Hydrophilic asparagus resin with good flexibility and emulsion

Abstract

The invention provides hydrophilic aspartic resin with good flexibility and an emulsion, and relates to the technical field of aspartic ester resin. The hydrophilic chain segment and the flexible chain segment are introduced into the structure of the asparagus resin, so that the asparagus resin with flexibility and hydrophilicity can be obtained. The hydrophilic asparagus resin can be self-emulsified and dispersed in water to form an emulsion.

Description

Technical Field

[0001] The invention belongs to the technical field of aspartic acid ester resins and relates to a hydrophilic aspartic acid resin with good flexibility and an emulsion. Background Art

[0002] Aspartic polyurea coatings, which are cured with polyaspartic acid resins and isocyanates, have the characteristics of good weather resistance, good chemical corrosion resistance, high mechanical strength, good adhesion, and fast curing speed. With the development of water-based coatings, the development of water-based aspartic polyurea coatings is imperative. Water-based aspartic polyurea coatings are generally composed of hydrophilic polyaspartic acid resins and water-based isocyanate curing agents. Based on the performance requirements of water-based aspartic polyurea coatings, certain requirements are also placed on water-based polyaspartic acid resins. If the hydrophilicity of the hydrophilic polyaspartic acid resin is too good, the water resistance and adhesion of the coating will be insufficient; if the hydrophilicity of the hydrophilic polyaspartic acid resin is not enough, additional emulsifiers need to be introduced, which will also affect the performance of the coating. Therefore, there are high requirements for hydrophilic polyaspartic acid resins. For example, existing technologies for preparing hydrophilic polyaspartic acid ester resins primarily involve grafting hydrophilic polyethylene glycol segments onto the side chains of polyaspartic acid ester resins through an ester exchange reaction, or by using a maleate containing polyethylene glycol segments and a dibasic primary amino compound for a Melk addition reaction. However, the hydrophilic polyaspartic acid esters obtained by this method are relatively high in hydrophilicity.

[0003] In addition, for water-based aspartame polyurea coatings, attention needs to be paid to the flexibility of the film layer after curing, but the flexibility of the existing water-based aspartame polyurea film layer is insufficient. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a hydrophilic asparagus resin and emulsion with good flexibility.

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

[0006] A hydrophilic asparagine resin with good flexibility, comprising a -N(X)CONH- group, a first polyether segment, a second polyether segment, and a structure of the following formula (1) and / or formula (2):

[0007] -NHCOO- group (1)

[0008] -OOC(N-)CONH- group (2)

[0009] Wherein, X is selected from H or the residue remaining after removing H from the amine group of an amino resin containing an amine group, and the amine group is a secondary amine group;

[0010] The molar content of the polyethylene glycol segment in the first polyether segment is not less than 80%, and the first polyether segment is directly chemically bonded to the -NHCOO- group and / or the -OOC(N-)CONH- group;

[0011] The molar content of the polyethylene glycol segment in the second polyether segment is not higher than 20%, and the second polyether segment is directly chemically bonded to the -NHCOO- group and / or the -OOC(N-)CONH- group;

[0012] Alternatively, the hydrophilic aspartame resin contains at least one of a -N(X)CONH- group, a cation-containing structure, and the structures represented by the above formula (1) and formula (2).

[0013] Preferably, the structure of the first polyether segment is shown in the following formula (3):

[0014] -(CH2CH2O) a D b E(3)

[0015] Wherein, D is selected from one or a combination of two or more of -CH2CH2CH2O-, -CH2CH3CHO-, -(CH2)4O-, -CH2CH2CH3CHO- and -(CH2)6O-, 4≤a≤50, b≥0, a / (a+b)≥0.8, and E is selected from C1-C4 alkyl.

[0016] Preferably, the structure of the second polyether segment is as shown in the following formula (4):

[0017] -(CH2CH2O) c T d -(4)

[0018] Wherein, T is selected from one or a combination of two or more of -CH2CH2CH2O-, -CH2CH3CHO-, -(CH2)4O-, -CH2CH2CH3CHO-, -(CH2)6O- and the divalent residue remaining after removing two active hydrogens from polyester diol, c≥0, 4≤d≤50, and c / (c+d)≤0.2.

[0019] More preferably, the weight proportion of the first polyether segment in the hydrophilic aspartame resin is 3-35%;

[0020] The weight proportion of the cationic structure in the hydrophilic aspartame resin is 2-15%.

[0021] Preferably, both ends of the second polyether segment are directly chemically bonded to the -NHCOO- group and / or the -OOC(N-)CONH- group.

[0022] Preferably, the weight proportion of the second polyether segment in the hydrophilic aspartame resin is 5-45%.

[0023] Preferably, the hydrophilic asparagus resin is obtained by reacting raw material component A) a hydrophilic isocyanate prepolymer with raw material component B) a second polyether diol and then reacting with raw material component C) a first amino resin;

[0024] The hydrophilic isocyanate prepolymer contains the first polyether segment;

[0025] The second polyether diol comprises the second polyether segment;

[0026] Alternatively, the hydrophilic asparagus resin is obtained by reacting the raw material component D) a tertiary amino group-containing isocyanate prepolymer with the raw material component E) a second amino resin and then neutralizing the reacted components;

[0027] The structures of the first amino resin and the second amino resin are independently shown in the following formula (5):

[0028]

[0029] Wherein, R is an n-valent organic group having a number average molecular weight of 50-5000 and being inert to reaction with isocyanate at 100° C., R1 and R2 are independently selected from C1-C8 alkyl groups, and n=2-4.

[0030] More preferably, the weight proportion of NCO in the hydrophilic isocyanate prepolymer and the tertiary amine group-containing isocyanate prepolymer is 5-40%.

[0031] Preferably, the molar ratio of the second polyether diol to the first amino resin is 1:10-1:1;

[0032] The ratio of the sum of the moles of active hydrogen in the second polyether diol and the active hydrogen in the first amino resin to the mole of NCO groups in the hydrophilic isocyanate prepolymer is 0.7-3:1;

[0033] The molar ratio of the NCO group and the NH group in the tertiary amino group-containing isocyanate prepolymer to the second amino resin is 1:1-5.

[0034] An emulsion is obtained by dispersing raw material components comprising the flexible hydrophilic asparagine resin described in any one of the above embodiments in water.

[0035] The beneficial effects of the present invention are:

[0036] (1) The present invention introduces a polyether segment with good hydrophilicity into the isocyanate prepolymer and adopts a polymer diol with good flexibility as one of the raw material components to react with the isocyanate prepolymer, so that the obtained asparagus resin has moderate hydrophilicity and can be self-emulsified and dispersed in water. The film layer obtained by emulsifying and dispersing the asparagus resin in water after curing has good flexibility and high elongation at break, and has little effect on the mechanical strength of the film layer. At the same time, the water resistance and other properties are also good.

[0037] (2) Alternatively, the hydrophilic aspartic acid ester resin of the present invention can also provide good hydrophilicity and good flexibility by introducing a cationic structure, and can be self-emulsified and dispersed in water. The film layer obtained by emulsifying and dispersing the aspartic acid ester resin in water after curing has good flexibility and high elongation at break. DETAILED DESCRIPTION

[0038] The technical solution of the present invention is further illustrated and described below through specific implementation methods.

[0039] In order to improve the flexibility of the water-based asparagine resin film layer, on the one hand, the present invention provides a hydrophilic asparagine resin with good flexibility, wherein the hydrophilic asparagine resin comprises an -N(X)CONH- group, a first polyether segment, a second polyether segment, and the following formula (1) and / or formula (2) structure:

[0040] -NHCOO- group (1)

[0041] -OOC(N-)CONH- group (2)

[0042] wherein X is selected from H or the residue remaining after removing H from the amine group of an amino resin containing an amine group, and the amine group is a secondary amine group;

[0043] The molar content of the polyethylene glycol segment in the first polyether segment is not less than 80%, and the first polyether segment is directly chemically bonded to the -NHCOO- group and / or the -OOC(N-)CONH- group;

[0044] The molar content of the polyethylene glycol segment in the second polyether segment is not higher than 20%, and the second polyether segment is directly chemically bonded to the -NHCOO- group and / or the -OOC(N-)CONH- group;

[0045] Alternatively, the hydrophilic aspartame resin contains at least one of a -N(X)CONH- group, a cation-containing structure, and the structures represented by the above formula (1) and formula (2).

[0046] In order to obtain a hydrophilic aspartic acid ester resin with good flexibility, the present invention can introduce a first polyether segment and a second polyether segment into the aspartic acid resin, wherein the first polyether segment has good hydrophilicity and can give the aspartic acid resin good hydrophilic properties, and the second polyether segment has good flexibility and can give the aspartic acid resin good flexibility, thereby obtaining a hydrophilic aspartic acid resin with good flexibility.

[0047] In the present invention, the hydrophilicity and flexibility of the hydrophilic aspartic acid resin can also be derived from cationic structures, such as cationic tertiary amine structures, quaternary ammonium salt structures, etc., and a hydrophilic aspartic acid ester resin with good flexibility can be obtained without the need to introduce additional flexible segments.

[0048] For example, the -N(X)CONH- group can be obtained by the reaction of an NCO group and an NH group, such as by the reaction of a polyisocyanate monomer or isocyanate prepolymer with a polyaspartic acid ester resin (such as Feiyang Junyan's F420 resin and F520 resin). In this case, X corresponds to the residue remaining after removing the H groups from the two secondary amine groups of the polyaspartic acid ester resin. Of course, the -N(X)CONH- group can also be obtained by the reaction of an NCO group and an NH2 group, such as by reacting with a polymer containing primary amino groups.

[0049] The direct chemical bonding between the first polyether segment and the -NHCOO- group shown in formula (1) can be obtained by reacting the first hydroxyl-terminated polyether corresponding to the first polyether segment with an NCO group (such as a polyisocyanate monomer or an isocyanate prepolymer). After the first hydroxyl-terminated polyether corresponding to the first polyether segment reacts with the NCO group to obtain the -NHCOO- group, the -NHCOO- group can further react with the NCO group to obtain the -OOC(N-)CONH- group shown in formula (2).

[0050] The direct chemical bonding between the second polyether segment and the -NHCOO- group shown in formula (1) can be obtained by reacting the second hydroxyl-terminated polyether corresponding to the second polyether segment with an NCO group (such as a polyisocyanate monomer or an isocyanate prepolymer). After the second hydroxyl-terminated polyether corresponding to the second polyether segment reacts with the NCO group to obtain the -NHCOO- group, the -NHCOO- group can further react with the NCO group to obtain the -OOC(N-)CONH- group shown in formula (2).

[0051] In some embodiments, the structure of the first polyether segment is shown in Formula (3),

[0052] -(CH2CH2O) a D b E(3)

[0053] Wherein, D is selected from one or a combination of two or more of -CH2CH2CH2O-, -CH2CH3CHO-, -(CH2)4O-, -CH2CH2CH3CHO- and -(CH2)6O-, a is the average degree of polymerization of -CH2CH2O-, b is the average degree of polymerization of the D structure, 4≤a≤50, b≥0, a / (a+b)≥0.8, and E is selected from a C1-C4 alkyl group.

[0054] In the present invention, the main function of the first polyether segment is to impart good hydrophilic properties to the asparagus resin. Therefore, the first polyether segment contains a relatively high proportion of hydrophilic polyethylene glycol segments. The first polyether segment can be either a pure polyethylene glycol segment or a copolymer of a polyethylene glycol segment and other polyether segments (such as a polypropylene glycol segment). The first hydroxyl-terminated polyether (single-terminated hydroxyl polyether) corresponding to the first polyether segment can be directly obtained from the market, such as polyethylene glycol monomethyl ether with a number average molecular weight of 200-2000, such as MPEG-200 (200 represents the number average molecular weight), MPEG-400, MPEG-600, MPEG-800, MPEG-1000, MPEG-1500, MPEG-2000, etc.

[0055] In some embodiments, the structure of the second polyether segment is shown in Formula (4),

[0056] -(CH2CH2O) c T d -(4)

[0057] Wherein, T is selected from one or a combination of two or more of -CH2CH2CH2O-, -CH2CH3CHO-, -(CH2)4O-, -CH2CH2CH3CHO-, -(CH2)6O- and the divalent residue remaining after removing two active hydrogens from polyester diol, c is the average degree of polymerization of -CH2CH2O-, d is the average degree of polymerization of T structure, c≥0, 4≤d≤50, c / (c+d)≤0.2.

[0058] In the present invention, the main function of the second polyether segment is to impart good flexibility to the asparagus resin. Therefore, the second polyether segment has good flexibility, and the corresponding second hydroxyl-terminated polyether (a double-terminated hydroxyl polyether) can be polypropylene glycol (PPO), polyethylene glycol polypropylene glycol (PEO-PPO), polytetramethylene ether glycol (PTMEG), etc.

[0059] Of course, as mentioned above, when the hydrophilic aspartic acid ester resin of the present invention contains a cationic structure, it can provide good hydrophilicity and improve good flexibility. In this case, there is no need to introduce the second polyether segment represented by the above formula (4) into the hydrophilic aspartic acid ester resin.

[0060] In some embodiments, the weight proportion of the first polyether segment in the hydrophilic asparagine resin is 3-35%. If the weight proportion of the first polyether segment in the hydrophilic asparagine resin is too low, the asparagine resin cannot be given good hydrophilicity; if the weight proportion of the first polyether segment in the hydrophilic asparagine resin is too high, the asparagine resin will be too hydrophilic, which will affect the water resistance and other properties of the coating. For example, the weight proportion of the first polyether segment in the hydrophilic asparagine resin can be any value among 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 27%, 28%, 30%, 32%, 33%, 35%, etc., or any value in between. Furthermore, the weight proportion of the first polyether segment in the hydrophilic aspartame resin may be 3-30%.

[0061] The weight proportion of the cationic structure in the hydrophilic aspartic resin is 2-15%. For example, the weight proportion can be any value among 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc. or any value therebetween. Furthermore, the weight proportion of the cationic structure in the hydrophilic aspartic resin can be 2-12%.

[0062] In some embodiments, both ends of the second polyether segment are directly chemically bonded to -NHCOO- groups and / or -OOC(N-)CONH- groups. That is, both terminal hydroxyl groups of the second hydroxyl-terminated polyether corresponding to the second polyether segment react with NCO groups to form -NHCOO- groups. The -NHCOO- groups can further react with NCO groups to form -OOC(N-)CONH- groups.

[0063] In some embodiments, the weight proportion of the second polyether segment in the hydrophilic asparagine resin is 5-45%, which can impart good flexibility to the hydrophilic asparagine resin. For example, the weight proportion of the second polyether segment in the hydrophilic asparagine resin can be any value among 5%, 6%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, etc., or any value in between. Generally, the higher the content of the second polyether segment, the better the flexibility of the hydrophilic asparagine resin. Furthermore, the weight proportion of the second polyether segment in the hydrophilic asparagine resin can be 10-35%.

[0064] In some embodiments, the hydrophilic asparagus resin is obtained by reacting raw material component A) a hydrophilic isocyanate prepolymer with raw material component B) a second polyether diol and then reacting with raw material component C) a first amino resin;

[0065] The hydrophilic isocyanate prepolymer contains a first polyether segment;

[0066] The second polyether diol is the second hydroxyl-terminated polyether mentioned above, comprising a second polyether segment;

[0067] Alternatively, the hydrophilic asparagus resin is obtained by reacting the raw material component D) a tertiary amino group-containing isocyanate prepolymer with the raw material component E) a second amino resin and then neutralizing the reacted resin;

[0068] The structures of the first amino resin and the second amino resin (which may be the above-mentioned amino resin containing an amino group, in which case the amino group is a secondary amino group) are shown in the following formula (5):

[0069]

[0070] Wherein, R is an n-valent organic group having a number average molecular weight of 50-5000 and being inert to reaction with isocyanate at 100° C., R1 and R2 are independently selected from C1-C8 alkyl groups, and n=2-4.

[0071] The end groups of the hydrophilic isocyanate prepolymer contain a certain amount of NCO groups, which can react with the second polyether diol to introduce a second polyether segment and form -NHCOO- groups. Or, when NCO is in excess (and under the action of a catalyst), it can further react to form -OOC(N-)CONH- groups. The end groups of the intermediate product obtained after the reaction also contain a certain amount of NCO groups, which can continue to react with the NH groups on the amino resin (such as Feiyang Junyan's F420 resin and F520 resin) to form -N(X)CONH- groups, where X is the residue remaining after the H on the secondary amine group of the amino resin such as F420 resin and F520 resin is removed, and the hydrophilic asparagus resin is obtained. For hydrophilic isocyanate prepolymers, they can be obtained by reacting polyisocyanate monomers (such as diisocyanate monomers such as IPDI, HMDI, TDI, HDI, etc.) with single-ended polyethylene glycol to form -NHCOO- groups. When NCO is in excess (and under the action of a catalyst), it further reacts to form -OOC(N-)CONH- groups.

[0072] Alternatively, a hydrophilic asparagine resin can be obtained by reacting a tertiary amine-containing isocyanate prepolymer with a second amino resin and then neutralizing it. There are no particular limitations on the preparation method for the tertiary amine-containing isocyanate prepolymer. For example, it can be obtained by reacting a monohydroxy tertiary amine compound (such as N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dimethylpropanolamine, hydroxyethylpiperidine, hydroxyethylmorpholine, etc.) with a polyisocyanate monomer (such as IPDI, HMDI, TDI, HDI, etc.) in a molar ratio of NCO groups to OH groups of 1:2-10. When NCO is in excess (and in the presence of a catalyst), the -NHCOO- group can further react to form an -OOC(N-)CONH- group. There are no particular limitations on the neutralizing agent, which can be an acidic neutralizing agent such as lactic acid, acetic acid, etc., or an agent that converts a tertiary amine into a quaternary ammonium salt, such as epichlorohydrin, dodecyl bromide, iodomethane, etc.

[0073] In some embodiments, the weight percentage of NCO in the hydrophilic isocyanate prepolymer and the tertiary amine-containing isocyanate prepolymer is 5-40%. For example, the weight percentage of NCO can be any value among 5%, 7%, 8%, 10%, 12%, 15%, 17%, 18%, 20%, 22%, 24%, 25%, 27%, 30%, 33%, 35%, 37%, 40%, etc., or any value in between. The preparation method of the hydrophilic isocyanate prepolymer is not particularly limited and can be obtained by reacting a polyisocyanate monomer (such as IPDI, HDI, HDI trimer, IPDI trimer, HMDI, etc.) with a first hydroxyl-terminated polyether (a single-hydroxyl-terminated polyether, such as MPEG). Furthermore, the weight percentage of NCO in the hydrophilic isocyanate prepolymer can be 15-40%.

[0074] In some embodiments, the molar ratio of the second polyether glycol to the first amino resin is 1:10-1:1. For example, the molar ratio can be any value of 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, etc., or any value therebetween.

[0075] The ratio of the sum of the molar numbers of active hydrogen in the second polyether diol (H on the hydroxyl group) and the first amino resin (H on the NH) to the molar number of NCO groups in the hydrophilic isocyanate prepolymer is 0.7-3:1. For example, the molar ratio can be any value among 0.7:1, 0.75:1, 0.8:1, 0.85:1, 0.9:1, 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.7:1, 3:1, etc. or any value in between. When the molar ratio of active hydrogen to NCO groups is less than 1:1, such as 0.7:1, 0.75:1, 0.8:1, 0.85:1, etc., the NCO groups are excessive, and the resulting hydrophilic asparagine resin still has a certain content of NCO groups. After self-emulsification in water, the NCO groups will continue to react with water to release CO2 and produce primary amino groups, which will continue to react with the NCO groups, increasing the molecular weight of the hydrophilic asparagine resin. Therefore, when the molar ratio of active hydrogen to NCO groups is less than 1:1, the resulting emulsion can form a film without the addition of a curing agent. When the molar ratio of active hydrogen to NCO groups is greater than 1:1, such as 1.2:1, 2:1, 3:1, etc., the resulting hydrophilic asparagine resin still has a certain content of NH groups, and the resulting emulsion can be cured by adding an isocyanate curing agent. When the ratio of the sum of the molar numbers of active hydrogen in the second polyether diol and the active hydrogen in the first amino resin to the molar number of NCO groups in the hydrophilic isocyanate prepolymer is close to 1:1, the molecular weight of the obtained hydrophilic asparagus resin is large, and the NCO groups or NH groups therein are relatively small. The hydrophilic asparagus resin with a larger molecular weight puts higher requirements on the self-emulsification process. Therefore, further, from the perspective of production convenience and economy, the ratio of the sum of the molar numbers of active hydrogen in the second polyether diol and the active hydrogen in the first amino resin to the molar number of NCO groups in the hydrophilic isocyanate prepolymer can be 0.7-0.85:1 or 1.1-3:1.

[0076] The molar ratio of the NCO group and the NH group in the tertiary amino group-containing isocyanate prepolymer to the second amino resin is 1:1-5. For example, the molar ratio can be any value among 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, etc. or any value in between.

[0077] On the other hand, the present invention also provides an emulsion obtained by dispersing raw material components comprising the flexible hydrophilic asparagus resin described in any of the above embodiments in water.

[0078] The hydrophilic asparagus resin of the present invention has good hydrophilicity and can self-emulsify in water to form an emulsion with a concentration of 20-50 wt%. A leveling agent, a wetting agent, a defoamer, a pigment, a filler, an anti-settling agent, a thixotropic agent, an anti-ultraviolet agent, an antioxidant, etc. can be added to the emulsion to prepare a water-based coating, which is then cured with an isocyanate curing agent to form a film layer.

[0079] The technical solution of the present invention is further described and illustrated below based on various embodiments.

[0080] Preparation Example 1-6 Preparation of hydrophilic isocyanate prepolymer

[0081] Preparation Example 1

[0082] 1680 g HDI (eq: 20 mol), 300 g MPEG-300 (eq: 1 mol), and 1 g tetramethylammonium hydroxide were mixed, heated to 90°C, and reacted until the NCO content reached 37.8 wt%. 1.3 g 85% aqueous phosphoric acid solution was added to terminate the reaction to obtain a hydrophilic isocyanate prepolymer, designated as isocyanate 1, with an equivalent weight of 111.1 g / mol and a polyethylene glycol segment content of 15.2 wt%.

[0083] Preparation Example 2

[0084] 1680 g HDI (eq: 20 mol), 1000 g MPEG-1000 (eq: 1 mol), and 0.7 g tetramethylammonium hydroxide were mixed, heated to 90° C., and reacted until the NCO content reached 29.4 wt %. The reaction was terminated by adding 0.9 g 85% aqueous phosphoric acid solution to obtain a hydrophilic isocyanate prepolymer, designated as Isocyanate 2, with an equivalent weight of 143 g / mol and a polyethylene glycol segment content of 37.3%.

[0085] Preparation Example 3

[0086] 1110 g IPDI (eq: 10 mol), 300 g MPEG-300 (eq: 1 mol), and 0.7 g tetramethylammonium hydroxide were mixed and reacted at 90° C. until the NCO content reached 23 wt %. The reaction was terminated by adding 0.9 g 85% aqueous phosphoric acid solution to obtain a hydrophilic isocyanate prepolymer, designated as isocyanate 3, having an equivalent weight of 182.6 g / mol and a polyethylene glycol segment content of 21.3%.

[0087] Preparation Example 4

[0088] 555 g IPDI (eq: 5 mol), 89.1 g N,N-dimethylethanolamine (eq: 1 mol), and 0.7 g tetramethylammonium hydroxide were mixed and reacted at 90° C. until the NCO content reached 19.6 wt %. The reaction was terminated by adding 0.9 g 85% aqueous phosphoric acid solution to obtain a tertiary amino group-containing isocyanate prepolymer, designated as isocyanate 4, with an equivalent weight of 214.3 g / mol and a hydrophilic monomer N,N-dimethylethanolamine content of 13.8%.

[0089] Preparation Example 5

[0090] 420 g HDI (eq: 5 mol), 266.4 g hydroxyethylmorpholine (eq: 2 mol), and 0.8 g tetramethylammonium hydroxide were mixed and reacted at 90° C. until the NCO content reached 15.1 wt %. The reaction was terminated by adding 0.9 g 85% aqueous phosphoric acid solution to obtain a tertiary amino group-containing isocyanate prepolymer, designated as Isocyanate 5, with an equivalent weight of 278.1 g / mol and a hydrophilic monomer hydroxyethylmorpholine content of 38.8%.

[0091] Preparation Example 6

[0092] 420 g HDI (eq: 5 mol), 1000 g MPEG-1000 (eq: 1 mol), and 0.7 g tetramethylammonium hydroxide were mixed, heated to 90° C., and reacted until the NCO content reached 8.3 wt %. The reaction was terminated by adding 0.9 g 85% aqueous phosphoric acid solution to obtain a hydrophilic isocyanate prepolymer, designated as isocyanate 6, with an equivalent weight of 506 g / mol and a polyethylene glycol segment content of 70.4%.

[0093] Example 1

[0094] Isocyanate 1 (eq. 1 mol) from Preparation Example 1 and 45 g of PPG-300 (eq. 0.3 mol) were added to a reaction vessel, heated to 90°C, and reacted completely. 263.2 g of F420 resin (eq. 0.95 mol) was then added and reacted completely at 80°C to obtain a hydrophilic asparagine resin. The hydrophilic asparagine resin contained 4% by weight of polyethylene glycol segments and 10.7% by weight of polypropylene glycol segments.

[0095] An appropriate amount of water was added to the hydrophilic asparagus resin, and the mixture was emulsified and dispersed at 30° C. to form an emulsion with a concentration of 50 wt %.

[0096] Comparative Example 1

[0097] Isocyanate 1 (eq: 1 mol) in Preparation Example 1 and 346.3 g of F420 resin (eq: 1.25 mol) were added to a reaction vessel, and the temperature was raised to 80° C. to complete the reaction, thereby obtaining a hydrophilic asparagus resin.

[0098] An appropriate amount of water was added to the hydrophilic asparagus resin, and the mixture was emulsified and dispersed at 30° C. to form an emulsion with a concentration of 50 wt %.

[0099] Example 2

[0100] Isocyanate 2 (eq. 1 mol) from Preparation Example 2 and 300 g of PTMEG-2000 (eq. 0.3 mol) were added to a reaction vessel, heated to 90°C, and reacted completely. 706.5 g of F420 resin (eq. 2.55 mol) was then added and reacted completely at 80°C to obtain a hydrophilic asparagine resin. The hydrophilic asparagine resin contained 4.6% by weight of polyethylene glycol segments and 26.1% by weight of PTMEG segments.

[0101] An appropriate amount of water was added to the hydrophilic asparagus resin, and the mixture was emulsified and dispersed at 30° C. to form an emulsion with a concentration of 50 wt %.

[0102] Example 3

[0103] Isocyanate 2 (eq. 1 mol) from Preparation Example 2 and 100 g of PTMEG-1000 (eq. 0.2 mol) were added to a reaction vessel, heated to 90°C, and reacted completely. 166.2 g of F420 resin (eq. 0.6 mol) was then added and reacted completely at 80°C to obtain a hydrophilic asparagine resin. The hydrophilic asparagine resin contained 13.0% by weight of polyethylene glycol segments and 24.4% by weight of PTMEG segments.

[0104] An appropriate amount of water was added to the hydrophilic asparagus resin, and the mixture was emulsified and dispersed at 30° C. to form an emulsion with a concentration of 50 wt %.

[0105] Comparative Example 2

[0106] Isocyanate 2 (eq: 1 mol) in Preparation Example 2 and 221.6 g of F420 resin (eq: 0.8 mol) were added to a reaction vessel, and the temperature was raised to 80° C. to complete the reaction, thereby obtaining a hydrophilic asparagus resin.

[0107] An appropriate amount of water was added to the hydrophilic asparagus resin, and the mixture was emulsified and dispersed at 30° C. to form an emulsion with a concentration of 50 wt %.

[0108] Example 4

[0109] Isocyanate 3 (eq. 1 mol) from Preparation Example 3 and 200 g of PPG-1000 (eq. 0.4 mol) were added to a reaction vessel, heated to 90°C, and reacted completely. 221.6 g of F420 resin (eq. 0.8 mol) was then added and reacted completely at 80°C to obtain a hydrophilic asparagine resin. The hydrophilic asparagine resin contained 6.4% by weight of polyethylene glycol segments and 33.1% by weight of PPG segments.

[0110] An appropriate amount of water was added to the hydrophilic asparagus resin, and the mixture was emulsified and dispersed at 30° C. to form an emulsion with a concentration of 50 wt %.

[0111] Example 5

[0112] Isocyanate 3 (eq. 1 mol) from Preparation Example 3 and 100 g of PPG-1000 (eq. 0.2 mol) were added to a reaction vessel, heated to 90°C, and reacted completely. 406 g of F520 resin (eq. 1.4 mol) was then added and reacted completely at 90°C to obtain a hydrophilic asparagine resin. The hydrophilic asparagine resin contained 5.8% by weight of polyethylene glycol segments and 14.5% by weight of PPG segments.

[0113] An appropriate amount of water was added to the hydrophilic asparagus resin, and the mixture was emulsified and dispersed at 30° C. to form an emulsion with a concentration of 40 wt %.

[0114] Example 6

[0115] Isocyanate 4 (eq. 1 mol) from Preparation Example 4 and F421 resin (eq. 2.5 mol) were added to a reaction vessel and the temperature was raised to 90°C for complete reaction. Lactic acid (eq. 0.33 mol) was then added and the reaction was completed at 80°C to obtain a hydrophilic asparagine resin. The weight content of N'N-dimethylethanolamine in the hydrophilic asparagine resin was 3.2%.

[0116] An appropriate amount of water was added to the hydrophilic asparagus resin, and the mixture was emulsified and dispersed at 50° C. to form an emulsion with a concentration of 50 wt %.

[0117] Example 7

[0118] Isocyanate 5 (eq. 1 mol) from Preparation Example 5 and F420 resin (eq. 4 mol) were added to a reaction vessel, heated to 90°C for complete reaction, then cooled to 50°C. Acetic acid (eq. 0.5 mol) was added and allowed to react at 50°C for complete reaction to obtain a hydrophilic asparagine resin. The weight content of hydroxyethylmorpholine in the hydrophilic asparagine resin was 7.6%.

[0119] An appropriate amount of water was added to the hydrophilic asparagus resin, and the mixture was emulsified and dispersed at 50° C. to form an emulsion with a concentration of 50 wt %.

[0120] Example 8

[0121] Isocyanate 6 (eq: 1 mol) in Preparation Example 6 and 250 g of PTMEG1000 (eq: 0.5 mol) were added to a reaction vessel, the temperature was raised to 90°C and the reaction was completed, and then 166.2 g of F420 resin (eq: 0.6 mol) was added and the reaction was completed at 80°C to obtain a hydrophilic asparagus resin.

[0122] An appropriate amount of water was added to the hydrophilic asparagine resin and emulsified and dispersed at 30°C to form a 50 wt% emulsion. The hydrophilic asparagine resin contained 38.6% by weight of polyethylene glycol segments and 27.1% by weight of polytetramethylene ether segments.

[0123] Comparative Example 3

[0124] Isocyanate 6 (eq: 1 mol) in Preparation Example 6 and 304.7 g of F420 resin (eq: 0.6 mol) were added to a reaction vessel, and the temperature was raised to 80° C. for complete reaction to obtain a hydrophilic asparagine resin.

[0125] An appropriate amount of water was added to the hydrophilic asparagus resin, and the mixture was emulsified and dispersed at 30° C. to form an emulsion with a concentration of 50 wt %.

[0126] Performance Testing

[0127] Emulsion stability test: stored at 40°C for 6 months.

[0128] Emulsion particle size test: tested by Malvern laser particle size analyzer.

[0129] Coating gloss test: The emulsions to be tested (excluding Example 3 and Comparative Example 2) were mixed with curing agent WL72-100 at a molar ratio of NH to NCO of 1:1.1. The mixture was diluted with purified water to 45% solids before spraying onto clean tinplate. After curing at room temperature for 7 days, the coating gloss at 60° was measured. The emulsions from Example 3 and Comparative Example 2 were sprayed directly onto clean tinplate. After curing at room temperature for 7 days, the coating gloss at 60° was measured.

[0130] Coating water resistance test: The test emulsion (excluding Example 3 and Comparative Example 2) was mixed with curing agent WL72-100 at a molar ratio of NH to NCO of 1:1.1, diluted with purified water to 45% solid content, and then sprayed onto a clean tinplate. Cured at room temperature for 7 days, half of the tinplate was immersed in water. After 48 hours, the coating at the water surface was observed for abnormalities such as bubbling, shedding, and edge lift. The emulsions of Example 3 and Comparative Example 2 were respectively sprayed directly onto a clean tinplate and cured at room temperature for 7 days before testing the coating water resistance.

[0131] Coating Mechanical Properties: The emulsions to be tested (excluding Example 3 and Comparative Example 2) were mixed with curing agent WL72-100 at a NH:NCO molar ratio of 1:1.1. The mixture was diluted with purified water to 45% solids before coating to form a 200 μm thick film. The film was cured at room temperature for 7 days, and the tensile strength and elongation at break were tested. The emulsions from Example 3 and Comparative Example 2 were sprayed directly onto clean tinplate. After curing at room temperature for 7 days, the tensile strength and elongation at break of the coatings were tested.

[0132] The results are shown in Table 1 below.

[0133] Table 1

[0134]

[0135] Therefore, based on the data in Table 1, it can be seen that the present invention, by introducing a highly flexible second polyether segment into the structure of a hydrophilic asparagine resin, can significantly improve the elongation at break of the film layer, while having little effect on the tensile strength. This demonstrates that the addition of the second polyether segment can improve the flexibility of the film layer. Similarly, the introduction of a cationic structure into the structure of a hydrophilic asparagine resin can also produce a film layer with excellent tensile strength and elongation at break.

[0136] 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. A flexible hydrophilic asparagus resin, characterized in that: The hydrophilic asparagine resin comprises a -N(X)CONH- group, a first polyether segment, a second polyether segment and the following formula (1) and / or formula (2) structure, -NHCOO- group (1) -OOC(N-)CONH- group (2) Wherein, X is selected from H or the residue remaining after removing H from the amine group of an amino resin containing an amine group, and the amine group is a secondary amine group; The molar content of the polyethylene glycol segment in the first polyether segment is not less than 80%, and the first polyether segment is directly chemically bonded to the -NHCOO- group and / or the -OOC(N-)CONH- group; The molar content of the polyethylene glycol segment in the second polyether segment is not higher than 20%, and the second polyether segment is directly chemically bonded to the -NHCOO- group and / or the -OOC(N-)CONH- group; Alternatively, the hydrophilic aspartame resin contains at least one of a -N(X)CONH- group, a cation-containing structure, and the structures represented by the above formula (1) and formula (2).

2. The flexible hydrophilic asparagine resin according to claim 1, characterized in that The structure of the first polyether segment is shown in the following formula (3): -(CH2CH2O) a D b E(3) Wherein, D is selected from one or a combination of two or more of -CH2CH2CH2O-, -CH2CH3CHO-, -(CH2)4O-, -CH2CH2CH3CHO- and -(CH2)6O-, 4≤a≤50, b≥0, a / (a+b)≥0.8, and E is selected from C1-C4 alkyl.

3. The flexible hydrophilic asparagine resin according to claim 1, characterized in that The structure of the second polyether segment is shown in the following formula (4): -(CH2CH2O) c T d -(4) Wherein, T is selected from one or a combination of two or more of -CH2CH2CH2O-, -CH2CH3CHO-, -(CH2)4O-, -CH2CH2CH3CHO-, -(CH2)6O- and the divalent residue remaining after removing two active hydrogens from polyester diol, c≥0, 4≤d≤50, and c / (c+d)≤0.

2.

4. The flexible hydrophilic asparagine resin according to claim 3, characterized in that: The weight proportion of the first polyether segment in the hydrophilic aspartame resin is 3-35%; The weight proportion of the cationic structure in the hydrophilic aspartame resin is 2-15%.

5. The flexible hydrophilic asparagine resin according to claim 1, characterized in that: Both ends of the second polyether segment are directly chemically bonded to the -NHCOO- group or the -OOC(N-)CONH- group.

6. The flexible hydrophilic asparagine resin according to claim 1, characterized in that The weight proportion of the second polyether segment in the hydrophilic aspartame resin is 5-45%.

7. The flexible hydrophilic asparagine resin according to any one of claims 1 to 6, characterized in that: The hydrophilic asparagus resin is obtained by reacting raw material component A) a hydrophilic isocyanate prepolymer with raw material component B) a second polyether diol and then reacting with raw material component C) a first amino resin; The hydrophilic isocyanate prepolymer contains the first polyether segment; The second polyether diol comprises the second polyether segment; Alternatively, the hydrophilic asparagus resin is obtained by reacting the raw material component D) a tertiary amino group-containing isocyanate prepolymer with the raw material component E) a second amino resin and then neutralizing the reacted components; The structures of the first amino resin and the second amino resin are independently shown in the following formula (5): Wherein, R is an n-valent organic group having a number average molecular weight of 50-5000 and being inert to reaction with isocyanate at 100° C., R1 and R2 are independently selected from C1-C8 alkyl groups, and n=2-4.

8. The flexible hydrophilic asparagine resin according to claim 7, characterized in that: The weight proportion of NCO in the hydrophilic isocyanate prepolymer and the tertiary amine group-containing isocyanate prepolymer is 5-40%.

9. The flexible hydrophilic asparagine resin according to claim 7, characterized in that: The molar ratio of the second polyether diol to the first amino resin is 1:10-1:1; The ratio of the sum of the moles of active hydrogen in the second polyether diol and the active hydrogen in the first amino resin to the mole of NCO groups in the hydrophilic isocyanate prepolymer is 0.7-3:1; The molar ratio of the NCO group and the NH group in the tertiary amino group-containing isocyanate prepolymer to the second amino resin is 1:1-5.

10. An emulsion, characterized in that The invention is obtained by dispersing raw material components comprising the flexible hydrophilic asparagus resin according to any one of claims 1 to 9 in water.

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