An imide aspartic acid ester resin

Abstract

The present invention provides an imide aspartic acid ester resin, relating to the technical field of aspartic acid ester resins. The imide aspartic acid ester resin comprises a secondary amine resin having a structure of YA2, where Y is a divalent hydrophilic polyether structure and A is an imide secondary amine structure. The imide aspartic acid ester resin may also comprise a hydrophobic secondary amine resin. The imide aspartic acid ester resin of the present invention can be dispersed in water to form an emulsion. After curing with a curing agent, the resin exhibits improved hydrolysis resistance, heat resistance, and mechanical strength compared to conventional aspartic acid ester resins.

Description

Technical Field

[0001] The invention belongs to the technical field of aspartic acid ester resins and relates to an imide aspartic acid ester resin. Background Art

[0002] Aspartic acid ester resin is a polyvalent secondary amino resin obtained by the Michael addition reaction of a polyvalent primary amine compound and a dialkyl maleate / dialkyl fumarate (such as diethyl maleate). It can be mixed with an isocyanate curing agent to produce a curing reaction to form a polyurea material. It has been widely used in surface protective coatings, caulking agents, and impact-resistant materials. The ester groups in the side chains of aspartic acid ester resin provide solvation and internal plasticization for the polyurea material, improving its flexibility. However, the ester groups have drawbacks such as poor heat resistance and susceptibility to hydrolysis (especially under alkaline conditions). Consequently, the polyurea material suffers from insufficient heat resistance, insufficient hydrolysis resistance, and low mechanical strength. In addition, hydrophilic aspartic acid ester resins are generally obtained in the prior art by an ester exchange reaction between a hydrophilic hydroxyl-terminated polyether and an aspartic acid ester resin. Since the polyether is linked to the ester group, as the ester group hydrolyzes, the polyether chain segments fall off, causing the hydrophilicity of the hydrophilic aspartic acid ester resin to gradually deteriorate or even lose its hydrophilicity, resulting in product instability.

[0003] For this reason, it is urgent to solve the above-mentioned deficiencies and problems of aspartic acid ester resin. Summary of the Invention

[0004] Imide structures have excellent thermal stability and hydrolysis resistance, and due to their cyclic structure, they also have high mechanical strength. Introducing imide structures into aspartic acid ester resins can address the aforementioned deficiencies or problems existing in current aspartic acid ester resins. The inventors conducted extensive testing and analysis, and based on this, proposed the present invention. The present invention provides an imide aspartic acid ester resin.

[0005] The technical solutions of the present invention are as follows:

[0006] An imide aspartic acid ester resin, comprising a secondary amino resin (I) having a structure represented by the following formula (1):

[0007] YA2(1)

[0008] Wherein, Y is a divalent hydrophilic polyether structure, and the structure of A is one or a combination of two structures shown in the following formula (2) or (3):

[0009]

[0010] Among them, R 1 and R 2independently selected from C1-C4 alkyl, R 3 is selected from a C1-C18 alkyl group, a C2-C18 substituted alkyl group, a cyclopentyl group, a cyclohexyl group, a C6-C12 substituted cycloalkyl group, or a polyether segment, wherein X is a divalent organic structure having an average molecular weight of 50-5000 and being inert to an isocyanate group at 100° C., which is left after removing the primary amino group from the polyamine compound.

[0011] Preferably, the weight proportion of the secondary amino resin (I) in the imide aspartic acid ester resin is not less than 10%.

[0012] More preferably, the weight proportion of the secondary amino resin (I) in the imide aspartic acid ester resin is 15-60%.

[0013] Preferably, the solubility of the double-terminated primary amino polyether corresponding to the divalent hydrophilic polyether structure in pure water at 25° C. is not less than 10 g / 100 g water.

[0014] Preferably, the structure of the polyether segment is as shown in the following formula (4):

[0015] -(CH2CH2O) c (CH2CHCH3O) d R 4 (4)

[0016] Where, c≥0, d≥0, 1≤c+d≤100, R 4 Selected from H or C1-C8 alkyl.

[0017] Preferably, the secondary amino resin (I) is obtained by an imide reaction between the double-terminated primary amino polyether corresponding to the divalent hydrophilic polyether structure and the secondary amino resin (II) shown in the following formula (5);

[0018]

[0019] Among them, R 1 、R 2 , X has the meaning as described above;

[0020] or,

[0021] The double-terminal primary amino polyether reacts with the secondary amino resin (II) to undergo an imide reaction and then reacts with the single-terminal amino compound NH2R 3 Imide reaction was performed to obtain R 3 The meaning of is as described above.

[0022] More preferably, the molar ratio of the double-terminated primary amino polyether to the secondary amino resin (II) is 1:1.8-2.2.

[0023] Preferably, the imide aspartic acid ester resin further comprises a secondary amino resin (III) having a structure as shown in the following formula (6):

[0024] YC m (6)

[0025] Wherein, Y is an m-valent organic structure having an average molecular weight of 50-5000 and being inert to the reaction with the isocyanate group at 100° C., which is left after the primary amino group of the second polyamine compound is removed, and m=2-3. The structure of C is shown in the following formula (7) or formula (8):

[0026]

[0027] Among them, R 5 and R 6 independently selected from C1-C4 alkyl;

[0028]

[0029] Among them, R 7 Selected from C1-C18 alkyl, C3-C20 substituted alkyl, cyclopentyl, cyclohexyl or C6-C12 substituted cycloalkyl.

[0030] More preferably, the weight proportion of the secondary amino resin (III) in the imide aspartic acid ester resin is 40-85%.

[0031] More preferably, the weight ratio of the secondary amino resin (I) to the secondary amino resin (III) is 5:1-1:4.

[0032] The beneficial effects of the present invention are:

[0033] (1) In the imide aspartic acid ester resin structure of the present invention, the hydrophilic polyether structure is directly connected to the N on the imide structure. The imide structure has good stability and high hydrolysis resistance. Therefore, the hydrophilic polyether segment is not easily separated from the resin structure. Even under alkaline or acidic conditions, it has high stability.

[0034] (2) The secondary amino resin (I) has a hydrophilic and hydrophobic structure and has certain hydrophilic and hydrophobic properties. It can be used as an emulsifier and emulsify the hydrophobic aspartic acid ester resin (secondary amino resin (III)) to form an emulsion. The emulsion has good stability. When combined with a curing agent, it can form a coating with good stability, high hydrolysis resistance, and good heat resistance. DETAILED DESCRIPTION

[0035] The technical solution of the present invention is further illustrated and described below through specific implementation methods.

[0036] In order to solve the problems of poor hydrolysis resistance, low heat resistance, and low mechanical strength after curing in the prior art aspartic acid ester resin, the present invention provides an imide aspartic acid ester resin, which comprises a secondary amino resin (I) having a structure shown in the following formula (1):

[0037] YA2(1)

[0038] Wherein, Y is a divalent hydrophilic polyether structure, and the structure of A is one or a combination of two structures shown in the following formula (2) or (3):

[0039]

[0040] Among them, R 1 and R 2 independently selected from C1-C4 alkyl, R 3 is selected from a C1-C18 alkyl group, a C2-C18 substituted alkyl group, a cyclopentyl group, a cyclohexyl group, a C6-C12 substituted cycloalkyl group, or a polyether segment, wherein X is a divalent organic structure having an average molecular weight of 50-5000 and being inert to an isocyanate group at 100° C., which is left after removing the primary amino group from the polyamine compound.

[0041] In the structure of the above-mentioned secondary amino resin (I), the hydrophilic polyether structure is directly connected to the N atom on the imide. The imide has good stability, high heat resistance, and good hydrolysis resistance, and can give the secondary amino resin (I) a certain hydrophilicity and hydrophobicity. The secondary amino resin (I) has good stability, even in alkaline and acidic environments. Moreover, the structure of formula (3) has better stability, heat resistance, hydrolysis resistance and other properties than the structure of formula (2), because the ester group in formula (2) is converted into the more stable imide structure in formula (3). From the perspective of practical application, the structure of A can also adopt a combination of the structures of formula (2) and formula (3), taking into account the characteristics of the imide structure and the ester structure.

[0042] In the above secondary amino resin (I), R 1 and R 2 They can be methyl and ethyl respectively, which is more preferable in industry; R 3 It can be a hydrophobic structure, such as methyl, n-hexyl, n-octyl, lauryl, stearyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-isopropylcyclohexyl, cyclopentyl, etc., or it can be a polyether segment with certain hydrophilicity and hydrophobicity. 3 Adjustment of the structure can give the secondary amino resin (Ⅰ) different properties, such as different hydrophilic and hydrophobic properties.

[0043] In a preferred embodiment of the present invention, the weight proportion of the secondary amino resin (I) in the imide aspartic acid ester resin is not less than 10%. By adopting the above technical solution, the performance of the secondary amino resin (I) can be brought into play in the imide aspartic acid ester resin. For example, the weight proportion of the secondary amino resin (I) in the imide aspartic acid ester resin can be any value among 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, etc., without special limitation. More preferably, the weight proportion of the secondary amino resin (I) in the imide aspartic acid ester resin is 15-60%. For example, the weight proportion can be any value of 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, etc., without special restrictions.

[0044] In a preferred embodiment of the present invention, the solubility of the double-terminated primary amino polyether corresponding to the divalent hydrophilic polyether structure in pure water at 25°C is not less than 10g / 100g. The solubility of the double-terminated primary amino polyether in water can be used to evaluate the hydrophilicity of the double-terminated primary amino polyether. The higher the solubility, the better the hydrophilicity. If the hydrophilicity of the double-terminated primary amino polyether is insufficient, the performance of the secondary amino resin (Ⅰ) cannot be exerted. For example, the solubility of the double-terminated primary amino polyether in pure water at 25°C can be any value of 10g / 100g, 20g / 100g, 30g / 100g, 50g / 100g, 70g / 100g, 80g / 100g, 90g / 100g, 100g / 100g, etc., without special restrictions. In the present invention, the structure of the double-terminated primary amino polyether can be as shown in the following formula (9), NH2(CH2CH2O) a (CH2CHCH3O) b CH2CH2NH2(9)

[0045] Wherein, a ≥ 4, b ≥ 0, 10 ≤ a + b ≤ 200, and a ≥ 1.3b. Double-terminated primary amino polyethers can be directly obtained from the market, such as ZED-601, ZED-901, and ZED-2031 from Zibo Zhengda Polyurethane Co., Ltd., CAED-900 and CAED-600 from Yangzhou Chenhua New Materials Co., Ltd., or double-terminated primary amino polyethylene glycol.

[0046] In a preferred embodiment of the present invention, the structure of the polyether segment is shown in the following formula (4):

[0047] -(CH2CH2O) c (CH2CHCH3O) d R 4 (4)

[0048] Where, c≥0, d≥0, 1≤c+d≤100, R 4 Selected from H or C1-C8 alkyl. EO represents -CH2CH2O-, PO represents -CH2CHCH3O-, and the structure of the polyether segment can be expressed as EO c PO d R 4 Adjusting the amount of EO and PO in the polyether segment can adjust the properties of the polyether segment, such as hydrophilicity and hydrophobicity. The corresponding single-terminated amino polyethers for the polyether segment are directly available on the market, such as ZM-1100 and ZM-160 from Zibo Zhengda Polyurethane Co., Ltd. and CAM-2070 and CAM-2005 from Yangzhou Chenhua New Materials Co., Ltd.

[0049] In a preferred embodiment of the present invention, the secondary amino resin (I) is obtained by an imide reaction between a double-terminated primary amino polyether corresponding to a divalent hydrophilic polyether structure and a secondary amino resin (II) as shown in the following formula (5);

[0050]

[0051] Among them, R 1 、R 2 , X has the meaning as described above;

[0052] or,

[0053] The double-terminal primary amino polyether reacts with the secondary amino resin (Ⅱ) to form an imide reaction, and then reacts with the single-terminal amino compound NH2R 3 Imide reaction was performed to obtain R 3 The meaning of is as described above.

[0054] The double-terminated primary amino polyether contains two terminal primary amino groups, which can undergo an imide reaction with the above-mentioned secondary amino resin (II). By adjusting the molar ratio of the double-terminated primary amino polyether and the secondary amino resin (II) to be close to or reach 2:1, the above-mentioned secondary amino resin (I) can be obtained. In the present invention, the secondary amino resin (II) can be purchased directly from the market, such as Feiyang Junyan Company's F420 resin, F520 resin, F524 resin, etc., or can be prepared according to existing technologies, such as diethyl maleate and 4,4'-diaminodicyclohexylmethane (or 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, isophoronediamine, etc.) to undergo Michael addition reaction to obtain it.

[0055] In a more preferred embodiment of the present invention, the molar ratio of the double-terminated primary amino polyether to the secondary amino resin (II) is 1:1.8-2.2. For example, the molar ratio of the double-terminated primary amino polyether to the secondary amino resin (II) can be any value in the range of 1:1.8, 1:1.85, 1:1.9, 1:1.95, 1:2, 1:2.05, 1:2.1, 1:2.15, 1:2.2, etc., without particular limitation. Further, the molar ratio of the double-terminated primary amino polyether to the secondary amino resin (II) can be 1:1.9-2.05. For example, the molar ratio can be any value in the range of 1:1.9, 1:1.92, 1:1.95, 1:1.96, 1:1.98, 1:2, 1:2.01, 1:2.02, 1:2.03, 1:2.05, etc., without particular limitation.

[0056] The double-terminal primary amino polyether and the secondary amino resin (II) react at a molar ratio close to or reaching 2:1. There are ester groups at both ends. The ester groups can partially or completely continue to react with the single-terminal amino compound to undergo an imide reaction, further converting some or all of the ester groups at both ends into an imide structure, thereby further exerting the effects of the imide structure such as hydrolysis resistance, high temperature resistance, and high mechanical strength.

[0057] For example, the preparation of the secondary amino resin (I) can be carried out according to the following steps: adding a double-terminated primary amino polyether to a reaction vessel, adding a catalyst (lauric acid, stearic acid, benzotriazole, 1-hydroxybenzotriazole, etc.) in an amount of 0.1-0.5% by weight of the double-terminated primary amino polyether, stirring evenly, adding the secondary amino resin (II), raising the temperature to 90-150° C. to react, waiting for reflux in the reaction system, introducing a gas (such as nitrogen) into the reaction system to remove the generated alcohol (such as methanol, ethanol) until no bubbles are generated in the reaction system, and reducing the pressure to -0.099 MPa or below to remove low-boiling substances to obtain a light yellow to brownish yellow transparent product, which is the secondary amino resin (I). Alternatively, after no bubbles are generated in the above reaction system, the single-terminal amino compound is continued to be added and the reaction is continued at a constant temperature. When reflux occurs in the reaction system, a gas (such as nitrogen) is introduced into the reaction system to remove the generated alcohol (such as methanol or ethanol) until no bubbles are generated in the reaction system. The pressure is reduced to -0.099 MPa or below to remove low-boiling substances, and a light yellow to brownish yellow transparent product is obtained, which is the secondary amino resin (I).

[0058] In a preferred embodiment of the present invention, the imide aspartic acid ester resin further comprises a secondary amino resin (III) having a structure shown in the following formula (6):

[0059] YC m (6)

[0060] Wherein, Y is an m-valent organic structure having an average molecular weight of 50-5000 and being inert to the reaction with the isocyanate group at 100° C., which is left after the primary amino group of the second polyamine compound is removed, and m=2-3. The structure of C is shown in the following formula (7) or formula (8):

[0061]

[0062] Among them, R 5 and R 6 independently selected from C1-C4 alkyl;

[0063]

[0064] Among them, R 7 Selected from C1-C18 alkyl, C3-C20 substituted alkyl, cyclopentyl, cyclohexyl or C6-C12 substituted cycloalkyl.

[0065] The aforementioned secondary amino resin (III) is a hydrophobic secondary amino resin. When combined with the secondary amino resin (I) having certain hydrophilic and emulsifying properties, water is added and dispersed to form an O / W emulsion. The oil phase is the secondary amino resin (III), and the emulsifier is the secondary amino resin (I). The secondary amino resin (III) and the secondary amino resin (I) can participate in the curing process together, and the addition of the secondary amino resin (III) improves the water resistance of the cured product. The O / W emulsion can further undergo a curing reaction with an isocyanate curing agent and solidify. By adding pigments and fillers, as well as additives such as leveling agents, wetting agents, defoamers, dispersants, thickeners, anti-settling agents, thixotropic agents, anti-aging agents, and UV protection agents, the O / W emulsion can be prepared into a water-based coating.

[0066] The structure of C can be either a single structure as shown in formula (7) or formula (8), or a combination of the structures shown in formula (7) and formula (8). In order to ensure the hydrophobicity of the secondary amino resin (III), Y can be a divalent structure remaining after removing two amino groups such as 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, isophorone diamine, etc., and R 7 It may be a hydrophobic group, such as n-butyl, isobutyl, n-hexyl, n-octyl, lauryl, cyclohexyl, cyclopentyl, 2-methylcyclohexyl, 4-methylcyclohexyl, 4-isopropylcyclohexyl, 2-ethylcyclohexyl, and the like.

[0067] The secondary amino resin (III) corresponding to the above formula (8) can be prepared by reacting the secondary amino resin (such as F420 resin, F520 resin, etc.) corresponding to the formula (7) with R 7 Corresponding R 7 The imide reaction can refer to the preparation steps of the secondary amino resin (I) above.

[0068] In a more preferred embodiment of the present invention, the weight proportion of the secondary amino resin (III) in the imide aspartic acid ester resin is 40-85%. For example, the weight proportion of the secondary amino resin (III) in the imide aspartic acid ester resin can be any value including 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, etc., without particular limitation.

[0069] In a more preferred embodiment of the present invention, the weight ratio of the secondary amino resin (I) to the secondary amino resin (III) is 5:1-1:4. For example, the weight ratio of the secondary amino resin (I) to the secondary amino resin (III) can be any value among 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, etc., without particular limitation. Furthermore, the weight ratio of the secondary amino resin (I) to the secondary amino resin (III) can be 2:1-1:4.

[0070] The technical solution of the present invention is further described and illustrated below based on various embodiments. Unless otherwise specified, the parts in the following embodiments are parts by weight.

[0071] Example 1-6 Preparation of secondary amino resin (I)

[0072] Example 1

[0073] 1 mol of double-terminated primary amino polyether ZED-601 was added to a reaction vessel, and 0.3% by weight of the double-terminated primary amino polyether catalyst 1-hydroxybenzoxazole was added, and the mixture was stirred evenly. 2 mol of F420 resin was gradually added, and the temperature was raised to 130° C. to react. When reflux occurred in the reaction system, nitrogen was introduced into the reaction system to remove generated ethanol until no bubbles were generated in the reaction system. The pressure was reduced to -0.099 MPa to remove low-boiling substances, and a light yellow transparent product was obtained, namely, secondary amino resin (I).

[0074] Example 2

[0075] The difference between this example and Example 1 is that in Example 1, after no bubbles were generated in the reaction system, 0.6 mol of n-octylamine was continued to be added, and when reflux occurred again in the reaction system, nitrogen was introduced into the reaction system again to remove the generated ethanol until no bubbles were generated in the reaction system. The pressure was reduced to -0.099 MPa to remove low-boiling substances, and a brown-yellow transparent product was obtained, which was the secondary amino resin (I).

[0076] Example 3

[0077] The difference between this embodiment and embodiment 2 is that in embodiment 2, the amount of n-octylamine is adjusted from 0.6 mol to 1.5 mol, while the other steps remain unchanged.

[0078] Example 4

[0079] 1 mol of double-terminated primary amino polyethylene glycol (number average molecular weight 1100) was added to a reaction vessel, and a catalyst 1-hydroxybenzoxazole (0.25% by weight of the double-terminated primary amino polyethylene glycol) was added and stirred evenly. 2.02 mol of F420 resin was gradually added and the temperature was raised to 130° C. to react. When reflux occurred in the reaction system, nitrogen was introduced into the reaction system to remove generated ethanol until no bubbles were generated in the reaction system. The pressure was then reduced to -0.099 MPa to remove low-boiling substances, thereby obtaining a light yellow transparent product, namely, secondary amino resin (I).

[0080] Example 5

[0081] The difference between this example and Example 4 is that in Example 4, after no bubbles are generated in the reaction system, 1 mol of single-end amino polyether ZM-160 is continued to be added, and when reflux occurs again in the reaction system, nitrogen is continued to be introduced into the reaction system to remove the generated ethanol until no bubbles are generated in the reaction system, and the pressure is reduced to -0.099 MPa to remove low-boiling substances to obtain a brownish-yellow transparent product, which is secondary amino resin (I).

[0082] Example 6

[0083] 1 mol of double-terminated primary amino polyether CAED-900 was added to a reaction vessel, and 0.35% by weight of the double-terminated primary amino polyether catalyst 1-hydroxybenzoxazole was added, and the mixture was stirred evenly. 1.95 mol of F420 resin was gradually added, and the temperature was raised to 130° C. to react. When reflux occurred in the reaction system, nitrogen was introduced into the reaction system to remove generated ethanol until no bubbles were generated in the reaction system. The pressure was then reduced to -0.099 MPa to remove low-boiling substances, and a light yellow transparent product was obtained, namely, secondary amino resin (I).

[0084] Comparative Example 1

[0085] The hydrophilic aspartic acid ester resin was prepared according to the method of Example 1 in the prior art CN111303368A.

[0086] Water solubility test method: At 25°C, weigh 100 grams of the resin sample to be tested and place it in a colorless, transparent container. Slowly add an appropriate amount of pure water while stirring until evenly mixed. Then, perform the test according to the method specified in GB 1721-2008, "Varnishes, Oils, and Thinners, Determination of Appearance and Transparency." Record the weight of pure water added when the instrument reading reaches 82. The results are shown in Table 1 below. The lower the weight of pure water, the less hydrophilic the resin to be tested.

[0087] The secondary amino resins (I) of Examples 1, 2, and 4, and the hydrophilic aspartic acid ester resin of Comparative Example 1, were added to a 2 wt % aqueous NaOH solution to prepare colorless, transparent solutions with a resin concentration of 20 wt %. The solutions were then placed at 25°C and the time it took for the solutions to become turbid, show oily ions, or precipitate was observed. Turbidity, oily ions, or precipitates indicate hydrolysis of the resin in the solution. A shorter time indicates poorer hydrolysis resistance.

[0088] Table 1

[0089]

[0090] From the data in Table 1 above, it can be seen that the hydrophilicity of the imido aspartic acid ester of the present invention can be adjusted by adjusting the structure, and the imido aspartic acid ester of the present invention has good resistance to alkaline hydrolysis.

[0091] Example 7

[0092] The imide aspartic acid ester resin is obtained by mixing the secondary amino resin (I) of Example 1 and the F420 resin of Feiyang Junyan Company in a weight ratio of 1:2 and stirring them evenly.

[0093] Example 8

[0094] The difference between Example 8 and Example 7 is that in Example 7, the secondary amino resin (I) of Example 1 is replaced by an equal weight of the secondary amino resin (I) of Example 2. The remaining steps remain unchanged.

[0095] Example 9

[0096] The difference between Example 9 and Example 7 is that in Example 7, the secondary amino resin (I) of Example 1 is replaced by an equal weight of the secondary amino resin (I) of Example 3. The remaining steps remain unchanged.

[0097] Example 10

[0098] 1 mol of 4-methylcyclohexylamine was added to a reaction vessel, and a catalyst of 1-hydroxybenzoxazole (0.5% by weight of 4-methylcyclohexylamine) was added, and the mixture was stirred evenly. 1 mol of F420 resin was gradually added, and the temperature was raised to 110° C. to react. When reflux occurred in the reaction system, nitrogen was introduced into the reaction system to remove generated ethanol until no bubbles were generated in the reaction system. The pressure was then reduced to -0.099 MPa to remove low-boiling substances, and a light yellow transparent product was obtained, namely, secondary amino resin (III).

[0099] The difference between Example 10 and Example 9 is that in Example 9, the F420 resin is replaced by an equal weight of 420 resin and the above secondary amino resin (III) in a weight ratio of 1:1. The remaining steps remain unchanged.

[0100] Example 11

[0101] The difference between Example 11 and Example 10 is that in Example 10, the F420 resin is replaced by an equal weight of the secondary amino resin (III) in Example 10. The remaining steps remain unchanged.

[0102] Example 12

[0103] The difference between Example 12 and Example 10 is that in Example 10, the amount of 4-methylcyclohexylamine was adjusted from 1 mol to 2 mol. The remaining steps remained unchanged.

[0104] Example 13

[0105] The difference between Example 13 and Example 12 is that in Example 12, the F420 resin is replaced by an equal weight of the secondary amino resin (III) in Example 12. The remaining steps remain unchanged.

[0106] Example 14

[0107] The imide aspartic acid ester resin is obtained by mixing the secondary amino resin (I) of Example 5 and the F420 resin in a weight ratio of 2:1 and stirring them uniformly.

[0108] Example 15

[0109] The difference between Example 15 and Example 14 is that in Example 14, the weight ratio of the secondary amino resin (I) to the F420 resin was adjusted from 2:1 to 1:1. The remaining steps remained unchanged.

[0110] Example 16

[0111] The difference between Example 16 and Example 14 is that in Example 14, the weight ratio of the secondary amino resin (I) to the F420 resin was adjusted from 2:1 to 1:2. The remaining steps remained unchanged.

[0112] Example 17

[0113] The difference between Example 17 and Example 14 is that in Example 14, the weight ratio of the secondary amino resin (I) to the F420 resin is adjusted from 2:1 to 1:4. The remaining steps remain unchanged.

[0114] Comparative Example 1

[0115] The difference between Comparative Example 1 and Example 7 is that in Example 7, the secondary amino resin (I) is replaced by a hydrophilic resin prepared by the method of Example 1 in the prior art CN111303368A. The remaining steps remain unchanged.

[0116] Comparative Example 2

[0117] The imide aspartic acid ester resin is the secondary amino resin (I) in Example 3.

[0118] 100 parts of the resin to be tested were added to the reaction bottle, and 150 parts of pure water were gradually added at a stirring speed of 1200 rpm. After the addition of pure water, constant stirring was continued for 10 minutes, and then the stirring speed was reduced to 500 rpm and continued to stir for 30 minutes to obtain an emulsion.

[0119] The emulsion and the water-based isocyanate curing agent Huntsman 9236 were mixed uniformly at a ratio of 1:1.05 between the total molar number of secondary amine and hydroxyl groups and the molar number of isocyanate. This resulted in a coating composition. A 0.1mm thick film was formed on a clean glass surface, heat-cured, and placed at 25°C and 55% humidity for 24 hours. The coating composition was then tested for its holding time in a 100°C 1wt% NaOH aqueous solution, with observations made every 0.5 hours. The boiling time was determined based on the time closest to the onset of abnormalities such as shedding, warping, or bubbling. For example, if abnormalities were observed after 3.5 hours, the boiling time was 3 hours. A longer boiling time indicates improved hydrolysis resistance.

[0120] Measure 2 ml of the emulsion into a test tube, add 4 ml of pure water, shake thoroughly, and let it stand. Observe the emulsion for abnormalities such as stratification and precipitation after 24 and 48 hours. If there are no abnormalities after 48 hours, the mark is "△"; if there are no abnormalities after 24 hours but abnormalities occur after 48 hours, the mark is "△△"; if abnormalities occur after 24 hours, the mark is "△△△".

[0121] The results are shown in Table 2 below.

[0122] Table 2

[0123]

[0124]

[0125] From the data results in Table 2, it can be seen that the emulsion of the imide aspartic acid ester resin composed of the hydrophilic secondary amino resin and the hydrophobic secondary amino resin in the present invention, after being emulsified with water, has good hydrolysis resistance after curing, and the emulsion has good dilution stability.

[0126] 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 to the above-described embodiments. The above-described embodiments are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. In other words, equivalent changes and modifications made within the scope of the present invention and the contents of the specification should still fall within the scope of the present invention. The scope of protection claimed in the present invention is defined by the appended claims and their equivalents.

Claims

1. An imide aspartic acid ester resin, characterized in that The imide aspartic acid ester resin comprises a secondary amino resin (I) having a structure represented by the following formula (1): YA2(1) Wherein, Y is a divalent hydrophilic polyether structure, and the structure of A is one or a combination of two structures shown in the following formula (2) or (3): Among them, R 1 and R 2 independently selected from C1-C4 alkyl, R 3 is selected from a C1-C18 alkyl group, a C2-C18 substituted alkyl group, a cyclopentyl group, a cyclohexyl group, a C6-C12 substituted cycloalkyl group, or a polyether segment, wherein X is a divalent organic structure having an average molecular weight of 50-5000 and being inert to an isocyanate group at 100° C., which is left after removing the primary amino group from the polyamine compound.

2. The imide aspartic acid ester resin according to claim 1, characterized in that The weight proportion of the secondary amino resin (I) in the imide aspartic acid ester resin is not less than 10%.

3. The imide aspartic acid ester resin according to claim 2, characterized in that The weight proportion of the secondary amino resin (I) in the imide aspartic acid ester resin is 15-60%.

4. The imide aspartic acid ester resin according to claim 1, characterized in that The solubility of the double-terminated primary amino polyether corresponding to the divalent hydrophilic polyether structure in pure water at 25° C. is not less than 10 g / 100 g water.

5. The imide aspartic acid ester resin according to claim 1, characterized in that The structure of the polyether segment is shown in the following formula (4): -(CH2CH2O) c (CH2CHCH3O) d R 4 (4) Where, c≥0, d≥0, 1≤c+d≤100, R 4 Selected from H or C1-C8 alkyl.

6. The imide aspartic acid ester resin according to claim 1, characterized in that The secondary amino resin (I) is obtained by an imide reaction between the double-terminated primary amino polyether corresponding to the divalent hydrophilic polyether structure and the secondary amino resin (II) shown in the following formula (5); Among them, R 1 、R 2 , X has the meaning as described above; or, The double-terminal primary amino polyether reacts with the secondary amino resin (II) to undergo an imide reaction and then reacts with the single-terminal amino compound NH2R 3 Imide reaction was performed to obtain R 3 The meaning of is as described above.

7. The imide aspartic acid ester resin according to claim 6, characterized in that The molar ratio of the double-terminated primary amino polyether to the secondary amino resin (II) is 1:1.8-2.

2.

8. The imide aspartic acid ester resin according to claim 1, characterized in that The imide aspartic acid ester resin further comprises a secondary amino resin (III) having a structure as shown in the following formula (6): YC m (6) Wherein, Y is an m-valent organic structure having an average molecular weight of 50-5000 and being inert to the reaction with the isocyanate group at 100° C., which is left after the primary amino group of the second polyamine compound is removed, and m=2-3. The structure of C is shown in the following formula (7) or formula (8): Among them, R 5 and R 6 independently selected from C1-C4 alkyl; Among them, R 7 Selected from C1-C18 alkyl, C3-C20 substituted alkyl, cyclopentyl, cyclohexyl or C6-C12 substituted cycloalkyl.

9. The imide aspartic acid ester resin according to claim 8, characterized in that The weight proportion of the secondary amino resin (III) in the imide aspartic acid ester resin is 40-85%.

10. The imide aspartic acid ester resin according to claim 8, characterized in that The weight ratio of the secondary amino resin (I) to the secondary amino resin (III) is 5:1-1:4.

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