CN112679687A - Hydroxysulfonic acid hydrophilic monomer and preparation method and application thereof - Google Patents
Hydroxysulfonic acid hydrophilic monomer and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a hydroxysulfonic acid hydrophilic monomer and a preparation method and application thereof, wherein the preparation method comprises the steps of mixing short-chain hydroxysulfonic acid with an organic solvent, then dropwise adding an epoxy compound and a catalyst into the mixture, reacting at 25-100 ℃ for 4-24h, separating and washing the reaction mixture to obtain the hydroxysulfonic acid hydrophilic monomer. The preparation process of the hydroxysulfonic acid hydrophilic monomer and the waterborne polyurethane curing agent is simple, the reaction conditions are mild, and the two-component waterborne polyurethane coating prepared by compounding the prepared curing agent and the waterborne hydroxy resin has the advantages of good water resistance, high glossiness and the like.
Description
Technical Field
The invention relates to a polyurethane curing agent, in particular to a novel hydroxysulfonic acid monomer and a preparation method and application thereof, the hydroxysulfonic acid hydrophilic monomer can be used for preparing a water-based bi-component polyurethane curing agent, and has the advantages of mild reaction conditions, high reaction speed, good water dispersibility of the prepared curing agent and good compatibility with hydroxyl resin; the waterborne polyurethane curing agent can be used as a crosslinking component of a waterborne two-component coating, and a paint film of the waterborne polyurethane curing agent is high in gloss and good in water resistance.
Background
The water-based double-component polyurethane coating consists of water-based hydroxyl resin and a water-based curing agent, has more excellent coating performance than a single-component polyurethane coating, and has lower VOC content than the traditional polyurethane coating, thereby becoming a hotspot of current research. The oil-based curing agent has a higher NCO content and a lower viscosity, but is not hydrophilic and is difficult to be compatible with a water-based hydroxyl resin, and therefore, is difficult to disperse in the water-based hydroxyl resin, and causes coating defects such as unevenness, lack of density, and poor resistance of a coating after application.
The method for improving the hydrophilicity of the polyurethane curing agent mainly comprises the step of introducing hydrophilic groups or components, and currently, the polyisocyanate is subjected to hydrophilic modification by adopting a nonionic or anionic hydrophilic monomer. As the nonionic polyurethane curing agent, Bayer first generation hydrophilic modified isocyanate curing agent Bayhydur 3100 is most representative, and is obtained by modifying HDI type polyisocyanate by insufficient amount of monofunctional polyethylene oxide polyether alcohol. Japanese patent JP044649 discloses hydrophilic modified polyisocyanate curing agents prepared by grafting 4-isocyanato-1, 8-octane diisocyanate onto polyethylene glycol monomethyl ether. The Chinese invention patent application CN101027331 adopts IPDI and TMP to prepare hyperbranched polyisocyanate, and then uses hydroxyl polyoxyethylene ether to modify to improve the hydrophilicity. Similar U.S. Pat. Nos. 5200489, 3996154, and CN101381443 all use different types of polyethers as hydrophilic modifiers, successfully improve the hydrophilicity of polyurethane, and obtain polyurethane with good water dispersibility and good matching performance with hydroxyl resin. However, a large amount of polyether is introduced in the modification process, so that the NCO content of the curing agent is reduced, the viscosity of the curing agent is greatly increased, the using amount of the curing agent during paint preparation and the viscosity of the two-component paint are increased, and the construction difficulty is greatly increased. Meanwhile, too high polyether chain segment easily causes the problems of low hardness and poor water resistance of a paint film.
Compared with a nonionic modification method, the anionic modification method has the advantages of less hydrophilic modifier consumption, good water dispersibility of polyisocyanate, good water resistance of a coating film and the like. Common anion-modifying substances are mainly carboxylates, sulfonates, phosphates, and the like. Isocyanate is modified by a compound containing carboxyl or sulfonic group and other anionic groups, and then the isocyanate is neutralized to form salt, so that the waterborne polyurethane curing agent is obtained. DE4433929A and EP0703255 propose that the curing agents prepared by modifying polyisocyanates with hydrophilic modifiers of hydroxysulfonic acid type, such as hydroxyethanesulfonic acid, hydroxypropanesulfonic acid, and hydroxypolyethersulfonic acid, have good water dispersibility, but tend to crystallize and have poor storage stability. Meanwhile, most of the commercially available hydroxysulfonic acid derivatives exist in the form of aqueous solution or sodium salt, and sodium ions can remain in a coating film for a long time after the hydroxysulfonic acid derivatives react with polyisocyanate, so that the water resistance and the gloss of the coating film are reduced.
U.S. Pat. No. 4,67958 discloses a water-based polyurethane curing agent with good hydrophilicity and ideal coating performance, which is prepared by using N, N-dimethylcyclohexylamine as a catalyst and modifying polyisocyanate by using 2-cyclohexylamino-ethanesulfonic acid and 3-cyclohexylamino-propanesulfonic acid. The invention patent CN104448232A of China successfully grafts 4-cyclohexylamino-butanesulfonic acid on polyisocyanate to prepare the waterborne polyurethane curing agent by improving the synthesis process. The Chinese patent application CN101754990A proposes that polyisocyanate is modified by 4-aminotoluene-2-sulfonic acid, and a certain amount of polyether alcohol PEO1 is added to obtain the aqueous polyurethane curing agent which is very easy to disperse in water. However, the hydrophilic modifier used in the above-mentioned techniques has a group having too large resistance such as cyclohexyl group, which results in low sulfonic acid equivalent of the hydrophilic modifier on the one hand and reduced reactivity of imino group on the other hand, and it is necessary to raise the reaction temperature or add a catalyst during the modification process to smoothly react, but the residual catalyst is difficult to remove, resulting in poor stability of the curing agent during storage.
The existing curing agents in the market generally have the defects of low NCO content, high viscosity, high reaction temperature and poor storage stability. Therefore, the preparation of the aqueous polyurethane curing agent which has mild reaction conditions, good storage stability, excellent water dispersibility and workability and good matching property with hydroxyl resin still has great technical difficulty.
Disclosure of Invention
The invention overcomes the problems in the prior art and provides the hydroxysulfonic acid hydrophilic monomer with low reaction temperature and high reaction speed and the preparation method thereof.
The invention also aims to provide the application of the hydroxy sulfonic acid hydrophilic monomer in the waterborne two-component polyurethane curing agent, the solid content of the obtained waterborne polyurethane curing agent is 99-100 wt%, the NCO mass content is 14-23%, and the viscosity at 25 ℃ is 1500-6500mPa & s; the two-component waterborne polyurethane coating prepared by compounding the prepared curing agent and the waterborne hydroxyl resin has the advantages of good water resistance, high glossiness and the like.
The hydroxy sulfonic acid hydrophilic monomer synthesized by the invention has the advantages of high reaction speed and mild reaction conditions. The mainstream sulfamic acid hydrophilic modifier mainly depends on the reaction of-NH-and-NCO in the hydrophilic modification process, the reaction activity is low, the grafting with polyisocyanate is difficult, the reaction temperature needs to be over 90 ℃, and the reaction can be smoothly carried out only by adding a catalyst. The invention adopts the hydroxysulfonic acid with a novel structure as a hydrophilic monomer, the hydrophilic modification process is a nucleophilic addition reaction of-NCO and-OH, and the reaction can be smoothly carried out at a lower temperature, so that compared with the sulfamic acid type hydrophilic modifier, the reaction process can greatly improve the production efficiency and save a large amount of energy consumption.
The hydroxysulfonic acid can change the structure of the substituent group by selecting epoxy compounds with different structures, thereby obtaining different curing agent performances. For example, an epoxy compound with a smaller molecular weight can be selected to perform a ring-opening reaction with hydroxysulfonic acid to synthesize a hydrophilic monomer with a lower molecular weight, so that the equivalent sulfonic acid content is increased, excellent water dispersibility can be obtained only by a small addition amount, the NCO content of a curing agent is increased, and more excellent film performance is obtained.
In order to achieve the purpose, the invention adopts the technical scheme that:
a hydrophilic monomer of hydroxysulfonic acid having the formula:
sulfonic group-SO in the hydroxysulfonic acid hydrophilic monomer3The mass content of H is 10-65%; r1Is one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, phenyl, tert-butyl, cyclohexyl, benzyl, phenethyl and halogen elements; r2Is an alkane containing 1 to 4 carbon atoms or a hydrogen atom.
The preparation method of the hydroxysulfonic acid hydrophilic monomer comprises the following steps: firstly, mixing short-chain hydroxysulfonic acid with an organic solvent, then dropwise adding an epoxy compound and a catalyst into the mixture, reacting for 4-24h at 25-100 ℃, and separating and washing the reaction mixture to obtain a hydroxysulfonic acid hydrophilic monomer; the short-chain hydroxysulfonic acid is one or more of hydroxyethylsulfonic acid, hydroxypropyl sulfonic acid, hydroxylamine oxysulfonic acid and 4-hydroxybenzenesulfonic acid.
To further achieve the object of the present invention, preferably, the catalyst is one or more of boron trifluoride diethyl etherate, tetrabutylammonium bromide and dibutyltin dilaurate; the epoxy compound is one of ethylene oxide, propylene oxide, cyclohexene oxide, epichlorohydrin, phenyl glycidyl ether, benzyl glycidyl ether and octyl glycidyl ether; the molar ratio of the epoxy compound to the hydroxysulfonic acid is 1.0-10.0: 1.
Preferably, the organic solvent is one or more of toluene, xylene, N-dimethylformamide, tetrahydrofuran, 1, 4-dioxane, acetone, diethyl ether and ethyl acetate.
Preferably, the volume ratio of the short-chain hydroxysulfonic acid to the organic solvent is 1: 0.5-10; the solvent for washing is one or more of N, N-dimethylformamide, 1, 4-dioxane, acetone, diethyl ether, ethyl acetate and butyl acetate.
The application of the hydroxysulfonic acid hydrophilic monomer in the two-component waterborne polyurethane curing agent is as follows: according to the mass percentage of the raw materials, 1.0-10.0% of hydroxysulfonic acid hydrophilic monomer and 85-95% of polyisocyanate are fully mixed for 10-30 minutes at normal temperature, the temperature is raised to 50-80 ℃ under the protection of nitrogen, the reaction lasts for 1-2 hours until the NCO content of the system reaches the theoretical value, a neutralizing agent is added for neutralization for 10-30 minutes, then a polymerization inhibitor is added to terminate the reaction, the reaction is stirred, and the temperature is reduced to the room temperature, so that the waterborne polyurethane curing agent is obtained.
Preferably, the polyisocyanate is one or more of Hexamethylene Diisocyanate (HDI) trimer, biuret polyisocyanate, isophorone diisocyanate (IPDI) trimer and Toluene Diisocyanate (TDI) trimer; the average functionality of the polyisocyanate is at least 1.8, and the mass content of NCO is 18-30%;
the neutralizer is one or more of triethylamine, N-dimethylcyclohexylamine, N-dimethylbutylamine, N-dimethyl-2-ethylhexylamine, N-diethylmethylamine, N-dimethylformamide, N-methylmorpholine and tetraethylmethylenediamine; the mole ratio of the neutralizing agent to the hydroxysulfonic acid is 1-1.5;
the polymerization inhibitor is one of methyl p-toluenesulfonate, benzoyl chloride and hydroquinone;
the stirring is carried out for 10-20min under the vacuum degree of 0.1-0.2MPa, and the residual neutralizing agent in the reaction is removed.
Preferably, the obtained aqueous polyurethane curing agent has the solid content of 99-100 wt%, the NCO mass content of 14-23%, the viscosity of 1500-6500 mPa.s at 25 ℃, and the appearance of colorless transparent or light yellow transparent viscous liquid.
Preferably, the waterborne two-component polyurethane curing agent and the waterborne polyurethane hydroxyl component are mixed and compounded for use, and the molar ratio of NCO/OH is controlled to be 1.0-4.5; the hydroxyl component of the waterborne polyurethane comprises waterborne hydroxyl resin and auxiliary materials, wherein the auxiliary materials comprise a defoaming agent, a leveling agent and a thickening agent.
Preferably, the aqueous hydroxyl resin comprises H2M0019, H2M0114, H2M0115, MG011, MG057 of Jia Bao Li company, and a two-component semi-gloss varnish of Xippe chemical company, Inc.;
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 from DOW company, A401, U902, 924NP and U300 from Wanhua company.
The hydroxysulfonic acid modified waterborne polyurethane curing agent has the advantages of mild reaction conditions, high reaction speed, low curing agent viscosity, good water dispersibility, good water resistance, high NCO content and excellent hydroxyl resin matching property, and is suitable for two-component waterborne polyurethane coatings. The paint film obtained by compounding the water-based curing agent and the hydroxyl resin has high hardness and excellent water resistance and chemical resistance, and can be widely applied to the fields of buildings, leather, furniture and the like as a good crosslinking component;
compared with the prior art, the invention has the following advantages and beneficial effects:
1) the hydrophilic modification process has the advantages of mild reaction conditions, high reaction speed and short reaction time, and saves a large amount of energy compared with the traditional modification process.
2) The hydroxy sulfonic acid prepared by the invention does not have the problem of crystallization after modifying polyisocyanate, the modified curing agent has low viscosity and clear and transparent appearance, the main reason is that the short-chain hydroxy sulfonic acid has higher order degree and tends to crystallize in the modification process, and the invention introduces a branched chain into the structure of the short-chain straight-chain hydroxy sulfonic acid, thereby destroying the order degree of the molecular arrangement of the hydroxy sulfonic acid and avoiding the crystallization problem in the modification process.
3) The invention adopts the polyisocyanate modified by the anionic hydroxysulfonic acid hydrophilic monomer, the obtained waterborne polyurethane curing agent has good compatibility with hydroxyl resins such as acrylic resin, alkyd resin, polyester resin and the like, and can be used for building interior and exterior walls, bridges, industrial products and furniture coatings by being compounded and used according to different proportions as required, and also can be used as a crosslinking component in waterborne leather finishing, waterborne adhesives and waterborne ink.
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 hydroxysulfonic acid-type aqueous polyurethane curing agent and the two-component aqueous coating were measured by the following methods:
determining the NCO content of the hydroxysulfonic acid type waterborne polyurethane curing agent by using a di-n-butylamine titration method according to GB/T12009; the viscosity of the hydroxysulfonic acid type aqueous polyurethane curing agent was measured using an NDJ-1 type rotational viscometer according to GB/T12009.3-89; measuring the coating hardness according to GB T6739-2006; the adhesion of the coating film was 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; determining the alcohol resistance of the coating according to GB-1763-79; 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.
Example 1
(1) Preparation of 2-epichlorohydrin-1-ethanesulfonic acid
The raw material components and the dosage are shown in the following table 1:
TABLE 1
The preparation process comprises the following steps: mixing hydroxyethyl sulfonic acid and N, N-dimethylformamide, adding into a three-neck round-bottom flask equipped with a mechanical stirring pipe, a reflux pipe and a thermometer, and slowly adding epoxy chloropropane and dibutyltin dilaurate into the system within 15 min. The mixture is stirred evenly and then heated to 80 ℃ for reaction for 5 h. And cooling to room temperature, and then washing the mixture by using acetone to obtain a light yellow liquid product.
(2) Preparation of the waterborne polyurethane curing agent:
the raw material components and the dosage are shown in the following table 2:
TABLE 2
The preparation process comprises the following steps: under the protection of nitrogen, HDI tripolymer and 2-epichlorohydrin-1-ethanesulfonic acid are fully and uniformly mixed at room temperature. The mixture was transferred to a four-necked round bottom flask equipped with mechanical stirring, reflux tube, thermometer and nitrogen inlet and outlet. And (3) uniformly stirring the mixture, heating to 60 ℃, reacting for 2h until the NCO content of the system reaches a theoretical value, adding a neutralizing agent for neutralization, finally adding methyl p-toluenesulfonate to terminate the reaction, keeping the temperature for 30min, stirring for 15min under the vacuum degree of-0.1 MPa, removing the residual neutralizing agent from the reaction, cooling to room temperature, and discharging.
(3) Preparing a two-component water-based paint:
the performance of the waterborne polyurethane curing agent is as follows: the solid content was 100%, the viscosity (25 ℃ C.) was 2000 mPas, 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 3:
(4) performance of two-component water paint
TABLE 3 combination of properties of two-component aqueous coating
From example 1, it can be seen that the theoretical NCO value can be reached by reacting the hydroxysulfonic acid hydrophilic monomer modified polyisocyanate at 60 ℃ for 2 hours, and the conventional sulfamic acid modified polyisocyanate can be reacted completely only by reacting at 90 ℃ for 4 hours, so that the novel structure hydrophilic monomer synthesized by the method has the advantages of mild reaction conditions and high reaction speed, and can save a large amount of energy consumption in the actual production process. From the film coating performance of the curing agent, the curing agent modified by the novel-structure hydroxysulfonic acid hydrophilic monomer has low viscosity, the NCO content can reach more than 21%, and the prepared film has the advantages of good compatibility with hydroxy resin and high glossiness, and has excellent water resistance, alkali resistance and solvent resistance.
DE4433929A and EP0703255 disclose hydrophilic modification of polyisocyanates with short-chain hydroxysulfonic acids such as isethionic acid and hydroxypropylsulfonic acid to produce curing agents with good water dispersibility, but tend to crystallize and have poor storage stability. The hydrophilic monomer of the hydroxysulfonic acid prepared by the invention has the advantages that the problem of crystallization does not occur, the modified curing agent has low viscosity and clear and transparent appearance, the main reason is that the short-chain hydroxysulfonic acid has higher order degree and tends to crystallize in the modification process, and the branched chain is introduced into the structure of the short-chain straight-chain hydroxysulfonic acid, so that the order degree of the molecular arrangement is damaged, and the problem of crystallization does not occur in the modification process.
The invention patent CN104448232A of China successfully grafts 4-cyclohexylamino-butanesulfonic acid on polyisocyanate to prepare the waterborne polyurethane curing agent by improving the synthesis process, the prepared waterborne curing agent has good water dispersibility and high coating film gloss, but the 4-cyclohexylamino-butanesulfonic acid has groups with larger steric hindrance such as cyclohexyl and butyl, so the 4-cyclohexylamino-butanesulfonic acid has to react at more than 90 ℃ in the hydrophilic modification process, and the reaction yield is low and can not react completely. Compared with the traditional curing agent, the hydrophilic modifier has similar film coating performance, but the hydrophilic modifier synthesized by the invention is a hydroxysulfonic acid monomer, has higher reaction activity with isocyanate, can normally react only at 50-80 ℃, does not need to add a catalyst, and is a curing agent type which saves a large amount of energy consumption.
The invention adopts the hydroxysulfonic acid hydrophilic monomer to modify the polyisocyanate, the obtained waterborne polyurethane curing agent has good compatibility with hydroxyl resins such as acrylic resin, alkyd resin, polyester resin and the like, and can be used for building interior and exterior walls, bridges, industrial products and furniture coatings by compounding and using according to different proportions, and also can be used as a crosslinking component in waterborne leather finishing, waterborne adhesives and water-based ink.
Example 2:
(1) preparation of 2-epoxypropyl-1-propanesulfonic acid
The raw material components and the use amounts are as follows in table 4:
TABLE 4
The preparation process comprises the following steps: mixing hydroxypropyl sulfonic acid and xylene, adding into a three-neck round-bottom flask equipped with a mechanical stirring tube, a reflux tube and a thermometer, and slowly adding propylene oxide and tetrabutylammonium bromide into the system within 15 min. The mixture is stirred evenly and then heated to 100 ℃ for reaction for 8 h. And cooling to room temperature, and then carrying out liquid separation washing on the mixture by using ethyl acetate to obtain a light yellow liquid product.
(2) Preparation of the waterborne 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, HDI tripolymer and 2-epoxypropyl-1-propanesulfonic acid are fully and uniformly mixed at room temperature. The mixture was transferred to a four-necked round bottom flask equipped with mechanical stirring, reflux tube, thermometer and nitrogen inlet and outlet. And (3) uniformly stirring the mixture, heating to 60 ℃, reacting for 1.5h until the NCO content of the system reaches a theoretical value, adding a neutralizing agent for neutralization, finally adding methyl p-toluenesulfonate to terminate the reaction, keeping the temperature for 30min, stirring for 15min under the vacuum degree of-0.1 MPa, removing the residual neutralizing agent from the reaction, cooling to room temperature, and discharging.
(3) Preparing a two-component water-based paint:
the performance of the waterborne polyurethane curing agent is as follows: the solid content was 100%, the viscosity (25 ℃ C.) was 3500 mPas, the NCO mass content was 20.78%, 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 6:
(4) performance of two-component water paint
TABLE 6 combination properties of two-component waterborne coatings
Example 3:
(1) preparation of 2-epoxycyclohexyl-4-benzenesulfonic acid
The raw material components and the dosage are shown in the following table 7:
TABLE 7
The preparation process comprises the following steps: 4-hydroxybenzenesulfonic acid and toluene are mixed, added into a three-neck round-bottom flask with a mechanical stirring device, a reflux pipe and a thermometer, and epoxy cyclohexane and boron trifluoride diethyl etherate are slowly added into the system within 15 min. The mixture is stirred evenly and then heated to 80 ℃ for reaction for 10 h. And cooling to room temperature, and then washing the mixture by using 1, 4-dioxane to obtain a light yellow liquid product.
(2) Preparation of the waterborne polyurethane curing agent:
the raw material components and the dosage are as follows in the following table 8:
TABLE 8
The preparation process comprises the following steps: under the protection of nitrogen, the TDI trimer and the 2-epoxy cyclohexyl-4-benzene sulfonic acid are fully and uniformly mixed at room temperature. The mixture was transferred to a four-necked round bottom flask equipped with mechanical stirring, reflux tube, thermometer and nitrogen inlet and outlet. And (3) uniformly stirring the mixture, heating to 60 ℃, reacting for 1h until the NCO content of the system reaches a theoretical value, adding a neutralizing agent for neutralization, finally adding methyl p-toluenesulfonate to terminate the reaction, keeping the temperature for 30min, stirring for 15min under the vacuum degree of-0.1 MPa, removing the residual neutralizing agent from the reaction, cooling to room temperature, and discharging.
(3) Preparing a two-component water-based paint:
the performance of the waterborne polyurethane curing agent is as follows: the solids content was 40%, the viscosity (25 ℃) was 2500 mPas, the NCO mass content was 11.67%, 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 9:
(4) performance of two-component water paint
TABLE 9 combination of properties of two-component waterborne coatings
Example 4:
(1) preparation of 2-oxirane-1-oxysulfonic acid
The raw material components and the dosage are as follows in table 10:
watch 10
The preparation process comprises the following steps: hydroxylamine oxysulphonic acid and N, N-dimethylformamide are mixed and then added into a three-neck round-bottom flask provided with a mechanical stirring pipe, a reflux pipe and a thermometer, and ethylene oxide and dibutyltin dilaurate are slowly added into the system within 15 min. The mixture is stirred evenly and then heated to 80 ℃ for reaction for 5 h. And cooling to room temperature, and then separating and washing the mixture by using butyl acetate to obtain a light yellow liquid product.
(2) Preparation of the waterborne polyurethane curing agent:
the raw material components and the dosage are as follows in table 11:
TABLE 11
The preparation process comprises the following steps: under the protection of nitrogen, IPDI tripolymer and 2-ethylene oxide-1-oxysulfonic acid are fully and uniformly mixed at room temperature. The mixture was transferred to a four-necked round bottom flask equipped with mechanical stirring, reflux tube, thermometer and nitrogen inlet and outlet. And (3) uniformly stirring the mixture, heating to 70 ℃, reacting for 3 hours until the NCO content of the system reaches a theoretical value, adding a neutralizing agent for neutralization, finally adding methyl p-toluenesulfonate to terminate the reaction, keeping the temperature for 30 minutes, stirring for 15 minutes under the vacuum degree of-0.1 MPa, removing the residual neutralizing agent from the reaction, cooling to room temperature, and discharging.
(3) Preparing a two-component water-based paint:
the performance of the waterborne polyurethane curing agent is as follows: the solid content was 70%, the viscosity (25 ℃) was 4000 mPas, the NCO mass content was 16.02%, 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 12:
(4) performance of two-component water paint
TABLE 12 combination of properties of two-component waterborne coatings
Example 5
(1) Preparation of 2-phenyl glycidyl ether-1-ethanesulfonic acid
The raw material components and the use amounts are as follows in table 13:
watch 13
The preparation process comprises the following steps: mixing the hydroxyethyl sulfonic acid and the xylene, adding the mixture into a three-neck round-bottom flask provided with a mechanical stirring pipe, a reflux pipe and a thermometer, and slowly adding the phenyl glycidyl ether and the tetrabutylammonium bromide into the system within 15 min. The mixture is stirred evenly and then heated to 80 ℃ for reaction for 5 h. And cooling to room temperature, and then washing the mixture by using acetone to obtain a light yellow liquid product.
(2) Preparation of the waterborne polyurethane curing agent:
the raw material components and the dosage are shown in the following table 14:
TABLE 14
The preparation process comprises the following steps: under the protection of nitrogen, HDI trimer and 2-phenyl glycidyl ether-1-ethanesulfonic acid are fully and uniformly mixed at room temperature. The mixture was transferred to a four-necked round bottom flask equipped with mechanical stirring, reflux tube, thermometer and nitrogen inlet and outlet. And (3) uniformly stirring the mixture, heating to 50 ℃, reacting for 1h until the NCO content of the system reaches a theoretical value, adding a neutralizing agent for neutralization, finally adding methyl p-toluenesulfonate to terminate the reaction, keeping the temperature for 30min, stirring for 15min under the vacuum degree of-0.1 MPa, removing the residual neutralizing agent from the reaction, cooling to room temperature, and discharging.
(3) Preparing a two-component water-based paint:
the performance of the waterborne polyurethane curing agent is as follows: the solid content was 100%, the viscosity (25 ℃) was 6000 mPas, the NCO mass content was 20.33%, 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 15:
(4) performance of two-component water paint
TABLE 15 combination of two-component aqueous coatings
Example 6
(1) Preparation of 2-octyl glycidyl ether-1-benzenesulfonic acid
The raw material components and the amounts are as follows in table 16:
TABLE 16
The preparation process comprises the following steps: 4-hydroxybenzenesulfonic acid and tetrahydrofuran are mixed and then added into a three-neck round-bottom flask with a mechanical stirring device, a reflux pipe and a thermometer, and octyl glycidyl ether and boron trifluoride diethyl etherate are slowly added into the system within 15 min. The mixture is stirred evenly and then heated to 80 ℃ for reaction for 10 h. And cooling to room temperature, and then washing the mixture by using N, N-dimethylformamide to obtain a light yellow liquid product.
(2) Preparation of the waterborne polyurethane curing agent:
the raw material components and the use amounts are as follows in table 17:
TABLE 17
The preparation process comprises the following steps: under the protection of nitrogen, HDI biuret and 2-octyl glycidyl ether-1-benzene sulfonic acid are fully and uniformly mixed at room temperature. The mixture was transferred to a four-necked round bottom flask equipped with mechanical stirring, reflux tube, thermometer and nitrogen inlet and outlet. And (3) uniformly stirring the mixture, heating to 60 ℃, reacting for 2h until the NCO content of the system reaches a theoretical value, adding a neutralizing agent for neutralization, finally adding methyl p-toluenesulfonate to terminate the reaction, keeping the temperature for 30min, stirring for 15min under the vacuum degree of-0.1 MPa, removing the residual neutralizing agent from the reaction, cooling to room temperature, and discharging.
(3) Preparing a two-component water-based paint:
the performance of the waterborne polyurethane curing agent is as follows: the solid content was 100%, the viscosity (25 ℃) was 8000 mPas, the NCO mass content was 18.46%, 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 18:
(4) performance of two-component water paint
TABLE 18 combination of two-component waterborne coatings
Example 7
(1) Preparation of 2-epichlorohydrin-1-oxysulfonic acid
The raw material components and the amounts are as follows in table 19:
watch 19
The preparation process comprises the following steps: hydroxylamine oxysulphonic acid and N, N-dimethylformamide are mixed and then added into a three-neck round-bottom flask provided with a mechanical stirring pipe, a reflux pipe and a thermometer, and epoxy chloropropane and dibutyltin dilaurate are slowly added into the system within 15 min. The mixture is stirred evenly and then heated to 80 ℃ for reaction for 5 h. And cooling to room temperature, and then washing the mixture by using acetone to obtain a light yellow liquid product.
(2) Preparation of the waterborne polyurethane curing agent:
the raw material components and the dosage are as follows 20:
watch 20
The preparation process comprises the following steps: under the protection of nitrogen, HDI tripolymer and 2-epichlorohydrin-1-oxysulfonic acid are fully and uniformly mixed at room temperature. The mixture was transferred to a four-necked round bottom flask equipped with mechanical stirring, reflux tube, thermometer and nitrogen inlet and outlet. And (3) uniformly stirring the mixture, heating to 50 ℃ for reaction for 2h until the NCO content of the system reaches a theoretical value, adding a neutralizing agent for neutralization, finally adding methyl p-toluenesulfonate to terminate the reaction, keeping the temperature for 30min, stirring for 15min under the vacuum degree of-0.1 MPa, removing the residual neutralizing agent from the reaction, cooling to room temperature, and discharging.
(3) Preparing a two-component water-based paint:
the performance of the waterborne polyurethane curing agent is as follows: the solids content was 100%, the viscosity (25 ℃ C.) was 3700 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 stirred uniformly, the mixture is filtered by 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 21:
(4) performance of two-component water paint
TABLE 21 combination of two-component waterborne coatings
Example 8
(1) Preparation of 2-epoxycyclohexyl-1-ethanesulfonic acid
The raw material components and the use amounts are as follows in table 22:
TABLE 22
The preparation process comprises the following steps: mixing hydroxyethyl sulfonic acid and N, N-dimethylformamide, adding into a three-neck round-bottom flask equipped with a mechanical stirring, a reflux pipe and a thermometer, and slowly adding epoxy cyclohexane and tetrabutylammonium bromide into the system within 15 min. The mixture is stirred evenly and then heated to 80 ℃ for reaction for 10 h. And cooling to room temperature, and then carrying out liquid separation washing on the mixture by using ethyl acetate to obtain a light yellow liquid product.
(2) Preparation of the waterborne polyurethane curing agent:
the raw material components and the amounts are as follows 23:
TABLE 23
The preparation process comprises the following steps: under the protection of nitrogen, HDI tripolymer and 2-epoxy cyclohexyl-1-ethanesulfonic acid are fully and uniformly mixed at room temperature. The mixture was transferred to a four-necked round bottom flask equipped with mechanical stirring, reflux tube, thermometer and nitrogen inlet and outlet. And (3) uniformly stirring the mixture, heating to 60 ℃, reacting for 4 hours until the NCO content of the system reaches a theoretical value, adding a neutralizing agent for neutralization, finally adding methyl p-toluenesulfonate to terminate the reaction, keeping the temperature for 30 minutes, stirring for 15 minutes under the vacuum degree of-0.1 MPa, removing the residual neutralizing agent from the reaction, cooling to room temperature, and discharging.
(3) Preparing a two-component water-based paint:
the performance of the waterborne polyurethane curing agent is as follows: the solid content was 100%, the viscosity (25 ℃) was 1700 mPas, the NCO mass content was 20.42%, 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 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 24:
(4) performance of two-component water paint
TABLE 24 combination of two-component waterborne coatings
It should be noted that the scope of the present invention is not limited by 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 construed as equivalents and included in the scope of the present invention.
Claims (10)
1. A hydroxysulfonic acid hydrophilic monomer characterized by: the chemical general formula is as follows:
sulfonic group-SO in the hydroxysulfonic acid hydrophilic monomer3The mass content of H is 10-65%; r1Is one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, phenyl, tert-butyl, cyclohexyl, benzyl, phenethyl and halogen elements; r2Is an alkane containing 1 to 4 carbon atoms or a hydrogen atom.
2. The method of claim 1, wherein the hydrophilic monomer is selected from the group consisting of: firstly, mixing short-chain hydroxysulfonic acid with an organic solvent, then dropwise adding an epoxy compound and a catalyst into the mixture, reacting for 4-24h at 25-100 ℃, and separating and washing the reaction mixture to obtain a hydroxysulfonic acid hydrophilic monomer; the short-chain hydroxysulfonic acid is one or more of hydroxyethylsulfonic acid, hydroxypropyl sulfonic acid, hydroxylamine oxysulfonic acid and 4-hydroxybenzenesulfonic acid.
3. The method of preparing a hydrophilic monomer of hydroxysulfonic acid according to claim 2, wherein: the catalyst is one or more of boron trifluoride diethyl etherate, tetrabutylammonium bromide and dibutyltin dilaurate; the epoxy compound is one of ethylene oxide, propylene oxide, cyclohexene oxide, epichlorohydrin, phenyl glycidyl ether, benzyl glycidyl ether and octyl glycidyl ether; the molar ratio of the epoxy compound to the hydroxysulfonic acid is 1.0-10.0: 1.
4. The method of preparing a hydrophilic monomer of hydroxysulfonic acid according to claim 2, wherein: the organic solvent is one or more of toluene, xylene, N-dimethylformamide, tetrahydrofuran, 1, 4-dioxane, acetone, diethyl ether and ethyl acetate.
5. The method of preparing a hydrophilic monomer of hydroxysulfonic acid according to claim 2, wherein: the volume ratio of the short-chain hydroxysulfonic acid to the organic solvent is 1: 0.5-10; the solvent for washing is one or more of N, N-dimethylformamide, 1, 4-dioxane, acetone, diethyl ether, ethyl acetate and butyl acetate.
6. The use of the hydrophilic monomer of hydroxysulfonic acid according to claim 1 in a two-component aqueous polyurethane curing agent, wherein: according to the mass percentage of the raw materials, 1.0-10.0% of hydroxysulfonic acid hydrophilic monomer and 85-95% of polyisocyanate are fully mixed for 10-30 minutes at normal temperature, the temperature is raised to 50-80 ℃ under the protection of nitrogen, the reaction lasts for 1-2 hours until the NCO content of the system reaches the theoretical value, a neutralizing agent is added for neutralization for 10-30 minutes, then a polymerization inhibitor is added to terminate the reaction, the reaction is stirred, and the temperature is reduced to the room temperature, so that the waterborne polyurethane curing agent is obtained.
7. The use of a hydroxysulfonic acid hydrophilic monomer according to claim 6 in an aqueous two-component polyurethane curing agent, wherein: the polyisocyanate is one or more of trimer of hexamethylene diisocyanate, biuret polyisocyanate, isophorone diisocyanate trimer and toluene diisocyanate trimer; the average functionality of the polyisocyanate is at least 1.8, and the mass content of NCO is 18-30%;
the neutralizer is one or more of triethylamine, N-dimethylcyclohexylamine, N-dimethylbutylamine, N-dimethyl-2-ethylhexylamine, N-diethylmethylamine, N-dimethylformamide, N-methylmorpholine and tetraethylmethylenediamine; the mole ratio of the neutralizing agent to the hydroxysulfonic acid is 1-1.5;
the polymerization inhibitor is one of methyl p-toluenesulfonate, benzoyl chloride and hydroquinone;
the stirring is carried out for 10-20min under the vacuum degree of 0.1-0.2MPa, and the residual neutralizing agent in the reaction is removed.
8. The use of the hydroxysulfonic acid hydrophilic monomer of claim 6 in an aqueous two-component polyurethane curing agent, wherein: the solid content of the obtained waterborne polyurethane curing agent is 99-100 wt%, the NCO mass content is 14-23%, the viscosity at 25 ℃ is 1500-6500mPa & s, and the appearance is colorless transparent or light yellow transparent viscous liquid.
9. The use of the hydroxysulfonic acid hydrophilic monomer of claim 6 in an aqueous two-component polyurethane curing agent, wherein: the waterborne two-component polyurethane curing agent and the waterborne polyurethane hydroxyl component are mixed and compounded for use, and the molar ratio of NCO/OH is controlled to be 1.0-4.5; the hydroxyl component of the waterborne polyurethane comprises waterborne hydroxyl resin and auxiliary materials, wherein the auxiliary materials comprise a defoaming agent, a leveling agent and a thickening agent.
10. The use of a hydroxysulfonic acid hydrophilic monomer in an aqueous two-component polyurethane curing agent according to claim 9, wherein: the water-based hydroxyl resin comprises H2M0019, H2M0114, H2M0115, MG011, MG057 and double-component semi-gloss varnish of Xiupo chemical company Limited;
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, BYK 378 and BYK 346;
the leveling agent is one of TEGO-450, TEGO-280, BYK 333, BYK346 and BYK 381;
the thickening agent is one of RW-8W, A401, U902, 924NP and U300.
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