A reactive polyurethane anionic emulsifier, its preparation method and application

Abstract

The present invention discloses a reactive polyurethane anionic emulsifier, its preparation method and application. The molecular structure of this emulsifier contains an anionic sulfonate group, with active hydroxyl groups and double bonds at the ends, having the hydrophilic-lipophilic functions of an emulsifier and also chemical reaction functions. The sulfonate group contained in this emulsifier has good hydrophilic properties, and the active functional groups at the ends can not only have good affinity with various solvent-based resins, but also participate in subsequent curing crosslinking reactions with the resins to form three-dimensional structure substances. The reactive polyurethane anionic emulsifier of the present invention has the characteristics of quickly making solvent-based polyurethane resins, acrylic resins, alkyd resins, ABS resins, epoxy resins, petroleum resins, etc. water-based, and has the advantages of simple process, high efficiency, stable quality and low cost. It can make these solvent-based resins use water instead of solvents during subsequent construction, greatly reducing VOC emissions and having broad application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of emulsifiers, and particularly relates to a reactive polyurethane anionic emulsifier, a preparation method thereof, and an application thereof. Background Art

[0002] In recent years, the research on waterborne resins has been carried out in full swing. However, the application popularity rate of waterborne resins in small and medium-sized enterprises is not high. The main reason is that waterborne resins have some deficiencies in terms of preparation technology, price, and product performance compared with the same type of solvent-based resins. The preparation technology of waterborne resins is complex and the cost is high. After the resin is made waterborne, the performance of the finished product decreases. Since the mature application of the solvent-based resin system has a history of nearly a hundred years, the matching between the formulations of different resins and the performance of the finished products has been very mature, forming an application system. While waterborne resins are a new technology developed in the past 20 - 30 years, the technical maturity and product matching are not as good as the former. Therefore, many enterprises are still using solvent-based products, and it is very difficult to change this situation in a short time.

[0003] The biggest VOC pollution source of solvent-based resins is that a large amount of solvent needs to be added for dilution before spraying can be carried out. Generally, the solid content of solvent-based resins is 50 - 75%, and the solid content for spraying after dilution is only 20 - 30%. Thus, a large amount of solvent volatilizes into the air during the spraying construction process. Therefore, how to solve the technical problems of producing waterborne resins and the decline in product performance, especially the problem of adding a large amount of solvent for dilution during construction, has become a technical problem that needs to be solved urgently by researchers in this field.

[0004] At present, there are few research reports on reactive emulsifiers of polyurethane prepolymers. Chinese Patent CN 113004481 A discloses a reactive polyurethane emulsifier and a preparation method thereof. Using pyromellitic dianhydride as the starting material to prepare sulfonated polyester polyol, selecting two different capping agents and controlling the feeding ratio, first preparing two semi-capped prepolymers, and then crosslinking with pentaerythritol to finally obtain a polyurethane emulsifier with reactive double bonds and characteristic functional groups at the ends. The reaction steps in the preparation process of this scheme are many and the process is cumbersome. The claims of CN1796431A disclose a preparation method of a polyurethane-type reactive emulsifier, using diisocyanate as an intermediate to make one end connected with two anionic groups of -COONa and -SO 3 Na, and the other end connected with a functional monomer containing a double bond of a reactive emulsifier. However, this patent does not list the specific preparation method of the reactive emulsifier by way of examples. In short, there are few reports on polyurethane reactive emulsifiers in the prior art. Summary of the Invention

[0005] The present invention aims to solve at least one of the above-mentioned technical problems in the prior art. To this end, one of the objectives of the present invention is to provide a reactive polyurethane anionic emulsifier, the molecular structure of which contains a sulfonate hydrophilic group, with active hydroxyl groups, double bonds or alkyl groups at the ends, having the hydrophilic-lipophilic function of an emulsifier and also a chemical reaction function. Another objective of the present invention is to provide a preparation method for such a reactive polyurethane anionic emulsifier. A third objective of the present invention is to provide the application of such a reactive polyurethane anionic emulsifier.

[0006] The reactive polyurethane anionic emulsifier provided by the present invention is prepared by reacting a sulfonate-modified diisocyanate with a hydroxyl compound to form an isocyanate prepolymer with a molecular structure containing a sulfonate group and having active functional groups such as hydroxyl groups / double bonds at the ends. Such a reactive polyurethane anionic emulsifier is mainly used by adding it to a solvent-based resin. After mixing and stirring evenly, the solvent-based resin can be transformed into the corresponding water-based resin. In this way, during construction, only water needs to be added to emulsify the water-based resin, and then it can be diluted with water to an appropriate viscosity for spray construction. The present invention not only saves a large amount of solvents for dilution and reduces costs, but also since the formulation of the solvent-based resin is not changed, the added reactive polyurethane anionic emulsifier can participate in chemical bonding reactions and will not cause a decline in the performance of the product. Therefore, it can quickly gain user recognition and achieve the goal of quickly water-basedizing solvent-based products.

[0007] To achieve the above objectives, the technical solutions adopted by the present invention are as follows:

[0008] In a first aspect of the present invention, there is provided a reactive polyurethane anionic emulsifier, and the general structural formula of the reactive polyurethane anionic emulsifier is shown as formula (Ⅰ):

[0009]

[0010] In formula (Ⅰ), M represents an alkali metal ion or an ammonium ion;

[0011] R 1 represents an alkylene chain containing a urethane group;

[0012] R 2 represents an alkylene chain;

[0013] R 3 represents an alkyl group, -R 4 -OH or -R 5 =CH 2 ; where R 4 represents an alkylene chain; R 5 represents a hydrocarbon group containing a carboxyl group.

[0014] Preferably, M represents a K ion or a Na ion; R 1represents a C1-C20 alkylene chain containing a carbamate group; R 2 represents a C1-C20 alkylene chain; R 3 represents a C1-C20 alkyl group, -R 4 -OH or -R 5 =CH 2 ; wherein R 4 represents a C1-C20 alkylene chain; R 5 represents a C1-C20 hydrocarbon group containing a carboxyl group.

[0015] Preferably, the structure of the reactive polyurethane anionic emulsifier is selected from one or more of the following formulas (A)-(C):

[0016]

[0017]

[0018] In the formulas (A), (B), and (C), R represents an alkylene chain containing a carbamate group; R' represents an alkylene chain; M represents an alkali metal ion or an ammonium ion;

[0019] In the formula (B), R'' represents an alkyl group;

[0020] In the formula (C), R''' represents a hydrocarbon group containing a carboxyl group.

[0021] Preferably, in the formulas (A), (B), and (C), R represents a C1-C20 alkylene chain containing a carbamate group; R' represents a C1-C20 alkylene chain; M represents a K ion or a Na ion.

[0022] Preferably, in the formula (B), R'' represents a C1-C20 alkyl group.

[0023] Preferably, in the formula (C), R''' represents a C1-C20 hydrocarbon group containing a carboxyl group.

[0024] The reactive polyurethane anionic emulsifier provided by the present invention is prepared from the following raw materials: sulfonate-modified diisocyanate, hydroxy compound.

[0025] Preferably, the molar ratio of the functional groups of the hydroxy compound to the sulfonate-modified diisocyanate is hydroxy:isocyanate group = (1.1-6):1.

[0026] Preferably, the hydroxy compound includes at least one of a monohydric alcohol, a polyhydric alcohol, and a hydroxy acrylate.

[0027] Preferably, the monohydric alcohol includes at least one of methanol, ethanol, propanol, butanol, decanol, dodecanol, tetradecanol, hexadecanol, and octadecanol.

[0028] The polyol is a diol or an alcohol containing two or more hydroxyl groups in the molecule. Preferably, the polyol includes at least one of 3-methyl-1,5-pentanediol, neopentyl glycol, 2,2-bis(4-hydroxyphenyl)propane, ethylene glycol, diethylene glycol, cyclohexanediol, methylpropanediol, 1,3-propanediol, 1,4-bis(hydroxymethyl)cyclohexane, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,2-propanediol, diglycol, tetrahydrofuran diol, 1,6-hexanediol, trimethylpentanediol, butylethylpropanediol, dipropylene glycol, tripropylene glycol, ethylhexanediol, dodecanediol, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, polyester polyol, polyether polyol, hydroxy silicone resin, and epoxy resin.

[0029] Preferably, the hydroxyacrylate includes at least one of hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, and hydroxyethyl methacrylate.

[0030] Preferably, the sulfonate-modified diisocyanate includes at least one of sulfonate-modified IPDI, sulfonate-modified HDI, sulfonate-modified TDI, sulfonate-modified MDI, and sulfonate-modified HMDI.

[0031] Preferably, the sulfonate-modified diisocyanate is prepared by reacting a small molecule sulfonate diol with a diisocyanate.

[0032] The chemical reaction formula for the reaction of a small molecule sulfonate diol with a diisocyanate to form a sulfonate-modified diisocyanate is as follows:

[0033]

[0034] In the reaction formula (1), M is an alkali metal ion or an ammonium ion; n = 1 to 6; R represents the remaining group of the diisocyanate except for the two -NCO groups, and R' represents a hydrocarbon group.

[0035] Preferably, the average molecular weight of the sulfonate-modified diisocyanate is 300 to 2000.

[0036] The structural feature of the sulfonate-modified diisocyanate used in the present invention: the molecular structure contains at least one sulfonate group, and the two ends are -NCO groups. Therefore, when the sulfonate-modified diisocyanate reacts with a hydroxy compound, according to different reaction materials and different functional group ratios, a polyurethane emulsifier with a sulfonate group at the end and a hydroxy group and / or a double bond in the molecular structure can be formed.

[0037] Preferably, the small molecule sulfonate diol includes at least one of sodium 1,2-dihydroxy-3-propane sulfonate, sodium 1,4-dihydroxybutane-2-sulfonate, the esterified product of sodium dicarboxybenzene sulfonate and small molecule polyol.

[0038] Preferably, the small molecule polyol includes at least one of 3-methyl-1,5-pentanediol, neopentyl glycol, ethylene glycol, cyclohexanediol, methyl propylene glycol, 1,3-propanediol, 1,4-bis(hydroxymethyl)cyclohexane, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,2-propanediol, diethylene glycol, tetrahydrofuran diol, 1,6-hexanediol, trimethylpentanediol, butylethylpropanediol, dipropylene glycol, tripropylene glycol, ethylhexanediol, trimethylolpropane, and trimethylolethane.

[0039] Preferably, the diisocyanate includes at least one of IPDI (isophorone diisocyanate), HDI (hexamethylene diisocyanate), TDI (toluene diisocyanate), MDI (diphenylmethane diisocyanate), and HMDI (4,4'-dicyclohexylmethane diisocyanate).

[0040] The second aspect of the present invention provides a method for preparing the reactive polyurethane anionic emulsifier according to the first aspect of the present invention, including the following three methods:

[0041] I. When the hydroxy compound only includes one polyol, the preparation method includes the following steps:

[0042] React the polyol with the sulfonate-modified diisocyanate to obtain the reactive polyurethane anionic emulsifier;

[0043] II. When the hydroxy compound includes two or more polyols, the preparation method includes the following steps:

[0044] React one of the polyols with the sulfonate-modified diisocyanate first, and then add the remaining polyols to continue the reaction to obtain the reactive polyurethane anionic emulsifier;

[0045] III. When the hydroxy compound includes at least two of a monohydric alcohol, a polyol, and a hydroxyacrylate, the preparation method includes the following steps:

[0046] React the monohydric alcohol and / or the hydroxyacrylate with the sulfonate-modified diisocyanate first, and then add the polyol to react to obtain the reactive polyurethane anionic emulsifier.

[0047] Preferably, in the first method of the preparation method of the reactive polyurethane anionic emulsifier, the reaction temperature is 70°C to 100°C.

[0048] Preferably, in the first preparation method of the reactive polyurethane anionic emulsifier, the reaction time is 2 hours to 30 hours.

[0049] Preferably, in the second preparation method of the reactive polyurethane anionic emulsifier, one of the polyols is first reacted with the sulfonate-modified diisocyanate, and the reaction temperature is 70 °C to 100 °C.

[0050] Preferably, in the second preparation method of the reactive polyurethane anionic emulsifier, one of the polyols is first reacted with the sulfonate-modified diisocyanate, and the reaction time is 2 hours to 30 hours.

[0051] Preferably, in the second preparation method of the reactive polyurethane anionic emulsifier, the remaining polyol is then added to continue the reaction, and the reaction temperature is 70 °C to 100 °C.

[0052] Preferably, in the second preparation method of the reactive polyurethane anionic emulsifier, the remaining polyol is then added to continue the reaction, and the reaction time is 2 hours to 30 hours.

[0053] Preferably, in the third preparation method of the reactive polyurethane anionic emulsifier, the monohydric alcohol and / or hydroxyacrylate are first reacted with the sulfonate-modified diisocyanate, and the reaction temperature is 70 °C to 100 °C.

[0054] Preferably, in the third preparation method of the reactive polyurethane anionic emulsifier, the monohydric alcohol and / or hydroxyacrylate are first reacted with the sulfonate-modified diisocyanate, and the reaction time is 2 hours to 30 hours.

[0055] Preferably, in the third preparation method of the reactive polyurethane anionic emulsifier, the polyol is then added to continue the reaction, and the reaction temperature is 70 °C to 100 °C.

[0056] Preferably, in the third preparation method of the reactive polyurethane anionic emulsifier, the polyol is then added to continue the reaction, and the reaction time is 2 hours to 30 hours.

[0057] Preferably, in the three preparation methods of the reactive polyurethane anionic emulsifier, the reaction is finally stopped when no NCO can be detected.

[0058] Preferably, in the preparation method of the reactive polyurethane anionic emulsifier, the hydroxy compound is dehydrated before use.

[0059] Preferably, in the preparation method of the reactive polyurethane anionic emulsifier, it also includes the step of adding a co-solvent to participate in the reaction.

[0060] Preferably, in the preparation method of the reactive polyurethane anionic emulsifier, the hydroxy compound and the co-solvent are dissolved at room temperature to 60 °C and then reacted with the sulfonate-modified diisocyanate.

[0061] Preferably, the co-solvent includes at least one of propylene glycol monomethyl ether acetate, acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, N-methylpyrrolidone, N,N-dimethylformamide, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, dioxane, dipropylene glycol dimethyl ether, diethylene glycol diacetate, and dipropylene glycol diacetate.

[0062] Preferably, the addition amount of the co-solvent is 0 to 40% of the total mass of the reactants (hydroxy compound and sulfonate-modified diisocyanate); more preferably, the addition amount of the co-solvent is 0 to 40% of the total mass of the reactants, but not 0.

[0063] In some preparation methods of the reactive polyurethane anionic emulsifier, first determine the order of the blocking reaction of the sulfonate-modified diisocyanate with different hydroxy compounds. The monofunctional hydroxy compound (such as monohydric alcohol, hydroxyacrylate) or the polyfunctional hydroxy compound with low activity is added first for reaction, and the polyfunctional hydroxy compound with high activity (such as polyol) is added later for reaction.

[0064] In some specific embodiments of the present invention, the chemical reaction formula for preparing the emulsifier with the structure shown in formula (A) by the reaction of sulfonate-modified diisocyanate and diol is as follows:

[0065]

[0066] In some specific embodiments of the present invention, the chemical reaction formula for preparing the emulsifier with the structure shown in formula (B) by the reaction of sulfonate-modified diisocyanate with monohydric alcohol and diol is as follows:

[0067]

[0068] In some specific embodiments of the present invention, the chemical reaction formula for preparing the emulsifier with the structure shown in formula (C) by the reaction of sulfonate-modified diisocyanate with hydroxyacrylate and diol is as follows:

[0069]

[0070] In the reaction formulas (2) to (4), the definitions of R, R’, R”, R”’ and M are the same as those of R, R’, R”, R”’ and M in the foregoing formulas (A) to (C).

[0071] The third aspect of the present invention provides an aqueous resin, which is prepared from raw materials including: the reactive polyurethane anionic emulsifier described in the first aspect of the present invention, and a solvent-based resin.

[0072] Since the sulfonate group carried by the reactive polyurethane anionic emulsifier of the present invention has strong hydrophilicity, it can emulsify various resins, and the various reactive functional groups it carries can be adapted to various resins and can produce the same curing effect as the resin in the later curing reaction. Therefore, the resin performance can be basically maintained without change. Generally, when selecting, the reactive functional groups of the emulsifier can be the same as those of the resin, or the structure of the emulsifier can be similar to that of the resin. Specifically, in actual applications, suitable emulsifier varieties can be selected according to the product performance requirements.

[0073] Preferably, the solvent-based resin includes at least one of polyurethane resin, acrylic resin, alkyd resin, SBS (styrene-butadiene-styrene) resin, petroleum resin, polyolefin resin, silicone resin, and epoxy resin. The reactive polyurethane anionic emulsifier of the present invention is mainly used for the rapid water-based conversion of solvent-based polyurethane resin, solvent-based acrylic resin, solvent-based alkyd resin, SBS resin, petroleum resin, polyolefin resin, silicone resin, epoxy resin, etc.

[0074] Preferably, the mass ratio of the reactive polyurethane anionic emulsifier to the solvent-based resin is (0.01 - 1):1; more preferably, the mass ratio of the reactive polyurethane anionic emulsifier to the solvent-based resin is (0.05 - 0.5):1; even more preferably, the mass ratio of the reactive polyurethane anionic emulsifier to the solvent-based resin is (0.1 - 0.3):1.

[0075] The fourth aspect of the present invention provides a preparation method of the aqueous resin according to the third aspect of the present invention, including the following steps: mixing and stirring the reactive polyurethane anionic emulsifier and the solvent-based resin to obtain the aqueous resin.

[0076] Preferably, in the preparation method of the aqueous resin, the mixing and stirring time is 0.4 hours to 1 hour; more preferably, the mixing and stirring time is 0.4 hours to 0.5 hours.

[0077] Preferably, in the preparation method of the aqueous resin, the mixing and stirring speed is 500 revolutions per minute to 1500 revolutions per minute; more preferably, the mixing and stirring speed is 800 revolutions per minute to 1200 revolutions per minute.

[0078] The fifth aspect of the present invention provides the use of the reactive polyurethane anionic emulsifier according to the first aspect of the present invention in the preparation of waterborne polyurethane coatings, waterborne polyurethane-modified alkyd resin coatings, waterborne polyurethane-modified epoxy resin coatings, waterborne polyurethane-modified acrylic coatings, waterborne polyurethane-modified silicone coatings, waterborne polyurethane adhesives, waterborne polyurethane binders, waterborne leather finishing agents, waterborne fabric finishing agents or waterborne ink binders.

[0079] The waterborne resins prepared with the reactive polyurethane anionic emulsifier of the present invention carry reactive active groups. By combining them, two-component waterborne polyurethane coatings, waterborne polyurethane paints, waterborne polyurethane adhesives, waterborne polyurethane binders, waterborne leather finishing agents, waterborne fabric finishing agents or waterborne ink binders can be prepared. Since the emulsifier carries the same reactive groups as the waterborne resin, it can participate in the subsequent crosslinking and curing reactions, playing a role in regulating the molecular structure and function, thereby retaining or improving the performance of the original resin. Therefore, the waterborne resins prepared with the reactive polyurethane anionic emulsifier of the present invention will not reduce the performance of the final product.

[0080] The beneficial effects of the present invention are as follows:

[0081] The molecular structure of the reactive polyurethane anionic emulsifier provided by the present invention contains an anionic sulfonate group, with active hydroxyl groups and double bonds at the ends. It has the hydrophilic-lipophilic function of an emulsifier and also has a chemical reaction function. The sulfonate group contained in this emulsifier has good hydrophilic properties. The active functional groups at the ends can not only have good affinity with a variety of solvent-based resins, but also participate in the subsequent curing and crosslinking reactions with the resin to form a three-dimensional structure substance. The reactive polyurethane anionic emulsifier of the present invention has the characteristics of quickly making solvent-based polyurethane resins, acrylic resins, alkyd resins, ABS resins, epoxy resins, petroleum resins, etc. waterborne, and has the advantages of simple process, high efficiency, stable quality and low cost. It can make these solvent-based resins use water instead of solvents during subsequent construction, greatly reducing VOC emissions and having broad application prospects.

[0082] Specifically, compared with the prior art, the present invention has the following advantages:

[0083] 1. Facilitate the popularization and application of waterborne resins. The reactive polyurethane anionic emulsifier of the present invention is added to solvent-based resins in a certain proportion, and after stirring and mixing for 0.4 - 1 hour, it becomes the corresponding waterborne resin. In contrast, the existing production technology of waterborne resins generally requires more than 20 hours of complex technological steps to produce waterborne resins. Therefore, the present invention simplifies the production of waterborne resins to the extreme, shortens the working hours, reduces the production cost, and improves the economic benefits. In addition, the production technology of waterborne resins in the present invention combines the mature technology of solvent-based resins over the past century. Only by producing the reactive polyurethane anionic emulsifier and adding it to the solvent-based resin can it become a waterborne resin. Since the original formula of the solvent-based resin remains unchanged, the product performance after waterborne conversion basically remains unchanged. The present invention brings great convenience to the popularization and application of waterborne resins by using a method of "the greatest simplicity".

[0084] 2. Maintain the normal connection of the industrial chain. For the application of the reactive polyurethane anionic emulsifier of the present invention, emulsifier varieties with the same functional groups as those of the solvent-based resin can be selected. In this way, the reaction performance of the functional groups of the emulsifier is basically the same as that of the functional groups of the resin, and the same curing effect as that of the resin can be produced in the later curing reaction, maintaining basically the same performance as the resin. Or, appropriate emulsifier varieties can be reasonably selected according to the product performance requirements to improve the product performance. Since the reactive polyurethane anionic emulsifier of the present invention can ensure that the product performance after the waterborne conversion of the resin is not affected, it thus guarantees the position of the resin in the upstream and downstream industrial chains, and solves the problem of fluctuations in the upstream and downstream industrial chains caused by the introduction of hydrophilic groups due to the waterborne conversion of the resin in the existing technology, resulting in a decline in product performance.

[0085] 3. Good environmental protection. After the polyurethane reactive anionic emulsifier of the present invention transforms the solvent-based resin into a waterborne resin, water is used to dilute the resin instead of the solvent during later construction, greatly reducing the VOC emissions and the production cost.

[0086] 4. Multiple varieties and wide application scope. The preparation raw materials of the reactive polyurethane anionic emulsifier of the present invention are extensive and there are multiple varieties, which can produce a series of varieties suitable for different needs. It can not only be used for the waterborne conversion of polyurethane resins, but also for the waterborne conversion of acrylic resins, alkyd resins, SBS resins, polyolefin resins, silicone resins, epoxy resins, etc. Moreover, the excellent properties of polyurethane can be introduced into these resin systems for modification, expanding the application scope of the resin systems. Detailed implementation mode

[0087] The content of the present invention will be further described in detail through specific examples below. Unless otherwise specified, the raw materials, reagents or devices used in the examples can be obtained from conventional commercial channels or can be obtained by existing technical methods. Unless otherwise specified, the test or measurement methods are conventional methods in the art.

[0088] Unless otherwise specified, the percentages used hereinafter represent weight percentages.

[0089] The raw materials used in the examples are described as follows:

[0090] 1. SSIPD-75 diisocyanate (sulfonate-modified IPDI) is produced by Foshan Jingxin Huiming Technology Co., Ltd., with a solid content of 75%, a viscosity of 2800 mPa·s / 25°C, and an NCO content of 13.5%.

[0091] 2. SSHD-80 diisocyanate (sulfonate-modified HDI) is produced by Foshan Jingxin Huiming Technology Co., Ltd., with a solid content of 80%, a viscosity of 1500 mPa·s / 25°C, and an NCO content of 15.5%.

[0092] 3. SSMD-80 diisocyanate (sulfonate-modified MDI) is produced by Foshan Jingxin Huiming Technology Co., Ltd., with a solid content of 80%, a viscosity of 16000 mPa·s / 25°C, and an NCO content of 12.2%.

[0093] 4. SSTD-80 diisocyanate (sulfonate-modified TDI) is produced by Foshan Jingxin Huiming Technology Co., Ltd., with a solid content of 80%, a viscosity of 1800 mPa·s / 25°C, and an NCO content of 13.6%.

[0094] 5. HDX-100 waterborne polyurethane curing agent is produced by Foshan Jingxin Huiming Technology Co., Ltd., with a solid content of 100%, an NCO content of 21.2%, and a viscosity of 7000 mPa·s / 25°C.

[0095] 6. HDXL-100 waterborne polyurethane curing agent is produced by Foshan Jingxin Huiming Technology Co., Ltd., with a solid content of 97%, an NCO content of 18.5%, and a viscosity of 2800 mPa·s / 25°C.

[0096] 7. AK2020 alkyd resin is produced by Guangdong Tongde New Materials Co., Ltd., with a viscosity of 25000 mPa·s / 30°C, a solid content of 70%, an acid value of 8 mg KOH / g, and a hydroxyl value of 134 mg KOH / g.

[0097] The detection methods for the following examples are described as follows:

[0098] 1. Appearance (visual method) is carried out in accordance with "GB / T 1721-2008 Determination Method for Appearance and Transparency of Varnishes, Drying Oils and Thinners".

[0099] 2. Detection of solid content is carried out in accordance with "GB / T 1725-2007 Determination of Non-Volatile Content of Paints, Varnishes and Plastics".

[0100] 3. The viscosity is detected according to "GB / T 2794-2013 Determination of Viscosity of Adhesives - Single Cylinder Rotating Viscometer Method".

[0101] 4. The hydroxyl value is detected according to the standard of the Ministry of Chemical Industry "HG / T2709-1995 Determination of Hydroxyl Value in Polyester Polyol".

[0102] 5. The NCO content is detected according to the standard of the Ministry of Chemical Industry "HG / T2409-1992 Determination of Isocyanate Group Content in Polyurethane Prepolymer".

[0103] Example 1

[0104] This example provides a reactive polyurethane anionic emulsifier with the structural formula (A), and its chemical reaction formula is as follows:

[0105]

[0106] In the above formula, R represents an alkylene chain containing a urethane group formed by the reaction of HDI and a small molecule sulfonate diol, R' represents a branched alkylene chain, and M represents a sodium ion.

[0107] The preparation method of this reactive polyurethane anionic emulsifier is specifically as follows:

[0108] In a three-necked reaction flask, add 94 g (1.286 equivalents) of trimethylpentanediol and 55 g of propylene glycol monomethyl ether acetate that have been dehydrated, and heat up to 50 °C for dissolution; then add 200 g (0.643 equivalents) of SSHD-80 diisocyanate for reaction. After no longer naturally heating up, raise the temperature to 100 °C and react for 6 h. Then, sample and measure the NCO content every 0.5 h. Stop the reaction when no NCO can be detected, cool down and discharge the material to obtain a polyurethane emulsifier with sulfonate groups at both ends and hydroxyl groups at the ends. After detection, the appearance of the product is a slightly yellow viscous liquid, the viscosity is 7200 mPa·s / 25 °C, the solid content is 70%, and the hydroxyl value is 103.8 mgKOH / g.

[0109] Example 2

[0110] The preparation of a reactive polyurethane anionic emulsifier (product of structural formula A):

[0111] In a three-necked reaction flask, add 36.9 g (0.3238 equivalent) of dehydrated bisphenol A and 111 g of propylene glycol monomethyl ether acetate. Start the stirrer and heat up to 40 °C for dissolution. Add 200 g (0.6476 equivalent) of SSTD-80 diisocyanate and react for 1 hour, then slowly heat up to 85 °C and react for 4 h. Then cool down to 60 °C, add 30.4 g (0.5828 equivalent) of neopentyl glycol and react. After the temperature no longer rises naturally, heat up to 85 °C and react for 7 h. Then take samples every 0.5 h to measure the NCO content. Stop the reaction when no NCO can be detected. Cool down and discharge the material to obtain a polyurethane emulsifier with sulfonate groups at both ends and hydroxyl groups at the ends. After testing, the appearance of the product is a slightly yellow viscous liquid, the viscosity is 11500 mPa·s / 25 °C, the solid content is 60%, and the hydroxyl value is 38.3 mg KOH / g.

[0112] Example 3

[0113] This example provides a reactive polyurethane anionic emulsifier with structural formula (B), and its chemical reaction formula is as follows:

[0114]

[0115] In the above formula, R represents an alkylene chain containing urethane groups formed by the reaction of MDI and a small molecule sulfonate diol, R' represents 4 alkylene chains, R" represents 12 alkylene chains, and M represents a sodium ion.

[0116] The preparation method of this reactive polyurethane anionic emulsifier is as follows:

[0117] In a three-necked reaction flask, add 54.1 g (0.2904 equivalent) of dehydrated dodecanol and 62 g of butanone. Start the stirrer and heat up to 50 °C for dissolution. Add 200 g (0.5809 equivalent) of SSMD-80 diisocyanate and react. Slowly heat up to 80 °C and react for 4 h. Then cool down to 50 °C, add 23.5 g (0.5228 equivalent) of 1,4-butanediol and react. After the temperature no longer rises naturally, heat up to 80 °C and react for 5 h. Then take samples every 0.5 h to measure the NCO content. Stop the reaction when no NCO can be detected. Cool down and discharge the material to obtain a polyurethane emulsifier with sulfonate groups and a hydroxyl group at one end. After testing, the appearance of the product is a slightly yellow viscous liquid, the viscosity is 9500 mPa·s / 25 °C, the solid content is 70%, and the hydroxyl value is 38.4 mg KOH / g.

[0118] Example 4

[0119] This example provides a reactive polyurethane anionic emulsifier with structural formula (C), and its chemical reaction formula is as follows:

[0120]

[0121] In the above formula, R represents an alkylene chain containing a urethane group formed by the reaction of HDI and a small molecule sulfonate diol, R' represents an alkylene chain of trimethylolpropane, R" represents an alkylene chain containing an acrylic carboxyl group, and M represents a sodium ion.

[0122] The preparation method of this reactive polyurethane anionic emulsifier is as follows:

[0123] In a three-necked reaction flask, add 48 g (0.369 equivalent) of hydroxypropyl acrylate dehydrated and 80 g of methyl ethyl ketone, stir evenly, add 200 g (0.7381 equivalent) of SSHD-80 diisocyanate to react, slowly raise the temperature to 80 °C and react for 6 h; then cool down to 50 °C, first add 46 g of methyl ethyl ketone, then add 41 g (0.9225 equivalent) of trimethylolpropane to react. After the temperature no longer rises naturally, raise the temperature to 80 °C and react for 7 h. Then, sample and measure the NCO content every 0.5 h. Stop the reaction when no NCO is detected, cool down and discharge to obtain a polyurethane emulsifier containing a sulfonate group, with a double bond at one end and a hydroxyl group at the other end. The appearance of the product is detected as a slightly yellow viscous liquid, with a viscosity of 6800 mPa·s / 25 °C, a solid content of 60%, and a hydroxyl value of 74.5 mgKOH / g.

[0124] Example 5

[0125] Preparation of a reactive polyurethane anionic emulsifier (product of Structure A formula):

[0126] In a three-necked reaction flask, add 57.8 g (1.286 equivalents) of 1,4-butanediol dehydrated and 39 g of N-methylpyrrolidone, stir and mix evenly; then add 200 g (0.6429 equivalent) of SSIPD-75 diisocyanate, react at 70 °C for 2 hours, raise the temperature to 90 °C and react for 8 h. Then, sample and measure the NCO content every 0.5 h. Stop the reaction when no NCO is detected, cool down and discharge to obtain a polyurethane emulsifier containing a sulfonate group with hydroxyl groups at both ends. The appearance of the product is detected as a slightly yellow viscous liquid, with a viscosity of 4200 mPa·s / 25 °C, a solid content of 70%, and a hydroxyl value of 121 mgKOH / g.

[0127] Example 6

[0128] Preparation of a reactive polyurethane anionic emulsifier (product of Structure A formula):

[0129] In a three-necked reaction flask, 162 g (0.3238 equivalent) of dehydrated poly (ethylene glycol adipate-neopentyl glycol) diol and 100 g of methyl ethyl ketone were added, stirred evenly, and then 200 g (0.6476 equivalent) of SSTD-80 diisocyanate was added. The temperature was slowly raised to 90 °C and reacted for 6 h; then the temperature was lowered to 50 °C. First, 92 g of propylene glycol monomethyl ether acetate was added, and then 26 g (0.5828 equivalent) of 1,4-butanediol was added for reaction. After the temperature no longer rose spontaneously, it was raised to 90 °C and reacted for 5 h. Then, samples were taken every 0.5 h to measure the NCO content. The reaction was stopped when no NCO was detected. After cooling, the product was discharged to obtain a polyurethane emulsifier containing sulfonate groups and hydroxyl groups at the ends. The appearance of the product was detected to be a slightly yellow viscous liquid, with a viscosity of 11800 mPa·s / 25 °C, a solid content of 60%, and a hydroxyl value of 25 mg KOH / g.

[0130] Application Example 1

[0131] Preparation of a waterborne polyurethane-modified acrylic resin:

[0132] In a three-necked reaction flask, 200 g of a solvent-based acrylic resin (solid content 50%, hydroxyl value 14 mg KOH / g) was added, the stirrer was started, and then 26 g of the reactive polyurethane anionic emulsifier prepared in Example 1 was added. The mixture was stirred at 1000 rpm for 0.5 h to obtain a waterborne polyurethane-modified acrylic resin.

[0133] The appearance of the product was detected to be a slightly yellow viscous liquid, with a viscosity of 2500 mPa·s / 25 °C, a solid content of 52.3%, and a hydroxyl value of 24.3 mg KOH / g.

[0134] Application Example 2

[0135] Preparation of a waterborne polyurethane resin:

[0136] In a three-necked reaction flask, 200 g of a solvent-based polyurethane resin (solid content 50%, hydroxyl value 4.0 mg KOH / g) was added, the stirrer was started, and then 30 g of the reactive polyurethane anionic emulsifier prepared in Example 2 was added. The mixture was stirred at 1000 rpm for 0.5 h to obtain a waterborne polyurethane resin.

[0137] The appearance of the product was detected to be a slightly yellow viscous liquid, with a viscosity of 4200 mPa·s / 25 °C, a solid content of 51.3%, and a hydroxyl value of 8.47 mg KOH / g.

[0138] Application Example 3

[0139] Preparation of a waterborne polyurethane-modified alkyd resin:

[0140] In a three-necked reaction flask, add 200 g of AK2020 alkyd resin (solid content: 70%, acid value: 8 mg KOH / g, hydroxyl value: 134 mg KOH / g). Start the stirrer, and then add 40 g of the reactive polyurethane anionic emulsifier prepared in Example 3. Stir and mix at 1000 revolutions per minute for 0.5 hour to obtain a waterborne polyurethane-modified alkyd resin.

[0141] The appearance of the detected product is a slightly yellowish viscous liquid, the viscosity is 16500 mPa·s / 25 °C, the solid content is 70%, the acid value is 6.7 mg KOH / g, and the hydroxyl value is 118 mg KOH / g.

[0142] Application Example 4

[0143] Preparation of a waterborne polyurethane-modified SBS resin:

[0144] In a three-necked reaction flask, add 200 g of solvent-based SBS resin (solid content: 50%). Start the stirrer, and then add 40 g of the reactive polyurethane anionic emulsifier prepared in Example 4. Stir and mix at 1000 revolutions per minute for 0.5 hour to obtain a waterborne polyurethane resin.

[0145] The appearance of the detected product is a slightly yellowish viscous liquid, the viscosity is 5100 mPa·s / 25 °C, and the solid content is 51.6%.

[0146] Application Example 5

[0147] Preparation of a waterborne polyurethane resin:

[0148] In a three-necked reaction flask, add 200 g of solvent-based polyurethane resin (solid content: 75%, hydroxyl value: 105 mg KOH / g). Start the stirrer, and then add 30 g of the reactive polyurethane anionic emulsifier prepared in Example 5. Stir and mix at 1000 revolutions per minute for 0.5 hour to obtain a waterborne polyurethane resin.

[0149] The appearance of the detected product is a slightly yellowish viscous liquid, the viscosity is 6500 mPa·s / 25 °C, the solid content is 74.3%, and the hydroxyl value is 107.1 mg KOH / g.

[0150] Application Example 6

[0151] Preparation of a waterborne polyurethane resin:

[0152] In a three-necked reaction flask, add 200 g of solvent-based polyurethane resin (solid content: 50%, hydroxyl value: 62 mg KOH / g). Start the stirrer, and then add 32 g of the reactive polyurethane anionic emulsifier prepared in Example 6. Stir and mix at 1000 revolutions per minute for 0.5 hour to obtain a waterborne polyurethane resin.

[0153] The appearance of the detected product is a slightly yellowish viscous liquid, with a viscosity of 4500 mPa·s / 25°C, a solid content of 51.3%, and a hydroxyl value of 56.9 mgKOH / g.

[0154] Application Example 7

[0155] The application of a two-component waterborne polyurethane-modified acrylic coating has the following construction method:

[0156] 1) Take 200 g of the waterborne polyurethane-modified acrylic resin from Application Example 1, dilute it with water to 18 seconds (Coating Cup - 4), and stir and mix at 1500 revolutions per minute for 0.5 hours to obtain a milky white emulsion with a blue light.

[0157] 2) Add 40 g of the HDXL-100 waterborne polyurethane curing agent to the emulsion, mix and stir evenly to prepare a two-component waterborne polyurethane-modified acrylic coating.

[0158] 3) Spray this coating on a tinplate sample, cure it at 50°C for 48 hours, and after standing at room temperature for 24 hours, test the film properties as follows: The film appearance (visual inspection) is flat and smooth; Gloss (60°): ≥89%; Hardness: Shore D48; Impact strength: 52 KJ / m 2 ; Adhesion: Grade 1; Flexibility: 1 mm; Water resistance (72 h) is normal.

[0159] The test method is described as follows: Gloss (60°) is in accordance with GB / T 9754-2007, hardness is in accordance with GB / T 1730-2007, impact strength is in accordance with GB / T 1732-2020, adhesion is in accordance with GB / T 1720-2020, flexibility is in accordance with GB / T 1731-2020, and water resistance is in accordance with GB / T1733-1993.

[0160] Application Example 8

[0161] The application of a two-component waterborne polyurethane adhesive has the following construction method:

[0162] 1) Take 200 g of the waterborne polyurethane resin from Application Example 2, dilute it with water to 1800 mPa·s / 25°C, and stir and mix at 1500 revolutions per minute for 0.5 hours to obtain a milky white emulsion with a blue light.

[0163] 2) Add 30 g of the HDX-100 waterborne polyurethane curing agent to the emulsion, mix and stir evenly to prepare a two-component waterborne polyurethane adhesive.

[0164] 3) Apply this adhesive to the composite of PET aluminized film and CPP film. The coater coats the adhesive onto the CPP film, places it in an oven and bakes at 150 °C for 2 minutes. Take it out, laminate the PET aluminized film on it, and perform rolling hot lamination at a pressure roller temperature of 80 - 90 °C. After standing at room temperature for 72 hours, conduct a 180 °C peel strength test according to GB / T 2791-1995 "Test Method for T Peel Strength of Adhesives, Flexible Material to Flexible Material", and the PET aluminized film is torn.

[0165] Application Example 9

[0166] Application of a two-component waterborne polyurethane modified alkyd paint, and its construction method is as follows:

[0167] 1) Take 200 g of the waterborne polyurethane modified alkyd resin from Application Example 3, add water to dilute it to 20 seconds (coat-4 cup), and stir and mix at 1500 revolutions per minute for 0.5 hour to obtain a milky white emulsion with blue light.

[0168] 2) Add 45 g of HDX-100 waterborne polyurethane curing agent to the emulsion, mix and stir evenly to prepare a two-component waterborne polyurethane modified alkyd paint.

[0169] 3) Apply this paint on a tinplate sample, cure it at 50 °C for 48 hours, and after standing at room temperature for 24 hours, test the film properties as follows: Film appearance (visual inspection) is flat and smooth; Gloss (60°): ≥85%; Hardness: Shore D47; Impact strength: 45 KJ / m 2 ; Adhesion: Grade 1; Flexibility: 1 mm; Water resistance (72 h) is normal.

[0170] Application Example 10

[0171] Application of a two-component waterborne polyurethane paint, and its construction method is as follows:

[0172] 1) Take 200 g of the waterborne polyurethane resin from Application Example 5, add water to dilute it to 17 seconds (coat-4 cup), and stir and mix at 1500 revolutions per minute for 0.5 hour to obtain a milky white emulsion with blue light.

[0173] 2) Add 50 g of HDX-100 waterborne polyurethane curing agent to the emulsion, mix and stir evenly to prepare a two-component waterborne polyurethane paint.

[0174] 3) Apply this paint on a tinplate sample, cure it at 50 °C for 48 hours, and after standing at room temperature for 24 hours, test the film properties as follows: Film appearance (visual inspection) is flat and smooth; Gloss (60°): ≥87%; Hardness: Shore D62; Impact strength: 47 KJ / m 2 ; Adhesion: Grade 1; Flexibility: 1 mm; Water resistance (72 h) is normal.

[0175] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. An aqueous resin, characterized in that, the aqueous resin is prepared from the following raw materials: a reactive polyurethane anionic emulsifier, a solvent-based resin; the structural general formula of the reactive polyurethane anionic emulsifier is shown in Formula (I): （Ⅰ） In Formula (I), M represents an alkali metal ion or an ammonium ion; R 1 represents an alkylene chain containing a carbamate group; R 2 represents an alkylene chain; R 3 represents an alkyl group or -R 5 =CH 2 ; where R 5 represents a hydrocarbon group containing a carboxyl group; the solvent-based resin includes at least one of polyurethane resin, acrylic resin, alkyd resin, SBS resin, petroleum resin, polyolefin resin, silicone resin, epoxy resin; the aqueous resin is prepared by the following preparation method: mixing and stirring the reactive polyurethane anionic emulsifier and the solvent-based resin to obtain the aqueous resin; the mixing and stirring time is 0.4 hours to 1 hour.

2. The aqueous resin according to claim 1, characterized in that, the reactive polyurethane anionic emulsifier is prepared from the following preparation raw materials: sulfonate-modified diisocyanate, hydroxy compound.

3. The aqueous resin according to claim 2, characterized in that, the functional group molar ratio of the hydroxy compound to the sulfonate-modified diisocyanate is hydroxy: isocyanate group = (1.1 to 6):

1.

4. The aqueous resin according to claim 2, characterized in that, the hydroxy compound includes at least one of monohydric alcohol, polyhydric alcohol, hydroxy acrylate; and / or, the monohydric alcohol includes at least one of methanol, ethanol, propanol, butanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol; and / or, the polyhydric alcohol is a dihydric alcohol or an alcohol containing more than two hydroxyl groups in the molecule; the polyhydric alcohol includes at least one of 3-methyl-1,5-pentanediol, neopentyl glycol, 2,2-bis(4-hydroxyphenyl)propane, ethylene glycol, diethylene glycol, cyclohexanediol, methylpropanediol, 1,3-propanediol, 1,4-dihydroxymethylcyclohexane, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,2-propanediol, diglycol, tetrahydrofuran diol, 1,6-hexanediol, trimethylpentanediol, butylethylpropanediol, dipropylene glycol, tripropylene glycol, ethylhexanediol, dodecanediol, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, polyester polyol, polyether polyol, hydroxy silicone resin; and / or, the hydroxy acrylate includes at least one of hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate; and / or, the sulfonate-modified diisocyanate includes at least one of sulfonate-modified IPDI, sulfonate-modified HDI, sulfonate-modified TDI, sulfonate-modified MDI, sulfonate-modified HMDI; and / or, the sulfonate-modified diisocyanate is prepared by reacting a small molecule sulfonate diol with a diisocyanate; and / or, the small molecule sulfonate diol includes at least one of 1,2-dihydroxy-3-propanesulfonate, 1,4-dihydroxybutane-2-sulfonate, an esterified product of sodium dicarboxybenzenesulfonate and a small molecule polyol; And / or, the diisocyanate includes at least one of IPDI, HDI, TDI, MDI, and HMDI.

5. The aqueous resin according to any one of claims 2 to 4, characterized in that the preparation method of the reactive polyurethane anionic emulsifier includes the following two methods: I. When the hydroxy compound includes two or more polyols, the preparation method includes the following steps: React one of the polyols with the sulfonate-modified diisocyanate first, and then add the remaining polyols to continue the reaction to obtain the reactive polyurethane anionic emulsifier; II. When the hydroxy compound includes at least two of a monohydric alcohol, a polyol, and a hydroxyacrylate, the preparation method includes the following steps: React the monohydric alcohol and / or hydroxyacrylate with the sulfonate-modified diisocyanate first, and then add the polyol to react to obtain the reactive polyurethane anionic emulsifier.

6. The aqueous resin according to claim 1, characterized in that the mass ratio of the reactive polyurethane anionic emulsifier to the solvent-based resin is (0.01~1):

1.

7. The preparation method of the aqueous resin according to claim 1 or 6, characterized in that the preparation steps are: mixing and stirring the reactive polyurethane anionic emulsifier and the solvent-based resin to obtain the aqueous resin; the mixing and stirring time is 0.4 hours to 1 hour.

8. The preparation method according to claim 7, characterized in that the rotation speed of the mixing and stirring is 500 revolutions per minute to 1500 revolutions per minute.

9. The application of the aqueous resin according to any one of claims 1 to 6 in the preparation of aqueous polyurethane coatings, aqueous polyurethane-modified alkyd resin coatings, aqueous polyurethane-modified epoxy resin coatings, aqueous polyurethane-modified acrylic coatings, aqueous polyurethane-modified silicone coatings, aqueous polyurethane adhesives, aqueous polyurethane binders, aqueous leather finishing agents, aqueous fabric finishing agents, or aqueous ink binders.

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