Hypoallergenic aspartic ester resin compound and preparation process thereof

Abstract

The invention provides a low-sensitization aspartic ester resin compound and a preparation process thereof, and relates to the technical field of aspartic resin. The aspartic ester resin compound comprises the following raw material components: (A) polyaspartic resin, (B) monoamino maleate adduct, and (C) diethyl fumarate and / or diethyl maleate accounting for not more than 0.5% of the weight of the aspartic ester resin compound. The aspartate resin compound disclosed by the invention has the characteristics that the weight percentage content of diethyl fumarate and diethyl maleate is low, sensitization to a human body is not generated, and the curing property is close to that of the existing polyaspartic resin.

Description

Technical Field

[0001] The invention belongs to the technical field of asparagine resins and relates to a low-allergenic aspartic acid ester resin complex and a preparation process thereof. Background Art

[0002] Asparagine resin is usually prepared by Michael addition reaction of dialkyl maleate and organic polyamine, and the most commonly used dialkyl maleate is diethyl maleate. In order to promote the more complete reaction of organic polyamine and avoid the influence of residual primary amine on the curing operation time of asparagine resin, excessive diethyl maleate is usually added, but diethyl maleate will gradually be converted into diethyl fumarate with low reaction activity under the reaction conditions of synthesizing asparagine resin, and the reaction activity of diethyl fumarate is significantly lower than that of diethyl maleate, resulting in a slow reaction rate, an increase in residual diethyl maleate and diethyl fumarate, and diethyl maleate and diethyl fumarate have greater irritation to human skin, bronchus, throat mucosa, etc. According to the above-mentioned method for preparing asparagine resin, the content of free diethyl maleate and / or diethyl fumarate in asparagine resin can reach 2wt% or even higher, and human skin, bronchus, throat mucosa, etc. produce stronger sensitization. The boiling point of diethyl maleate at 1 atmosphere is 225°C, and the conventional vacuum distillation method cannot reduce the content of diethyl maleate and / or diethyl fumarate in asparagine resin to 2wt% or less. In order to reduce the free diethyl maleate and / or diethyl fumarate in asparagine resin, the industry generally adopts a short-range molecular distillation method, which can reduce the content of free diethyl maleate and / or diethyl fumarate to 0.5wt% or less. When the content of diethyl maleate and / or diethyl fumarate in asparagine resin does not exceed 0.5wt%, the irritation and sensitization to the human body are very low, and it can be considered that no sensitization will occur. However, the short-range molecular distillation method has the problems of expensive equipment, increased production cycle, and increased cost, which greatly restricts the application of asparagine resin and the development of the industry.

[0003] Therefore, the industry urgently needs to improve the current process method to reduce equipment investment, improve production efficiency, and thus reduce the cost of asparagine resin while controlling the content of diethyl maleate and / or diethyl fumarate in asparagine resin to no more than 0.5wt%. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides a low-allergenic aspartic acid ester resin complex and a preparation process thereof.

[0005] The technical solution of the present invention is as follows:

[0006] A low-allergenic aspartic acid ester resin complex, the aspartic acid ester resin complex comprising the following raw material components:

[0007] (A) a polyaspartic acid resin having a structure as shown in the following formula (1),

[0008]

[0009] Among them, R 1 and R 2 independently selected from C1-C4 alkyl, X is selected from a polyvalent organic structure having an average molecular weight of 50-5000 which is inert to react with isocyanate groups at 100° C. after removing the primary amino group from the polyvalent primary amine compound, and n=2-3;

[0010] (B) a monoamine maleate adduct having a structure represented by the following formula (2),

[0011]

[0012] Among them, R 3 An organic group selected from an organic amine compound containing one primary amino group or one secondary amino group with a molecular weight not exceeding 100, which is obtained by removing one H atom from the N atom, wherein Et represents an ethyl group;

[0013] as well as,

[0014] (C) diethyl fumarate and / or diethyl maleate in an amount not exceeding 0.5% by weight of the aspartic acid ester resin complex.

[0015] Preferably, the R 1 and the R 2 Independently selected from ethyl.

[0016] Preferably, the monoamine maleate adduct accounts for 3-15% by weight of the aspartic acid ester resin composite.

[0017] Preferably, the chemical formula of the organic amine compound is one or a combination of two or more of the following formulas (3) or (4):

[0018] R 4 NH2(3)

[0019] Among them, R 4 Selected from C5-C6 cycloalkyl or C6-C10 substituted cycloalkyl;

[0020] R 5 NHR 6 (4)

[0021] Among them, R 5 and R 6 Independently selected from C1-C4 alkyl.

[0022] A preparation process of a low-allergenic aspartic acid ester resin complex according to any of the above embodiments, wherein the diethyl maleate is slowly added dropwise to the polyamine compound according to a molar ratio of primary amino groups to diethyl maleate in the polyamine compound of 0.7-0.95:1, the temperature is raised to 40-80°C after the addition is completed, and the reaction is carried out for 48-168h, the organic amine compound is continuously added, and the temperature is controlled at 40-100°C to react until the sum of the weight percentages of diethyl maleate and diethyl fumarate in the reaction system does not exceed 0.5%, the temperature is controlled to 80°C-135°C, the vacuum degree is above -0.098MPa, and the residual low-boiling substances are removed by vacuum to obtain the low-allergenic aspartic acid ester resin complex.

[0023] Preferably, the molar ratio of the primary amino group in the polyamine compound to the diethyl maleate is 0.8-0.95:1.

[0024] Preferably, the polyamine compound is selected from 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, isophoronediamine, 1,6-hexanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 1-methyl-2,4-cyclohexanediamine, 1,3-cyclohexanedimethylamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-cyclopentanediamine, o-diaminomethylcyclopentane and polyetheramine, or a combination of two or more thereof.

[0025] Preferably, the molar ratio of the organic amine compound to the diethyl maleate is 0.1-0.5:1.

[0026] Preferably, the ratio of the sum of the molar numbers of the primary amino groups in the polyamine compound and the organic amine compound to the molar number of the diethyl maleate is 1-1.2:1.

[0027] Preferably, the organic amine compound is selected from one or a combination of two or more of cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, cyclopentylamine, 2-methylcyclopentylamine, 3-methylcyclopentylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-n-butylamine and diisobutylamine.

[0028] The beneficial effects of the present invention are:

[0029] (1) The present invention adopts a method of combining a monoamine maleate adduct with a conventional aspartic acid ester resin to reduce the content of diethyl fumarate and / or diethyl maleate to 0.5 wt % or less.

[0030] (2) The present invention adopts a method in which insufficient amount of polyvalent primary amine compounds are first reacted with diethyl maleate, and the reaction can be carried out at a relatively low temperature. Under the condition of promoting the complete reaction of the polyvalent primary amine compounds, the conversion of diethyl maleate into diethyl fumarate during the reaction can be reduced or avoided, and by adding sufficient or excessive amount of monofunctional organic amine compounds to react with the remaining unreacted diethyl maleate and / or diethyl fumarate and the reaction is relatively complete, the content of the residual diethyl maleate and / or diethyl fumarate is controlled to be 0.5wt% or less. Even if the monofunctional organic amine compound is not completely reacted due to excess, since the monofunctional organic amine compound used in the present invention has a relatively low boiling point, it can be removed by reduced pressure distillation, and the residual monofunctional organic amine compound can be as low as 1% or less, which has no significant effect on the curing performance of the aspartic acid ester resin composite of the present invention.

[0031] (3) The content of the raw material component (B) in the aspartic acid ester resin composite of the present invention is relatively low, and therefore has no significant effect on the performance of the aspartic acid ester resin composite after curing with the curing agent. DETAILED DESCRIPTION

[0032] The technical solution of the present invention is further illustrated and described below through specific implementation methods.

[0033] In order to solve the problems of expensive equipment, increased production cycle, increased cost, etc. in the short-range molecular distillation method used in the prior art to control the content of diethyl maleate and / or diethyl fumarate in asparagine resin to 0.5wt% or less, the present invention provides a low-allergenic aspartic acid ester resin composite, which comprises the following raw material components:

[0034] (A) a polyaspartic acid resin having a structure as shown in the following formula (1),

[0035]

[0036] Among them, R 1 and R 2 independently selected from C1-C4 alkyl, X is selected from a polyvalent organic structure having an average molecular weight of 50-5000 which is inert to react with isocyanate groups at 100° C. after removing the primary amino group from the polyvalent primary amine compound, and n=2-3;

[0037] (B) a monoamine maleate adduct having a structure represented by the following formula (2),

[0038]

[0039] Among them, R 3An organic group selected from an organic amine compound containing one primary amino group or one secondary amino group with a molecular weight not exceeding 100, which is obtained by removing one H atom from the N atom, wherein Et represents an ethyl group;

[0040] as well as,

[0041] (C) diethyl fumarate and / or diethyl maleate in an amount not exceeding 0.5% by weight of the aspartate resin complex.

[0042] The aspartic acid ester resin composite of the present invention comprises the above-mentioned raw material components (A), (B) and (C), the performance of the aspartic acid ester resin is mainly reflected by the raw material component (A) aspartic acid resin, the raw material component (B) monoamine maleate adduct plays the role of a diluent and the raw material component (B) makes the content of diethyl fumarate and / or diethyl maleate in the aspartic acid ester resin composite not exceed 0.5wt%.

[0043] In the present invention, the organic amine compound is a monofunctional compound, and contains only one primary amino group or one secondary amino group in the molecule. When the organic amine compound contains one primary amino group, the raw material component (B) monoamine maleate adduct contains one secondary amino group, and can participate in the subsequent curing reaction of the asparagine resin and the curing agent, and is an active diluent; when the organic amine compound contains one secondary amino group, the raw material component (B) monoamine maleate adduct does not contain active H, cannot participate in the subsequent curing reaction, and is an inert diluent.

[0044] In a preferred embodiment of the present invention, R 1 and R 2 The ethyl group is selected alone, and in this case, the polyamine compound undergoes Michael addition reaction with diethyl maleate.

[0045] In a preferred embodiment of the present invention, the weight percentage of the monoamine maleate adduct in the aspartic acid ester resin composite is 3-15%. The monoamine maleate adduct plays the role of a diluent in the aspartic acid ester resin composite of the present invention. Whether it is an active diluent or an inert diluent, a high content will affect the subsequent curing performance of the aspartic acid ester resin composite, such as slowing down the curing or even failing to cure, and will also cause the tensile strength and modulus of the cured product to decrease, and the elongation at break to increase. For example, the weight percentage of the monoamine maleate adduct in the aspartic acid ester resin composite in the present invention can be any value of 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc., without special restrictions.

[0046] In a preferred embodiment of the present invention, the chemical formula of the organic amine compound is one or a combination of two or more of the following formulas (3) or (4):

[0047] R 4 NH2(3)

[0048] Among them, R 4 is selected from C5-C6 cycloalkyl or C6-C10 substituted cycloalkyl; for example, R 4 NH2 can be cyclohexylamine (boiling point at normal pressure is about 135°C), 2-methylcyclohexylamine (boiling point at normal pressure is about 150°C), 3-methylcyclohexylamine (boiling point at normal pressure is about 150°C), cyclopentylamine (boiling point at normal pressure is about 107°C), 4-ethylcyclohexylamine (boiling point at normal pressure is about 170°C), 4-propylcyclohexylamine (boiling point at normal pressure is about 194°C), etc.;

[0049] R 5 NHR 6 (4)

[0050] Among them, R 5 and R 6 are independently selected from C1-C4 alkyl. 5 NHR 6 It may be dimethylamine, diethylamine, dipropylamine (boiling point at normal pressure is about 108°C), diisopropylamine (boiling point at normal pressure is about 84°C), di-tert-butylamine, dibutylamine (boiling point at normal pressure is about 150°C), etc.

[0051] On the other hand, the present invention also proposes a preparation process of a low-allergenic aspartic acid ester resin complex described in any of the above-mentioned embodiments, wherein diethyl maleate is slowly added dropwise to the polyamine compound according to a molar ratio of primary amino groups to diethyl maleate in the polyamine compound of 0.7-0.95:1, and after the addition is completed, the temperature is raised to 40-80°C for reaction for 48-168h, and the organic amine compound is continuously added, and the temperature is controlled at 40-100°C for reaction, and the reaction is carried out until the sum of the weight percentages of diethyl maleate and diethyl fumarate in the reaction system does not exceed 0.5%, and the temperature is controlled to 80°C-135°C and the vacuum degree is above -0.098MPa, and the residual low-boiling substances are removed by vacuum to obtain a low-allergenic aspartic acid ester resin complex.

[0052] In the above preparation method, when the polyamine compound reacts with diethyl maleate, the polyamine compound reacts insufficiently with respect to diethyl maleate, which can promote the complete reaction of the polyamine compound. The remaining unreacted diethyl maleate is reacted completely by adding a sufficient or excessive amount of an organic amine compound. The sum of the weight percentages of diethyl maleate and diethyl fumarate in the product does not exceed 0.5%, and even if the organic amine compound remains unreacted due to excess, it can be easily removed by reduced pressure distillation. The content of the organic amine compound in the product aspartic acid ester resin composite does not exceed 1wt%. In the present invention, the weight percentage of diethyl maleate and / or diethyl fumarate and the weight percentage of the organic amine compound in the reaction system or product can be detected by gas chromatography or high performance liquid chromatography, or the weight percentage of the organic amine compound can be detected by gas chromatography, and the weight percentage of diethyl maleate and / or diethyl fumarate can be detected by high performance liquid chromatography. For specific detection methods, reference can be made to the prior art "Determination of diethyl maleate by high performance liquid chromatography" (Zhejiang Chemical Industry, Vol. 37, No. 7, 2006, 21-22).

[0053] In a preferred embodiment of the present invention, the molar ratio of primary amino group to diethyl maleate in the polyamine compound is 0.8-0.95: 1. For example, the molar ratio of primary amino group to diethyl maleate in the polyamine compound can be any value of 0.8: 1, 0.82: 1, 0.84: 1, 0.85: 1, 0.87: 1, 0.88: 1, 0.9: 1, 0.92: 1, 0.93: 1, 0.95: 1, etc., without any particular limitation.

[0054] In a preferred embodiment of the present invention, the polyamine compound is selected from 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, isophoronediamine, 1,6-hexanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 1-methyl-2,4-cyclohexanediamine, 1,3-cyclohexanedimethylamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-cyclopentanediamine, o-diaminomethylcyclopentane and polyetheramine, or a combination of two or more thereof. The polyamine compounds listed above are all polyamine compounds commonly used in the field of asparagus resin, and contain cycloalkyl groups or are polyetheramines in their structures. The polyetheramine can be directly obtained from the market, for example, polyetheramine D-230, polyetheramine D-400, polyetheramine D-2000, polyetheramine ED-600, polyetheramine ED-900, polyetheramine T-403, polyetheramine T-5000, etc., but not limited to the above-mentioned ones.

[0055] In a preferred embodiment of the present invention, the molar ratio of the organic amine compound to diethyl maleate is 0.1-0.5: 1. For example, the molar ratio of the organic amine compound to diethyl maleate can be any value in 0.1: 1, 0.12: 1, 0.15: 1, 0.18: 1, 0.2: 1, 0.22: 1, 0.25: 1, 0.27: 1, 0.3: 1, 0.33: 1, 0.35: 1, 0.37: 1, 0.4: 1, 0.42: 1, 0.45: 1, 0.48: 1, 0.5: 1, etc., without particular limitation.

[0056] In a preferred embodiment of the present invention, the ratio of the sum of the moles of primary amino groups and organic amine compounds in the polyamine compound to the moles of diethyl maleate is 1-1.2:1. By adopting the above technical scheme, the diethyl maleate and / or diethyl fumarate in the reaction system can be reacted completely. For example, the ratio of the sum of the moles of primary amino groups and organic amine compounds in the polyamine compound to the moles of diethyl maleate can be any value in 1:1, 1.02:1, 1.05:1, 1.07:1, 1.08:1, 1.1:1, 1.12:1, 1.15:1, 1.17:1, 1.18:1, 1.2:1, etc., without special restrictions.

[0057] In a preferred embodiment of the present invention, the organic amine compound is selected from one or a combination of two or more of cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, cyclopentylamine, 2-methylcyclopentylamine, 3-methylcyclopentylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-n-butylamine and diisobutylamine. The above-mentioned organic amine compounds have small molecules, high reactivity with diethyl maleate and / or diethyl fumarate, low boiling point under 1 atmosphere, and can be removed by simple vacuum distillation even if they are excessive, so that the content of the organic amine compound in the product aspartic acid ester resin composite does not exceed 1wt%, and has no significant effect on the curing performance of the aspartic acid ester resin composite.

[0058] The technical solution of the present invention is further described and illustrated according to various embodiments below. Unless otherwise specified, the parts described in the following embodiments are parts by weight.

[0059] Example 1

[0060] Add 1 mol of 4,4'-diaminodicyclohexylmethane to a four-necked flask, slowly drop 2.2 mol of diethyl maleate, and control the reaction at 55°C for 48 hours after the dropwise addition is completed. Then add 0.2 mol of cyclohexylamine, control the reaction at 60°C for 48 hours, take a sample and use high performance liquid chromatography to detect the sum of the weight percentage of diethyl maleate and diethyl fumarate, which is 0.33%. Keep the temperature at 100-105°C and -0.099MPa to remove low boiling points and obtain a low-sensitization aspartic acid resin complex. The sum of the weight percentage of diethyl maleate and diethyl fumarate in the complex is 0.38%, the weight percentage of cyclohexylamine is 0.1%, and the solid content of the complex is 98.2%.

[0061] The test conditions for solid content are as follows: 2 g of sample is baked in an oven at 105 °C for 2 h.

[0062] Example 2

[0063] The difference between this embodiment and embodiment 1 is that in embodiment 1, the cyclohexylamine is adjusted from 0.2 mol to 0.4 mol. The other steps remain unchanged. The sum of the weight percentages of diethyl maleate and diethyl fumarate in the obtained hypoallergenic aspartic acid ester resin composite is measured to be 0.17%, the weight percentage of cyclohexylamine is 0.34%, and the solid content of the composite is 98.4%.

[0064] Example 3

[0065] Add 1 mol of 4,4'-diaminodicyclohexylmethane to a four-necked flask, slowly drop 2.2 mol of diethyl maleate, and control the reaction at 55°C for 48 hours after the dropwise addition is completed. Then, pass dimethylamine gas through the trachea to the reaction liquid surface and keep bubbling until the amount of dimethylamine introduced is about 13.5g (0.3mol), stop passing dimethylamine, plug the bottle stopper, keep 50°C and continue to react for 96 hours, take samples and use high performance liquid chromatography to detect the sum of the weight percentage of diethyl maleate and diethyl fumarate, which is 0.18%. Keep 80-85°C and -0.099MPa to remove low boiling points by vacuum, and obtain a low-sensitization aspartic acid resin complex. The sum of the weight percentage of diethyl maleate and diethyl fumarate in the complex is measured to be 0.23%, the weight percentage of dimethylamine is 0.02%, and the solid content of the complex is 97.7%.

[0066] Example 4

[0067] Add 1 mol of 4,4'-diaminodicyclohexylmethane to a four-necked flask, slowly drop 2.2 mol of diethyl maleate, and control the reaction at 55°C for 48 hours after the dropwise addition is completed. Then add 0.4 mol of diisobutylamine, control the reaction at 75°C for 128 hours, take a sample and use high performance liquid chromatography to detect the sum of the weight percentage of diethyl maleate and diethyl fumarate, which is 0.07%. Keep the low boiling point at 130-135°C and -0.099MPa to remove the low-boiling substances by vacuum, and obtain a low-sensitization aspartic acid resin complex. The sum of the weight percentage of diethyl maleate and diethyl fumarate in the complex is measured to be 0.08%, the weight percentage of diisobutylamine is 0.42%, and the solid content of the complex is 97.4%.

[0068] Example 5

[0069] Add 1 mol of 4,4'-diaminodicyclohexylmethane to a four-necked flask, slowly drop 2.5 mol of diethyl maleate, and control the reaction at 55°C for 60 hours after the dropwise addition is completed. Then add 0.6 mol of 2-methylcyclohexylamine, control the reaction at 90°C for 96 hours, take a sample and use high performance liquid chromatography to detect the sum of the weight percentage of diethyl maleate and diethyl fumarate, which is 0.15%. Keep the low boiling point at 130-135°C and -0.099MPa to remove the low-boiling substances by vacuum, and obtain a low-sensitization aspartic acid resin complex. The sum of the weight percentage of diethyl maleate and diethyl fumarate in the complex is measured to be 0.22%, the weight percentage of 2-methylcyclohexylamine is 0.61%, and the solid content of the complex is 97.8%.

[0070] Comparative Example 1

[0071] Add 1 mol of 4,4'-diaminodicyclohexylmethane into a four-necked flask, slowly drop 2.1 mol of diethyl maleate, and after the dropwise addition is completed, control the reaction at 60°C for 96 hours, maintain 130°C-135°C, -0.099MPa and evacuate for 1 hour to obtain asparagine resin. Sampling and high performance liquid chromatography are used to measure the sum of the weight percentages of diethyl maleate and diethyl fumarate in the product aspartic acid ester resin to be 2.4%. The weight percentage of diethyl fumarate in the product aspartic acid ester resin is measured by high performance liquid chromatography to be 2.2%.

[0072] Example 6

[0073] Add 1 mol of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane to a four-necked flask, slowly drop 2.4 mol of diethyl maleate, and control the reaction at 70°C for 72 hours after the dropwise addition is completed. Then add 0.6 mol of 2-methylcyclohexylamine, control the reaction at 90°C for 100 hours, take a sample and use high performance liquid chromatography to detect the sum of the weight percentage of diethyl maleate and diethyl fumarate, which is 0.10%. Keep the low boiling point at 130-135°C and -0.099MPa to remove the low-boiling substances and obtain a low-sensitization aspartic acid resin complex. The sum of the weight percentage of diethyl maleate and diethyl fumarate in the complex is measured to be 0.18%, the weight percentage of 2-methylcyclohexylamine is 0.55%, and the solid content of the complex is 98.1%.

[0074] Comparative Example 2

[0075] In a four-necked flask, 1 mol of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane was added, and 2.1 mol of diethyl maleate was slowly added dropwise. After the addition was completed, the reaction was controlled at 70°C for 96 hours, and the vacuum was maintained at 130°C-135°C and -0.099MPa for 1 hour to obtain aspartic acid ester resin. The sum of the weight percentages of diethyl maleate and diethyl fumarate in the product aspartic acid ester resin was measured by high performance liquid chromatography, and the weight percentage of diethyl fumarate in the product aspartic acid ester resin was 2.5%. The weight percentage of diethyl fumarate in the product aspartic acid ester resin was measured by high performance liquid chromatography and was 2.4%.

[0076] Performance test comparison

[0077] The polyaspartic acid coating was prepared according to the following formulation.

[0078] Component A: It is composed of 64% of the aspartic acid resin complex or aspartic acid resin to be tested, 5% of hydroxy acrylic resin, 5% of titanium dioxide, 25% of barium sulfate, 0.2% of dispersant, 0.4% of defoaming agent, 0.2% of leveling agent and 0.2% of anti-settling agent.

[0079] Component B: It is composed of an adduct curing agent prepared from 3% HDI trimer, 10% HMDI and 87% IPDI and polyether polyol.

[0080] Component A and component B are mixed evenly in a ratio of the total molar content of secondary amine and hydroxyl groups in component A: the molar content of isocyanate groups NCO in component B = 1:1.05 to obtain a polyaspartic acid ester coating. The obtained polyaspartic acid ester coating is made into a coating film with a thickness of 0.5 mm, cured at 35±2°C for 15 days, and referred to the test methods and indicators of T / CWA204-2021 "Asparagine Polyurea Waterproof Coating Standard". The test performance data results are shown in Table 1.

[0081] Table 1 Performance data

[0082]

[0083]

[0084] It can be seen from the results of the above embodiments and Table 1 that the sum of the weight percentages of diethyl maleate and diethyl fumarate in the low-allergenic aspartic acid ester resin of the present invention does not exceed 0.5wt%, and the residual organic amine compound content is very low, which has no significant effect on the curing properties of the product aspartic acid ester resin.

[0085] As described above, the basic principles, main features and advantages of the present invention are shown and described. Those skilled in the art should understand that the present invention is not limited by the above embodiments, which are only preferred embodiments of the present invention and cannot be used to limit the scope of the present invention. That is, equivalent changes and modifications made according to the scope of the present invention and the content of the specification should still be within the scope of the present invention. The scope of protection required by the present invention is defined by the attached claims and their equivalents.

Claims

1. A low-allergenic aspartic acid ester resin complex, characterized in that: The aspartic acid ester resin complex comprises the following raw material components: (A) a polyaspartic acid resin having a structure as shown in the following formula (1), Among them, R 1 and R 2 independently selected from C1-C4 alkyl, X is selected from a polyvalent organic structure having an average molecular weight of 50-5000 which is inert to react with isocyanate groups at 100° C. after removing the primary amino group from the polyvalent primary amine compound, and n=2-3; (B) a monoamine maleate adduct having a structure represented by the following formula (2), Among them, R 3 An organic group selected from an organic amine compound containing one primary amino group or one secondary amino group with a molecular weight not exceeding 100, which is obtained by removing one H atom from the N atom, wherein Et represents an ethyl group; as well as, (C) diethyl fumarate and / or diethyl maleate in an amount not exceeding 0.5% by weight of the aspartic acid ester resin complex.

2. The hypoallergenic aspartic acid ester resin complex according to claim 1, characterized in that: The R 1 and the R 2 Independently selected from ethyl.

3. The hypoallergenic aspartic acid ester resin complex according to claim 1, characterized in that: The monoamine maleate adduct accounts for 3-15% by weight of the aspartic acid ester resin composite.

4. The hypoallergenic aspartic acid ester resin complex according to claim 1, characterized in that: The chemical formula of the organic amine compound is one or a combination of two or more of the following formulas (3) or (4): R 4 NH2(3) Among them, R 4 Selected from C5-C6 cycloalkyl or C6-C10 substituted cycloalkyl; R 5 NHR 6 (4) Among them, R 5 and R 6 Independently selected from C1-C4 alkyl.

5. A process for preparing the low-allergenic aspartic acid ester resin complex according to any one of claims 1 to 4, characterized in that: According to the molar ratio of primary amino group to diethyl maleate in the polyamine compound of 0.7-0.95:1, the diethyl maleate is slowly added dropwise to the polyamine compound, and after the addition is completed, the temperature is raised to 40-80°C for reaction for 48-168h, and the organic amine compound is continuously added, and the temperature is controlled at 40-100°C for reaction, and the reaction is carried out until the sum of the weight percentages of diethyl maleate and diethyl fumarate in the reaction system does not exceed 0.5%, and the temperature is controlled to 80°C-135°C and the vacuum degree is above -0.098MPa, and the residual low-boiling substances are removed by vacuum to obtain the low-sensitivity aspartic acid resin complex.

6. The process for preparing the hypoallergenic aspartic acid ester resin complex according to claim 5, characterized in that: The molar ratio of the primary amino group in the polyamine compound to the diethyl maleate is 0.8-0.95:

1.

7. The process for preparing the hypoallergenic aspartic acid ester resin complex according to claim 5, characterized in that: The polyamine compound is selected from 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, isophoronediamine, 1,6-hexanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 1-methyl-2,4-cyclohexanediamine, 1,3-cyclohexanedimethylamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-cyclopentanediamine, o-diaminomethylcyclopentane and polyetheramine, or a combination of two or more thereof.

8. The process for preparing the hypoallergenic aspartic acid ester resin complex according to claim 5, characterized in that: The molar ratio of the organic amine compound to the diethyl maleate is 0.1-0.5:

1.

9. The process for preparing the hypoallergenic aspartic acid ester resin complex according to claim 5, characterized in that: The ratio of the sum of the moles of the primary amino group in the polyamine compound and the organic amine compound to the mole of the diethyl maleate is 1-1.2:

1.

10. The process for preparing the hypoallergenic aspartic acid ester resin complex according to claim 5, characterized in that: The organic amine compound is selected from one or a combination of two or more of cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, cyclopentylamine, 2-methylcyclopentylamine, 3-methylcyclopentylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-n-butylamine and diisobutylamine.

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