CN109897160B - Blocked polyurethane curing agent emulsion and preparation method and application thereof - Google Patents
Blocked polyurethane curing agent emulsion and preparation method and application thereof Download PDFInfo
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- CN109897160B CN109897160B CN201910023087.7A CN201910023087A CN109897160B CN 109897160 B CN109897160 B CN 109897160B CN 201910023087 A CN201910023087 A CN 201910023087A CN 109897160 B CN109897160 B CN 109897160B
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Abstract
The invention discloses a closed polyurethane curing agent emulsion and a preparation method and application thereof. The blocked polyurethane curing agent emulsion is prepared by the following preparation method: a) preparing a polyisocyanate prepolymer containing sulfonic acid groups; b) preparing a blocked polyisocyanate prepolymer; c) and preparing the blocked polyurethane curing agent emulsion. Also discloses the application of the blocked polyurethane curing agent emulsion. The blocked polyurethane curing agent emulsion of the invention exists in the form of aqueous emulsion and can be independently stored for a long time. The emulsion has no organic solvent, high solid content and high NCO content, can be directly diluted by water, can be directly mixed with water-based resin containing active hydrogen and then stored for a long time, and the prepared water-based baking varnish and water-based high-temperature adhesive are convenient to use, and endow the product with good water resistance and high strength.
Description
Technical Field
The invention relates to a polyurethane curing agent material, in particular to a closed polyurethane curing agent emulsion and a preparation method and application thereof.
Background
At present, the research on the waterborne polyurethane curing agent by technical personnel in the polyurethane field is actively carried out, and a plurality of patent documents are disclosed, so that a plurality of new products enter into trial sale, and the original varieties of a plurality of international companies such as Japan, Germany and the like are supplemented with diversified applications. However, the conventional aqueous polyurethane curing agent has a common problem in application, that is, the polyurethane curing agent must be added with water to be dispersed and emulsified at a high speed before use and then mixed with a hydroxyl group-containing resin, which causes inconvenience in use, and the emulsified polyurethane curing agent emulsion has a short pot life, and active ingredients are continuously consumed due to the reaction of the active NCO groups contained therein with water in the emulsion, thereby causing waste of raw materials.
The research on the water-based blocked polyurethane curing agent required by water-based high-temperature baking paint and water-based high-temperature adhesive has made some progress in recent years, partial patent documents are disclosed, a small amount of new products are tried and sold, and the situation that imported products monopolize the water-based blocked curing agent market is changed. The water-based blocked polyurethane curing agent emulsion has the advantages that because the active-NCO group is blocked, the emulsion can stably coexist with water-based resin with active hydrogen for a long time at normal temperature, and releases-NCO when heated to react with hydroxyl, carboxyl, amino and other groups on the molecular chain of the water-based resin to form a cross-linked structure; it also has the advantage of not having strict requirements on the ionic properties of the resin system and can be used in both anionic and cationic systems as well as in nonionic systems. However, the water-based blocked polyurethane curing agent emulsion sold in the market at present has few varieties and low solid content of products, and the solid content of the products is below 40% and the NCO content of the products is below 6% no matter the products are imported or made in China, which increases the manufacturing cost, the packaging cost, the transportation cost and the use cost. In addition, there are also water-based blocked polyurethane curing agents, which are not in the form of aqueous emulsion but in the form of organic solution, and thus not only have environmental problems due to solvents, but also require water to be added and emulsified into a dispersion before use. The amount of water added is strictly limited, when more water is added, demulsification can be realized, when less water is added, emulsification is not good, and when a user without an emulsification machine stirs the mixture by hand, the dispersion is not uniform, and particles are easy to generate; even if the curing agent emulsion formed by machine stirring is mixed into the emulsion resin immediately, or the emulsion resin is layered after being left for a certain period of time (generally several hours to more than 20 hours), which causes great inconvenience to users.
CN101649036A discloses a polyisocyanate curing agent, which is an aqueous blocked polyisocyanate curing agent prepared by reacting a diisocyanate monomer with a mixture of dihydric alcohol and trihydric alcohol in a cosolvent to generate branched polyisocyanate, carrying out hydrophilic chain extension, blocking NCO, neutralizing to form salt, diluting with a viscosity-reducing protective solvent to a solid content of 50-70%, wherein the product contains 30-50% of an organic solvent, cannot be directly mixed with a resin emulsion, and only needs to be added with water before use to emulsify into a dispersion liquid to be added into the resin emulsion. CN107793544A discloses an environment-friendly polyurethane curing agent, which is an enclosed aqueous polyurethane curing agent prepared by using micromolecular sulfonate as a hydrophilic group, prepolymerizing the micromolecular sulfonate with polyisocyanate and diisocyanate into a polyisocyanate prepolymer containing a sulfonic acid group, and then enclosing an active-NCO group in the prepolymer, wherein the product also contains 25-50% of an organic solvent, and the product can be mixed with a resin emulsion only by adding water and emulsifying into a dispersion liquid before use.
The methods for preparing aqueous blocked isocyanate curing agents disclosed in the prior patent documents are very limited, the research on the methods is not deep enough, and the following two technical problems need to be overcome: firstly, the solid content of the emulsion is low and the cost is high, and secondly, the emulsion exists in a solution form and brings inconvenience for users and environmental protection problems.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a blocked polyurethane curing agent emulsion, a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a blocked polyurethane curing agent emulsion comprises the following steps:
a) preparation of polyisocyanate prepolymers containing sulfonic acid groups: in an organic solvent, preparing a polyisocyanate prepolymer containing sulfonic acid groups by using micromolecule sulfonate dihydric alcohol, polyisocyanate prepolymer and diisocyanate as raw materials or using micromolecule sulfonate dihydric alcohol, diisocyanate and trihydric alcohol as raw materials;
b) preparation of blocked polyisocyanate prepolymer: reacting a polyisocyanate prepolymer containing sulfonic acid groups with a sealing agent to seal the isocyanate groups to obtain a sealed polyisocyanate prepolymer;
c) preparing a closed polyurethane curing agent emulsion: mixing the blocked polyisocyanate prepolymer with an emulsification aid, adding water for emulsification, and removing an organic solvent to obtain the blocked polyurethane curing agent emulsion.
Preferably, in the preparation method of the blocked polyurethane curing agent emulsion, the step a) of preparing the polyisocyanate prepolymer containing sulfonic acid groups is any one of the following methods:
the method comprises the following steps:
s1: dissolving micromolecular sulfonate dihydric alcohol in an organic solvent, and adding a polyisocyanate prepolymer for reaction;
s2: adding diisocyanate to react to obtain a polyisocyanate prepolymer containing sulfonic acid groups;
the second method comprises the following steps:
s1: dissolving micromolecular sulfonate dihydric alcohol in an organic solvent, and adding diisocyanate for reaction;
s2: adding trihydric alcohol for reaction to obtain the polyisocyanate prepolymer containing sulfonic acid groups.
Preferably, in the preparation method of the blocked polyurethane curing agent emulsion, in the step a), the molecular weight of the micromolecule sulfonate dihydric alcohol is 350-1000; further preferably, the small-molecular sulfonate diol is one or more of sulfonate diol with the molecular weight of 350-1000 or water-dispersible sulfonated polyester diol.
Preferably, in the step a) of the preparation method of the blocked polyurethane curing agent emulsion, the polyisocyanate prepolymer is at least one of prepolymer of diisocyanate and triol, TDI trimer, MDI trimer, HDI trimer, IPDI trimer, HDI biuret and PAPI.
Preferably, in the step a) of the preparation method of the blocked polyurethane curing agent emulsion, the diisocyanate is at least one of MDI, HMDI, TDI, HDI and IPDI.
Preferably, in the step a) of the preparation method of the blocked polyurethane curing agent emulsion, the triol is at least one of trimethylolpropane, trimethylolethane, glycerol and 1,2, 6-hexanetriol.
Preferably, in the step a) of the preparation method of the blocked polyurethane curing agent emulsion, the organic solvent is at least one of an ester solvent and a ketone solvent; further preferably, the organic solvent is an ester and/or ketone solvent with a boiling point lower than 100 ℃; still more preferably, the organic solvent is at least one of acetone, methyl ethyl ketone, ethyl acetate, isopropyl acetate, methyl acetate, propyl acetate, methyl isopropyl ketone, and ethylene glycol dimethyl ether.
It is further noted that the purpose of the preferred ester and/or ketone solvent having a boiling point of 100 ℃ or lower is to facilitate the removal of the solvent during subsequent evacuation at room temperature or 50 ℃ or lower, without removing the water in the emulsion together.
Preferably, in the first method of step a) of the preparation method of the blocked polyurethane curing agent emulsion, the molar ratio of the isocyanate groups of the polyisocyanate prepolymer to the isocyanate groups of the diisocyanate is 1: (0 to 0.8); the hydroxyl molar ratio of the total isocyanate groups to the micromolecular sulfonate dihydric alcohol is (1.5-8): 1.
preferably, in the first step a) of the preparation method of the blocked polyurethane curing agent emulsion, the reaction temperature is 40-100 ℃, and the reaction is stopped when the percentage content of NCO of reactants is detected to be reduced and tend to be stable.
It is further stated that in the first process step a), the small molecule sulfonate diol is reacted with the polyisocyanate prepolymer for a certain period of time at a low temperature, and then the diisocyanate is added to react together, because the reactivity of the polyisocyanate prepolymer is lower than that of the diisocyanate, in order to make the hydrophilic sulfonic acid groups distributed more uniformly.
Preferably, in the second S1 in the step a), the molar ratio of the small molecule sulfonate diol to the diisocyanate is (0.05-0.2): 1.
preferably, in the second method S1 of the step a) of the preparation method of the blocked polyurethane curing agent emulsion, the reaction is specifically carried out for 1h to 2h at 45 ℃ to 70 ℃, and then for 2h to 10h at 70 ℃ to 100 ℃.
Preferably, in the second S2 in the step a), the molar ratio of the hydroxyl group of the triol to the residual NCO after the reaction of S1 is (0.4-0.5): 1.
preferably, the second method S2 in the step a) of the preparation method of the blocked polyurethane curing agent emulsion is that the reaction temperature is controlled to be 50-70 ℃, the trihydric alcohol is added in 3-8 times in 2-3 h in batches, then the reaction is carried out at 60-100 ℃, and the reaction is stopped when the percentage content of NCO of the reactants is reduced and tends to be stable after 3 h.
Preferably, in the step b) of the preparation method of the blocked polyurethane curing agent emulsion, the blocking agent is a hydrogen-containing compound; further preferably, the blocking agent is at least one of methanol, ethanol, isopropanol, tert-butanol, propylene glycol monomethyl ether, methyl ethyl ketoxime, acetone oxime, methyl isobutyl oxime, imidazole, 2-methylpyrazole, 3, 5-dimethylpyrazole, 3-methyl-5-ethylpyrazole, 3-ethyl-5-propylpyrazole, acetylacetone, ethyl acetoacetate, diethyl malonate, epsilon-caprolactam, phenol and catechol; more preferably, the blocking agent is at least one of methanol, ethanol, isopropanol, tert-butanol, methyl ethyl ketoxime, acetone oxime, methyl isobutyl oxime, 2-methylpyrazole, 3, 5-dimethylpyrazole, 3-methyl-5-ethylpyrazole, 3-ethyl-5-propylpyrazole, epsilon-caprolactam, phenol, and catechol.
Preferably, in the step b) of the preparation method of the blocked polyurethane curing agent emulsion, the molar ratio of active hydrogen of the hydrogen-containing compound of the blocking agent to the blocked terminal isocyanate group is (1.02-1.2): 1.
preferably, the preparation method of the blocked polyurethane curing agent emulsion, step b), is specifically as follows: adjusting the temperature in the reaction kettle to be 20-70 ℃, adding the hydrogen-containing compound in batches within 1-3 hours, and then reacting at the temperature of 20-80 ℃ for 1-5 hours.
Preferably, in the step c) of the preparation method of the blocked polyurethane curing agent emulsion, the emulsification assistant is a halogenated hydrocarbon solvent; further preferably, the emulsification aid is a halogenated hydrocarbon solvent insoluble in water; still further preferably, the emulsification aid is a chlorinated hydrocarbon solvent insoluble in water; more preferably, the emulsification aid is a water-insoluble low-boiling point highly polar solvent selected from at least one of dichloromethane, dichloroethane, dichloroethylene and trichloroethylene.
Preferably, in the step c) of the preparation method of the blocked polyurethane curing agent emulsion, the addition amount of the emulsification assistant is 10-50% of the total solid mass of the blocked polyisocyanate prepolymer.
Preferably, in the step c) of the preparation method of the blocked polyurethane curing agent emulsion, the temperature for adding water for emulsification is 20-40 ℃.
Preferably, in the step c) of the preparation method of the blocked polyurethane curing agent emulsion, the stirring speed of emulsification is not less than 1000 revolutions per minute; more preferably, the stirring speed for emulsification is 1000 rpm to 1500 rpm.
Preferably, in the step c) of the preparation method of the blocked polyurethane curing agent emulsion, the emulsifying time is 5 min-20 min.
Preferably, in the step c) of the preparation method of the blocked polyurethane curing agent emulsion, the method for removing the organic solvent is vacuum distillation.
Further preferably, the preparation method of the blocked polyurethane curing agent emulsion specifically comprises the following steps:
a) preparation of polyisocyanate prepolymers containing sulfonic acid groups
Method 1
S1: dissolving micromolecular sulfonate dihydric alcohol into an organic solvent in a reactor, adding a polyisocyanate prepolymer, and carrying out heating reaction;
s2: adding diisocyanate, and carrying out heating reaction to obtain a polyisocyanate prepolymer containing sulfonic groups;
method 2
S1: dissolving micromolecular sulfonate dihydric alcohol into an organic solvent in a reactor, and adding diisocyanate for heating reaction;
s2: adding trihydric alcohol, and carrying out heating reaction to obtain a polyisocyanate prepolymer containing sulfonic acid groups;
b) preparation of blocked polyisocyanate prepolymers
Adding a sealing agent into a reactor to carry out heating reaction with a polyisocyanate prepolymer containing sulfonic acid groups to obtain a sealed polyisocyanate prepolymer;
c) preparation of blocked polyurethane curing agent emulsion
Adding an emulsifying aid into a reactor to be mixed with the blocked polyisocyanate prepolymer, adding water for emulsification, removing the organic solvent in vacuum, and discharging to obtain the blocked polyurethane curing agent emulsion.
Further preferably, the time for adding the blocking agent in the step b) is 1 h-3 h, and the reaction time after the blocking agent is added is 1 h-5 h.
Further preferably, the time for adding water in the step c) is 10-30 min, and the emulsification is carried out by continuously stirring for 5-20 min after the water is added.
Further preferably, the time for removing the organic solvent in vacuum in the step c) is 1-3 h; the temperature for removing the organic solvent in vacuum is between room temperature and 50 ℃; the vacuum degree for removing the organic solvent in vacuum is 0.01MPa to 0.09 MPa.
A blocked polyurethane curing agent emulsion is prepared by the preparation method.
The invention also provides application of the blocked polyurethane curing agent emulsion in preparation of waterborne polyurethane baking varnish and/or waterborne polyurethane high-temperature adhesive.
Preferably, such applications are in particular: respectively preparing the closed polyurethane curing agent emulsion and the waterborne polyurethane resin/waterborne acrylic resin into waterborne baking paint or waterborne high-temperature adhesive; or the blocked polyurethane curing agent emulsion and the water-based amino resin/water-based alkyd resin are prepared into the water-based baking paint.
The invention has the beneficial effects that:
the blocked polyurethane curing agent emulsion of the invention exists in the form of aqueous emulsion and can be independently stored for a long time. The emulsion has no organic solvent, high solid content and high NCO content, can be directly diluted by water, can be directly mixed with water-based resin containing active hydrogen and then stored for a long time, and the prepared water-based baking varnish and water-based high-temperature adhesive are convenient to use, and endow the product with good water resistance and high strength.
Compared with the prior art, the invention has the following advantages:
1) according to the invention, dichloroethane, dichloromethane, dichloroethylene and trichloroethylene are selected as the emulsification aids of the water-based blocked polyurethane curing agent, and although the emulsification aids are the emulsification aids, the emulsification aids play a decisive role in the formation of emulsion stability, so that the problems of the preparation technology and the stability of independent storage of high-concentration blocked polyurethane curing agent emulsion are solved.
2) The blocked polyurethane curing agent emulsion provided by the invention provides a product in the form of aqueous emulsion, the product can be mixed with aqueous resin or emulsion glue without emulsification before use, the mixed emulsion can be stored for a long time, the use is convenient for users, and the quality of the mixed emulsion is ensured.
3) The blocked polyurethane curing agent emulsion has wide application range, has no strict requirement on the ionic property of a matched resin system, and can be used in an anionic system, a cationic system and a non-ionic system.
4) The product of the invention has high solid content and high effective functional group content. The solid content of the blocked polyurethane curing agent emulsion prepared from HDI and PAPI can reach more than 55 percent, and the NCO percent can reach more than 9 percent; the solid content of the closed polyurethane curing agent emulsion prepared from MDI, TDI and IPDI can reach more than 50%, and the NCO% can reach more than 6%. The invention has high content of effective components, and can endow the product with higher strength performance by lower adding amount in the water-based resin, so the utilization ratio of the curing agent is higher, thereby being beneficial to reducing the user cost and improving the strength performance of the cured product.
5) The low-boiling-point solvent in the preparation process of the product is extracted, and the product does not contain an organic solvent, and is a real environment-friendly emulsion; and the solvent with the boiling point below 100 ℃ is preferred, and the solvent can be removed in vacuum at room temperature or below 50 ℃, so that the energy is saved.
6) The invention has the advantages of convenient raw material source and simple preparation process.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The small molecule sulfonate diol used in the examples can be prepared by the method of CN107793544A example 1, and can also be purchased as water dispersible sulfonated polyester diol. Other starting materials are available from conventional commercial sources unless otherwise specified.
The detection methods in the examples are illustrated below:
1. the viscosity is detected according to the national standard GB/T2794-2013 single-cylinder rotational viscometer method for measuring the viscosity of the adhesive.
2. The percentage content of NCO was measured according to the Standard of Ministry of chemical industry "determination of isocyanate group content in HG/T2409-92 polyurethane prepolymer".
3. The detection of the solid content is carried out according to the national standard GB/T2793-1995 determination of the content of the adhesive non-volatile matter.
Example 1
a) Preparation of polyisocyanate prepolymer containing sulfonic acid group
In a reactor, 140g of sulfonate diol (with the molecular weight of 550 and the solid content of 70%) and 110 g of ethyl acetate are mixed, the mixture is uniformly stirred, 300 g of HDI trimer (with the solid content of 100%) is added, the temperature is increased to 55-60 ℃ for reaction for 2 hours, 106.2 g of HMDI is added, the temperature is increased to 60 ℃ for reaction for 1 hour, the temperature is 70 ℃ for reaction for 1 hour, the temperature is 80 ℃ for reaction for 4 hours, the NCO percentage content of a reactant is measured after the reaction is carried out for 4 hours at 90 ℃, and the reaction is stopped when the NCO content is reduced to be stable and close to 14%;
b) preparation of blocked polyisocyanate prepolymers
Cooling to 50 ℃, adding 190g of methyl ethyl ketoxime for four times, controlling the feeding temperature to be 50-55 ℃, completing the feeding within 2 hours, reacting at 60-70 ℃ for 1 hour after the feeding is completed, and reacting at 75-80 ℃ for 3 hours to obtain a closed polyisocyanate prepolymer, namely a closed polyurethane curing agent; the temperature was reduced to 40 ℃ and 282 g of reaction product were removed and retained for comparative experiment 1.
c) Preparation of blocked polyurethane curing agent emulsion
Cooling to 40 ℃, adding 120 g of dichloromethane into the rest reaction materials, uniformly stirring, increasing the rotating speed to 1500 rpm, slowly adding 413 g of deionized water, completing the addition in about 10 minutes, and continuing to stir and emulsify for 10 minutes; starting a vacuum pump, vacuumizing for 1 hour at 45 ℃ under the vacuum degree of 0.08MPa, increasing the temperature to 50 ℃, and vacuumizing for 1 hour under the vacuum degree of 0.08 MPa; discharging to obtain the closed polyurethane curing agent emulsion.
The curing agent of this example was tested as a white, slightly blue emulsion having a solids content of 55%, a viscosity of 260 mPas (25 ℃), an NCO% of 9.9% after deblocking, and a pH of 7. The obtained blocked polyurethane curing agent emulsion is observed after being placed at room temperature for 3 months, and the emulsion has no layering phenomenon.
Comparative example 1
Adding 282 g of reaction product taken out in the step b) of the embodiment 1 into an emulsifier, adjusting the rotating speed of the stirrer to 2000 r/min, slowly adding 170 g of deionized water, stirring and emulsifying for 10 minutes continuously after the addition of the deionized water is finished for about 10 minutes, and discharging to obtain the white emulsion of the blocked polyurethane curing agent.
The obtained white emulsion is placed at room temperature and observed, and the emulsion is layered after 24 hours.
Example 2
a) Preparation of polyisocyanate prepolymer containing sulfonic acid group
Mixing 150 g of sulfonate diol (the molecular weight is 550 and the solid content is 70%) with 80g of acetone in a reactor, uniformly stirring, adding 400 g of TDI prepolymer (prepolymer of TDI and trimethylolpropane) into the mixture, heating the mixture to 55-60 ℃ to react for 2 hours, adding 120 g of MDI into the mixture, reacting the mixture for 1 hour at 60 ℃, reacting the mixture for 1 hour at 70 ℃, reacting the mixture for 3 hours at 80 ℃, measuring the percentage content of NCO in the reactant, and stopping the reaction when the NCO is reduced to be stable and close to 11%;
b) preparation of blocked polyisocyanate prepolymers
Cooling to 50 ℃, adding 180g of methyl ethyl ketoxime for four times, controlling the feeding temperature to be 50-55 ℃, finishing the feeding within 2 hours, and reacting at 65-70 ℃ for 1.5 hours after the feeding is finished to obtain a closed polyisocyanate prepolymer, namely a closed polyurethane curing agent; the temperature was reduced to 40 ℃ and 310 g of reaction product were removed and retained for comparative experiment 2.
c) Preparation of blocked polyurethane curing agent emulsion
Cooling to 40 ℃, adding 120 g of dichloromethane into the rest reaction materials, uniformly stirring, increasing the rotating speed to 1500 rpm, slowly adding 410 g of deionized water, completing the addition in about 10 minutes, and continuing to stir and emulsify for 10 minutes; starting a vacuum pump, and vacuumizing for 2 hours at 45 ℃ under the vacuum degree of 0.08 MPa; discharging to obtain the closed polyurethane curing agent emulsion.
By detecting that the curing agent of the embodiment is white slightly blue light emulsion, the solid content is 50.2%, the viscosity is 300 mPa.s (25 ℃), the NCO% after deblocking is 6.1%, the pH value is 7, and the obtained blocked polyurethane curing agent emulsion is observed after being placed at room temperature for 3 months, and the emulsion has no layering phenomenon.
Comparative example 2
Adding 310 g of reaction product taken out in the step b) of the embodiment 2 into an emulsifier, adjusting the rotating speed of the stirrer to 2000 r/min, slowly adding 310 g of deionized water, stirring and emulsifying for 10 minutes continuously after the addition of the deionized water is finished for about 10 minutes, and discharging to obtain the white emulsion of the blocked polyurethane curing agent.
The obtained white emulsion is placed at room temperature, observed, the emulsion is layered after being placed for 2 hours, the emulsion is changed into water at the upper layer and white slag at the lower layer after being placed for 4 hours.
Through the analysis of the example 1, the comparative example 1, the example 2 and the comparative example 2, the product use performance of the blocked polyurethane curing agent emulsion is different from that of the blocked polyurethane curing agent solution prepared by CN 107793544A.
Example 3
a) Preparation of polyisocyanate prepolymer containing sulfonic acid group
In a reactor, 120 g of sulfonate diol (with the molecular weight of 550 and the solid content of 70%) and 180g of methyl acetate are mixed and stirred uniformly, 400 g of MDI is added, the mixture is heated to 50 ℃ for reaction for 1 hour, and the mixture is heated to 70-75 ℃ for reaction for 3 hours. Cooling to 50 ℃, adding 55 g of trimethylolpropane in four times within 2 hours, reducing the temperature in the kettle to 50-55 ℃ in each feeding, reacting for 1 hour at 60-65 ℃ after the feeding is finished, measuring the percentage content of NCO of the reactant after the reaction is carried out for 2 hours at 70-75 ℃, and stopping the reaction when the NCO is reduced to be stable and close to 10%;
b) preparation of blocked polyisocyanate prepolymers
Cooling to 50 ℃, adding 92 g of ethanol for four times, controlling the feeding temperature to be 50-55 ℃, finishing the feeding within 2 hours, and continuously keeping at 60-65 ℃ for reacting for 2 hours.
c) Preparation of blocked polyurethane curing agent emulsion
Cooling to 40 ℃, adding 180g of dichloromethane, uniformly stirring, increasing the rotating speed to 1300 rpm, slowly adding 538 g of deionized water, finishing the addition within about 15 minutes, and continuing stirring and emulsifying for 15 minutes; starting a vacuum pump, and vacuumizing for 2 hours at 45 ℃ under the vacuum degree of 0.08 MPa; discharging to obtain the closed polyurethane curing agent emulsion.
The curing agent of this example was tested as a white, slightly blue emulsion having a solids content of 50% and a viscosity of 320 mPas (25 ℃), and having an NCO% of 6.3% after deblocking.
Example 4
a) Preparation of polyisocyanate prepolymer containing sulfonic acid group
In a reactor, 104 g of sulfonate diol (with the molecular weight of 550 and the solid content of 70%) and 200 g of butanone are mixed, 400 g of IPDI trimer is added after uniform stirring, the temperature is increased to 55-60 ℃ for reaction for 1 hour, the temperature is 60-70 ℃ for reaction for 1 hour, 80g of HMDI is added, the reaction is carried out at 70 ℃ for 1 hour and at 80 ℃ for 4 hours, the NCO percentage content of reactants is measured after the reaction is carried out at 90 ℃ for 1 hour, and the reaction is stopped when the NCO content is reduced and tends to be stable and close to 8.5%;
b) preparation of blocked polyisocyanate prepolymers
Cooling to 50 ℃, adding 140g of methyl ethyl ketoxime for four times, controlling the feeding temperature to be 50-55 ℃, completing the feeding within 2 hours, reacting at 60-70 ℃ for 1 hour after the feeding is completed, and reacting at 70-80 ℃ for 3 hours;
c) preparation of blocked polyurethane curing agent emulsion
Cooling to 40 ℃, adding 160 g of dichloroethylene, uniformly stirring, increasing the rotating speed to 1200 rpm, slowly adding 432 g of deionized water, completing the addition in about 10 minutes, and continuously stirring and emulsifying for 10 minutes; starting a vacuum pump, vacuumizing for 1 hour at 45 ℃ under the vacuum degree of 0.08MPa, raising the temperature to 50 ℃, and vacuumizing for 1 hour under the vacuum degree of 0.085 MPa; discharging to obtain the closed polyurethane curing agent emulsion.
The curing agent of this example was tested to be a white, slightly blue emulsion having a solids content of 50.2% and a viscosity of 340 mPas (25 ℃), and having an NCO% of 7.0% after deblocking.
Example 5
a) Preparation of polyisocyanate prepolymer containing sulfonic acid group
In a reactor, mixing 150 g of sulfonate diol (with the molecular weight of 550 and the solid content of 70%) and 150 g of isopropyl acetate, uniformly stirring, adding 300 g of PAPI, heating to 55-60 ℃ for reaction for 2 hours, reacting at 70 ℃ for 2 hours, measuring the percentage content of NCO in a reactant after reacting at 80 ℃ for 1 hour, and stopping the reaction when the NCO drops to be stable and close to 14%;
b) preparation of blocked polyisocyanate prepolymers
Cooling to 50 ℃, adding 197g of phenol in four times, controlling the feeding temperature to be 50-55 ℃, finishing the feeding within 2 hours, and reacting for 2 hours at 70-75 ℃ after finishing the feeding;
c) preparation of blocked polyurethane curing agent emulsion
Cooling to 40 ℃, adding 180g of dichloroethane, uniformly stirring, increasing the rotating speed to 1000 rpm, slowly adding 330 g of deionized water, completing the addition in about 10 minutes, and continuously stirring and emulsifying for 10 minutes; starting a vacuum pump, vacuumizing for 1 hour at 45 ℃ under the vacuum degree of 0.08MPa, raising the temperature to 50 ℃, and vacuumizing for 2 hours under the vacuum degree of 0.085 MPa; discharging to obtain the closed polyurethane curing agent emulsion.
The curing agent of this example was tested to be a slightly blue white emulsion having a solids content of 55.1% and a viscosity of 280 mPas (25 ℃), and having an NCO% of 10.5% after deblocking.
Example 6
a) Preparation of polyisocyanate prepolymer containing sulfonic acid group
In a reactor, 160 g of water dispersible sulfonated polyester diol (molecular weight is 650, solid content is 70%) and 120 g of methyl isopropyl ketone are mixed, after uniform stirring, 300 g of HDI biuret (solid content is 100%) are added, the temperature is raised to 55-60 ℃ for reaction for 1 hour, the temperature is raised to 60-70 ℃ for reaction for 3.5 hours, 100 g of IPDI is added, the reaction is carried out at 70 ℃ for 1 hour, the reaction is carried out at 80 ℃ for 3 hours, the NCO percentage content of reactants is measured after the reaction is carried out at 90 ℃ for 1 hour, and when the NCO content is reduced and tends to be stable and close to 14%, the reaction is stopped;
b) preparation of blocked polyisocyanate prepolymers
Cooling to 50 ℃, adding 276g of epsilon-caprolactam for five times, controlling the feeding temperature to be 50-55 ℃, finishing the feeding within 2 hours, reacting for 1 hour at 60-65 ℃ after the feeding is finished, and reacting for 2 hours at 70-75 ℃;
c) preparation of blocked polyurethane curing agent emulsion
Cooling to 40 ℃, adding 220 g of trichloroethylene, uniformly stirring, increasing the rotating speed to 1500 rpm, slowly adding 402 g of deionized water, completing the addition for about 15 minutes, and continuously stirring and emulsifying for 15 minutes; starting a vacuum pump, vacuumizing for 1 hour at 45 ℃ under the vacuum degree of 0.08MPa, raising the temperature to 50 ℃, and vacuumizing for 2 hours under the vacuum degree of 0.085 MPa; discharging to obtain the closed polyurethane curing agent emulsion.
The curing agent of this example was tested to be a slightly blue white emulsion having a solids content of 56.1% and a viscosity of 310 mPas (25 ℃), and having an NCO% of 9.8% after deblocking.
Example 7
a) Preparation of polyisocyanate prepolymer containing sulfonic acid group
In a reactor, 170 g of sulfonate diol (molecular weight is 600, solid content is 70%) and 140g of acetone are mixed, 300 g of HDI tripolymer is added after uniform stirring, the temperature is increased to 55-60 ℃ for reaction for 1 hour, the temperature is 60-70 ℃ for reaction for 3 hours, 104 g of IPDI is added, the reaction is carried out at 70 ℃ for 1 hour, the reaction is carried out at 80 ℃ for 3 hours, the NCO percentage content of reactants is measured after the reaction is carried out at 90 ℃ for 1 hour, and the reaction is stopped when the NCO content is reduced to be stably 14%;
b) preparation of blocked polyisocyanate prepolymers
Cooling to 30 ℃, adding 230g of 3, 5-dimethylpyrazole five times, controlling the feeding temperature at 30-40 ℃, completing the addition within 2 hours, reacting at 50-60 ℃ for 1 hour after the addition is completed, and reacting at 60-75 ℃ for 2 hours;
c) preparation of blocked polyurethane curing agent emulsion
Cooling to 30 ℃, adding 210 g of dichloroethylene, uniformly stirring, increasing the rotating speed to 1200 rpm, slowly adding 424 g of deionized water, finishing the addition within about 15 minutes, and continuously stirring and emulsifying for 10 minutes; starting a vacuum pump, and vacuumizing for 2 hours at 45 ℃ under the vacuum degree of 0.08 MPa; discharging to obtain the closed polyurethane curing agent emulsion.
The curing agent of this example was tested to be a slightly blue white emulsion having a solids content of 55.4% and a viscosity of 450 mPas (25 ℃), and having an NCO% of 9.5% after deblocking.
Application example 1
60 g of the blocked polyurethane curing agent emulsion obtained in the example 1 and 200 g of polyurethane emulsion are directly stirred and mixed to prepare aqueous polyurethane baking paint, the baking paint is sprayed and constructed to prepare a sample plate, the sample plate is cured in an oven at 150 ℃ for 60 minutes, and after the sample plate is placed at room temperature for 24 hours, the prepared paint film has the following properties: the paint film appearance (visual inspection) is flat and smooth; gloss (60 °): more than or equal to 92 percent; hardness: shore D58; impact strength: 52KJ/m2(ii) a Adhesion force: grade 1; flexibility: 1 mm; the water resistance (72h) was not abnormal.
The detection method comprises the following steps: the gloss (60 ℃) is GB9754-2007, the hardness is GB1730-79, the impact strength is GB/T2571-1995, the adhesion is GB1720-89, the flexibility is GB1731-79 standard, and the water resistance is GB/T1733-1993.
Application example 2
40g of the blocked polyurethane curing agent emulsion and 200 g of the polyurethane dispersion liquid in the embodiment 2 are directly stirred and mixed to prepare the aqueous polyurethane high-temperature adhesive, and the mixed emulsion is free of layering phenomenon after being stored for 3 months at room temperature.
The waterborne polyurethane high-temperature adhesive is used for compounding a PET film and a PET film. Coating glue on a piece of PET film by a coating machine, placing the piece of PET film in an oven for baking for 2 minutes at 150 ℃, taking out the piece of PET film, compounding the other piece of PET film on the piece of PET film, rolling and hot-pressing the piece of PET film at the temperature of 80-90 ℃ by a compression roller for compounding, placing the piece of PET film at room temperature for 48 hours, and carrying out a T-shaped peeling strength test according to/T2791-1995 flexible material to flexible material by an adhesive T-peeling strength test method, wherein the PET film is torn.
Application example 3
60 g of the blocked polyurethane curing agent emulsion of example 3 and 200 g of aqueous amino resin were directly stirred and mixed to prepare an aqueous amino baking paint, which was applied to a sample plate, cured in an oven at 120 ℃ for 30 minutes, and left at room temperature for 24 hours to prepare a paint film having the following properties: the paint film appearance (visual inspection) is flat and smooth; light (es)Ze (60 °): more than or equal to 86 percent; hardness: shore D61; impact strength: 46KJ/m2(ii) a Adhesion force: grade 1; flexibility: 1 mm; the water resistance (72h) was not abnormal.
Application example 4
60 g of the blocked polyurethane curing agent emulsion of example 4 and 200 g of the aqueous acrylic resin are directly stirred and mixed to prepare the aqueous acrylic polyurethane baking paint, the aqueous acrylic polyurethane baking paint is sprayed and constructed to prepare a sample plate, the sample plate is cured in an oven at 160 ℃ for 50 minutes, and after the sample plate is placed at room temperature for 24 hours, the prepared paint film has the following properties: the paint film appearance (visual inspection) is flat and smooth; gloss (60 °): more than or equal to 92 percent; hardness: shore D66; impact strength: 62KJ/m2(ii) a Adhesion force: grade 1; flexibility: 1 mm; the water resistance (72h) was not abnormal.
Application example 5
40g of the blocked polyurethane curing agent emulsion and 200 g of the polyurethane emulsion in the embodiment 5 are directly stirred and mixed to prepare the waterborne polyurethane high-temperature adhesive, the adhesive is coated on a cloth surface through a machine, flocking is carried out, the cloth surface is placed in an oven to be cured for 30 minutes at 120 ℃, after the cloth surface is placed for 24 hours at room temperature, the tensile strength, the elongation at break, the wear resistance, the washing size stability and the like of the flannelette are tested to meet the strength performance requirements of the flannelette, and the appearance, the hand feeling and the comfort are also met the requirements of the flannelette.
Application example 6
60 g of the blocked polyurethane curing agent emulsion obtained in the example 6 and 200 g of waterborne alkyd resin are directly stirred and mixed to prepare waterborne alkyd polyurethane baking paint, the baking paint is sprayed and constructed to prepare a sample plate, the sample plate is cured in an oven at 120 ℃ for 60 minutes, and after the sample plate is placed at room temperature for 24 hours, the prepared paint film has the following properties: the paint film appearance (visual inspection) is flat and smooth; gloss (60 °): more than or equal to 86 percent; hardness: shore D42; impact strength: 48KJ/m2(ii) a Adhesion force: grade 1; flexibility: 1 mm; the water resistance (72h) was not abnormal.
The main difference between the present invention and the technical proposal of CN107793544A is that the present invention is in the form of aqueous emulsion and CN107793544A is in the form of solution. The difference between the two methods is mainly as follows: the invention adds emulsification assistant after preparing the blocked polyurethane curing agent solution, and then adds water to emulsify into emulsion. The reason for this is: the inventor finds in practice that after the closed aqueous polyurethane curing agent solution is emulsified with water at a high speed, the formed emulsion can be stored for a long time only after being immediately mixed with aqueous resin, if the formed emulsion is placed for several hours alone and is placed for one day at most, the emulsion can be layered to generate polymer slag which can not be mixed with the aqueous resin any more, and the waste of raw materials is caused; and the water adding amount during high-speed emulsification is also strictly limited, the emulsification is not good due to less water adding, and polymer slag is formed due to more water adding. Thus, when a user uses the aqueous blocked polyurethane curing agent solution, the user is required to be equipped with a high-speed emulsifying machine, and the user is required to emulsify the aqueous blocked polyurethane curing agent solution before using the aqueous blocked polyurethane curing agent solution, and the aqueous blocked polyurethane curing agent solution must be mixed with the aqueous resin as soon as possible. As the variety of the resin of users is various, the application is different, the proportion quantity of the curing agent is different, the order quantity of the product is uncertain and other factors, the mixture emulsion of the aqueous resin and the curing agent cannot be prepared in advance, and the mixture emulsion can only be prepared at present, namely when the aqueous baking varnish or the aqueous high-temperature glue is used, the closed aqueous polyurethane curing agent solution can be emulsified by adding water at high speed, and the amount of the mixture emulsion is used. The curing agent emulsion cannot be stored separately, which presents many difficulties to the user in use. Therefore, there is a need for market development to continue to investigate blocked polyurethane curing agent emulsions that can be stored separately.
The technical scheme of the invention is that an emulsifying auxiliary agent is added after a waterborne closed polyurethane curing agent is prepared, and then water is added to emulsify the mixture into a product. The reason why the emulsification aid is added in the case where the hydrophilic sulfonic acid group is already present on the molecular structure of the blocked polyisocyanate is that: the inventor analyzes that the reason why the water-based blocked polyurethane curing agent prepared by the technical scheme of CN107793544A is demulsified quickly after being emulsified by water is that the emulsion has larger particles and poorer stability. How to prepare emulsion particles with smaller particle size becomes a technical problem to be solved. Only when the emulsion is emulsified by adding water, the oily polymer particles wrapped by water are smaller, even reach the nanometer level and the molecular level, and emulsion particles with small particle size can be obtained. One skilled in the art generally considers that the prepolymer is completely dissolved by the solvent, and the force between the macromolecules is minimal, so that smaller emulsion particles can be formed by adding water under high-speed stirring. According to the technical scheme of CN107793544A, the prepared water-based blocked polyurethane curing agent is in a state of being completely dissolved by solvent, why can not be emulsified into emulsion with small particle size? The inventor further analyzes the technical scheme of CN107793544A, and finds that the solvent capable of dissolving the prepolymer in the aqueous blocked polyurethane curing agent solution can be dissolved in water or slightly dissolved in water, when the aqueous blocked polyurethane curing agent solution is emulsified by adding water, the originally lipophilic solvent is inverted to be hydrophilic, namely, the solubility of the solvent to the prepolymer is reduced, the prepolymer is in an incomplete dissolving state, polymer colloidal particles are generated, and the polymer colloidal particles can not be dispersed even under high-speed stirring, so the emulsion has larger particle diameter ratio and poorer stability. Experiments prove that: the method adopts a strong polar organic solvent (dichloromethane, dichloroethane, dichloroethylene and trichloroethylene) which can dissolve a prepolymer but is insoluble in water as an emulsification aid of the water-based blocked polyurethane curing agent, and the prepared curing agent emulsion is light blue white and can be stored for a long time without layering and precipitation (related documents report that when the particle size of the emulsion is 100-250 nm, the color of the emulsion is blue white, and when the particle size of the emulsion is larger than 300nm, the color of the emulsion is milky white). Experiments also prove that the requirement on the rotating speed of a stirrer is greatly reduced when water is added for emulsification because a water-insoluble strong polar solvent is added into the blocked polyisocyanate prepolymer, and the emulsification can be realized at the rotating speed of more than 200 revolutions per minute.
Before the preparation of the blocked polyurethane curing agent emulsion, an emulsification aid is added before emulsification by adding water, and the emulsification aid is a water-insoluble low-boiling-point strong-polarity organic solvent and has 3 characteristics: water insoluble, low boiling point and strong polar organic solvent. When the emulsifying assistant is added into the reaction system, the strong polarity of the emulsifying assistant makes the emulsifying assistant easy to dissolve the polyisocyanate prepolymer, and the emulsifying assistant has very good solubility and is in a complete dissolved state; the water-insoluble prepolymer has incompatibility with water, so that the prepolymer has oleophilic phase and hydrophobic phase, and can be well dissolved even when the prepolymer is emulsified and dispersed in water; because the macromolecules of the prepolymer are dispersed by the micromolecules of the emulsifying aid, the macromolecules of the prepolymer are dispersed in water in the form of emulsion particles under high-speed stirring to form emulsion with tiny particle size. The smaller the particle size of the emulsion, the better the stability of the emulsion, and the emulsion thus obtained is very stable, not to delaminate or break apart during storage. After the emulsion is formed, the prepolymer macromolecules are wrapped by the water phase, and the prepolymer macromolecules can not be agglomerated even if the solvent is pumped out in vacuum, so that the emulsion has very good stability and can be independently stored for a long time. The special emulsifying aid plays a decisive role in the generation of the final emulsion.
The low boiling point characteristic of the emulsifying aid is to facilitate vacuum removal after emulsion formation, and other similar lipophilic and non-hydrophilic emulsifying aids can be selected, which are within the protection scope of the invention. The invention prefers strong polar organic solvent with boiling point below 100 ℃, and is real VOC-free environment-friendly polyurethane curing agent emulsion after vacuum removal at room temperature or below 50 ℃.
Claims (10)
1. A preparation method of a blocked polyurethane curing agent emulsion is characterized by comprising the following steps: the method comprises the following steps:
a) preparation of polyisocyanate prepolymers containing sulfonic acid groups: in an organic solvent, preparing a polyisocyanate prepolymer containing sulfonic acid groups by using micromolecule sulfonate dihydric alcohol, polyisocyanate prepolymer and diisocyanate as raw materials or using micromolecule sulfonate dihydric alcohol, diisocyanate and trihydric alcohol as raw materials;
b) preparation of blocked polyisocyanate prepolymer: reacting a polyisocyanate prepolymer containing sulfonic acid groups with a sealing agent to seal the isocyanate groups to obtain a sealed polyisocyanate prepolymer;
c) preparing a closed polyurethane curing agent emulsion: mixing the blocked polyisocyanate prepolymer with an emulsification aid, adding water for emulsification, and removing an organic solvent to obtain a blocked polyurethane curing agent emulsion;
in the step c), the emulsification aid is at least one selected from dichloromethane, dichloroethane, dichloroethylene and trichloroethylene.
2. The method for preparing a blocked polyurethane curing agent emulsion according to claim 1, wherein the method comprises the following steps: step a) preparation of the polyisocyanate prepolymer containing sulfonic acid groups is any one of the following methods:
the method comprises the following steps:
s1: dissolving micromolecular sulfonate dihydric alcohol in an organic solvent, and adding a polyisocyanate prepolymer for reaction;
s2: adding diisocyanate to react to obtain a polyisocyanate prepolymer containing sulfonic acid groups;
the second method comprises the following steps:
s1: dissolving micromolecular sulfonate dihydric alcohol in an organic solvent, and adding diisocyanate for reaction;
s2: adding trihydric alcohol for reaction to obtain the polyisocyanate prepolymer containing sulfonic acid groups.
3. The method for preparing a blocked polyurethane curing agent emulsion according to claim 1 or 2, wherein: in the step a), the molecular weight of the micromolecule sulfonate dihydric alcohol is 350-1000; the polyisocyanate prepolymer is at least one of prepolymer of diisocyanate and triol, TDI trimer, MDI trimer, HDI trimer, IPDI trimer, HDI biuret and PAPI; the diisocyanate is at least one of MDI, HMDI, TDI, HDI and IPDI; the trihydric alcohol is at least one of trimethylolpropane, trimethylolethane, glycerol and 1,2, 6-hexanetriol.
4. The method for preparing a blocked polyurethane curing agent emulsion according to claim 1 or 2, wherein: in the step a), the organic solvent is at least one of an ester solvent and a ketone solvent.
5. The method for preparing a blocked polyurethane curing agent emulsion according to claim 1, wherein the method comprises the following steps: in the step b), the sealing agent is a hydrogen-containing compound, and the molar ratio of active hydrogen of the hydrogen-containing compound to the blocked terminal isocyanate group is (1.02-1.2): 1.
6. the method for preparing a blocked polyurethane curing agent emulsion according to claim 1 or 5, wherein: in the step b), the reaction temperature is 20-80 ℃, and the reaction time is 1-5 h.
7. The method for preparing a blocked polyurethane curing agent emulsion according to claim 1, wherein the method comprises the following steps: in the step c), the addition amount of the emulsification assistant is 10-50% of the total solid mass of the blocked polyisocyanate prepolymer.
8. The method for preparing a blocked polyurethane curing agent emulsion according to claim 1 or 7, wherein: in the step c), the temperature for emulsifying by adding water is 20-40 ℃; the stirring speed of emulsification is not less than 1000 revolutions per minute; the emulsifying time is 5 min-20 min; the method for removing the organic solvent is vacuum distillation.
9. A blocked polyurethane curing agent emulsion is characterized in that: is prepared by the preparation method of any one of claims 1 to 8.
10. The use of the blocked polyurethane curing agent emulsion of claim 9 in the preparation of aqueous polyurethane baking varnish and/or aqueous polyurethane high temperature adhesives.
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