol) (R)-2-(4-chloro-2-methylphenoxy) propionic acid, 29.0 g (0.25 mol) hydroxyethyl acrylate, 0.4 g polymerization inhibitor HQ and 0.4 g sulfuric acid into 100 mL toluene solvent, heat to 80°C and reflux to carry out esterification reaction. During the reaction, the generated water is discharged to make the reaction proceed in the direction of product. Then, the reaction progress was tracked by gas chromatography every hour. When the amount of (R)-2-(4-chloro-2-methylphenoxy)propionic acid no longer changed (about 6 hours), the temperature of the reaction system was lowered to room temperature, water was added and stirred for 25 minutes, and extracted with dichloromethane three times. The organic phases were combined, and the organic phases were backwashed three times with a 5% NaOH aqueous solution and a 20% NaCl aqueous solution. Then, anhydrous sodium sulfate was added to absorb the residual water in the organic phase, and finally filtered and concentrated under reduced pressure to obtain 60.1 g (theoretical 66.1 g) of a light yellow oily intermediate. In this embodiment, the intermediate is specifically (R)-2-(4-chloro-2-methylphenoxy)propionic acid acrylate.

[0044] S2. 18.8 g of dibasic fatty amine HMDA was added to the above-mentioned (R)-2-(4-chloro-2-methylphenoxy) propionic acid acrylate, and the temperature was raised to 80° C. under nitrogen protection, and the reaction was carried out for 3 days, and then the temperature was raised to 90° C. and the reaction was carried out for 1 day, and finally the temperature was cooled to room temperature to obtain a root penetration resistant asparagus polyurea coating resin.

[0045] [Example 6] A root penetration resistant asparagine polyurea coating resin, the preparation method of which comprises the following steps: S1. Add 42.9 g (0.2 mol) (R)-2-(4-chloro-2-methylphenoxy) propionic acid, 32.5 g (0.25 mol) hydroxyethyl methacrylate, 0.4 g polymerization inhibitor HQ and 0.4 g sulfuric acid into 100 mL toluene solvent, heat to 80°C and reflux to carry out esterification reaction. During the reaction, the generated water is discharged to make the reaction proceed in the direction of product. Then, the reaction progress was tracked by gas chromatography every hour. When the amount of (R)-2-(4-chloro-2-methylphenoxy)propionic acid no longer changed (about 6 hours), the temperature of the reaction system was lowered to room temperature, water was added and stirred for 25 minutes, and extracted with dichloromethane three times. The organic phases were combined, and the organic phases were backwashed three times with a 5% aqueous NaOH solution and a 20% aqueous NaCl solution. Then, anhydrous sodium sulfate was added to absorb the residual water in the organic phase, and finally filtered and concentrated under reduced pressure to obtain 57.2 g (theoretical 68.9 g) of a light yellow oily intermediate. In this embodiment, the intermediate is specifically (R)-2-(4-chloro-2-methylphenoxy)propionic acid-methylacrylate.

[0046] S2. 17.2 g of dibasic fatty amine HMDA was added to the above-mentioned (R)-2-(4-chloro-2-methylphenoxy) propionic acid-methyl acrylate, and the temperature was raised to 80° C. under nitrogen protection, and the reaction was carried out for 3 days, and then the temperature was raised to 90° C. and the reaction was carried out for 1 day, and finally the temperature was cooled to room temperature to obtain a root penetration-resistant asparagus polyurea coating resin.

[0047] [Example 7] A root penetration resistant asparagus polyurea coating resin, which is different from [Example 1] in that the dibasic fatty amine added in step S2 is DMDC, with a mass of 20g.

[0048] [Example 8] A root penetration resistant asparagus polyurea coating resin, which is different from [Example 2] in that the dibasic fatty amine added in step S2 is DMDC, with a mass of 20.5 g.

[0049] [Example 9] A root penetration resistant asparagus polyurea coating resin, which is different from [Example 3] in that the dibasic fatty amine added in step S2 is DMDC, with a mass of 19.5 g.

[0050] [Example 10] A root penetration resistant asparagus polyurea coating resin, which differs from [Example 4] in that: in step S2, the mass of the dibasic fatty amine HMDA added is 20.3g.

[0051] [Example 11] A root penetration resistant asparagus polyurea coating resin, which differs from [Example 5] in that: in step S2, the mass of the dibasic fatty amine HMDA added is 21.1 g.

[0052] [Example 12] A root penetration resistant asparagus polyurea coating resin, which differs from [Example 6] in that: in step S2, the mass of the dibasic fatty amine HMDA added is 19.2g.

[0053] [Example 13] A root penetration resistant asparagus polyurea coating resin, which differs from [Example 1] in that: In step S1, the mass of hydroxyethyl methacrylate added is 52.1 g (0.4 mol), and the esterification reaction time is extended to 8 h, and 64.8 g (theoretical 68.9 g) of light yellow oily intermediate, i.e. (R)-2-(4-chloro-2-methylphenoxy) propionic acid-methylacrylate, is obtained; in step S2, the mass of dibasic fatty amine HMDA added is 19.5 g.

[0054] [Example 14] A root penetration resistant asparagus polyurea coating resin, which differs from [Example 2] in that: In step S1, the temperature of the esterification reaction is 70°C, i.e., a rapid reflux reaction is carried out in an oil bath at 70°C, to obtain 51.6 g (theoretical 66.1 g) of a light yellow oily intermediate, i.e., (R)-2-(4-chloro-2-methylphenoxy) propionic acid-methylacrylate; In step S2, the mass of dibasic fatty amine HMDA added was 16.1 g.

[0055] [Example 15] A root penetration resistant asparagus polyurea coating resin, which differs from [Example 3] in that: In step S1, the mass of p-toluenesulfonic acid added is 0.8 g, and the esterification reaction temperature is 90° C., and 62.0 g (theoretical 68.9 g) of a light yellow oily intermediate, namely (R)-2-(4-chloro-2-methylphenoxy) propionic acid-methylacrylate, is obtained; In step S2, the mass of dibasic fatty amine HMDA added is 18.5 g.

[0056] Application Examples

Application Example 1-15

[0057]

Application example 16-30

[0058] Performance testing 1. Root penetration resistance: refer to Appendix A of GB / T35468-2017 "Root penetration resistant waterproofing membrane for green roofs", and the test period is 3 years. Among them, the root penetration resistant asparagus polyurea coating in Application Examples 1-30 of this application is used to replace the conventional asparagus resin waterproof coating (including conventional asparagus resin F420 and isocyanate curing agent, the molar ratio of the imino group in the conventional asparagus resin F420 to the isocyanate group in the isocyanate curing agent is 1:1.05) to prepare the test group waterproofing membrane, and the dry film thickness of the root penetration resistant asparagus polyurea coating is 0.8mm and 1.2mm respectively. In addition, the waterproofing membrane made of conventional asparagus resin waterproof coating is used as the control group waterproofing membrane, and 6 waterproofing membranes are randomly selected from each test group waterproofing membrane and the control group waterproofing membrane for root penetration resistance test. After the test, if no root puncture occurs in each test box, and the growth of the plants in the test box during the test period reaches at least 80% of the average growth of the plants in the control box (height, stem diameter), then the root puncture resistant asparagus polyurea coating can be determined to have root puncture resistance. Note: The difference between the waterproof membranes in each experimental group and the control group is the different waterproof coatings.

[0059] Table 1 Root penetration resistance test results 2. Coating performance: The root penetration resistant asparagus polyurea coating in Application Example 1-30, the reactive root penetration resistant polyurethane waterproof coating root inhibitor in patent application CN110358425A and the isocyanate curing agent GB805B-100 were used in a molar ratio of 1:1.05 to prepare 0.05 mm, 0.25 mm, 0.75 mm and 1.5 mm samples by a one-time coating method, and observe whether the samples are locally bubbling.

[0060] Table 2 Coating performance 3. Mechanical properties: The tensile strength and elongation at break of the 1.5 mm thick sample in test (2) were tested in accordance with GB / T 19250-2013 Polyurethane Waterproof Coatings.

[0061] Table 3 Mechanical properties Sample Tensile Strength Elongation at break Application Example 1-30 >15MPa >300％ According to the test results in Table 1 above, it can be seen that when the coating thickness of the root penetration resistant asparagine polyurea coating is above 1.2 mm, the waterproof membranes made of the root penetration resistant asparagine polyurea coating in each application example can pass the root penetration resistance test, but when the coating thickness is further reduced to 0.8 mm, the main agent of the root penetration resistant asparagine polyurea coating should not be mixed with conventional asparagine resin.

[0062] According to the test results in Table 2 above, the root penetration resistant asparagus polyurea coating in each application example of the present application has better construction performance. For thick coatings with a thickness of more than 0.25 mm, it can also be achieved through a one-time coating without the need for multiple thin coatings. The construction is more convenient and efficient, and the practicality is higher.

[0063] According to the test results in Table 3 above, it can be seen that the tensile strength of the coating film formed by the root penetration resistant asparagus polyurea coating in each application example of the present application is above 15 MPa, and the elongation at break is above 300%.

[0064] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A root penetration resistant asparagine polyurea coating resin, characterized in that: The root penetration resistant asparagine polyurea coating resin is obtained by an esterification reaction between (R)-2-(4-chloro-2-methylphenoxy) propionic acid and a hydroxyl-containing acrylate monomer under the action of a catalyst to obtain an intermediate, and then the intermediate is reacted with a fatty amine to produce a Michael reaction, wherein the molecular structure of the root penetration resistant asparagine polyurea coating resin contains a (R)-2-(4-chloro-2-methylphenoxy) propionic acid group and at least one imine group.

2. The root penetration resistant asparagine polyurea coating resin according to claim 1, characterized in that: The molar ratio of the (R)-2-(4-chloro-2-methylphenoxy)propionic acid to the hydroxyalkyl acrylate is 1:(1-3).

3. The root penetration resistant asparagine polyurea coating resin according to claim 1, characterized in that: The hydroxyl-containing acrylic acid ester monomer is at least one of a hydroxyalkyl acrylate monomer or a hydroxyalkyl methacrylate monomer.

4. The root penetration resistant asparagine polyurea coating resin according to claim 1, characterized in that: The catalyst is at least one of sulfuric acid, trifluoromethanesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid and dibutyltin dilaurate.

5. The root penetration resistant asparagine polyurea coating resin according to claim 4, characterized in that: The amount of the catalyst used is 0.05-1% (by weight) of the sum of the amounts of (R)-2-(4-chloro-2-methylphenoxy)propionic acid and the acrylate monomer containing a hydroxyl group.

6. The root penetration resistant asparagine polyurea coating resin according to claim 1, characterized in that: The molar ratio of the unsaturated double bonds in the intermediate to the amino groups in the fatty amine is (1-1.05):

1.

7. The root penetration resistant asparagine polyurea coating resin according to claim 1, characterized in that: The fatty amine is a dibasic fatty amine.

8. The root penetration resistant asparagine polyurea coating resin according to claim 7, characterized in that: The dibasic fatty amine is at least one of HMDA, DMDC, polyetheramine D230 and polyetheramine D400.

9. A method for preparing a root-penetration-resistant asparagine polyurea coating resin, for preparing the root-penetration-resistant asparagine polyurea coating resin according to any one of claims 1 to 8, characterized in that: The following steps are involved: (R)-2-(4-chloro-2-methylphenoxy)propionic acid, a hydroxyl-containing acrylic acid ester monomer, a catalyst and a polymerization inhibitor are added to a solvent, the temperature is raised to 60-120° C., and the heated reflux is performed to perform an esterification reaction, and the generated water is discharged during the reaction. After the reaction is completed, an organic phase is extracted and separated, and then the organic phase is washed and dried, and finally concentrated under reduced pressure to obtain an intermediate; The intermediate is added to a fatty amine, and under nitrogen protection, the temperature is raised to 90-140° C. to carry out Michael reaction to obtain a root penetration resistant asparagine polyurea coating resin.

10. A root penetration resistant asparagine polyurea coating, characterized in that: The invention comprises a main agent and an isocyanate curing agent, wherein the main agent is a composition of the root penetration resistant asparagus polyurea coating resin according to any one of claims 1 to 8 and conventional asparagus resin on the market in a weight ratio of 1:(0-5), and the molar ratio of the imino group in the main agent to the isocyanate group in the isocyanate curing agent is 1:(1-1.05).

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