A reactive polyurethane anionic-nonionic emulsifier and its preparation method and application

Abstract

The invention discloses a reactive polyurethane anionic nonionic emulsifier and a preparation method and application thereof. The molecular structure of the emulsifier contains anionic sulfonate groups and nonionic polyethoxy chain segments, and is prepared by reacting a hydroxy compound with a sulfonate-modified diisocyanate. The reactive polyurethane anionic nonionic emulsifier has the hydrophilic and lipophilic functions of an emulsifier, as well as a chemical reaction function. The active functional groups at the ends of the emulsifier not only have good affinity with a variety of solvent-based resins, but also can participate in subsequent curing and cross-linking reactions with the resin to become part of the body structure. The reactive polyurethane anionic nonionic emulsifier of the present invention has the characteristics of rapidly water-based a variety of polymer resins, and has a simple process, high efficiency, stable quality, and low cost, so that such solvent-based resins can be replaced by water instead of solvents during subsequent construction, greatly reducing VOC emissions, and can be applied to rapidly water-based a variety of solvent-based resins.

Description

Technical Field

[0001] The invention relates to the technical field of emulsifiers, and in particular to a reactive polyurethane anionic-nonionic emulsifier and a preparation method and application thereof. Background Art

[0002] Since the biggest VOC pollution source of solvent-based resins is that a large amount of solvent must be added before construction before spraying, the solid content of general solvent-based resins is 50-75%, and the solid content used for spraying after dilution is only 20-30%, so a large amount of solvent evaporates into the air during the spraying construction process. Therefore, the water-based conversion of polyurethane resins, acrylic resins, epoxy resins, alkyd resins, polyolefin resins, etc. is still the current research focus. However, the existing technology for directly producing water-based resins is not only complex and costly, but also has problems such as the performance of the finished product after the resin is water-based, so researchers are considering studying the method of adding emulsifiers.

[0003] The method of adding emulsifiers can overcome the problems of complex process and high cost in producing water-based resins. However, traditional external emulsifiers reduce product performance. They are physically adsorbed on the surface of latex particles. During the film-forming process, the emulsifier will migrate to the surface of the coating to form a non-chemically bonded hydrophilic emulsifier layer. Once it encounters water or moisture, it will cause the coating to absorb water and swell. Reactive emulsifiers are composed of hydrophobic groups, hydrophilic groups and reactive groups. During the film-forming process, the reactive groups are chemically bonded to the polymer structure and become part of the polymer, which can maintain or improve the performance of the product.

[0004] At present, there are few research reports on polyurethane reactive anionic nonionic emulsifiers. Chinese patent CN113004481A discloses a reactive polyurethane emulsifier and its preparation method. It uses pyromellitic anhydride as the starting material to prepare sulfonated polyester polyol. In the end-capping process, two different end-capping agents are selected and the feed ratio is controlled to first obtain two semi-end-capped prepolymers, and then tetrafunctional pentaerythritol is used for cross-linking, and finally a polyurethane emulsifier with reactive double bonds and characteristic functional groups at the end is obtained, which has anionic nonionic properties; the preparation process of this scheme has many reaction steps and the process is relatively complicated. The emulsifier prepared by the emulsifier is only suitable for the polymerization reaction of acrylate double bonds. There are few reports on reactive anionic nonionic emulsifiers in the prior art, and the scope of application is very narrow, and there is no report on the water-based reaction of polymer resins by reactive polyurethane anionic nonionics. Summary of the invention

[0005] The present invention aims to solve at least one of the above-mentioned technical problems existing in the prior art. To this end, the purpose of the present invention is to provide a reactive polyurethane anionic-nonionic emulsifier, the molecular structure of which contains anionic sulfonate groups and polyethoxy chain nonionic groups, and the ends are active functional hydroxyl groups, double bonds or epoxy groups, and have the hydrophilic and lipophilic functions of an emulsifier, as well as chemical reaction functions. The second purpose of the present invention is to provide a method for preparing the reactive polyurethane anionic-nonionic emulsifier. The third purpose of the present invention is to provide the application of the reactive polyurethane anionic-nonionic emulsifier.

[0006] The reactive polyurethane anionic-nonionic emulsifier provided by the present invention is an isocyanate prepolymer with a characteristic functional group at the end of a molecular structure containing a sulfonate group and a polyethoxy chain segment. The reactive polyurethane anionic-nonionic emulsifier can be used in a solvent-based system in which a variety of resins are added. The solvent-based resin can be converted into a corresponding water-based resin by mixing and stirring evenly. In this way, the water-based resin can be emulsified by adding water during construction, and then diluted with water to a suitable viscosity before spraying. The present invention not only saves a large amount of solvent for dilution and reduces costs, but also, since the formula of the solvent-based resin is not changed, the added reactive polyurethane anionic-nonionic emulsifier can participate in the chemical bonding reaction, and will not reduce the performance of the product, and can achieve the goal of rapid water-based conversion of solvent-based products.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is:

[0008] The first aspect of the present invention provides a reactive polyurethane anionic-nonionic emulsifier, the molecular structure of which contains anionic sulfonate groups and nonionic polyethoxy chain segments;

[0009] The emulsifier is prepared by reacting a hydroxy compound with a sulfonate-modified diisocyanate;

[0010] The hydroxy compound includes a polymer containing polyoxyethylene chain segments, or includes a polymer containing polyoxyethylene chain segments and at least one of monohydric alcohol, polyol, hydroxy acrylate, and epoxy resin; the polymer containing polyoxyethylene chain segments includes at least one of polyethylene glycol and fatty alcohol polyoxyethylene ether.

[0011] Preferably, the structural formula of the reactive polyurethane anionic-nonionic emulsifier is as shown in formula (I):

[0012]

[0013] In formula (I), M represents an alkali metal ion or an ammonium ion;

[0014] R represents an alkylene chain containing a carbamate group;

[0015] X represents a characteristic functional group of a hydroxy compound, selected from a hydroxyl group, an epoxy group, a double bond or an alkyl group;

[0016] R' represents the remaining groups of the hydroxy compound except the characteristic functional groups;

[0017] R" represents H, or a C12-C18 hydrocarbon group;

[0018] n=3~30.

[0019] Further preferably, in the formula (I), M represents K ion or Na ion;

[0020] R represents a C1-C20 alkylene chain containing a carbamate group;

[0021] X represents a characteristic functional group of a hydroxy compound, selected from a hydroxyl group, an epoxy group, a double bond or a C1-C20 alkyl group;

[0022] R' represents the remaining groups of the hydroxy compound except the characteristic functional groups;

[0023] R" represents H, or a C12-C18 hydrocarbon group;

[0024] n=6~30.

[0025] Preferably, the molar ratio of the hydroxy compound to the sulfonate-modified diisocyanate is (1.5-2):1.

[0026] 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.

[0027] Preferably, the sulfonate-modified diisocyanate is prepared by reacting a small molecule sulfonate diol with a diisocyanate.

[0028] The chemical reaction formula of the reaction of small molecule sulfonate diol and diisocyanate to generate sulfonate modified diisocyanate is as follows:

[0029]

[0030] In the reaction formula (1), M is an alkali metal ion or an ammonium ion; n=1 to 6; R represents the remaining groups of the diisocyanate except the two -NCO groups; and R' represents a hydrocarbon group.

[0031] Preferably, the average molecular weight of the sulfonate-modified diisocyanate is 300-2000.

[0032] The structural characteristics of the sulfonate-modified diisocyanate used in the present invention are: at least one sulfonate group is contained in the molecular structure, and the two ends are -NCO groups. Therefore, the sulfonate-modified diisocyanate reacts with the hydroxyl compound to generate a prepolymer containing a sulfonate group in the molecular structure according to different reaction materials and different functional group ratios.

[0033] Preferably, the small molecule sulfonate diol includes at least one of esters of sodium 1,2-dihydroxy-3-propanesulfonate, sodium 1,4-dihydroxybutane-2-sulfonate, sodium dicarboxybenzenesulfonate and small molecule polyols.

[0034] Preferably, the small molecule polyol includes at least one of 3-methyl-1,5-pentanediol, neopentyl glycol, ethylene glycol, cyclohexanediol, methylpropylene glycol, 1,3-propylene glycol, 1,4-dihydroxymethylcyclohexane, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,2-propylene glycol, diethylene glycol, tetrahydrofuran diol, 1,6-hexanediol, trimethylpentanediol, butyl ethyl propylene glycol, dipropylene glycol, tripropylene glycol, ethyl hexanediol, trimethylolpropane, and trimethylolethane.

[0035] 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).

[0036] Preferably, in the hydroxy compound, the monohydric alcohol includes at least one of methanol, ethanol, propanol, butanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecyl alcohol, and glycidyl glycidol.

[0037] Preferably, among the hydroxy compounds, the polyol is a diol or an alcohol containing more than two hydroxyl groups in the molecule, including at least one of 3-methyl-1,5-pentanediol, neopentyl glycol, 2,2-bis(4-hydroxyphenyl)propane, ethylene glycol, diethylene glycol, cyclohexanediol, methylpropylene glycol, 1,3-propylene glycol, 1,4-dihydroxymethylcyclohexane, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,2-propylene glycol, diethylene glycol, tetrahydrofuran diol, 1,6-hexanediol, trimethylpentanediol, butylethylpropylene glycol, dipropylene glycol, tripropylene glycol, ethyl hexanediol, dodecanediol, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, hydroxy silicone oil, polyester polyol, and polyether polyol.

[0038] Preferably, the hydroxyacrylate includes at least one of hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate.

[0039] Preferably, the epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, and hydrogenated bisphenol A epoxy resin.

[0040] Preferably, the hydroxyl value of the epoxy resin is 0.16 mol / 100 g to 0.39 mol / 100 g.

[0041] Preferably, the molecular weight of the polyethylene glycol is 200-3000.

[0042] Preferably, the structural formula of the fatty alcohol polyoxyethylene ether is R1(CH2CH2O) m H, wherein R1 represents a C12-C18 hydrocarbon group, m=3-30; more preferably, m=6-30.

[0043] Preferably, the fatty alcohol polyoxyethylene ether includes at least one of AEO3, AEO5, AEO7, and AEO9.

[0044] The second aspect of the present invention provides a method for preparing the reactive polyurethane anionic-nonionic emulsifier according to the first aspect of the present invention, comprising the following three methods:

[0045] 1. When the hydroxy compound only includes a polymer containing polyoxyethylene chain segments, and the polymer containing polyoxyethylene chain segments is polyethylene glycol, the preparation method comprises the following steps:

[0046] The polyethylene glycol is reacted with the sulfonate-modified diisocyanate, or the polyethylene glycol is mixed with a cosolvent and then reacted with the sulfonate-modified diisocyanate to obtain the reactive polyurethane anionic-nonionic emulsifier;

[0047] 2. When the hydroxy compound only includes a polymer containing polyoxyethylene chain segments, and the polymer containing polyoxyethylene chain segments is polyethylene glycol and fatty alcohol polyoxyethylene ether, the preparation method comprises the following steps:

[0048] a) reacting fatty alcohol polyoxyethylene ether with sulfonate modified diisocyanate, or mixing fatty alcohol polyoxyethylene ether with a cosolvent, and then reacting with sulfonate modified diisocyanate;

[0049] b) continuing to add polyethylene glycol to react to obtain the reactive polyurethane anionic-nonionic emulsifier;

[0050] 3. When the hydroxy compound comprises a polyoxyethylene chain polymer and at least one of a monohydric alcohol, a polyhydric alcohol, a hydroxy acrylate, and an epoxy resin, the preparation method comprises the following steps:

[0051] a) reacting the remaining hydroxyl compounds except the polyoxyethylene chain-joined polymer with the sulfonate-modified diisocyanate, or mixing the remaining hydroxyl compounds except the polyoxyethylene chain-joined polymer with a cosolvent, and then reacting with the sulfonate-modified diisocyanate;

[0052] b) continuing to add the polyoxyethylene chain segment polymer to react to obtain the reactive polyurethane anionic-nonionic emulsifier.

[0053] Preferably, in the first preparation method, the polyethylene glycol is dehydrated before use.

[0054] Preferably, in the first preparation method, the reaction temperature is 70°C to 100°C.

[0055] Preferably, in the first preparation method, the reaction time is 2 hours to 15 hours.

[0056] Preferably, in the first preparation method, the reaction is stopped when no NCO is detected.

[0057] Preferably, in step a) of the second preparation method, the fatty alcohol polyoxyethylene ether and the cosolvent are dissolved at room temperature to 70° C. and then reacted with the sulfonate-modified diisocyanate.

[0058] Preferably, in step a) of the second preparation method, the fatty alcohol polyoxyethylene ether is dehydrated before use.

[0059] Preferably, in step a) of the second preparation method, the reaction temperature is 70°C to 100°C.

[0060] Preferably, in step a) of the second preparation method, the reaction time is 2 hours to 15 hours.

[0061] Preferably, in step b) of the second preparation method, the reaction temperature is 70°C to 100°C.

[0062] Preferably, in step b) of the second preparation method, the reaction time is 2 hours to 15 hours.

[0063] Preferably, in step b) of the second preparation method, the reaction is stopped when no NCO is detected.

[0064] In the preparation methods of some reactive polyurethane anionic-nonionic emulsifiers, the order of the end-capping reaction of different hydroxyl compounds on sulfonate-modified diisocyanate is first determined, and the low-activity or monofunctional hydroxyl compounds (such as monohydric alcohols, polyols, hydroxy acrylates, epoxy resins) are added to the reaction first, and the high-activity or difunctional hydroxyl compounds (such as polyoxyethylene chain polymers) are added to the reaction later.

[0065] Preferably, in step a) of the third preparation method, the remaining hydroxyl compounds and cosolvents except the polyoxyethylene chain polymer are dissolved at room temperature to 70° C. and then reacted with the sulfonate-modified diisocyanate.

[0066] Preferably, in step a) of the third preparation method, the remaining hydroxyl compounds except the polyoxyethylene chain-containing polymer are dehydrated before use.

[0067] Preferably, in step a) of the third preparation method, the reaction temperature is 70°C to 100°C.

[0068] Preferably, in step a) of the third preparation method, the reaction time is 2 hours to 15 hours.

[0069] Preferably, in step b) of the third preparation method, the reaction temperature is 70°C to 100°C.

[0070] Preferably, in step b) of the third preparation method, the reaction time is 2 hours to 15 hours.

[0071] Preferably, in step b) of the third preparation method, the reaction is stopped when no NCO is detected.

[0072] Preferably, the cosolvent includes at least one of propylene glycol monomethyl ether acetate, acetone, butanone, 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.

[0073] Preferably, the amount of the cosolvent added is 0-40% of the total mass of the reactants (hydroxy compound and sulfonate-modified diisocyanate); further preferably, the amount of the cosolvent added is 0-40% of the total mass of the reactants, but not 0.

[0074] In some specific embodiments of the present invention, the chemical reaction formula of step a) of the third preparation method is as follows:

[0075]

[0076] In some specific embodiments of the present invention, the chemical reaction formula of step b) of the third preparation method is as follows:

[0077]

[0078] In the reaction formulas (2) to (3), the definitions of X, R, R', R", M and n are the same as those of X, R, R', R", M and n in the above formula (I).

[0079] The third aspect of the present invention provides an aqueous resin, which is prepared from the following raw materials: the reactive polyurethane anionic-nonionic emulsifier and solvent-based resin described in the first aspect of the present invention.

[0080] Preferably, in the water-based resin, the solvent-based resin includes at least one of polyurethane resin, acrylic resin, alkyd resin, SIS (styrene-isoprene-styrene) resin, SBS (styrene-butadiene-styrene) resin, petroleum resin, polyolefin resin, terpene resin, epoxy resin, and silicone resin. The reactive polyurethane anionic-nonionic emulsifier provided by the present invention can be used to quickly water-based these types of solvent-based resins.

[0081] The reactive polyurethane anionic-nonionic emulsifier of the present invention has an anionic sulfonate group and a nonionic polyethoxy group with strong hydrophilicity. The combination of the two hydrophilic groups produces a good emulsification effect on a variety of resins, especially epoxy resins, polyolefin resins, alkyd resins, SBS resins, SIS resins, petroleum resins, and terpene resins. The multiple active functional groups it carries can be adapted to a variety of resins (adapted according to the principle that the active functional groups of the emulsifier and the resin are similar), and can produce the same curing effect as the resin in the later curing reaction, so that the resin performance can be kept basically unchanged. In practical applications, suitable emulsifier varieties can be selected according to product performance requirements.

[0082] Preferably, the mass ratio of the reactive polyurethane anionic nonionic emulsifier to the solvent-based resin is (0.01-0.5):1; further preferably, the mass ratio of the reactive polyurethane anionic nonionic emulsifier to the solvent-based resin is (0.02-0.4):1; further preferably, the mass ratio of the reactive polyurethane anionic nonionic emulsifier to the solvent-based resin is (0.03-0.3):1.

[0083] The fourth aspect of the present invention provides a method for preparing the water-based resin according to the third aspect of the present invention, comprising the following steps: mixing and stirring a reactive polyurethane anionic-nonionic emulsifier with a solvent-based resin to obtain the water-based resin.

[0084] Preferably, in the method for preparing the water-based resin, the mixing and stirring time is 0.3 hour to 1 hour; more preferably, the mixing and stirring time is 20 minutes to 0.5 hour.

[0085] Preferably, in the method for preparing the water-based resin, the rotation speed of the mixing and stirring is 500 rpm to 1500 rpm; further preferably, the rotation speed of the mixing and stirring is 800 rpm to 1000 rpm.

[0086] The fifth aspect of the present invention provides the use of the reactive polyurethane anionic-nonionic emulsifier according to the first aspect of the present invention in the preparation of waterborne polyurethane resin, waterborne polyurethane modified alkyd resin coating, waterborne polyurethane modified epoxy resin coating, waterborne polyurethane modified acrylic coating, waterborne polyurethane modified silicone coating, waterborne polyurethane modified SIS / SBS ​​adhesive, waterborne vehicle, waterborne leather finishing agent, waterborne fabric finishing agent or waterborne ink vehicle.

[0087] The reactive polyurethane anionic-nonionic emulsifier of the present invention is mainly used for emulsifying various different types of polymer resins. The various reactive groups carried by the reactive polyurethane anionic-nonionic emulsifier can adapt to different resins and have the same reaction performance as the resins. When combined with a corresponding curing agent, the reactive groups in the emulsifier and the active groups in the resin participate in the curing reaction together, play a role in regulating the molecular structure and function, thereby retaining or improving the performance of the original resin. Therefore, the water-based resin prepared by the reactive polyurethane anionic-nonionic emulsifier of the present invention will not reduce the performance of the final product.

[0088] The beneficial effects of the present invention are:

[0089] The reactive polyurethane anionic-nonionic emulsifier provided by the present invention has a molecular structure that contains not only sulfonate anions and polyethoxy nonions, but also active functional hydroxyl groups, double bonds or epoxy groups at the ends, and has the hydrophilic and lipophilic functions of the emulsifier, as well as chemical reaction functions. The active functional groups at the ends of the emulsifier not only have good affinity with a variety of solvent-based resins, but also can participate in the subsequent curing and cross-linking reaction with the resin to become a part of the body structure. The reactive polyurethane anionic-nonionic emulsifier of the present invention has the characteristics of rapidly converting a variety of polymer resins to water, and has a simple process, high efficiency, stable quality, and low cost. It can enable this type of solvent-based resin to replace the solvent with water during subsequent construction, greatly reducing VOC emissions, and can be used to rapidly convert a variety of solvent-based resins to water.

[0090] Specifically, compared with the prior art, the present invention has the following advantages:

[0091] 1. Better emulsification effect. The reactive polyurethane anionic-nonionic emulsifier of the present invention has dual emulsification functions of anion and nonion, and has a good emulsification effect on a variety of polymer resins, especially on some non-polar polymer resins that are difficult to emulsify. For example, when an anionic-nonionic emulsifier with a double bond is used to emulsify alkyd resin (Application Example 3), a smaller addition amount (10:300) can achieve the same emulsification effect as an anionic emulsifier (20:100) (Comparative Example 1); in addition, different types of anionic-nonionic emulsifiers have a good emulsification effect on SBS resin (Application Example 6), SIS resin (Application Example 2), petroleum resin (Application Example 5), polyolefin resin and other difficult-to-emulsify resins. The emulsifier of the present invention has a good emulsification effect, a small amount of emulsifier is added, and the effect on the product performance is smaller, which is conducive to maintaining the performance of the original polymer resin.

[0092] 2. Maintaining the normal connection of the industrial chain. The application of the reactive polyurethane anionic-nonionic emulsifier of the present invention can select the emulsifier variety with the same functional group as the solvent-based resin, so that the emulsifier has basically the same reaction performance as the resin, and can produce the same curing effect as the resin in the later curing reaction, thereby maintaining the resin performance basically unchanged; it is also possible to reasonably select suitable emulsifier varieties according to product performance requirements to improve product performance. Since the reactive polyurethane anionic-nonionic emulsifier of the present invention can keep the product performance of the resin after water-based, it ensures the position of the resin in the upstream and downstream industrial chain, and solves the problem of fluctuations in the upstream and downstream industrial chain caused by the prior art due to the introduction of hydrophilic groups into the resin water-based, which changes the resin formula and reduces product performance.

[0093] 3. Good environmental protection. After the polyurethane reactive anionic nonionic emulsifier of the present invention converts the solvent-based resin into a water-based resin, water is used to replace the solvent to dilute the resin during the later construction, which greatly reduces VOC emissions and reduces production costs.

[0094] 4. Wider scope of application. The reactive polyurethane anionic-nonionic emulsifier of the present invention can be used not only for water-based emulsification of commonly used polyurethane resins, acrylic resins, and alkyd resins, but also for water-based emulsification of SIS resins, SBS resins, polyolefin resins, petroleum resins, terpene resins, epoxy resins, etc., which are difficult to emulsify by conventional methods, and also introduces the excellent properties of polyurethane into these resin systems, so the scope of application is wider. DETAILED DESCRIPTION

[0095] The present invention is further described in detail below by specific examples. Unless otherwise specified, the raw materials, reagents or devices used in the examples and comparative examples can be obtained from conventional commercial sources or can be obtained by prior art methods. Unless otherwise specified, the experiments or test methods are conventional methods in the art.

[0096] Unless otherwise specified, the percentages used below are by weight.

[0097] The raw materials used in the examples are described as follows:

[0098] 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 2800mPa·s / 25℃, and an NCO content of 13.5%.

[0099] 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 1500mPa·s / 25℃, and an NCO content of 15.5%.

[0100] 3. SSTD-80 diisocyanate (sulfonate modified TDI) is produced by Foshan Jingxin Huiming Technology Co., Ltd., with a solid content of 80%, a viscosity of 1800mPa·s / 25℃, and an NCO content of 13.6%.

[0101] 4. HDX-100 water-based 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 7000mPa·s / 25℃.

[0102] 5. 3015B alkyd resin is produced by Guangdong Tongde New Materials Co., Ltd., with a viscosity of 21000mPa·s / 30℃, a solid content of 70%, an acid value of 6mgKOH / g, and a hydroxyl value of 130mgKOH / g.

[0103] The detection methods of the following embodiments are described as follows:

[0104] 1. Appearance (visual inspection) shall be carried out in accordance with GB / T 1721-2008 Determination of appearance and transparency of varnish, clear oil and thinner.

[0105] 2. The solid content shall be tested in accordance with GB / T 1725-2007 Determination of non-volatile matter content of paints, varnishes and plastics.

[0106] 3. The viscosity test shall be carried out in accordance with GB / T 2794-2013 Determination of viscosity of adhesives - Single cylinder rotational viscometer method.

[0107] 4. The hydroxyl value is tested according to the standard of the Ministry of Chemical Industry "HG / T2709-1995 Determination of Hydroxyl Value in Polyester Polyols".

[0108] 5. The NCO content is tested according to the standard of the Ministry of Chemical Industry "HG / T2409-1992 Determination of Isocyanate Content in Polyurethane Prepolymer".

[0109] Example 1

[0110] Preparation of a polyurethane anionic-nonionic emulsifier with epoxy group:

[0111] a) Add 324g (0.324 mol) of dehydrated epoxy resin E20 and 284g of propylene glycol monomethyl ether acetate into a three-necked reaction bottle, turn on the stirrer, heat to 70°C to dissolve, cool to 50°C after complete dissolution, add 200g (0.324 mol) of SSTD-80 to react, and slowly heat to 80°C to react for 3h after the temperature stops rising naturally;

[0112] b) Cooling to 60°C, adding 118 g (0.295 mol) of PEG-400 for reaction, and slowly heating to 85°C for reaction for 4 h after the temperature stops rising naturally, stopping the reaction when NCO is no longer detected, cooling and discharging the material to obtain a reactive polyurethane anionic-nonionic emulsifier.

[0113] The emulsifier product of this example was tested to be a transparent light yellow viscous liquid with a viscosity of 20500 mPa·s / 25° C., a solid content of 65%, and a hydroxyl value of 35.7 mgKOH / g.

[0114] Example 2

[0115] Preparation of a reactive polyurethane anionic-nonionic emulsifier:

[0116] a) In a three-necked reaction bottle, add 102g (0.3214 mol) of dehydrated fatty alcohol polyoxyethylene ether (AEO-3) and 122g of propylene glycol monomethyl ether acetate, stir evenly, heat to 50°C, add 200g (0.3214 mol) of SSIPD-75 to react, and slowly heat to 85°C to react for 5h after the temperature stops rising naturally;

[0117] b) Cooling to 60°C, adding 116 g (0.289 mol) of PEG-400 for reaction, and slowly heating to 90°C for reaction for 8 h after the temperature stops rising naturally, stopping the reaction when NCO is no longer detected, cooling and discharging to obtain a reactive polyurethane anionic-nonionic emulsifier.

[0118] The emulsifier product of this example was tested to be a yellowish turbid liquid, with a viscosity of 1360 mPa·s / 25° C., a solid content of 70%, and a hydroxyl value of 61.7 mgKOH / g.

[0119] Example 3

[0120] Preparation of a reactive polyurethane anionic-nonionic emulsifier with double bonds:

[0121] a) Add 46.6 g (0.3238 mol) of dehydrated hydroxypropyl methacrylate and 98 g of propylene glycol monomethyl ether acetate into a three-necked reaction flask, turn on the stirrer, heat to 50°C, add 200 g (0.3238 mol) of SSTD-80 and react. After the temperature stops rising naturally, slowly heat to 80°C and react for 3 hours;

[0122] b) Cooling to 60°C, adding 116.6 g (0.2914 mol) of PEG-400 for reaction, and slowly heating to 80°C for reaction for 5 h after the temperature stops rising naturally, stopping the reaction when NCO is no longer detected, cooling and discharging to obtain a reactive polyurethane anionic-nonionic emulsifier.

[0123] The emulsifier product of this example was tested to be a transparent light yellow viscous liquid with a viscosity of 1400 mPa·s / 25° C., a solid content of 70%, and a hydroxyl value of 70.9 mgKOH / g.

[0124] Example 4

[0125] Preparation of a reactive polyurethane anionic-nonionic emulsifier:

[0126] a) Add 369g (0.3690 mol) of dehydrated poly(1,4-butylene adipate) glycol and 355g of butanone into a three-necked reaction flask, turn on the stirrer, heat to 60°C to dissolve, cool to 50°C after complete dissolution, add 200g (0.3690 mol) of SSHD-80 to react, and slowly heat to 85°C to react for 5h after the temperature stops rising naturally;

[0127] b) Cooling to 60°C, adding 130 g (0.3247 mol) of PEG-400 for reaction, and slowly heating to 85°C for reaction for 7 h after the temperature stops rising naturally, stopping the reaction when NCO is no longer detected, cooling and discharging to obtain a reactive polyurethane anionic-nonionic emulsifier.

[0128] The emulsifier product of this example was tested to be a transparent light yellow viscous liquid with a viscosity of 11500 mPa·s / 25° C., a solid content of 65%, and a hydroxyl value of 35.9 mgKOH / g.

[0129] Example 5

[0130] Preparation of a reactive polyurethane anionic emulsifier:

[0131] In a three-necked reaction bottle, add 233.2g (0.583 mol) of dehydrated PEG-400 and 128.6g of propylene glycol monomethyl ether acetate, stir evenly, add 200g (0.3238 mol) of SSTD-80 to react, and when the temperature stops rising naturally, slowly raise the temperature to 80°C and react for 6h. Stop the reaction when NCO is no longer detected, cool and discharge the material to obtain a reactive polyurethane anionic-nonionic emulsifier.

[0132] The emulsifier product of this example was tested to be a transparent, slightly yellow viscous liquid with a viscosity of 2550 mPa·s / 25° C., a solid content of 70%, and a hydroxyl value of 51.7 mgKOH / g.

[0133] Example 6

[0134] Preparation of a reactive polyurethane anionic-nonionic emulsifier:

[0135] a) In a three-necked reaction bottle, add 155.4 g (0.3238 mol) of dehydrated fatty alcohol polyoxyethylene ether (AEO-7) and 144 g of propylene glycol monomethyl ether acetate, stir evenly, heat to 50°C, add 200 g (0.3238 mol) of SSTD-80 to react, and slowly heat to 95°C to react for 3 h after the temperature stops rising naturally;

[0136] b) Cooling to 60°C, adding 115 g (0.288 mol) of PEG-400 for reaction, and slowly heating to 95°C for reaction for 4 h after the temperature stops rising naturally, stopping the reaction when NCO is no longer detected, cooling and discharging to obtain a reactive polyurethane anionic-nonionic emulsifier.

[0137] The emulsifier product of this example was tested to be a transparent, slightly yellow viscous liquid with a viscosity of 1385 mPa·s / 25° C., a solid content of 70%, and a hydroxyl value of 52.5 mgKOH / g.

[0138] Application Example 1

[0139] Preparation of waterborne epoxy floor paint:

[0140] 400 g of E12 epoxy resin solution (ethyl acetate solution with a solid content of 50%) was added with 40 g of the reactive polyurethane anionic-nonionic emulsifier with epoxy groups obtained in Example 1 and 220 g of deionized water, and the mixture was stirred and emulsified at 800 rpm for 20 minutes to obtain a milky white waterborne polyurethane modified epoxy resin emulsion.

[0141] Amine waterborne epoxy curing agent (including fillers and additives) is added into waterborne polyurethane modified epoxy resin emulsion, and the mixture is mixed and stirred evenly to obtain waterborne epoxy floor coating.

[0142] The water-based epoxy floor coating has been used on-site by customers. After the two components are mixed, it has a long applicability period of 2-3 hours. It is easy to construct. The prepared floor has good moisture and heat resistance and good wear resistance, and is suitable for outdoor floors.

[0143] Application Example 2

[0144] Preparation of a water-based SIS resin emulsion:

[0145] 200g SIS resin solution (cyclohexane solution with 20% solid content) was added with 40g reactive polyurethane anionic nonionic emulsifier prepared in Example 2 and 120g deionized water, and stirred and emulsified at 800 rpm for 20 minutes to obtain a milky white water-based SIS resin emulsion. The emulsion was applied on a PET film, and after drying, the coating was observed to be smooth and flat without shrinkage cavities.

[0146] Application Example 3

[0147] 1. Preparation of waterborne polyurethane modified alkyd resin emulsion

[0148] 300 g of 3015B alkyd resin solution (50% solid content ethyl acetate-toluene solution) was added with 10 g of the reactive polyurethane anionic-nonionic emulsifier with double bonds prepared in Example 3 and 155 g of deionized water, and the mixture was stirred and emulsified at 800 rpm for 20 minutes to obtain a milky white waterborne polyurethane modified alkyd resin emulsion with blue light.

[0149] 2. Two-component waterborne polyurethane modified alkyd coating

[0150] Add 60g HDX-100 waterborne polyurethane curing agent and 60g deionized water to the above emulsion, mix and stir evenly to prepare a two-component waterborne polyurethane modified alkyd paint. Apply this paint on a tinplate sample, cure at 50°C for 48 hours, and place at room temperature for 24 hours. Test the paint film properties as follows: the paint film appearance (visual inspection) is flat and smooth; gloss (60°): ≥86%; hardness: Shore D48; impact strength: 52KJ / m 2 ; Adhesion: Level 1; Flexibility: 1mm; Water resistance (72h) no abnormality.

[0151] The test methods are as follows: gloss (60°) shall be in accordance with GB / T 9754-2007, hardness shall be in accordance with GB / T 1730-2007, impact strength shall be in accordance with GB / T 1732-2020, adhesion shall be in accordance with GB / T 1720-2020, flexibility shall be in accordance with GB / T 1731-2020, and water resistance shall be in accordance with GB / T1733-1993.

[0152] Comparative Example 1

[0153] In a three-necked reaction bottle, add 54.1g (0.2904 equivalent) of dehydrated dodecanol and 62g of butanone, turn on the stirrer, and heat to 50°C to dissolve; add 200g (0.5809 equivalent) of SSMD-80 diisocyanate to react, slowly heat to 80°C to react for 4h; then cool to 50°C, add 23.5g (0.5228 equivalent) of 1,4-butanediol to react, and after the temperature stops rising naturally, heat to 80°C to react for 5h, then take samples every 0.5h to measure the NCO content, stop the reaction when no NCO is detected, cool and discharge, and obtain a reactive polyurethane anionic emulsifier containing a sulfonate group and a hydroxyl group at one end.

[0154] In another three-necked reaction bottle, add 100 g of alkyd resin solution (model: 3015B), turn on the stirrer, add 20 g of the reactive polyurethane anionic emulsifier prepared above, stir and mix at 1000 rpm for 0.5 hour to obtain a milky white waterborne polyurethane modified alkyd resin emulsion with blue light.

[0155] The comparison of the emulsification conditions between the comparative example 1 and the application example 3 shows that for the emulsification of the alkyd resin, the amount of the reactive anionic-nonionic emulsifier added is less than that of the reactive anionic emulsifier, and therefore, the reactive anionic-nonionic emulsifier has a better emulsification effect.

[0156] Application Example 4

[0157] 1. Preparation of waterborne polyurethane resin emulsion

[0158] 200 g of solvent-based polyurethane resin (ethyl acetate solution with a solid content of 75%) was added with 30 g of the reactive polyurethane anionic-nonionic emulsifier prepared in Example 4 and 115 g of deionized water, and the mixture was stirred and emulsified at 800 rpm for 20 minutes to obtain a milky white aqueous polyurethane resin emulsion.

[0159] 2. Two-component water-based polyurethane adhesive

[0160] Add 30g HDX-100 waterborne polyurethane curing agent to the emulsion, mix and stir evenly to obtain a two-component waterborne polyurethane adhesive. This adhesive is used to laminate PET aluminized film and CPP film. The coating machine coats the adhesive on the CPP film, places it in an oven and bakes it at 150℃ for 2 minutes, takes it out, laminates the PET aluminized film on it, rolls and hot-presses it at a roller temperature of 80-90℃, and places it at room temperature for 72 hours. According to GB / T 2791-1995 "Adhesive T peel strength test method, flexible material to rigid material", a 180℃ peel strength test is carried out, and the PET aluminized film is torn.

[0161] Application Example 5

[0162] Emulsification of C5 petroleum resin:

[0163] 200g of C5 petroleum resin solution (65% solid content ethyl acetate solution) was added with 30g of the reactive polyurethane anionic-nonionic emulsifier prepared in Example 5 and 120g of deionized water, and stirred and emulsified at 800 rpm for 20 minutes to obtain a milky white water-based C5 petroleum resin emulsion. The emulsion was applied on a PET film, and after drying, the coating was observed to be smooth and flat without shrinkage cavities.

[0164] Application Example 6

[0165] Emulsification of SBS resin

[0166] 200g of SBS resin solution (cyclohexane solution with 20% solid content) was added with 35g of the reactive polyurethane anionic nonionic emulsifier prepared in Example 6 and 120g of deionized water, and stirred and emulsified at 800 rpm for 20 minutes to obtain a milky white water-based SBS resin emulsion. The emulsion was applied on a PET film, and after drying, the coating was observed to be smooth and flat without shrinkage cavities.

[0167] The reactive polyurethane anionic-nonionic emulsifier of the present invention has many varieties and a wide range of applications. It is mainly used to emulsify a variety of difficult-to-emulsify polymer resins and can participate in the subsequent cross-linking and curing reaction of the polymer to become a part of the structure. Its outstanding advantages will be widely used in the water-based treatment of multiple resin fields.

[0168] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A water-based resin, characterized in that: The water-based resin is prepared from the following raw materials: reactive polyurethane anionic-nonionic emulsifier, solvent-based resin; The molecular structure of the emulsifier contains anionic sulfonate groups and nonionic polyethoxy chain segments; The structural formula of the emulsifier is shown in formula (I): In formula (I), M represents an alkali metal ion or an ammonium ion; R represents an alkylene chain containing a carbamate group; X represents a characteristic functional group of a hydroxy compound, selected from a hydroxyl group, an epoxy group, a double bond or an alkyl group; R' represents the remaining groups of the hydroxy compound except the characteristic functional groups; R" represents H, or a C12-C18 hydrocarbon group; n＝3～30； The emulsifier is prepared by reacting a hydroxy compound with a sulfonate-modified diisocyanate; The hydroxy compound includes a polymer containing polyoxyethylene chain segments, or includes a polymer containing polyoxyethylene chain segments and at least one of monohydric alcohol, polyol, hydroxy acrylate, and epoxy resin; the polymer containing polyoxyethylene chain segments includes at least one of polyethylene glycol and fatty alcohol polyoxyethylene ether; The solvent-based resin includes at least one of polyurethane resin, acrylic resin, alkyd resin, SIS resin, SBS resin, petroleum resin, polyolefin resin, terpene resin, epoxy resin, and silicone resin.

2. The water-based resin according to claim 1, characterized in that The molar ratio of the hydroxy compound to the sulfonate-modified diisocyanate is (1.5-2):

1.

3. The water-based resin according to claim 1 or 2, characterized in that: 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; And / or, the sulfonate-modified diisocyanate is prepared by reacting a small molecular weight sulfonate diol with a diisocyanate; And / or, the small molecule sulfonate diol includes at least one of esters of sodium 1,2-dihydroxy-3-propanesulfonate, sodium 1,4-dihydroxybutane-2-sulfonate, sodium dicarboxybenzenesulfonate and small molecule polyols; And / or, the diisocyanate includes at least one of IPDI, HDI, TDI, MDI, and HMDI.

4. The water-based resin according to claim 1 or 2, characterized in that: In the hydroxy compound: The monohydric alcohol includes at least one of methanol, ethanol, propanol, butanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecyl alcohol, and glycidyl glycidol; And / or, the polyol is a diol or an alcohol containing two or more hydroxyl groups in the molecule, including at least one of 3-methyl-1,5-pentanediol, neopentyl glycol, 2,2-bis(4-hydroxyphenyl)propane, ethylene glycol, diethylene glycol, cyclohexanediol, methylpropylene glycol, 1,3-propylene glycol, 1,4-dihydroxymethylcyclohexane, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,2-propylene glycol, diethylene glycol, tetrahydrofurandiol, 1,6-hexanediol, trimethylpentanediol, butylethylpropylene glycol, dipropylene glycol, tripropylene glycol, ethylhexanediol, dodecanediol, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, hydroxy silicone oil, polyester polyol, and polyether polyol; And / or, the hydroxy acrylate includes at least one of hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, and hydroxyethyl methacrylate; And / or, the epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, and hydrogenated bisphenol A epoxy resin; And / or, the molecular weight of the polyethylene glycol is 200 to 3000; And / or, the structural formula of the fatty alcohol polyoxyethylene ether is R1(CH2CH2O) m H, wherein R1 represents a C12-C18 hydrocarbon group, and m=3-30.

5. The water-based resin according to claim 1, characterized in that The preparation method of the reactive polyurethane anionic-nonionic emulsifier includes the following three methods:

1. When the hydroxy compound only includes a polymer containing polyoxyethylene chain segments, and the polymer containing polyoxyethylene chain segments is polyethylene glycol, the preparation method comprises the following steps: The polyethylene glycol is reacted with the sulfonate-modified diisocyanate, or the polyethylene glycol is mixed with a cosolvent and then reacted with the sulfonate-modified diisocyanate to obtain the reactive polyurethane anionic-nonionic emulsifier; 2. When the hydroxy compound only includes a polymer containing polyoxyethylene chain segments, and the polymer containing polyoxyethylene chain segments is polyethylene glycol and fatty alcohol polyoxyethylene ether, the preparation method comprises the following steps: a) reacting fatty alcohol polyoxyethylene ether with sulfonate modified diisocyanate, or mixing fatty alcohol polyoxyethylene ether with a cosolvent, and then reacting with sulfonate modified diisocyanate; b) continuing to add polyethylene glycol to react to obtain the reactive polyurethane anionic-nonionic emulsifier; 3. When the hydroxy compound comprises a polyoxyethylene chain polymer and at least one of a monohydric alcohol, a polyhydric alcohol, a hydroxy acrylate, and an epoxy resin, the preparation method comprises the following steps: a) reacting the remaining hydroxyl compounds except the polyoxyethylene chain-joined polymer with the sulfonate-modified diisocyanate, or mixing the remaining hydroxyl compounds except the polyoxyethylene chain-joined polymer with a cosolvent, and then reacting with the sulfonate-modified diisocyanate; b) continuing to add the polyoxyethylene chain segment polymer to react to obtain the reactive polyurethane anionic-nonionic emulsifier.

6. The water-based resin according to claim 1, characterized in that The mass ratio of the reactive polyurethane anionic-nonionic emulsifier to the solvent-based resin is (0.01-0.5):

1.

7. The method for preparing the water-based resin according to claim 1 or 6, characterized in that: The following steps are involved: Mixing and stirring a reactive polyurethane anionic-nonionic emulsifier and a solvent-based resin to obtain the water-based resin; The mixing and stirring time is 0.3 hours to 1 hour; The rotating speed of the mixing and stirring is 500 rpm to 1500 rpm.

8. Use of the aqueous resin according to any one of claims 1 to 6 in the preparation of aqueous polyurethane resins, aqueous polyurethane modified alkyd resin coatings, aqueous polyurethane modified epoxy resin coatings, aqueous polyurethane modified acrylic coatings, aqueous polyurethane modified silicone coatings, aqueous polyurethane modified SIS / SBS ​​adhesives, aqueous vehicles, aqueous leather finishing agents, aqueous fabric finishing agents or aqueous ink vehicles.

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