CN112680087A - Long-activation-period water-based bi-component polyurethane curing agent and preparation method and application thereof - Google Patents
Long-activation-period water-based bi-component polyurethane curing agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a long-activation-period water-based bi-component polyurethane curing agent, a preparation method and application thereof, wherein the preparation method comprises the following steps: uniformly mixing monofunctional hydrophilic polyether and diisocyanate monomer at room temperature, adding a catalyst, heating to 50-90 ℃, reacting for 1-4h until the NCO content of the system reaches a theoretical value, adding a polymerization inhibitor, cooling to room temperature, discharging, and adding a polyisocyanate curing agent accounting for 80-99.5% of the total mass of the raw materials into the obtained product to prepare the long-activation-period water-based double-component polyurethane curing agent. According to the invention, the isocyanate compound containing the nonionic hydrophilic long chain is introduced into the isocyanate curing agent, and when the isocyanate compound is matched with the water-based hydroxyl resin for paint preparation, the reaction speed of-NCO and-OH is slowed down due to the shielding effect of the hydrophilic long chain in the film forming process, so that the activation time of paint preparation is prolonged, the gloss of a coated film can be reduced, and the construction performance of the curing agent is improved.
Description
Technical Field
The invention relates to a polyurethane curing agent, in particular to a long-activation-period water-based double-component polyurethane curing agent and a preparation method thereof.
Background
The water-based bi-component polyurethane coating has the characteristics of low film forming temperature, strong adhesive force, good wear resistance, good weather resistance and the like, is an environment-friendly coating capable of replacing solvent-based bi-component polyurethane coatings, and gradually becomes a research hotspot at present. The aqueous hydroxyl resin curing agent consists of aqueous hydroxyl resin (A component) and aqueous polyisocyanate curing agent (B component), wherein the hydroxyl resin is easy to generate crosslinking reaction with isocyanate in the aqueous polyisocyanate curing agent under normal conditions, and if the reaction speed is too high, a series of problems are caused, even the loss is caused because the construction cannot be carried out. In the actual construction process, the construction can be carried out for a while after the paint is prepared, so that the reaction speed of the AB component after mixing is required to be as slow as possible, the paint can still be used within a certain time, and the requirement for prolonging the activation period of the curing agent is also provided.
Too long or too short activation period is not an optimal choice, and too short activation period can cause short paint usable time, thereby providing higher requirements for construction, increasing uncertain factors of the construction process and being incapable of accurately ensuring the construction quality; if the activation period is too long, a series of negative effects can be caused, such as a series of problems of slow film forming speed, reduced gloss, poor dust resistance, reduced crosslinking density of a coating film and the like, so that the method has important significance in prolonging the activation period of the curing agent as far as possible on the premise of ensuring good comprehensive performance of the coating film.
Chinese patent application CN101381443 discloses polyisocyanates containing allophanate groups and silane groups, the technical process comprising reacting: A) at least one hydroxycarbamate and/or hydroxyamide comprising silane groups, which is obtainable from the reaction of an aminosilane with a cyclic carbonate and/or lactone; reacting with a molar excess of B) at least one diisocyanate having aliphatically, cycloaliphatically, araliphatically and/or aromatically attached isocyanate groups, based on the NCO-reactive groups of A); and optionally subsequently removing unreacted excess diisocyanate. This technique is mainly directed to the problem of a reduction in the average isocyanate functionality, an increase in the viscosity and a random distribution of the silane functional groups. The basic ideas of the U.S. Pat. Nos. 5200489 and 3996154 are the same as the basic ideas of the Chinese patent CN101381443, and polyethers of different types are adopted as hydrophilic modifiers to modify the polyisocyanate curing agent, so that the hydrophilicity of the curing agent is successfully improved, and the water dispersible curing agent with good water dispersibility and good matching performance with hydroxyl resin is obtained. However, due to poor hydrophilicity of polyether, a large amount of polyether needs to be introduced to achieve ideal water dispersibility, so that the NCO content of the curing agent is low, the viscosity of the curing agent is high, and the workability is reduced.
German patent DE4433929A and European patent EP0703255 have proposed the modification of polyisocyanates with more hydrophilic hydroxyethanesulfonic acid and hydroxypropanesulfonic acid to produce curing agents with low viscosity and good water dispersibility. However, the hydroxysulfonic acids generally available on the market exist in the form of sodium salts, and sodium ions remain in the coating film for a long time after reacting with the polyisocyanate, reducing the alkali resistance, water resistance and gloss of the paint film.
U.S. Pat. No. 4,67958 uses N, N-dimethylcyclohexylamine as catalyst, 2-cyclohexylamino-ethanesulfonic acid and 3-cyclohexylamino-propanesulfonic acid to modify polyisocyanate to prepare the aqueous polyurethane curing agent with good hydrophilicity and ideal coating performance, but the reaction speed of the curing agent and hydroxy resin can be greatly improved due to the catalytic action of tertiary amine, so that the activation period of the curing agent is shorter; and the sulfonic acid group has strong hydrophilicity and is distributed on the surface of the coating after film formation, so that the water resistance, acid resistance and water resistance of the coating are reduced to different degrees.
The chinese patent application CN101754990A discloses a preparation method of aqueous polyisocyanate for two-component polyurethane coating or adhesive based on aqueous dispersion, which uses 4-aminotoluene-2-sulfonic acid to modify polyisocyanate, and simultaneously adds a certain amount of polyether alcohol PEO1 to obtain aqueous polyurethane curing agent which is very easy to disperse water. The technology uses 4-aminotoluene-2-sulfonic acid as a hydrophilic modifier, has a group with over-large steric hindrance, requires grafting reaction under the condition of over 100 ℃, and is relatively difficult to react.
In general, the market at present urgently needs to provide a long-activation-period aqueous bi-component polyurethane curing agent to meet the requirements of high-performance aqueous woodenware coatings and terrace coatings.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a long-activation-period water-based bi-component polyurethane curing agent with an activation period of 4-5h and a preparation method thereof.
The invention also aims to provide the application of the long-activation-period water-based double-component polyurethane curing agent in wood coatings or floor coatings.
According to the invention, on the basis of the traditional waterborne two-component polyurethane curing agent, the nonionic hydrophilic long chain is introduced to form a shielding effect on NCO groups, and in the process of paint preparation of the AB component, the contact chance of-NCO and-OH is reduced due to the protection effect of the hydrophilic long chain, so that the reaction speed between the AB component is slowed down, and the activation period of the waterborne curing agent is finally prolonged.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a long-activation-period water-based bi-component polyurethane curing agent comprises the following steps: at room temperature, mixing monofunctional hydrophilic polyether and diisocyanate monomer according to a molar ratio of 1.0-3.5: 1, uniformly mixing, adding a catalyst, heating to 50-90 ℃, reacting for 1-4h until the NCO content of the system reaches a theoretical value, adding a polymerization inhibitor, cooling to room temperature, and discharging; adding polyisocyanate curing agent accounting for 80-99.5% of the total mass of the raw materials into the obtained product to prepare the long-activation-period waterborne two-component polyurethane curing agent;
the monofunctional hydrophilic polyether is one or more of polyethylene glycol monomethyl ether 200, polyethylene glycol monomethyl ether 400, polyethylene glycol monomethyl ether 550, polyethylene glycol monomethyl ether 600 and polyethylene glycol monomethyl ether 750;
the catalyst is one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate and N, N-dimethyl cyclohexylamine.
To further achieve the object of the present invention, preferably, the diisocyanate is Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), phenyl Methane Diisocyanate (MDI), and hydrogenatedPhenyl methane diisocyanate (H)12MDI).
Preferably the polyisocyanate curing agent is Hexamethylene Diisocyanate (HDI) trimer, biuret and hydrophilically modified HDI trimer.
Preferably, the polyisocyanate curing agent is one of N3390, Bayhydur2655, Bayhydur3100, Bayhydur2487, G610 from Carbaoli, Vawawa HT100, HT600, Aquolin 163, Aquolin 166 and Aquolin 269 from Corsia.
Preferably, the polymerization inhibitor is one or more of methyl p-toluenesulfonate, hydroquinone and benzoyl chloride; the dosage of the catalyst is 0.1-1 wt% of the total mass of the raw materials.
A long-activation-period water-based bi-component polyurethane curing agent is prepared by the preparation method; the activation period of the long-activation-period waterborne two-component polyurethane curing agent is 4-5 h; the solid content of the long-activation-period waterborne two-component polyurethane curing agent is 99-100 wt%, and the NCO mass content is 10-22%.
Preferably, the viscosity of the long-activation-period waterborne two-component polyurethane curing agent at 25 ℃ is 1500-6500mPa & s;
preferably, the appearance of the long-activation-period water-based two-component polyurethane curing agent is colorless transparent or yellowish transparent viscous liquid.
The long-activation-period water-based double-component polyurethane curing agent is applied to wood coatings or terrace coatings: mixing and compounding the aqueous hydroxy resin and the long-activation-period aqueous double-component polyurethane curing agent, controlling the NCO/OH molar ratio to be 1.0-4.5, adding auxiliary materials, uniformly stirring, adding water to adjust the solid content, and obtaining a coating film, wherein the auxiliary materials comprise a defoaming agent, a leveling agent and a thickening agent;
the alkali resistance of the obtained coating does not change obviously in a 20% NaOH solution for 72H, and the pencil hardness of the coating reaches more than 2H.
Preferably, the dosage of the defoaming agent is 0.1 to 1.5 weight percent, the dosage of the flatting agent is 0.5 to 1.5 weight percent and the dosage of the thickening agent is 0.1 to 3 weight percent;
the defoaming agent is one of TEGO 810, TEGO 900, TEGO 902W, TEGO 825 of Germany Digao company, BYK 378 and BYK346 of Bike company;
the leveling agent is one of TEGO-450, TEGO-280, BYK 333, BYK346 and BYK 381 of Degaodigao company;
the thickener is one of RW-8W of DOW company, A401, U902, 924NP and U300 of Wanhua company;
the water-based hydroxyl resin comprises H2M0019, H2M0114, H2M0115, MG011 and MG057 of Jia Bao Li company and a double-component semi-gloss varnish of Xiupo chemical company Limited.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1) the waterborne two-component polyurethane curing agent prepared by the invention has a long activation period, a non-ionic hydrophilic long chain is introduced into a system, and the NCO group is protected by the hydrophilic non-ionic long chain in the process of mixing the AB components by utilizing the shielding effect of the hydrophilic non-ionic long chain on the NCO group, so that the reaction speed between the AB components is slowed down, the activation time of the curing agent is prolonged, and the activation period of the curing agent can be prolonged by 1-2h compared with that of a traditional method (only carrying out anion modification), and is basically equivalent to each performance of Bayer 2547.
2) The coating film prepared by the invention is flat and compact, has higher water resistance and alkali resistance compared with the traditional water-based double-component polyurethane coating, and can meet the requirements of high-performance water-based wood paint and floor paint on the market.
3) The preparation method has the advantages of simple operation process and mild reaction conditions, and the two-component waterborne polyurethane coating prepared by compounding the prepared curing agent and the waterborne hydroxy resin has the advantages of high activation period, high alkali resistance and the like.
Detailed Description
In order to better understand the present invention, the following further description is made with reference to the following examples, which should be construed as limiting the scope of the present invention.
In the following examples, the properties of the aqueous two-component isocyanate curing agent composition and the two-component aqueous coating material were measured by the following methods:
determining the NCO content of the water-based isocyanate curing agent by using a di-n-butylamine titration method according to GB/T12009;
the viscosity of the cyanate ester curing agent is measured by using NDJ-1 type rotational viscometer according to GB/T12009.3-89;
measuring the surface drying time of the coating according to GB/T1728-1989;
measuring the coating hardness according to GB T6739-2006;
the coating adhesion is determined according to ISO 2409-2007 Chinese edition;
the impact resistance of the coating is determined according to GB/T1732-93;
the gloss of the coating film was measured according to GB/T9754-2007 using a gloss meter model WGG60-E4 at an angle of 60 °;
the water resistance of the coating is determined by adopting a room temperature soaking method according to GB/T5209-1985;
according to GB/T6753.3-1986, the appearance and viscosity of the curing agent before and after storage and the hardness, the resistance, the adhesion and the like of a coating film after being compounded with the hydroxyl resin are measured and compared, so that the storage stability of the curing agent is judged;
other properties of the coating were determined according to GB/T7123.1-2002 et al.
The method for measuring the activation period of the curing agent comprises the following steps: the AB component is fully and uniformly mixed at 25 ℃, the viscosity of the paint is measured every half hour, the gloss of the coating film is measured, the viscosity of the paint is gradually increased along with the increase of time, and the time point of the viscosity mutation can be regarded as the activation period of the curing agent.
Example 1
(1) Preparation of waterborne two-component polyurethane curing agent
The raw material components and the dosage are shown in the following table 1:
TABLE 1
The preparation process comprises the following steps: under the protection of nitrogen, transferring HDI, MPEG-400 and dibutyltin dilaurate into a four-neck round-bottom flask provided with a mechanical stirrer, a reflux pipe, a thermometer and a nitrogen inlet and outlet, heating the mixture to 80 ℃ for reaction for 3h, cooling to 50 ℃ when the NCO content of the system reaches a theoretical value, preserving the temperature for 30min, cooling to room temperature, and discharging.
(2) Preparing a two-component water-based paint: the prepared components are uniformly mixed with Bayhydur XP 2487 according to the mass of 3% of the raw materials of the long-activation-period water-based double-component polyurethane curing agent to prepare the long-activation-period water-based double-component polyurethane curing agent.
The performance of the waterborne polyurethane curing agent is as follows: the solid content was 100%, the viscosity (25 ℃ C.) was 2000mPas, the NCO mass content was 21.02%, and the appearance was a colorless transparent viscous liquid.
Weighing and metering water-based hydroxyl resin (two-component semi-gloss varnish, Xiupo chemical group Co., Ltd.), putting into a dispersion barrel, adding 0.1 wt% of defoamer (Germany Digao TEGO-810 water-based defoamer), 0.15 wt% of flatting agent (Germany Digao TEGO-450 flatting agent) and 0.5 wt% of thickener (RM-8W of DOW), and dispersing for 30min at the rotating speed of 500rpm to obtain the water-based hydroxyl component. Then slowly adding the prepared long-activation-period waterborne two-component polyurethane curing agent into the polyurethane coating according to the NCO/OH molar ratio of 1.5:1, stirring for 3min, and adjusting the solid content of the coating to 40% by adding a proper amount of tap water. After being uniformly stirred, the mixture is filtered by a 300-mesh filter cloth to obtain the two-component water-based paint, and the paint film properties of the two-component water-based paint are shown in the following table 2:
(3) performance of two-component water paint
TABLE 2 combination of properties of two-component aqueous coating
As can be seen from example 1, compared with the Bayhydur XP 2547 curing agent which is commercially available, the waterborne two-component polyurethane curing agent prepared by the invention has longer activation period, the activation period of the curing agent is prolonged from 3.5h to 4h, and meanwhile, the curing agent has better alkali resistance.
Bayer Bayhydur XP 2547 is a matte curing agent commonly used in the existing double-component floor coating, the viscosity is below 2000mpas, the percentage content of NCO is more than 21%, the coating has good construction performance with the component A, the hardness of a coating pencil reaches more than 2H, the coating has good adhesive force and impact resistance, and the coating can meet the occasions with higher requirements on mechanical properties, such as the floor coating, and the like, and is a high-performance curing agent. Bayer Bayhydur XP 2547 is a waterborne curing agent which is modified by sulfamic acid in a hydrophilic way, the used initiator is HDI tripolymer, the hydrophilic modifier is sulfamic acid compound and is an anionic modified curing agent, the dosage of the hydrophilic modifier is 0.5-10%, and the mass content of the sulfonate is 1-25%. The hydrophilic group faces to a water phase in the process of preparing the paint with the component A to form a protection effect on an NCO group and form good compatibility with a hydroxyl resin, but the protection effect is temporary, and the-NCO group and the-OH group can quickly react due to the strong hydrophilicity and polarity of a sulfonic acid group, so that a curing phenomenon occurs before film coating, and the whole activation period of the curing agent is short. In the process of coating, NCO groups approach to each other along with the evaporation of surface moisture to form a crosslinking reaction, and finally the curing of the coating is realized.
Compared with Bayhydur XP 2547, the activation period of the waterborne curing agent prepared by the invention is prolonged by 0.5-1.5h, other performances of a coating film are basically equivalent, and the waterborne curing agent is a high-performance curing agent with an ultra-long activation period. The long activation period can obviously improve the construction performance of the coating, and particularly in large-area roll coating construction operation, the long activation period can ensure the construction flexibility and improve the construction stability and quality due to the long operation time difference among different processes. The long-activation-period curing agent can prolong the quality guarantee period of paint preparation, can ensure the quality of construction operation, and has better practical significance in the actual construction process.
Compared with the traditional hydrophilic modification method of the curing agent, the invention combines the advantages of nonionic modification and anionic modification, and uses the two modification methods simultaneously to form an anionic-nonionic modification scheme. At present, the hydrophilic modification of the curing agent by using the Cyclohexylaminopropanesulfonic Acid (CAPS) is a mainstream method, but on one hand, strong hydrogen bonds can be formed among molecules to increase the overall viscosity of the curing agent and cause the reduction of the construction performance due to the strong hydrophilicity and polarity of a sulfonate group in the CAPS; on the other hand, the stronger polarity can cause the reaction speed between the curing agent and the hydroxyl resin to be faster, the viscosity can be suddenly increased in the process of mixing the AB component, the paint preparation can not be used for coating under severe conditions, or a large amount of clear water is required to be added as a diluent to reduce the overall viscosity, and the negative effect can be caused on the comprehensive performance of the final coating. Therefore, it is an important research subject to study how to reduce the reaction rate between the AB components and prolong the activation period of the curing agent as much as possible.
According to the invention, long-chain segment hydrophilic polyether is introduced on the basis of CAPS as a main hydrophilic modifier, and the ether bond also has certain hydrophilicity, so that the long-chain segment hydrophilic polyether can form a wrapping effect and a shielding effect on a sulfonate group according to the principle of similar affinity, and the temporary shielding effect is the key for prolonging the activation period. During the process of preparing the AB component paint, the micelle formed by the curing agent in the water dispersion phase is shielded by the long-chain nonionic polyether, so that the mutual reaction between the micelle and the long-chain nonionic polyether is slowed down, but the shielding effect is released along with the continuous volatilization of surface moisture during the film forming process, and the crosslinking reaction between the AB components is continued. As can be seen from example 1, compared with Bayhydur XP 2547, the curing agent prepared by the invention has the advantages that the activation period is prolonged by about 0.5h, the indexes of pencil hardness, luster, water resistance, adhesive force and the like of a coating film are basically close to those of 2547, the alkali resistance is improved, and the coating film is not obviously changed after being soaked in a 20% NaOH solution for 72h (3 days). Therefore, the anion-nonionic mixed modification method not only ensures that the activation period of the curing agent is prolonged, but also ensures that the comprehensive performance of the final coating film is not greatly influenced.
The curing agent prepared by the embodiment can be widely applied to the fields of high-grade wood coatings and floor coatings, has a higher activation period, is better in flexibility and higher in stability in actual construction operation, and is particularly suitable for the construction condition of using the floor coatings. The excellent alkali resistance of the coating can endow the coating with longer service time, and particularly in some alkaline working environments, the coating can endow the coating with better impact resistance and coating hardness in the field of floor coatings, and the performances are difficult to achieve by common curing agents, so that the coating has remarkable advantages.
In the prior art, nonionic hydrophilic polyether is independently used for hydrophilic modification of a curing agent, so that a curing agent variety with excellent performance and good water dispersibility, such as a first-generation Bayer curing agent, is prepared. However, since nonionic general hydrophilicity is not so strong, and a large amount is required to achieve satisfactory water dispersibility, the curing agent has a low NCO percentage, which eventually results in a decrease in water resistance of the coating film and pencil hardness. The prior art also has a technology of mixing and modifying non-ions and anions, which mainly aims at improving the drying speed of the curing agent, but the prior art has not been used for preparing the curing agent with long activation period.
The chinese patent application CN101754990A discloses a preparation method of aqueous polyisocyanate for two-component polyurethane coating or adhesive based on aqueous dispersion, which uses 4-aminotoluene-2-sulfonic acid to modify polyisocyanate, and simultaneously adds a certain amount of polyether alcohol PEO1 to obtain aqueous polyurethane curing agent which is very easy to disperse water. The technology uses 4-aminotoluene-2-sulfonic acid as a hydrophilic modifier, has a group with overlarge steric hindrance, and needs to carry out grafting reaction at the temperature of over 100 ℃, so that the reaction is relatively difficult; on the other hand, nonionic compounds such as polyether alcohol are used in the process of synthesizing the curing agent, so that the drying speed of the curing agent is improved, but the application is not used for preparing the long-activation-period curing agent.
Example 2
(1) Preparation of waterborne two-component polyurethane curing agent
The raw material components and the dosage are shown in the following table 3:
TABLE 3
The preparation process comprises the following steps: transferring TDI and MPEG-400 into a four-neck round-bottom flask with a mechanical stirrer, a reflux pipe, a thermometer and a nitrogen inlet and outlet under the protection of nitrogen, heating the mixture to 50 ℃ for reaction for 2 hours, keeping the temperature for 30min when the NCO content of the system reaches a theoretical value, cooling to room temperature, and discharging.
(2) Preparing a two-component water-based paint: the prepared components are uniformly mixed with Bayhydur XP 2487 according to the raw material mass of 5% of the long-activation-period waterborne two-component polyurethane curing agent to prepare the long-activation-period waterborne two-component polyurethane curing agent.
The performance of the waterborne polyurethane curing agent is as follows: the solid content was 100%, the viscosity (25 ℃) was 3800 mPas, the NCO mass content was 20.66%, and the appearance was a colorless transparent viscous liquid.
Weighing and metering water-based hydroxyl resin (H2M0119, Jia Bao Li chemical group Co., Ltd.), putting the water-based hydroxyl resin into a dispersing barrel, adding 1 wt% of defoaming agent (German Digao TEGO-900 water-based defoaming agent), 0.5 wt% of flatting agent (BYK 333 flatting agent of Bick Co., Ltd.), 1 wt% of thickening agent (RM-8W thickening agent of DOW Co., Ltd.), and dispersing for 30min at the rotating speed of 600rpm to obtain the water-based hydroxyl component. Then slowly adding the prepared waterborne polyurethane curing agent into the waterborne polyurethane curing agent according to the NCO/OH molar ratio of 2:1, stirring for 3min, and adding a proper amount of tap water to adjust the solid content of the paint to 50%. After being uniformly stirred, the mixture is filtered by 400-mesh filter cloth to obtain the two-component water-based paint, and the paint film properties of the two-component water-based paint are shown in the following table 4:
(3) performance of two-component water paint
TABLE 4 comprehensive Properties of two-component Water-based paint
Example 3
(1) Preparation of waterborne two-component polyurethane curing agent
The raw material components and the use amount are as follows in the following table 5:
TABLE 5
The preparation process comprises the following steps: under the protection of nitrogen, IPDI, MPEG-550 and dibutyltin dilaurate are transferred into a four-neck round-bottom flask provided with a mechanical stirrer, a reflux pipe, a thermometer and a nitrogen inlet and outlet, then the temperature is increased to 80 ℃ for reaction for 3 hours, when the NCO content of the system reaches a theoretical value, the temperature is reduced to 50 ℃, the temperature is kept for 30 minutes, and the product is discharged after being cooled to room temperature.
(2) Preparing a two-component water-based paint: the prepared components are uniformly mixed with Bayhydur XP 2655 according to the mass of 2.5 percent of the raw materials of the long-activation-period water-based double-component polyurethane curing agent to prepare the novel long-activation-period water-based double-component polyurethane curing agent.
The performance of the waterborne polyurethane curing agent is as follows: the solid content was 100%, the viscosity (25 ℃ C.) was 3700 mPas, the NCO mass content was 20.32%, and the appearance was a colorless transparent viscous liquid.
Weighing and metering water-based hydroxyl resin (H2M0115, Jia Bao Li chemical group Co., Ltd.), putting the water-based hydroxyl resin into a dispersion barrel, adding 1.5 wt% of an antifoaming agent (German Digao TEGO-902W water-based antifoaming agent), 0.7 wt% of a flatting agent (BYK 346 flatting agent of Bike Co., Ltd.), 2 wt% of a thickening agent (Wanhua U902 thickening agent), and dispersing for 50min at the rotating speed of 500rpm to obtain the water-based hydroxyl component. Then slowly adding the prepared waterborne polyurethane curing agent into the waterborne polyurethane curing agent according to the NCO/OH molar ratio of 3:1, stirring for 40min, and adding a proper amount of tap water to adjust the solid content of the paint to 30%. After being uniformly stirred, the mixture is filtered by a 300-mesh filter cloth to obtain the two-component water-based paint, and the paint film properties of the two-component water-based paint are shown in the following table 6:
(3) performance of two-component water paint
TABLE 6 combination properties of two-component waterborne coatings
Example 4
(1) Preparation of waterborne two-component polyurethane curing agent
The raw material components and the dosage are shown in the following table 7:
TABLE 7
The preparation process comprises the following steps: under the protection of nitrogen, MDI, MPEG-600 and dibutyltin dilaurate are transferred into a four-neck round-bottom flask provided with a mechanical stirrer, a reflux pipe, a thermometer and a nitrogen inlet and a nitrogen outlet, then the temperature is increased to 60 ℃ for reaction for 3 hours, when the NCO content of a system reaches a theoretical value, the temperature is reduced to 50 ℃, the temperature is kept for 30min, and the product is discharged after being cooled to room temperature.
(2) Preparing a two-component water-based paint: the prepared components are uniformly mixed with Bayhydur XP 3100 according to the raw material mass of 8% of the long-activation-period waterborne two-component polyurethane curing agent to prepare the novel long-activation-period waterborne two-component polyurethane curing agent.
The performance of the waterborne polyurethane curing agent is as follows: the solid content was 100%, the viscosity (25 ℃) was 5500 mPas, the NCO mass content was 19.57%, and the appearance was a colorless transparent viscous liquid.
Weighing and metering water-based hydroxyl resin (H2M0114, Jia Bao Li chemical group Co., Ltd.), putting the water-based hydroxyl resin into a dispersion barrel, adding 0.8 wt% of defoaming agent (German Digao TEGO-825 water-based defoaming agent), 1.5 wt% of flatting agent (German Digao TEGO-280 flatting agent) and 0.9 wt% of thickening agent (Wanhua chemical U300 thickening agent), and dispersing for 30min at the rotating speed of 800rpm to obtain the water-based hydroxyl component. Then slowly adding the prepared waterborne polyurethane curing agent into the waterborne polyurethane curing agent according to the NCO/OH molar ratio of 4.5:1, stirring for 3min, and adding a proper amount of tap water to adjust the solid content of the paint to 60%. After being uniformly stirred, the mixture is filtered by a 300-mesh filter cloth to obtain the two-component water-based paint, and the paint film properties of the two-component water-based paint are shown in the following table 8:
(3) performance of two-component water paint
TABLE 8 combination of properties of two-component waterborne coatings
Example 5
(1) Preparation of waterborne two-component polyurethane curing agent
The raw material components and the dosage are as follows in the following table 9:
TABLE 9
The preparation process comprises the following steps: under the protection of nitrogen, transferring HDI, MPEG-600 and dibutyltin dilaurate into a four-neck round-bottom flask provided with a mechanical stirrer, a reflux pipe, a thermometer and a nitrogen inlet and a nitrogen outlet, then heating to 60 ℃ for reaction for 3h, cooling to 50 ℃ when the NCO content of a system reaches a theoretical value, preserving heat for 30min, cooling to room temperature, and discharging.
(2) Preparing a two-component water-based paint: the prepared components are uniformly mixed with Bayhydur XP 3100 according to the raw material mass of 2% of the long-activation-period waterborne two-component polyurethane curing agent to prepare the novel long-activation-period waterborne two-component polyurethane curing agent.
The performance of the waterborne polyurethane curing agent is as follows: the solid content was 100%, the viscosity (25 ℃ C.) was 4500 mPas, the NCO mass content was 19.89%, and the appearance was a colorless transparent viscous liquid.
Weighing and metering the water-based hydroxyl resin (MG011, Jia Bao Li chemical group Co., Ltd.), putting the water-based hydroxyl resin into a dispersing barrel, adding 1 wt% of a defoaming agent (BYK 378 water-based defoaming agent of Pico Co., Ltd.), 1 wt% of a flatting agent (TEGO-450 flatting agent of Germany) and 1.8 wt% of a thickening agent (RM-8W thickening agent of DOW Co., Ltd.), and dispersing for 60min at the rotating speed of 800rpm to obtain the water-based hydroxyl component. Then slowly adding the prepared waterborne polyurethane curing agent into the polyurethane curing agent according to the NCO/OH molar ratio of 1.8:1, stirring for 5min, and adding a proper amount of tap water to adjust the solid content of the paint to 50%. After being uniformly stirred, the mixture is filtered by a 300-mesh filter cloth to obtain the two-component water-based paint, and the paint film properties of the two-component water-based paint are shown in the following table 10:
(3) performance of two-component water paint
TABLE 10 combination of properties of two-component waterborne coatings
Example 6
(1) Preparation of waterborne two-component polyurethane curing agent
The raw material components and the dosage are as follows:
TABLE 11
The preparation process comprises the following steps: transferring TDI and MPEG-800 into a four-neck round-bottom flask with a mechanical stirrer, a reflux pipe, a thermometer and a nitrogen inlet and outlet under the protection of nitrogen, then raising the temperature to 50 ℃ for reaction for 3 hours, cooling to room temperature when the NCO content of the system reaches a theoretical value, and discharging.
(2) Preparing a two-component water-based paint: the prepared components are uniformly mixed with Bayhydur XP 3100 mixed Jiabaoli G610 according to the raw material mass of 10% of the long-activation-period water-based double-component polyurethane curing agent to prepare the novel long-activation-period water-based double-component polyurethane curing agent.
The performance of the waterborne polyurethane curing agent is as follows: the solid content was 100%, the viscosity (25 ℃ C.) was 5000 mPas, the NCO mass content was 19.67%, and the appearance was a colorless transparent viscous liquid.
Weighing and metering the water-based hydroxyl resin (MG057, Jia Bao Li chemical group Co., Ltd.), putting the water-based hydroxyl resin into a dispersing barrel, adding 0.1 wt% of defoaming agent (BYK 3789 water-based defoaming agent of Picker Co., Ltd.), 0.3 wt% of flatting agent (BYK 333 of Picker Co., Ltd.) and 3 wt% of thickening agent (U300 of Wanhua Co., Ltd.), and dispersing for 20min at the rotating speed of 400rpm to obtain the water-based hydroxyl component. Then slowly adding the prepared waterborne polyurethane curing agent into the waterborne polyurethane curing agent according to the NCO/OH molar ratio of 2:1, stirring for 6min, and adding a proper amount of tap water to adjust the solid content of the paint to 40%. After being uniformly stirred, the mixture is filtered by a 300-mesh filter cloth to obtain the two-component water-based paint, and the paint film properties of the two-component water-based paint are shown in the following table 12:
(3) performance of two-component water paint
TABLE 12 combination of properties of two-component waterborne coatings
Example 7
(1) Preparation of waterborne two-component polyurethane curing agent
The raw material components and the dosage are as follows:
watch 13
The preparation process comprises the following steps: under the protection of nitrogen, IPDI and MPEG-600 are transferred into a four-neck round bottom flask provided with a mechanical stirring pipe, a reflux pipe, a thermometer and a nitrogen inlet and outlet, then the temperature is increased to 90 ℃ for reaction for 3 hours, when the NCO content of the system reaches a theoretical value, the system is cooled to room temperature and then discharged.
(2) Preparing a two-component water-based paint: the prepared components are uniformly mixed with Aquolon 163 according to the mass of 0.5% of the raw materials of the long-activation-period water-based double-component polyurethane curing agent to prepare the novel long-activation-period water-based double-component polyurethane curing agent.
The performance of the waterborne polyurethane curing agent is as follows: the solid content was 100%, the viscosity (25 ℃ C.) was 5000 mPas, the NCO mass content was 19.67%, and the appearance was a colorless transparent viscous liquid.
Weighing and metering water-based hydroxyl resin (H2M0119, Jia Bao Li chemical group Co., Ltd.), putting the water-based hydroxyl resin into a dispersion barrel, adding 0.5 wt% of defoaming agent (German Digao TEGO-825 water-based defoaming agent), 0.45 wt% of flatting agent (German Digao TEGO-280 flatting agent) and 0.36 wt% of thickening agent (924 NP of Wanhua Co., Ltd.), and dispersing for 30min at the rotating speed of 500rpm to obtain the water-based hydroxyl component. Then slowly adding the prepared waterborne polyurethane curing agent into the waterborne polyurethane curing agent according to the NCO/OH molar ratio of 1.8:1, stirring for 3min, and adding a proper amount of tap water to adjust the solid content of the paint to 40%. After being uniformly stirred, the mixture is filtered by a 300-mesh filter cloth to obtain the two-component water-based paint, and the paint film properties of the two-component water-based paint are shown in the following table 14:
(3) performance of two-component water paint
TABLE 14 combination of properties of two-component waterborne coatings
Example 8
(1) Preparation of waterborne two-component polyurethane curing agent
The raw material components and the dosage are as follows:
TABLE 14
The preparation process comprises the following steps: under the protection of nitrogen, IPDI and MPEG-600 are transferred into a four-neck round bottom flask provided with a mechanical stirring pipe, a reflux pipe, a thermometer and a nitrogen inlet and outlet, then the temperature is increased to 90 ℃ for reaction for 3 hours, when the NCO content of the system reaches a theoretical value, the system is cooled to room temperature and then discharged.
(2) Preparing a two-component water-based paint: the prepared components are uniformly mixed with Aquolon 163 according to the mass of 6% of the raw materials of the long-activation-period waterborne two-component polyurethane curing agent, so as to prepare the novel long-activation-period waterborne two-component polyurethane curing agent.
The performance of the waterborne polyurethane curing agent is as follows: the solid content was 100%, the viscosity (25 ℃ C.) was 5000 mPas, the NCO mass content was 19.67%, and the appearance was a colorless transparent viscous liquid.
Weighing and metering water-based hydroxyl resin (two-component semi-gloss varnish, Xiupo chemical group Co., Ltd.), putting into a dispersion barrel, adding 0.1 wt% of defoaming agent (Germany Digao TEGO-810 water-based defoaming agent), 0.55 wt% of flatting agent (BYK 381 flatting agent of Bike Co.), and 2.5 wt% of thickener (RM-8W thickener of DOW Co.), and dispersing for 50min at the rotating speed of 500rpm to obtain the water-based hydroxyl component. Then slowly adding the prepared waterborne polyurethane curing agent into the polyurethane curing agent according to the NCO/OH molar ratio of 1.9:1, stirring for 10min, and adding a proper amount of tap water to adjust the solid content of the paint to 40%. After being uniformly stirred, the mixture is filtered by a 300-mesh filter cloth to obtain the two-component water-based paint, and the paint film properties of the two-component water-based paint are shown in the following table 14:
(3) performance of two-component water paint
TABLE 15 combination of two-component aqueous coatings
Example 9
(1) Preparation of waterborne two-component polyurethane curing agent
The raw material components and the dosage are as follows:
watch 15
The preparation process comprises the following steps: under the protection of nitrogen, HDI and MPEG-400 were transferred to a four-neck round-bottom flask equipped with mechanical stirring, reflux tube, thermometer and nitrogen inlet and outlet, and then the temperature was raised to 90 ℃ for reaction for 3h, when the NCO content of the system reached the theoretical value, the reaction was cooled to room temperature and discharged.
(2) Preparing a two-component water-based paint: the prepared components are uniformly mixed with HT-600 according to the mass of 15% of the raw materials of the long-activation-period water-based double-component polyurethane curing agent, so as to prepare the novel long-activation-period water-based double-component polyurethane curing agent.
The performance of the waterborne polyurethane curing agent is as follows: the solid content was 100%, the viscosity (25 ℃ C.) was 1900 mPas, the NCO mass content was 21.12%, and the appearance was a colorless transparent viscous liquid.
Weighing and metering water-based hydroxyl resin (two-component semi-gloss varnish, Xiupo chemical group Co., Ltd.), putting the water-based hydroxyl resin into a dispersion barrel, adding 0.1 wt% of defoaming agent (Germany Digao TEGO-810 water-based defoaming agent), 0.15 wt% of flatting agent (BYK 381 flatting agent of Bike corporation) and 1.5 wt% of thickening agent (Wanhua corporation U300), and dispersing for 30min at the rotating speed of 500rpm to obtain the water-based hydroxyl component. Then slowly adding the prepared waterborne polyurethane curing agent into the waterborne polyurethane curing agent according to the NCO/OH molar ratio of 1:1, stirring for 3min, and adding a proper amount of tap water to adjust the solid content of the paint to 40%. After being uniformly stirred, the mixture is filtered by a 300-mesh filter cloth to obtain the two-component water-based paint, and the paint film properties of the two-component water-based paint are shown in the following table 16:
(3) performance of two-component water paint
TABLE 16 combination of properties of two-component waterborne coatings
Example 10
(1) Preparation of waterborne two-component polyurethane curing agent
The raw material components and the dosage are as follows:
TABLE 17
The preparation process comprises the following steps: under the protection of nitrogen, HDI and MPEG-600 were transferred to a four-neck round-bottom flask equipped with mechanical stirring, reflux pipe, thermometer and nitrogen inlet and outlet, and then the temperature was raised to 90 ℃ for reaction for 3h, when the NCO content of the system reached the theoretical value, the reaction was cooled to room temperature and discharged.
(2) Preparing a two-component water-based paint: the prepared components are uniformly mixed with HT-100 according to the mass of 20% of the raw materials of the long-activation-period water-based double-component polyurethane curing agent, so as to prepare the novel long-activation-period water-based double-component polyurethane curing agent.
The performance of the waterborne polyurethane curing agent is as follows: the solid content was 100%, the viscosity (25 ℃) was 4900 mPas, the NCO mass content was 20.23%, and the appearance was a colorless transparent viscous liquid.
Weighing and metering the water-based hydroxyl resin (two-component semi-gloss varnish, Xiupo chemical group Co., Ltd.), putting the water-based hydroxyl resin into a dispersion barrel, adding 0.15 wt% of defoaming agent (BYK 346 water-based defoaming agent of Bick company), 0.6 wt% of flatting agent (BYK 346 flatting agent of Bick company) and 1.5 wt% of thickening agent (thickening agent RM-8W of DOW company), and dispersing for 40min at the rotating speed of 300rpm to obtain the water-based hydroxyl component. Then slowly adding the prepared waterborne polyurethane curing agent into the waterborne polyurethane curing agent according to the NCO/OH molar ratio of 4.5:1, stirring for 3min, and adding a proper amount of tap water to adjust the solid content of the paint to 50%. After being uniformly stirred, the mixture is filtered by a 300-mesh filter cloth to obtain the two-component water-based paint, and the paint film properties of the two-component water-based paint are shown in the following table 18:
(3) performance of two-component water paint
TABLE 18 combination of two-component waterborne coatings
It should be noted that the present invention is not limited to the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations and simplifications which are made without departing from the spirit and principle of the present invention should be regarded as equivalent alternatives which are included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a long-activation-period water-based bi-component polyurethane curing agent is characterized in that monofunctional hydrophilic polyether and diisocyanate monomer are mixed according to a molar ratio of 1.0-3.5: 1, uniformly mixing, adding a catalyst, heating to 50-90 ℃, reacting for 1-4h until the NCO content of the system reaches a theoretical value, adding a polymerization inhibitor, cooling to room temperature, and discharging; adding polyisocyanate curing agent accounting for 80-99.5% of the total mass of the raw materials into the obtained product to prepare the long-activation-period waterborne two-component polyurethane curing agent;
the monofunctional hydrophilic polyether is one or more of polyethylene glycol monomethyl ether 200, polyethylene glycol monomethyl ether 400, polyethylene glycol monomethyl ether 550, polyethylene glycol monomethyl ether 600 and polyethylene glycol monomethyl ether 750;
the catalyst is one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate and N, N-dimethyl cyclohexylamine.
2. The method of claim 1, wherein the diisocyanate is one or more of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, phenyl methane diisocyanate, and hydrogenated phenyl methane diisocyanate.
3. The method for preparing a long-pot waterborne two-component polyurethane curing agent according to claim 1, wherein the polyisocyanate curing agent is hexamethylene diisocyanate trimer, biuret, or hydrophilically modified HDI trimer.
4. The method of claim 3, wherein the polyisocyanate curing agent is one of N3390, Bayhydur2655, Bayhydur3100, Bayhydur2487, G610, HT100, HT600, Aquolin 163, Aquolin 166 and Aquolin 269.
5. The preparation method of the long-life waterborne two-component polyurethane curing agent as claimed in claim 1, wherein the polymerization inhibitor is one or more of methyl p-toluenesulfonate, hydroquinone and benzoyl chloride; the dosage of the catalyst is 0.1-1 wt% of the total mass of the raw materials.
6. A long-life waterborne two-component polyurethane curing agent, characterized in that it is prepared by the preparation method of any one of claims 1 to 5; the activation period of the long-activation-period waterborne two-component polyurethane curing agent is 4-5 h; the solid content of the long-activation-period waterborne two-component polyurethane curing agent is 99-100 wt%, and the NCO mass content is 10-22%.
7. The long-pot waterborne two-component polyurethane curing agent as claimed in claim 6, wherein the viscosity of the long-pot waterborne two-component polyurethane curing agent at 25 ℃ is 1500-6500 mPa-s.
8. The long-life waterborne two-component polyurethane curing agent of claim 6, wherein the long-life waterborne two-component polyurethane curing agent is colorless, transparent or yellowish, transparent viscous liquid in appearance.
9. The application of the long-activation-period aqueous double-component polyurethane curing agent in the wood coating or the floor coating is characterized in that the aqueous hydroxyl resin and the long-activation-period aqueous double-component polyurethane curing agent are mixed and compounded for use, the NCO/OH molar ratio is controlled to be 1.0-4.5, auxiliary materials are added and stirred uniformly, water is added to adjust the solid content, and a coating film is obtained, wherein the auxiliary materials comprise a defoaming agent, a leveling agent and a thickening agent;
the alkali resistance of the obtained coating does not change obviously in a 20% NaOH solution for 72H, and the pencil hardness of the coating reaches more than 2H.
10. The application of the long-activation-period water-based double-component polyurethane curing agent in the wood coating or the floor coating as claimed in claim 9, wherein the amount of the defoaming agent is 0.1-1.5 wt%, the amount of the leveling agent is 0.5-1.5 wt% and the amount of the thickening agent is 0.1-3 wt%;
the defoaming agent is one of TEGO 810, TEGO 900, TEGO 902W, TEGO 825, BYK 378 and BYK 346;
the leveling agent is one of TEGO-450, TEGO-280, BYK 333, BYK346 and BYK 381;
one of the thickening agents RW-8W, A401, U902, 924NP and U300;
the water-based hydroxyl resin comprises one of H2M0019, H2M0114, H2M0115, MG011, MG057 and Xiupo chemical company Limited bi-component semi-gloss varnish.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113185643A (en) * | 2021-04-23 | 2021-07-30 | 万华化学集团股份有限公司 | Synthesis and application of modified aqueous polyurethane resin dispersoid |
| CN115746258A (en) * | 2022-11-18 | 2023-03-07 | 广州秀珀化工涂料有限公司 | Silicon modified double-crosslinking water-based polyisocyanate curing agent and preparation method thereof |
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| CN113185643A (en) * | 2021-04-23 | 2021-07-30 | 万华化学集团股份有限公司 | Synthesis and application of modified aqueous polyurethane resin dispersoid |
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| CN115746258A (en) * | 2022-11-18 | 2023-03-07 | 广州秀珀化工涂料有限公司 | Silicon modified double-crosslinking water-based polyisocyanate curing agent and preparation method thereof |
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