Imide asparaginic acid ester resin

Abstract

The invention provides imide aspartic acid ester resin, and relates to the technical field of aspartic acid ester resin. The imide asparaginic acid ester resin comprises secondary amino resin with a structure of YA2, Y is a divalent hydrophilic polyether structure, and A is an imide secondary amino structure. The imide asparaginic acid ester resin may also include a hydrophobic secondary amine-based resin. The imide aspartic ester resin can be dispersed in water to form an emulsion, and after being cured together with a curing agent, the imide aspartic ester resin has better hydrolysis resistance, heat resistance, mechanical strength and the like compared with conventional aspartic ester resin.

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 kind of polyvalent secondary amino resin obtained by Michael addition reaction of polyvalent primary amine compound and dialkyl maleate / dialkyl fumarate (such as diethyl maleate). It can be mixed with isocyanate curing agent to undergo curing reaction and obtain polyurea material. It has been widely used in surface protective coatings, seam beautifiers, impact-resistant materials and other fields. The ester group of the side chain in aspartic acid ester resin provides solvation and internal plasticization for polyurea material, improving the flexibility of polyurea material. However, the ester group has the disadvantages of poor heat resistance and easy hydrolysis (especially under alkaline conditions), resulting in the disadvantages of insufficient heat resistance, insufficient hydrolysis resistance and low mechanical strength of polyurea material. In addition, the hydrophilic aspartic acid ester resin is generally obtained by an ester exchange reaction between a hydrophilic terminal hydroxyl polyether and an aspartic acid ester resin in the prior art. Since the polyether is linked to the ester group, as the ester group is hydrolyzed, the polyether chain segment falls off, causing the hydrophilicity of the hydrophilic aspartic acid ester resin to gradually deteriorate or even lose its hydrophilicity, resulting in an unstable product.

[0003] Therefore, it is urgent to solve the above-mentioned deficiencies and problems of aspartic acid ester resin. Summary of the invention

[0004] The imide structure has the characteristics of good thermal stability and hydrolysis resistance, and because it is a cyclic structure, the mechanical strength is also high. Introducing the imide structure into the aspartic acid ester resin can solve the above-mentioned shortcomings or problems existing in the current aspartic acid ester resin. The inventor has conducted a large number of experiments and analyses on this, and based on this, the present invention is proposed. The present invention provides an imide aspartic acid ester resin.

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

[0006] An imide aspartic acid ester resin, the imide aspartic acid ester resin comprising a secondary amine resin (I) having a structure as shown in 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 C1-C18 alkyl, C2-C18 substituted alkyl, cyclopentyl, cyclohexyl, C6-C12 substituted cycloalkyl or polyether segment, X is a divalent organic structure with an average molecular weight of 50-5000 that is inert to the isocyanate group at 100°C and is left after the primary amino group is removed 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-terminal 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 amine resin (I) is obtained by an imide reaction between the double-terminal primary amino polyether corresponding to the divalent hydrophilic polyether structure and the secondary amine 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 The imide reaction was carried out to obtain R 3 has the same meaning as 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 amine 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 with an average molecular weight of 50-5000 which is inert to react with isocyanate groups at 100° C. and which is left after the primary amino group of the second polyamine compound is removed, m=2-3, and 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 amine resin (III) in the imide aspartic acid ester resin is 40-85%.

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

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

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

[0034] (2) The secondary amine resin (I) has hydrophilic and hydrophobic structures in its structure and has certain hydrophilic and hydrophobic properties. It can be used as an emulsifier and emulsify the hydrophobic aspartic acid ester resin (secondary amine resin (III)) to form an emulsion. The emulsion has good stability and can form a coating with good stability, high hydrolysis resistance and good heat resistance when combined with a curing agent. 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, low mechanical strength after curing, etc. of aspartic acid ester resin in the prior art, on the one hand, the present invention provides an imide aspartic acid ester resin, the imide aspartic acid ester resin comprising a secondary amine resin (I) having a structure as 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 C1-C18 alkyl, C2-C18 substituted alkyl, cyclopentyl, cyclohexyl, C6-C12 substituted cycloalkyl or polyether segment, X is a divalent organic structure with an average molecular weight of 50-5000 that is inert to the isocyanate group at 100°C and is left after the primary amino group is removed from the polyamine compound.

[0041] In the structure of the secondary amine resin (I) above, 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 amine resin (I) a certain hydrophilicity and hydrophobicity. The secondary amine resin (I) has good stability, even in alkaline and acidic environments. Moreover, the structure of formula (3) above 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 a 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 preferred 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 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 amine resin (I) in the imide aspartic acid ester resin is not less than 10%. By adopting the above technical scheme, the performance of the secondary amine resin (I) can be brought into play in the imide aspartic acid ester resin. For example, the weight proportion of the secondary amine resin (I) in the imide aspartic acid ester resin can be any value of 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, etc., without special restrictions. 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 any 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, a≥1.3b. Double-terminated primary amino polyether can be directly obtained from the market, such as ZED-601, ZED-901, ZED-2031 of Zibo Zhengda Polyurethane Co., Ltd., CAED-900, CAED-600 of 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 By adjusting the amount of EO and PO in the polyether segment, the performance of the polyether segment, such as hydrophilicity and hydrophobicity, can be adjusted. The single-terminated amino polyether corresponding to the polyether segment can be directly obtained from the market, such as ZM-1100 and ZM-160 from Zibo Zhengda Polyurethane Co., Ltd., CAM-2070 and CAM-2005 from Yangzhou Chenhua New Materials Co., Ltd., etc.

[0049] In a preferred embodiment of the present invention, the secondary amine resin (I) is obtained by an imide reaction between a double-terminal primary amino polyether corresponding to a divalent hydrophilic polyether structure and a secondary amine 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 undergo an imide reaction and then reacts with the single-terminal amino compound NH2R 3 The imide reaction was carried out to obtain R 3 The meaning of is as described above.

[0054] The double-terminal primary amino polyether contains two terminal primary amino groups, which can react with the above-mentioned secondary amino resin (II) to undergo an imide reaction. By adjusting the molar ratio of the double-terminal 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 F420 resin, F520 resin, F524 resin, etc. of Feiyang Junyan Company, or it can be prepared according to the existing technology, such as diethyl maleate and 4,4'-diaminodicyclohexylmethane (or 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, isophoronediamine, etc.) to undergo a 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 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 special restrictions. 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 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 special restrictions.

[0056] The molar ratio of the double-terminal primary amino polyether and the secondary amino resin (II) is close to or reaches 2:1 for reaction. 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, 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: add a double-terminal primary amino polyether into a reaction vessel, add a catalyst (lauric acid, stearic acid, benzotriazole, 1-hydroxybenzotriazole, etc.) in an amount of 0.1-0.5% by weight of the double-terminal primary amino polyether, stir evenly, add the secondary amino resin (II), raise the temperature to 90-150°C for reaction, wait for reflux to occur in the reaction system, introduce 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, reduce the pressure to -0.099 MPa or less to remove low boiling points, and 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 amine compound is continued to be added and reacted at a constant temperature, and 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, ethanol), until no bubbles are generated in the reaction system, and 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 amine resin (I).

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

[0059] YC m (6)

[0060] Wherein, Y is an m-valent organic structure with an average molecular weight of 50-5000 which is inert to react with isocyanate groups at 100° C. and which is left after the primary amino group of the second polyamine compound is removed, m=2-3, and 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 secondary amine resin (III) is a hydrophobic secondary amine resin, which is combined with a secondary amine resin (I) having certain hydrophilicity and emulsification properties, and after adding water and dispersing, an O / W emulsion can be formed, wherein the oil phase is the secondary amine resin (III), and the emulsifier is the secondary amine resin (I). The secondary amine resin (III) and the secondary amine resin (I) can participate in curing together, and the water resistance of the cured product can be improved by adding the secondary amine resin (III). The O / W emulsion can further undergo a curing reaction with an isocyanate curing agent and be cured. The O / W emulsion can be prepared into a water-based coating by adding pigments and fillers, as well as additives such as a leveling agent, a wetting agent, a defoaming agent, a dispersant, a thickener, an anti-settling agent, a thixotropic agent, an anti-aging agent, and an anti-ultraviolet agent.

[0066] The structure of C can be either a single structure as shown in the above 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 from 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, isophoronediamine, 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 amine resin (III) corresponding to the above formula (8) can be prepared by reacting a secondary amine resin (such as F420 resin, F520 resin, etc.) corresponding to the formula (7) with R 7 The corresponding R 7 The imide reaction can be obtained by referring 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 amine resin (III) in the imide aspartic acid ester resin is 40-85%. For example, the weight proportion of the secondary amine resin (III) in the imide aspartic acid ester resin can be any value of 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, etc., without special restrictions.

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

[0070] 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.

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

[0072] Example 1

[0073] 1 mol of double-terminated primary amino polyether ZED-601 is added to a reaction container, and 0.3% by weight of the double-terminated primary amino polyether catalyst 1-hydroxybenzoxazole is added, stirred evenly, and 2 mol of F420 resin is gradually added, and the temperature is raised to 130° C. for reaction. When reflux occurs in the reaction system, nitrogen is 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 points to obtain a light yellow transparent product, which is secondary amino resin (I).

[0074] Example 2

[0075] The difference between this embodiment and embodiment 1 is that in embodiment 1, after no bubbles are generated in the reaction system, 0.6 mol of n-octylamine is added continuously, and when reflux occurs again in the reaction system, nitrogen is introduced into the reaction system again 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, thereby obtaining a brown-yellow transparent product, which is secondary amino resin (I).

[0076] Example 3

[0077] The difference between this embodiment and embodiment 2 is that in embodiment 2, the n-octylamine is adjusted from 0.6 mol to 1.5 mol. 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 container, and 0.25% by weight of the double-terminated primary amino polyethylene glycol catalyst 1-hydroxybenzoxazole was added, stirred evenly, and 2.02 mol of F420 resin was gradually added, and the temperature was raised to 130° C. for reaction. When reflux occurred in the reaction system, nitrogen was introduced into the reaction system to remove the generated ethanol until no bubbles were generated in the reaction system, and the pressure was reduced to -0.099 MPa to remove low boiling points to obtain a light yellow transparent product, which was secondary amino resin (I).

[0080] Example 5

[0081] The difference between this embodiment and embodiment 4 is that in embodiment 4, after no bubbles are generated in the reaction system, 1 mol of single-end amino polyether ZM-160 is 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, thereby obtaining a brown-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. for reaction. When reflux occurred in the reaction system, nitrogen was introduced into the reaction system 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 light yellow transparent product was obtained, which was 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: Under 25℃, weigh 100g of the resin sample to be tested and place it in a colorless and transparent container. Slowly add an appropriate amount of pure water while stirring, stir evenly, and then measure according to the method specified in GB 1721-2008 "Appearance and transparency test method for varnish, clear oil and thinner". Record the weight of pure water added when the instrument measurement value reaches 82. The results are shown in Table 1 below. The less the weight of pure water, the worse the hydrophilicity of 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 2wt% NaOH aqueous solution to prepare a colorless transparent solution with a resin concentration of 20wt%, and then placed in an environment of 25°C to observe the time when the solution becomes turbid, oily or precipitated. Turbidity, oily or precipitated in the solution indicates that the resin in the solution has been hydrolyzed. The shorter the time, the worse the hydrolysis resistance.

[0088] Table 1

[0089]

[0090] It can be seen from the data results in Table 1 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 other 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 other steps remain unchanged.

[0097] Example 10

[0098] 1 mol of 4-methylcyclohexylamine was added to a reaction vessel, and a catalyst 1-hydroxybenzoxazole (0.5% by weight of 4-methylcyclohexylamine) was added, the mixture was stirred evenly, and 1 mol of F420 resin was gradually added. The temperature was raised to 110° C. for reaction. When reflux occurred in the reaction system, nitrogen was introduced into the reaction system 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 points, and a light yellow transparent product was obtained, which was the secondary amino resin (III).

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

[0100] Embodiment 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 amine resin (III) in Example 10. The other steps remain unchanged.

[0102] Example 12

[0103] The difference between Example 12 and Example 10 is that in Example 10, 4-methylcyclohexylamine is adjusted from 1 mol to 2 mol. The other steps remain unchanged.

[0104] Embodiment 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 amine resin (III) in Example 12. The other steps remain unchanged.

[0106] Embodiment 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 evenly.

[0108] Embodiment 15

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

[0110] Example 16

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

[0112] Embodiment 17

[0113] The difference between Example 17 and Example 14 is that in Example 14, the weight ratio of the secondary amine resin (I) to the F420 resin is adjusted from 2:1 to 1:4. The other 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 pure water was added, constant stirring was continued for 10 minutes, and then the stirring speed was reduced to 500 rpm, and stirring was continued for 30 minutes to obtain an emulsion.

[0119] The emulsion and the water-based isocyanate curing agent Huntsman 9236 were mixed evenly according to the ratio of the total molar number of secondary amine and hydroxyl groups to the molar number of isocyanate of 1:1.05 to obtain a coating composition, and a film was formed on a clean glass surface with a film thickness of 0.1 mm. The film was cured by heating and placed at 25°C and 55% humidity for 24 hours. The retention time of boiling in a 100°C 1wt% NaOH aqueous solution was tested, and the film was observed every 0.5 hours. The boiling time was the time closest to the film layer falling off, warping, bubbling and other abnormalities. For example, if the film layer was observed to be abnormal at 3.5 hours, the boiling time was 3 hours. The longer the time, the better the hydrolysis resistance.

[0120] Measure 2 ml of the emulsion into a test tube, add 4 ml of pure water, shake well and let stand, and observe the emulsion for abnormal phenomena such as stratification and precipitation after 24 hours and 48 hours. If there is no abnormality after 48 hours, it is "△"; if there is no abnormality after 24 hours, but an abnormality occurs after 48 hours, it is "△△"; if an abnormality occurs after 24 hours, it 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 in the present invention, the imide aspartic acid ester resin composed of a hydrophilic secondary amine resin and a hydrophobic secondary amine resin has good hydrolysis resistance after being emulsified with water, 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 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. An imide aspartic acid ester resin, characterized in that: The imide aspartic acid ester resin comprises a secondary amine resin (I) having a structure as shown in 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 C1-C18 alkyl, C2-C18 substituted alkyl, cyclopentyl, cyclohexyl, C6-C12 substituted cycloalkyl or polyether segment, X is a divalent organic structure with an average molecular weight of 50-5000 that is inert to the isocyanate group at 100°C and is left after the primary amino group is removed from the polyamine compound.

2. The imide aspartic acid ester resin according to claim 1, characterized in that The weight proportion of the secondary amine 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 amine 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-terminal 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 amine resin (I) is obtained by an imide reaction between the double-terminal primary amino polyether corresponding to the divalent hydrophilic polyether structure and the secondary amine 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 The imide reaction was carried out to obtain R 3 has the same meaning as above.

7. The imide aspartic acid ester resin according to claim 6, characterized in that: The molar ratio of the double-terminal 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 amine resin (III) having a structure as shown in the following formula (6): YC m (6) Wherein, Y is an m-valent organic structure with an average molecular weight of 50-5000 which is inert to react with isocyanate groups at 100° C. and which is left after the primary amino group of the second polyamine compound is removed, m=2-3, and 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 amine 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 amine resin (I) to the secondary amine resin (III) is 5:1-1:4.

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