A low-sensitizing aspartate resin complex and a preparation process thereof

Abstract

The application provides a low-sensitization aspartic acid ester resin composite and a preparation process thereof, and relates to the technical field of aspartic acid resin. The aspartic acid ester resin composite comprises the following raw material components: (A) polyaspartic acid resin, (B) monoamine maleate adduct, and (C) diethyl fumarate and / or diethyl maleate, which accounts for no more than 0.5% of the weight of the aspartic acid ester resin composite. The aspartic acid ester resin composite has the characteristics that the weight percentage of diethyl fumarate and diethyl maleate is low, no sensitization is caused to human body, and the curing performance is close to that of the existing polyaspartic acid resin.

Description

Technical Field

[0001] This invention belongs to the field of aspartic resin technology and relates to a low-allergenic aspartic acid ester resin composite and its preparation process. Background Technology

[0002] Aspartic resin is typically prepared by a Michael addition reaction between dialkyl maleate and organic polyamines, with diethyl maleate being the most commonly used dialkyl maleate. To promote a more complete reaction of the organic polyamines and avoid the influence of residual primary amines on the curing time of the aspartic resin, an excess of diethyl maleate is usually added. However, under the reaction conditions used in the synthesis of aspartic resin, diethyl maleate gradually converts to diethyl fumarate, which has lower reactivity. Diethyl fumarate has significantly lower reactivity than diethyl maleate, resulting in a slower reaction rate and an increase in residual diethyl maleate and diethyl fumarate. Both diethyl maleate and diethyl fumarate are highly irritating to human skin, bronchial mucosa, and throat mucosa. Using the above method for preparing aspartic resin, the content of free diethyl maleate and / or diethyl fumarate in the aspartic resin can reach 2 wt% or even higher, causing strong sensitization to human skin, bronchial mucosa, and throat mucosa. Diethyl maleate has a boiling point of 225°C at 1 atmosphere. Conventional vacuum distillation methods cannot reduce the content of diethyl maleate and / or diethyl fumarate in aspartic resin to 2 wt% or less. To reduce the free diethyl maleate and / or diethyl fumarate in aspartic resin, the industry generally uses short-path molecular distillation, which can reduce the content of free diethyl maleate and / or diethyl fumarate to 0.5 wt% or less. When the content of diethyl maleate and / or diethyl fumarate in aspartic resin does not exceed 0.5 wt%, its irritant and sensitizing effects on humans are very low, and it can be considered that it will not cause sensitization. However, short-path molecular distillation has problems such as expensive equipment, increased production cycle, and increased costs, which greatly restricts the application of aspartic resin and the development of the industry.

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

[0004] To address the aforementioned technical problems, this invention provides a low-allergenic aspartic acid ester resin composite and its preparation process.

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

[0006] A hypoallergenic aspartic acid ester resin complex, wherein the aspartic acid ester resin complex comprises the following raw material components:

[0007] (A) Polyaspartic resin with the structure shown in formula (1) below.

[0008]

[0009] Among them, R 1 and R 2 The individual is selected from C1-C4 alkyl groups, X is selected from polyvalent organic structures with an average molecular weight of 50-5000 that are reactive with isocyanate groups after the removal of the primary amino group from polyamine compounds, and n = 2-3.

[0010] (B) The monoamine maleate adduct with the structure shown in formula (2) below.

[0011]

[0012] Among them, R 3 The organic group remaining after removing one H atom from the N atom of an organic amine compound containing one primary amino or one secondary amino group with a molecular weight not exceeding 100; Et represents ethyl.

[0013] as well as,

[0014] (C) Diethyl fumarate and / or diethyl maleate comprising no more than 0.5% by weight of the aspartic acid ester resin complex.

[0015] Preferably, the R 1 and the R 2 The single one is selected from ethyl.

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

[0017] Preferably, the organic amine compound has one or more of the general chemical formulas shown in formula (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 The individual is selected from C1-C4 alkyl groups.

[0022] A preparation process for the low-allergenic aspartic acid ester resin complex according to any of the above embodiments involves slowly adding diethyl maleate dropwise to the polyamine compound at a molar ratio of primary amino group to diethyl maleate of 0.7-0.95:1. After the addition is complete, the temperature is raised to 40-80℃ and reacted for 48-168 hours. The organic amine compound is then added, and the temperature is controlled at 40-100℃. The reaction continues 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 then controlled at 80℃-135℃, and a vacuum degree of -0.098MPa or higher is applied to remove residual low-boiling substances, thereby obtaining the low-allergenic aspartic acid ester resin complex.

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

[0024] Preferably, the polyamine compound is selected from one or a combination of two or more of the following: 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, isophorone diamine, 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 polyetheramines.

[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 group and the organic amine compound in the polyamine 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 this invention are:

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

[0030] (2) In this invention, a method of reacting a primary polyamine compound with diethyl maleate in insufficient quantity is employed. The reaction can be carried out at a relatively low temperature, which can reduce or avoid the conversion of diethyl maleate to diethyl fumarate during the reaction process by promoting the complete reaction of the primary polyamine compound. Furthermore, by adding sufficient or excessive amounts of monofunctional organic amine compounds to react with the remaining unreacted diethyl maleate and / or diethyl fumarate, the reaction is relatively complete, and the content of residual diethyl maleate and / or diethyl fumarate is controlled at 0.5 wt% or lower. Even if the monofunctional organic amine compound does not react completely due to excess, since the monofunctional organic amine compound used in this invention has a relatively low boiling point, it can be removed by vacuum distillation. The residual monofunctional organic amine compound can be as low as 1% or less, which has no significant impact on the curing performance of the aspartic acid ester resin composite of this invention.

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

[0032] The technical solution of the present invention will be further explained and described below through specific embodiments.

[0033] To address the problems of expensive equipment, increased production cycle, and higher costs associated with the short-path molecular distillation method used in existing technologies to control the content of diethyl maleate and / or diethyl fumarate in aspartic resin to 0.5 wt% or less, this invention proposes a low-allergenic aspartic acid ester resin complex comprising the following raw material components:

[0034] (A) Polyaspartic resin with the structure shown in formula (1) below.

[0035]

[0036] Among them, R 1 and R 2 The individual is selected from C1-C4 alkyl groups, X is selected from polyvalent organic structures with an average molecular weight of 50-5000 that are reactive with isocyanate groups after the removal of the primary amino group from polyamine compounds, and n = 2-3.

[0037] (B) The monoamine maleate adduct with the structure shown in formula (2) below.

[0038]

[0039] Among them, R 3The organic group remaining after removing one H atom from the N atom of an organic amine compound containing one primary amino or one secondary amino group with a molecular weight not exceeding 100; Et represents ethyl.

[0040] as well as,

[0041] (C) Diethyl fumarate and / or diethyl maleate comprising no more than 0.5% by weight of the aspartic acid ester resin complex.

[0042] The aspartic acid ester resin complex 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 aspartic resin of raw material component (A). The monoamine maleate adduct of raw material component (B) acts as a diluent and ensures that the content of diethyl fumarate and / or diethyl maleate in the aspartic acid ester resin complex does not exceed 0.5 wt%.

[0043] In this invention, the aforementioned organic amine compound is a monofunctional compound containing only one primary amino group or one secondary amino group in its molecule. When the aforementioned organic amine compound contains one primary amino group, the raw material component (B) monoamino maleate adduct contains one secondary amino group, which can participate in the subsequent curing reaction between aspartic resin and curing agent, and is an active diluent; when the aforementioned organic amine compound contains one secondary amino group, the raw material component (B) monoamino maleate adduct does not contain an active H group, 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 single component is selected from ethyl groups, where a polyamine compound undergoes a Michael addition reaction with diethyl maleate.

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

[0046] In a preferred embodiment of the present invention, the organic amine compound has one or more of the general chemical formulas shown in formula (3) or (4) below.

[0047] R 4 NH2(3)

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

[0049] R 5 NHR 6 (4)

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

[0051] On the other hand, the present invention also proposes a preparation process for the low-allergenic aspartic acid ester resin complex described in any of the above embodiments. The process involves slowly adding diethyl maleate dropwise to the polyamine compound at a molar ratio of primary amino group to diethyl maleate of 0.7-0.95:1. After the addition is complete, the temperature is raised to 40-80℃ and reacted for 48-168 hours. Then, an organic amine compound is added, and the temperature is controlled at 40-100℃. The reaction continues 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 then controlled at 80℃-135℃, and a vacuum degree of -0.098 MPa or higher is applied to remove residual low-boiling substances, thus obtaining the 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 less with diethyl maleate, which can promote the complete reaction of the polyamine compound. The remaining unreacted diethyl maleate is completely reacted by adding sufficient or excessive organic amine compound. The total weight percentage of diethyl maleate and diethyl fumarate in the product does not exceed 0.5%. Moreover, even if there is unreacted organic amine compound due to excess, it can be easily removed by vacuum distillation. The content of organic amine compound in the aspartic acid ester resin complex does not exceed 1 wt%. In this invention, the weight percentage of diethyl maleate and / or diethyl fumarate, and the weight percentage of organic amine compounds in the reaction system or products can be detected by gas chromatography or high-performance liquid chromatography. Alternatively, the weight percentage of organic amine compounds 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, please refer to the prior art "Determination of Diethyl Maleate by High-Performance Liquid Chromatography" (Zhejiang Chemical Industry, Vol. 37, No. 7, 2006, pp. 21-22).

[0053] In a preferred embodiment of the present invention, the molar ratio of the primary amino group to diethyl maleate in the polyamine compound is 0.8-0.95:1. For example, the molar ratio of the primary amino group to diethyl maleate in the polyamine compound can be any value from 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 one or a combination of two or more of the following: 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, isophorone diamine, 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 polyetheramines. The polyamine compounds listed above are commonly used in the field of aspartic resins, and their structures contain cycloalkyl groups or are polyetheramines. Polyetheramines can be obtained directly from the market. Examples include polyetheramine D-230, polyetheramine D-400, polyetheramine D-2000, polyetheramine ED-600, polyetheramine ED-900, polyetheramine T-403, and polyetheramine T-5000, but are not limited to those listed above.

[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 selected from 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 any particular limitation.

[0056] In a preferred embodiment of the present invention, the ratio of the sum of the molar numbers of the primary amino group and the organic amine compound in the polyamine compound to the molar number of diethyl maleate is 1-1.2:1. Using the above technical solution, the reaction of diethyl maleate and / or diethyl fumarate in the reaction system can be complete. For example, the ratio of the sum of the molar numbers of the primary amino group and the organic amine compound in the polyamine compound to the molar number of diethyl maleate can be any value from 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 particular limitation.

[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 organic amine compounds listed above have small molecules, high reactivity with diethyl maleate and / or diethyl fumarate, and low boiling points at 1 atmosphere. Even in excess, they can be removed by simple vacuum distillation, ensuring that the content of organic amine compounds in the resulting aspartic acid ester resin composite does not exceed 1 wt%, and has no significant impact on the curing performance of the aspartic acid ester resin composite.

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

[0059] Example 1

[0060] 1 mol of 4,4'-diaminodicyclohexylmethane was added to a four-necked flask, followed by the slow dropwise addition of 2.2 mol of diethyl maleate. The reaction was maintained at 55°C for 48 hours after the addition was complete. Then, 0.2 mol of cyclohexylamine was added, and the reaction was maintained at 60°C for another 48 hours. A sample was taken and analyzed by high-performance liquid chromatography (HPLC), revealing that the sum of the weight percentages of diethyl maleate and diethyl fumarate was 0.33%. Low-boiling-point substances were removed under vacuum at 100-105°C and -0.099 MPa to obtain a low-sensitivity aspartic acid ester resin complex. The weight percentages of diethyl maleate and diethyl fumarate in the complex were measured to be 0.38%, the weight percentage of cyclohexylamine was 0.1%, and the solid content of the complex was 98.2%.

[0061] The solid content was tested by baking 2g of sample in an oven at 105℃ for 2 hours.

[0062] Example 2

[0063] The difference between this embodiment and Example 1 is that in Example 1, the cyclohexylamine was adjusted from 0.2 mol to 0.4 mol. The remaining steps remained unchanged. The obtained low-sensitivity aspartic acid ester resin composite showed a total weight percentage of 0.17% for diethyl maleate and diethyl fumarate, a weight percentage of 0.34% for cyclohexylamine, and a solid content of 98.4% for the composite.

[0064] Example 3

[0065] 1 mol of 4,4'-diaminodicyclohexylmethane was added to a four-necked flask, followed by the slow dropwise addition of 2.2 mol of diethyl maleate. The reaction mixture was maintained at 55°C for 48 hours. Dimethylamine gas was then introduced through a gas tube below the surface of the reaction mixture, maintaining bubbling, until approximately 13.5 g (0.3 mol) of dimethylamine was introduced. The flask was then stopped, the stopper was tightened, and the reaction was maintained at 50°C for another 96 hours. A sample was taken and analyzed by high-performance liquid chromatography (HPLC), revealing a total weight percentage of 0.18% for diethyl maleate and diethyl fumarate. Low-boiling-point substances were removed under vacuum at 80-85°C and -0.099 MPa, yielding a low-sensitivity aspartic acid ester resin complex. The total weight percentage of diethyl maleate and diethyl fumarate in the complex was 0.23%, the weight percentage of dimethylamine was 0.02%, and the solid content of the complex was 97.7%.

[0066] Example 4

[0067] 1 mol of 4,4'-diaminodicyclohexylmethane was added to a four-necked flask, followed by the slow dropwise addition of 2.2 mol of diethyl maleate. The reaction was maintained at 55°C for 48 hours. Then, 0.4 mol of diisobutylamine was added, and the reaction was maintained at 75°C for 128 hours. A sample was taken and analyzed by high-performance liquid chromatography (HPLC), revealing that the sum of the weight percentages of diethyl maleate and diethyl fumarate was 0.07%. Low-boiling-point substances were removed under vacuum at 130-135°C and -0.099 MPa to obtain a low-sensitivity aspartic acid ester resin complex. The weight percentages of diethyl maleate and diethyl fumarate in the complex were measured to be 0.08%, the weight percentage of diisobutylamine was 0.42%, and the solid content of the complex was 97.4%.

[0068] Example 5

[0069] 1 mol of 4,4'-diaminodicyclohexylmethane was added to a four-necked flask, followed by the slow dropwise addition of 2.5 mol of diethyl maleate. The reaction was maintained at 55°C for 60 h after the addition was complete. Then, 0.6 mol of 2-methylcyclohexylamine was added, and the reaction was maintained at 90°C for 96 h. A sample was taken and analyzed by high-performance liquid chromatography (HPLC), and the sum of the weight percentages of diethyl maleate and diethyl fumarate was found to be 0.15%. Low-boiling-point substances were removed under vacuum at 130-135°C and -0.099 MPa to obtain a low-sensitivity aspartic acid ester resin complex. The sum of the weight percentages of diethyl maleate and diethyl fumarate in the complex was found to be 0.22%, the weight percentage of 2-methylcyclohexylamine was 0.61%, and the solid content of the complex was 97.8%.

[0070] Comparative Example 1

[0071] 1 mol of 4,4'-diaminodicyclohexylmethane was added to a four-necked flask, and 2.1 mol of diethyl maleate was slowly added dropwise. After the addition was completed, the reaction was controlled at 60℃ for 96 h, and then vacuumed for 1 h at 130℃-135℃ and -0.099 MPa to obtain aspartic resin. The weight percentage of diethyl maleate and diethyl fumarate in the product aspartic ester resin was determined by high performance liquid chromatography (HPLC) to be 2.4%, and the weight percentage of diethyl fumarate in the product aspartic ester resin was determined by HPLC to be 2.2%.

[0072] Example 6

[0073] 1 mol of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane was added to a four-necked flask, and 2.4 mol of diethyl maleate was slowly added dropwise. After the addition was complete, the reaction was maintained at 70℃ for 72 h. Then, 0.6 mol of 2-methylcyclohexylamine was added, and the reaction was maintained at 90℃ for 100 h. The weight percentage of diethyl maleate and diethyl fumarate was determined by high-performance liquid chromatography (HPLC) to be 0.10%. Low-boiling substances were removed by vacuum at 130-135℃ and -0.099 MPa to obtain a low-sensitivity aspartic acid ester resin complex. The weight percentage of diethyl maleate and diethyl fumarate in the complex was measured to be 0.18%, the weight percentage of 2-methylcyclohexylamine was 0.55%, and the solid content of the complex was 98.1%.

[0074] Comparative Example 2

[0075] 1 mol of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane was added to a four-necked flask, and 2.1 mol of diethyl maleate was slowly added dropwise. After the addition was completed, the reaction was controlled at 70℃ for 96 h, and then vacuumed for 1 h at 130℃-135℃ and -0.099 MPa to obtain aspartic acid ester resin. The weight percentage of diethyl maleate and diethyl fumarate in the aspartic acid ester resin product was determined by high performance liquid chromatography (HPLC) to be 2.5%, and the weight percentage of diethyl fumarate in the aspartic acid ester resin product was determined by HPLC to be 2.4%.

[0076] Performance test comparison

[0077] Prepare polyaspartic acid ester coatings according to the following formula.

[0078] Component A consists of 64% aspartic acid ester resin complex or aspartic acid ester resin to be tested, 5% hydroxyl acrylic resin, 5% titanium dioxide, 25% barium sulfate, 0.2% dispersant, 0.4% defoamer, 0.2% leveling agent and 0.2% anti-settling agent.

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

[0080] Component A and component B were mixed uniformly in a ratio of 1:1.05, where the total molar content of secondary amine and hydroxyl groups in component A was equal to the molar content of isocyanate NCO groups in component B, to obtain a polyaspartic ester coating. The prepared polyaspartic ester coating was made into a film with a thickness of 0.5 mm and cured at 35±2℃ for 15 days. The testing methods and indicators were performed according to T / CWA204-2021 "Aspartic Polyurea Waterproof Coating Standard". The test performance data are shown in Table 1.

[0081] Table 1 Performance Data

[0082]

[0083]

[0084] As can be seen from the above embodiments and the results in Table 1, the total weight percentage of diethyl maleate and diethyl fumarate in the low-sensitivity aspartic acid ester resin of the present invention does not exceed 0.5 wt%, and the residual organic amine compound content is very low, which has no significant impact on the curing performance of the aspartic acid ester resin product.

[0085] As described above, the basic principles, main features, and advantages of the present invention have been shown and described. Those skilled in the art should understand that the present invention is not limited to the above embodiments, which are merely preferred embodiments and should not be construed as limiting the scope of the invention. All equivalent changes and modifications made in accordance with the scope of the patent and the description should still fall within the scope of the present invention. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A preparation process for a low-allergenic aspartic acid ester resin composite, characterized in that, According to the molar ratio of primary amine compound to diethyl maleate in the polyamine compound being 1:1.1, diethyl maleate is slowly added dropwise to the polyamine compound. After the addition is complete, the temperature is raised to 55°C and reacted for 48 hours. Organic amine compound is then added, and the temperature is controlled at 40-100°C. The reaction continues 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 then controlled at 80°C-135°C and the vacuum degree is above -0.098 MPa to remove residual low-boiling substances, thus obtaining the low-allergenic aspartic acid ester resin composite. The aspartic acid ester resin complex comprises the following raw material components: (A) Polyaspartic resin with the structure shown in formula (1) below, （1） Among them, R 1 and R 2 All are ethyl groups, and X is selected from the polyvalent organic structures with an average molecular weight of 50-5000 that are reactive with isocyanate groups at 100℃ after the removal of the primary amino group from the polyamine compound, and n=2-3. (B) Monoamino maleate adducts with the structure shown in formula (2) below, （2） Among them, R 3 The organic group remaining after removing one H atom from the N atom of the organic amine compound containing one primary amino group or one secondary amino group and having a molecular weight not exceeding 100; Et represents ethyl. as well as, (C) Diethyl fumarate and / or diethyl maleate comprising no more than 0.5% by weight of the aspartic ester resin complex; The polyamine compound is selected from one or more of 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, isophorone diamine, 1-methyl-2,4-cyclohexanediamine, 1,3-cyclohexanedimethylamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-cyclopentanediamine, and o-diaminomethylcyclopentane; The organic amine compound has one or more of the general chemical formulas shown in formula (3) below. R 4 NH2(3) Among them, R 4 Selected from C5-C6 cycloalkyl or C6-C10 substituted cycloalkyl.

2. The preparation process of the low-allergenic aspartic acid ester resin composite according to claim 1, characterized in that, The molar ratio of the organic amine compound to the diethyl maleate is 0.1-0.5:

1.

3. The preparation process of the low-allergenic aspartic acid ester resin composite according to claim 1, characterized in that, The ratio of the sum of the molar numbers of the primary amino group and the organic amine compound in the polyamine compound to the molar number of the diethyl maleate is 1-1.2:

1.

4. The preparation process of the low-allergenic aspartic acid ester resin composite according to claim 1, characterized in that, The organic amine compound is selected from one or more combinations of cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, cyclopentylamine, 2-methylcyclopentylamine and 3-methylcyclopentylamine.

5. The preparation process of the low-allergenic aspartic acid ester resin composite according to claim 1, characterized in that, The monoamine maleate adduct accounts for 3-15% of the weight of the aspartic acid ester resin complex.

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