CN114230764A - Water-based closed polyisocyanate curing agent and preparation method and application thereof - Google Patents
Water-based closed polyisocyanate curing agent and preparation method and application thereof Download PDFInfo
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- CN114230764A CN114230764A CN202111576048.3A CN202111576048A CN114230764A CN 114230764 A CN114230764 A CN 114230764A CN 202111576048 A CN202111576048 A CN 202111576048A CN 114230764 A CN114230764 A CN 114230764A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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Abstract
The invention belongs to the technical field of coating curing agents, and discloses a water-based closed polyisocyanate curing agent, and a preparation method and application thereof. The preparation method comprises the following steps: and mixing sulfonate, diisocyanate trimer and a catalyst, carrying out a first reaction, adding bisulfite after the reaction is finished, and carrying out a second reaction to obtain the water-based closed polyisocyanate curing agent. The water-based blocked polyisocyanate curing agent provided by the invention takes the hydrosulfite as the blocking agent, has low unblocking temperature and excellent water dispersibility and storage stability, and can be applied to various baking coatings. The waterborne polyurethane coating prepared by the waterborne closed polyisocyanate curing agent provided by the invention has strong stability, small viscosity change during storage at high temperature, and high glossiness and transparency of the formed paint film.
Description
Technical Field
The invention belongs to the technical field of coating curing agents, and particularly relates to a water-based closed polyisocyanate curing agent, and a preparation method and application thereof.
Background
With the environmental protection importance of people, the environmental requirements are continuously improved, and the water-based paint is undoubtedly one of the important development directions of the current paint technology. Wherein, the obtained film has very excellent wear resistance, drug resistance and stain resistance by using the waterborne polyurethane coating with the crosslinking function of the isocyanate compound, and the application is wide.
The water-based isocyanate curing agent has excellent performance, and can be crosslinked and cured with polymers with active hydrogen atoms such as alcohols, amines and the like at room temperature due to the high reactivity of isocyanate groups, so that the water-based isocyanate curing agent can be basically only used in two-component coatings, and the application of the water-based isocyanate curing agent is limited. And because a large number of hydrophilic groups are introduced into the waterborne isocyanate curing agent, the waterborne isocyanate curing agent is extremely sensitive to water in the environment, and the storage difficulty of the waterborne isocyanate curing agent is greatly increased. In order to solve the technical problem, the waterborne closed type polyisocyanate curing agent is produced at the same time, and active isocyanate groups are protected by utilizing the micromolecule blocking agent, so that the cross-linking agent can stably coexist with other components in the coating at room temperature, and the storage difficulty is also greatly reduced.
At present, the blocked polyisocyanate is prepared by reacting 3, 5-dimethylpyrazole or methyl ethyl ketoxime serving as a blocking agent with HDI trimer (hexamethylene diisocyanate trimer) or IPDI trimer. Then mixing the acrylic resin or the amino resin according to a certain proportion to prepare the automobile coating, wherein the product has the advantages of good chemical resistance, yellowing resistance and the like, but the deblocking temperature (baking temperature) is higher and is generally 100-150 ℃; and most contain a large amount of a low boiling point solvent.
Therefore, it is highly desirable to provide a water-based blocked polyisocyanate curing agent which can reduce the amount of low boiling point solvent and the deblocking temperature, and can produce polyurethane coatings with good storage stability.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a water-based closed polyisocyanate curing agent, and a preparation method and application thereof. The water-based blocked polyisocyanate curing agent provided by the invention can reduce the using amount of a low-boiling-point solvent and the deblocking temperature, and the prepared polyurethane coating has good storage stability.
The invention provides a preparation method of a water-based blocked polyisocyanate curing agent.
Specifically, the preparation method of the water-based closed polyisocyanate curing agent comprises the following steps:
and mixing sulfonate, diisocyanate trimer and a catalyst, carrying out a first reaction, adding bisulfite after the reaction is finished, and carrying out a second reaction to obtain the water-based closed polyisocyanate curing agent.
Preferably, the sulfonate is a sulfamate; further preferably, the sulfamate is at least one of sodium 2-tert-butyl-4- (cyclohexylamino) -1-butane sulfonate, sodium 2-tert-butyl-3- (cyclohexylamino) -1-propane sulfonate or sodium 2-isopentyl-3- (cyclohexylamino) -1-propane sulfonate; the polyisocyanate is synthesized by using the sulfamate and the diisocyanate trimer, so that the hydrophilic property is provided for the polyisocyanate, and the excellent dispersibility of the water-based polyisocyanate curing agent without solvent dilution is ensured.
Preferably, the diisocyanate trimer is selected from at least one of isophorone diisocyanate trimer, hexamethylene diisocyanate trimer, toluene diisocyanate trimer or diphenylmethane diisocyanate trimer; further preferably, the diisocyanate trimer is selected from isophorone diisocyanate trimer and/or hexamethylene diisocyanate trimer. The hexamethylene diisocyanate tripolymer and the isophorone diisocyanate tripolymer react mildly and are easy to control in the hydrophilization process.
Preferably, the diisocyanate trimer has a-NCO content of 18 to 28% by weight; further preferably, the diisocyanate trimer has a content of-NCO of 21% by weight to 24% by weight.
Preferably, the temperature of the first reaction is 70-110 ℃, and the time of the first reaction is 1-15 h; further preferably, the temperature of the first reaction is 80-100 ℃, and the time of the first reaction is 3-10 h.
Preferably, the bisulfite is selected from at least one of sodium bisulfite, potassium bisulfite, magnesium bisulfite, or calcium bisulfite.
Preferably, in the preparation method, the sulfonate is 1-8 parts, the diisocyanate trimer is 80-120 parts, and the bisulfite is 40-70 parts by weight.
Further preferably, in the preparation method, the sulfonate is 1.5 to 5 parts, the diisocyanate trimer is 95 to 100 parts, and the bisulfite is 50 to 60 parts by weight.
Preferably, the catalyst is nitrogen dimethylbenzylamine. The catalyst accounts for 0.15 to 0.5 weight portion.
Preferably, the temperature of the second reaction is 40-70 ℃; the time of the second reaction is 2-10 h; further preferably, the temperature of the second reaction is 50-60 ℃; the time of the second reaction is 3-8 h.
Preferably, the second reaction is ended when the mass content of-NCO in the reaction system is less than 0.05%. The end point of the second reaction is based on the fact that the mass content of the isocyanic acid radical is reduced to be less than 0.05 percent, and the content of the isocyanic acid radical is measured by a toluene-di-n-butylamine titration method. By controlling the content of-NCO in the reaction system, excessive residual-NCO reacts with water to extend chain when water is added for dilution in the subsequent processes of preparing coating and the like, so that the viscosity of the system is too high, and the dispersion and the use are not facilitated.
Preferably, the first reaction and the second reaction are carried out under a protective gas. Such as nitrogen.
Preferably, the preparation method of the water-based blocked polyisocyanate curing agent comprises the following steps:
mixing sulfonate, diisocyanate trimer and a catalyst, reacting for 1-15 hours at 70-110 ℃, adding bisulfite after the reaction is finished, and finishing the reaction when the mass content of-NCO is less than 0.05 percent at 40-70 ℃ to prepare the water-based closed polyisocyanate curing agent.
Further preferably, the preparation method of the water-based blocked polyisocyanate curing agent comprises the following steps:
mixing sulfonate, diisocyanate trimer and a catalyst, reacting for 3-10 hours at 80-100 ℃, adding bisulfite after the reaction is finished, and finishing the reaction when the content of-NCO is less than 0.05 percent by weight at 50-60 ℃ to prepare the water-based closed polyisocyanate curing agent.
The second aspect of the present invention provides a water-based blocked polyisocyanate curing agent.
Specifically, the water-based blocked polyisocyanate curing agent is prepared by the preparation method, wherein the solid content of the polyisocyanate curing agent is 99-100%, and the blocking rate is more than 99.9%.
The third aspect of the invention provides an application of a water-based blocked polyisocyanate curing agent.
In particular to the application of the water-based blocked polymeric isocyanate curing agent in polyurethane coating. Preferably, the polyurethane coating is an aqueous polyurethane coating.
The aqueous polyurethane coating comprises a component A and a component B, wherein the component A comprises an aqueous polyurethane dispersion, and the component B comprises the aqueous blocked polyisocyanate curing agent.
Further preferably, the a component further comprises a wetting agent, a thickener, a leveling agent and a solvent.
Preferably, the mass ratio of the A component to the B component is (3-8): 1.
Preferably, the preparation method of the waterborne polyurethane coating comprises the following steps: and mixing the component A and the component B to obtain the product. Actually, the component A and the component B in the waterborne polyurethane coating provided by the invention can be mixed and stored, and the storage stability is good; the a-component and the B-component may also be stored separately and mixed at the time of use. The specific mode can be selected according to different environments and requirements.
The invention utilizes the bisulfite to seal the water-based polyisocyanate obtained by the reaction of sulfonate and diisocyanate trimer, thus obtaining the water-based closed polyisocyanate curing agent. Specifically, the isocyanate group of the aqueous polyisocyanate is blocked in the preparation by using the catalyst present in the reaction system as a phase transfer catalyst for a bisulfite (blocking agent). The reaction condition is mild, and no additional catalyst is needed, so that the system is more stable during later storage; the prepared water-based blocked polyisocyanate curing agent has low unblocking temperature (about 75 ℃) and can be applied to various baking coatings; the waterborne polyurethane coating prepared by the method has strong stability, small viscosity change during storage at high temperature, and high glossiness of the formed paint film.
Compared with the prior art, the invention has the following beneficial effects:
(1) the water-based blocked polyisocyanate curing agent provided by the invention takes bisulfite as a blocking agent, has excellent water dispersibility and storage stability, has low unblocking temperature (not more than 80 ℃) and can be applied to various baking coatings.
(2) The waterborne polyurethane coating prepared by the waterborne closed polyisocyanate curing agent provided by the invention has strong stability, small viscosity change during storage at high temperature, and high glossiness and transparency of a formed paint film.
(3) The water-based closed polyisocyanate curing agent can reduce the dosage of a low-boiling point solvent, does not need any high-boiling point solvent or ketone solvent for viscosity reduction, and effectively controls VOC in the curing agent and paint; and the preparation process is simple and environment-friendly.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
In the following examples, comparative examples, application examples or comparative application examples, the aqueous polyurethane dispersion Bayhydrol @2470 was purchased from Corcission Polymer (China) Ltd, wetting agent
Twin 4100、
Twin 810 was purchased from Wingchungdi corporation and thickener COAPUR XS71 was purchased from Gaotai France. The remaining materials, reagents or apparatus may be conventionally obtained commercially or may be those which are conventionally available, unless otherwise specifiedObtained by a known method.
Example 1
A preparation method of a water-based blocked polyisocyanate curing agent comprises the following steps:
the raw materials were prepared according to the formulations shown in table 1. Putting 97.1 parts by mass of hexamethylene diisocyanate trimer into a four-neck flask provided with a stirrer, a thermometer and a nitrogen inlet, heating to 60 ℃, adding 2.8 parts by mass of 2-tert-butyl-4- (cyclohexylamino) -1-butanesulfonic acid sodium salt and 0.2 part by mass of azoxylidine under the stirring condition, reacting for 6 hours under the condition of 80 ℃, sampling and detecting the content of the isocyanate (the content of the isocyanate is determined by adopting a toluene-di-n-butylamine titration method in HGT 2409 and 1992) when the content is close to a theoretical value (the difference with the theoretical value of 0.05 percent is not more than 0.5 percent), adding sodium bisulfite, reacting for 5 hours under the condition of 55 ℃, sampling and detecting the content of the isocyanate, and finishing the reaction when the content of the isocyanate is less than 0.05 percent to obtain the water-based blocked polyisocyanate curing agent. The solid content of the prepared water-based blocked polyisocyanate curing agent is 99.7 percent, and the blocking rate is 99.97 percent. (the blocking rate was calculated by measuring the mass content of-NCO, and the blocking rate was (mass content of-NCO before blocking-mass content of-NCO after blocking)/mass content of-NCO before blocking.)
TABLE 1
| Kind of raw material | Mass portion of |
| Hexamethylene diisocyanate trimer | 97.1 |
| 2-tert-butyl-4- (cyclohexylamino) -1-butanesulfonic acid sodium salt | 2.8 |
| Nitrogen-nitrogen dimethylbenzylamine | 0.2 |
| Sodium bisulfite | 60 |
Example 2
A preparation method of a water-based blocked polyisocyanate curing agent comprises the following steps:
the raw materials were prepared according to the formulations shown in table 2. Putting 96.9 parts by mass of hexamethylene diisocyanate trimer into a four-neck flask provided with a stirrer, a thermometer and a nitrogen inlet, heating to 60 ℃, adding 3.0 parts by mass of 2-tert-butyl-4- (cyclohexylamino) -1-butanesulfonic acid sodium salt and 0.35 part by mass of azoxylyl benzylamine under the stirring condition, reacting for 4.5 hours under the condition of 90 ℃, sampling and detecting the content of the isocyanic acid group (the content of the isocyanic acid group is measured by adopting a toluene-di-n-butylamine titration method in HGT 2409 1992) until the content is close to a theoretical value (the difference with the theoretical value is not more than 0.5 percent), adding sodium bisulfite, reacting for 5 hours under the condition of 55 ℃, and finishing the reaction when the content of the isocyanic acid group is less than 0.05 percent to obtain the water-based blocked polyisocyanate curing agent. The solid content of the prepared water-based blocked polyisocyanate curing agent is 99.5 percent, and the blocking rate is 99.5 percent.
TABLE 2
| Kind of raw material | Mass portion of |
| Hexamethylene diisocyanate trimer | 96.9 |
| 2-tert-butyl-4- (cyclohexylamino) -1-butanesulfonic acid sodium salt | 3.0 |
| Nitrogen-nitrogen dimethylbenzylamine | 0.35 |
| Sodium bisulfite | 55 |
Example 3
A preparation method of a water-based blocked polyisocyanate curing agent comprises the following steps:
the raw materials were prepared according to the formulation shown in table 3. Putting 97.1 parts by mass of hexamethylene diisocyanate trimer into a four-neck flask provided with a stirrer, a thermometer and a nitrogen inlet, heating to 60 ℃, and adding 2.8 parts by mass of 2-tert-butyl-4- (cyclohexylamino) -1-butanesulfonic acid sodium salt and 0.5 part by mass of azoxylylbenzylamine under the stirring condition; after 5.5 hours of reaction at 80 ℃ sampling was carried out to determine the isocyanate group content (determination of the isocyanate group content was carried out by the toluene-di-n-butylamine titration method in HGT 2409-1992), and sodium bisulfite was added until the theoretical value (not more than 0.5% difference from the theoretical value of 0.05% by mass); and reacting for 5 hours at 55 ℃, and finishing the reaction when the mass content of the isocyanic acid radical is less than 0.05 percent to obtain the water-based closed polyisocyanate curing agent. The solid content of the prepared water-based blocked polyisocyanate curing agent is 99.5 percent, and the blocking rate is 99.96 percent.
TABLE 3
| Kind of raw material | Mass portion of |
| Hexamethylene diisocyanate trimer | 97.1 |
| 2-tert-butyl-4- (cyclohexylamino) -1-butanesulfonic acid sodium salt | 2.8 |
| Nitrogen-nitrogen dimethylbenzylamine | 0.5 |
| Sodium bisulfite | 58 |
Example 4
A preparation method of a water-based blocked polyisocyanate curing agent comprises the following steps:
the raw materials were prepared according to the formulation shown in table 4. Putting 97.1 parts by mass of isophorone diisocyanate trimer into a four-neck flask provided with a stirrer, a thermometer and a nitrogen inlet, heating to 60 ℃, adding 2.8 parts by mass of 2-tert-butyl-3- (cyclohexylamino) -1-propane sodium sulfonate and 0.2 part by mass of nitrogen dimethyl benzylamine under the stirring condition, reacting for 6 hours under the condition of 80 ℃, sampling and detecting the content of the isocyanate (the content of the isocyanate is determined by adopting a toluene-di-n-butylamine titration method in HGT 2409 and 1992) until the content is close to a theoretical value (the difference with the theoretical value of 0.05 percent is not more than 0.5 percent), adding potassium hydrogen sulfite, reacting for 5 hours under the condition of 55 ℃, sampling and detecting the content of the isocyanate, and finishing the reaction when the content of the isocyanate is less than 0.05 percent to obtain the water-based closed type polyisocyanate curing agent. The solid content of the prepared water-based blocked polyisocyanate curing agent is 99.8 percent, and the blocking rate is 99.97 percent.
TABLE 4
Comparative example 1
Comparative example 1 differs from example 3 in that the same amount of methyl ethyl ketoxime was used instead of sodium bisulfite as the blocking agent, and the remaining raw materials and preparation method were the same as in example 3.
Specifically, the preparation method of the water-based closed polyisocyanate curing agent comprises the following steps:
putting 97.1 parts by mass of hexamethylene diisocyanate trimer into a four-neck flask provided with a stirrer, a thermometer and a nitrogen inlet, heating to 60 ℃, and adding 2.8 parts by mass of 2-tert-butyl-4- (cyclohexylamino) -1-butanesulfonic acid sodium salt and 0.5 part by mass of azoxylylbenzylamine under the stirring condition; after 5.5 hours of reaction at 80 ℃ sampling was carried out to determine the isocyanate group content (determination of the isocyanate group content was carried out by the toluene-di-n-butylamine titration method in HGT 2409-1992), 58 parts of methyl ethyl ketoxime was added until the theoretical value was reached (the difference from the theoretical value of 0.05% by mass was not more than 0.5%); and reacting for 5 hours at 55 ℃, and finishing the reaction when the mass content of the isocyanic acid radical is less than 0.05 percent to obtain the water-based closed polyisocyanate curing agent. The solid content of the prepared water-based blocked polyisocyanate curing agent is 99.8 percent, and the blocking rate is 99.95 percent.
Comparative example 2
Comparative example 2 differs from example 3 in that sodium 2-tert-butyl-4- (cyclohexylamino) -1-butanesulfonate was not added and the remaining raw materials and preparation method were the same as in example 3.
A preparation method of a blocked polyisocyanate curing agent comprises the following steps:
the raw materials were prepared according to the formulation shown in table 3. Putting 97.1 parts by mass of hexamethylene diisocyanate trimer into a four-neck flask provided with a stirrer, a thermometer and a nitrogen inlet, heating to 60 ℃, and adding 0.5 part by mass of azoxylylamine and 58 parts by mass of sodium bisulfite under the stirring condition; and (3) reacting for 5 hours at 55 ℃, and finishing the reaction when the mass content of the isocyanic acid radical is less than 0.05%, thereby obtaining the blocked polyisocyanate curing agent. The solid content of the prepared blocked polyisocyanate curing agent is 99.9 percent, and the blocking rate is 99.96 percent.
Comparative example 3
Comparative example 3 differs from example 3 in that no sodium bisulfite, a blocking agent, was added, and the remaining raw materials and preparation method were the same as in example 3.
A preparation method of a water-based polyisocyanate curing agent comprises the following steps:
putting 97.1 parts by mass of hexamethylene diisocyanate trimer into a four-neck flask provided with a stirrer, a thermometer and a nitrogen inlet, heating to 60 ℃, and adding 2.8 parts by mass of 2-tert-butyl-4- (cyclohexylamino) -1-butanesulfonic acid sodium salt and 0.5 part by mass of azoxylylbenzylamine under the stirring condition; after 5.5 hours of reaction at 80 ℃, a sample is taken to detect the content of the isocyanate group (the content of the isocyanate group is determined by adopting a toluene-di-n-butylamine titration method in HGT 2409-1992), and the reaction is ended when the mass content of the isocyanate group is less than 0.05 percent, so as to obtain the aqueous polyisocyanate curing agent. The solid content of the prepared water-based polyisocyanate curing agent is 99.9 percent, and the curing agent is not blocked and has no blocking rate data.
Application examples 1 to 4
Aqueous polyurethane coatings were prepared using the aqueous blocked polyisocyanate curing agents prepared in examples 1-4, respectively.
Specifically, the preparation method of the waterborne polyurethane coating comprises the following steps:
(1) according to the mass percentage, 80 percent of waterborne polyurethane dispersoid Bayhydrol @2470 and 0.25 percent of wetting agent are taken
Twin 4100, 0.15% humectant
Twin 810, 2.5 percent of dipropylene glycol butyl ether, 2.5 percent of dipropylene glycol monomethyl ether, 0.25 percent of thickener COAPUR XS71, 0.35 percent of aqueous flatting agent BYK-333 and 14 percent of water are mixed to prepare a component A;
(2) according to the mass ratio of A, B components of 5: 1, respectively weighing the component B (the water-based closed type polyisocyanate curing agent prepared in the examples 1-4) and adding the component B into the component A, and uniformly mixing to obtain the water-based polyurethane coating.
Comparative application examples 1 to 3
The polyisocyanate curing agents prepared in comparative examples 1 to 3 were used to prepare aqueous polyurethane coatings.
Specifically, the preparation method of the waterborne polyurethane coating comprises the following steps:
(1) according to the mass percentage, 80 percent of waterborne polyurethane dispersoid Bayhydrol @2470 and 0.25 percent of wetting agent are taken
Twin 4100, 0.15% humectant
Twin 810, 2.5 percent of dipropylene glycol butyl ether, 2.5 percent of dipropylene glycol monomethyl ether, 0.25 percent of thickener COAPUR XS71, 0.35 percent of aqueous flatting agent BYK-333 and 14 percent of water are mixed to prepare a component A;
(2) according to the mass ratio of A, B components of 5: 1, respectively weighing the component B (the polyisocyanate curing agent prepared in the comparative examples 1-3) and adding the component B into the component A, and uniformly mixing to obtain the waterborne polyurethane coating.
Product effectiveness testing
Respectively using the waterborne polyurethane coatings prepared in the application examples 1-4 and the comparative application examples 1-3 to prepare paint films by using a 150-micron wet film preparation device, baking according to deblocking temperatures of the paint films, and drying and crosslinking to obtain the paint films. And (3) carrying out performance test on the waterborne closed polyisocyanate curing agent, the waterborne polyurethane coating and the prepared paint film. The tests for the aqueous blocked polyisocyanate curing agents included water solubility and deblocking temperature tests, the tests for the aqueous polyurethane coatings included high temperature storage (6 months at 50 ℃) stability tests (viscosity, paint film gloss) and the paint film tests included paint film gloss tests. The test method of the basic questions is as follows:
(1) the deblocking temperature measuring method comprises the following steps: dissolving the water-based blocked isocyanate curing agent by using acetone, adding a plurality of drops of phenol, and heating. The temperature at which cloudiness occurs is the initial deblocking temperature of the sample.
(2) Measurement standards for viscosity: GB/T1723 + 1993.
(3) Measurement standards for gloss of paint films: GBT 9754-.
The test results are shown in Table 5.
TABLE 5 technical indexes of water-based blocked polyisocyanate curing agent and test results of water-based polyurethane coating prepared from the same
As can be seen from Table 5, the water-based blocked polyisocyanate curing agent provided by the embodiment of the invention has excellent water solubility, and tends to form extremely fine particles (the particle size of 90% of the system is less than 0.9 μm) after being dispersed in water, so that the transparency and the glossiness of the water-based polyurethane coating are improved; the deblocking temperature of the water-based blocked polyisocyanate curing agent is as low as 70 ℃; the waterborne polyurethane coating prepared from the waterborne polyurethane coating has strong stability, and the viscosity change is small after the waterborne polyurethane coating is stored for 6 months at 50 ℃; the glossiness of a paint film prepared by using the waterborne polyurethane paint is high and reaches 90 degrees or above, the glossiness of the paint film prepared by the waterborne polyurethane paint after the paint film is stored for 6 months at 50 ℃ is high and basically unchanged, and the waterborne polyurethane paint has good storage stability. In the comparative application example 1, the deblocking temperature is up to 140 ℃; the curing agent in comparative application example 2 has a lower deblocking temperature, but the water solubility is poor, and the glossiness of the paint film is obviously lower than that of the application example; comparative application example 3 had poor storage stability. Meanwhile, through tests, the haze of the paint film prepared by the application example of the invention is lower than 20%, the light transmittance is higher than 85%, and the paint film has high transparency.
Claims (10)
1. A preparation method of a polyisocyanate curing agent is characterized by comprising the following steps: and mixing sulfonate, diisocyanate trimer and a catalyst, carrying out a first reaction, adding bisulfite after the reaction is finished, and carrying out a second reaction to obtain the water-based closed polyisocyanate curing agent.
2. The method according to claim 1, wherein the sulfonic acid salt is a sulfamate.
3. The method according to claim 1, wherein the diisocyanate trimer is at least one selected from the group consisting of isophorone diisocyanate trimer, hexamethylene diisocyanate trimer, toluene diisocyanate trimer, and diphenylmethane diisocyanate trimer.
4. The method according to claim 1, wherein the bisulfite is at least one selected from the group consisting of sodium bisulfite, potassium bisulfite, magnesium bisulfite, and calcium bisulfite.
5. The production method according to any one of claims 1 to 4, characterized in that in the production method, the sulfonate is 1 to 8 parts, the diisocyanate trimer is 80 to 120 parts, and the bisulfite is 40 to 70 parts by weight.
6. The method according to claim 1, wherein the temperature of the second reaction is 40 to 70 ℃.
7. The production method according to claim 6, wherein the second reaction is terminated when the mass content of-NCO in the reaction system is less than 0.05%.
8. A polyisocyanate curing agent prepared by the preparation method of any one of claims 1 to 7, wherein the solid content of the polyisocyanate curing agent is 99 to 100%, and the blocking rate is more than 99.9%.
9. Use of the polyisocyanate curing agent of claim 8 in polyurethane coatings.
10. An aqueous polyurethane coating comprising an a-side comprising an aqueous polyurethane dispersion and a B-side comprising the polyisocyanate curing agent of claim 8.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111576048.3A CN114230764B (en) | 2021-12-20 | 2021-12-20 | Water-based closed polyisocyanate curing agent and preparation method and application thereof |
| PCT/CN2022/128657 WO2023116204A1 (en) | 2021-12-20 | 2022-10-31 | Water-based blocked polyisocyanate curing agent, and preparation method therefor and application thereof |
| ZA2023/08970A ZA202308970B (en) | 2021-12-20 | 2023-09-21 | Water-based sealed polyisocyanate curing agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111576048.3A CN114230764B (en) | 2021-12-20 | 2021-12-20 | Water-based closed polyisocyanate curing agent and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115613369A (en) * | 2022-10-20 | 2023-01-17 | 莆田达凯新材料有限公司 | Heat-resistant polyurethane shoe upper coating, heat-resistant polyurethane coating shoe upper and preparation method thereof |
| WO2023116204A1 (en) * | 2021-12-20 | 2023-06-29 | 嘉宝莉化工集团股份有限公司 | Water-based blocked polyisocyanate curing agent, and preparation method therefor and application thereof |
| CN117304429A (en) * | 2023-11-29 | 2023-12-29 | 大庆市唯品科技开发有限公司 | Composite high-temperature-resistant and salt-resistant water shutoff agent and preparation method thereof |
| CN117624548A (en) * | 2023-12-19 | 2024-03-01 | 广东东旭化学工业制造有限公司 | Preparation method of curing agent for producing water-based closed polyurethane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114230764B (en) * | 2021-12-20 | 2023-06-13 | 嘉宝莉化工集团股份有限公司 | Water-based closed polyisocyanate curing agent and preparation method and application thereof |
-
2021
- 2021-12-20 CN CN202111576048.3A patent/CN114230764B/en active Active
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2022
- 2022-10-31 WO PCT/CN2022/128657 patent/WO2023116204A1/en unknown
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| CN1429240A (en) * | 2000-05-18 | 2003-07-09 | 拜尔公司 | Modified polysocyanates |
| CN101675132A (en) * | 2007-05-04 | 2010-03-17 | 巴斯福涂料股份公司 | Water-based two-layer coating system based on urethane, use thereof and substrates coated therewith |
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| CN104448232A (en) * | 2013-09-13 | 2015-03-25 | 万华化学集团股份有限公司 | Sulfamic acid modified polyisocyanate and preparation method and application thereof |
| CN108047645A (en) * | 2017-12-22 | 2018-05-18 | 合肥工业大学 | The melamine foams that a kind of isophorone diisocyanate using sealing end is prepared as curing agent |
| CN111154069A (en) * | 2020-01-15 | 2020-05-15 | 广州康狄夫环保科技有限公司 | Polyurethane curing agent, waterborne polyurethane, coating and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023116204A1 (en) * | 2021-12-20 | 2023-06-29 | 嘉宝莉化工集团股份有限公司 | Water-based blocked polyisocyanate curing agent, and preparation method therefor and application thereof |
| CN115613369A (en) * | 2022-10-20 | 2023-01-17 | 莆田达凯新材料有限公司 | Heat-resistant polyurethane shoe upper coating, heat-resistant polyurethane coating shoe upper and preparation method thereof |
| CN115613369B (en) * | 2022-10-20 | 2024-04-16 | 莆田达凯新材料有限公司 | Heat-resistant polyurethane vamp coating, heat-resistant polyurethane coating vamp and preparation method thereof |
| CN117304429A (en) * | 2023-11-29 | 2023-12-29 | 大庆市唯品科技开发有限公司 | Composite high-temperature-resistant and salt-resistant water shutoff agent and preparation method thereof |
| CN117304429B (en) * | 2023-11-29 | 2024-02-02 | 大庆市唯品科技开发有限公司 | Composite high-temperature-resistant and salt-resistant water shutoff agent and preparation method thereof |
| CN117624548A (en) * | 2023-12-19 | 2024-03-01 | 广东东旭化学工业制造有限公司 | Preparation method of curing agent for producing water-based closed polyurethane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114230764B (en) | 2023-06-13 |
| WO2023116204A1 (en) | 2023-06-29 |
| ZA202308970B (en) | 2023-10-25 |
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