CN111233723B - Hydroxyl-containing sulfonate and preparation method and application thereof - Google Patents

Hydroxyl-containing sulfonate and preparation method and application thereof Download PDF

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CN111233723B
CN111233723B CN202010066790.9A CN202010066790A CN111233723B CN 111233723 B CN111233723 B CN 111233723B CN 202010066790 A CN202010066790 A CN 202010066790A CN 111233723 B CN111233723 B CN 111233723B
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hydroxyl
containing sulfonate
curing agent
waterborne polyurethane
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CN111233723A (en
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张心亚
戴飞
莫锐彬
汪辉辉
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/60—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
    • C07C323/66—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfo, esterified sulfo or halosulfonyl groups, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7812—Nitrogen containing -N-C=0 groups containing amide groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

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Abstract

The invention discloses a hydroxyl-containing sulfonate and a preparation method and application thereof. Dissolving a vinyl sulfonic acid monomer in water for dilution, adding a sulfydryl reducing agent and a neutralizing agent for neutralization, reacting at 40-80 ℃ for 2-6h, carrying out vacuum filtration on a reaction product to remove excessive reducing agent and neutralizing agent, and absorbing waste gas by using an ammonium persulfate solution to obtain a hydroxyl-containing sulfonate intermediate; and reacting the product with polyisocyanate to prepare the waterborne polyurethane curing agent, wherein the curing agent has the advantages of easy water dispersion, low viscosity, high NCO content and good matching property with hydroxyl resin. The preparation process of the hydroxyl-containing sulfonate and waterborne polyurethane curing agent is simple, the reaction conditions are mild, and the prepared waterborne polyurethane curing agent and the waterborne hydroxyl resin are compounded to prepare the two-component waterborne polyurethane coating which has the advantages of good water resistance, good corrosion resistance, high hardness and the like.

Description

Hydroxyl-containing sulfonate and preparation method and application thereof
Technical Field
The invention belongs to the technical field of water-based paint, and relates to novel hydroxyl-containing sulfonate, a preparation method and application thereof, wherein the novel hydroxyl-containing sulfonate can be used for preparing a water-based polyurethane curing agent, and the prepared curing agent has good water dispersibility, high NCO content, low viscosity and excellent hydroxyl resin compatibility; the waterborne polyurethane curing agent can be used as a crosslinking part of a waterborne two-component polyurethane coating, and after the waterborne two-component polyurethane curing agent is compounded with waterborne hydroxyl resin, a prepared paint film has high hardness and excellent water resistance and corrosion resistance.
Background
With the increasingly popular concept of green coating industry, the prospect of the two-component waterborne polyurethane is also increasingly broad. On the other hand, two-component aqueous polyurethanes are comparable in performance to solvent-borne polyurethane coatings, which has led to an increasing development of two-component aqueous polyurethane coatings. Meanwhile, with the strict limitation of the content of Volatile Organic Compounds (VOC) in a coating system in the international coating standard, the solvent-based coating is forced to fade out of the market gradually, and the development of the environment-friendly water-based coating with low pollution and high performance is promoted. Further promotes the rapid development of the water-based polyisocyanate curing agent and is widely applied to a plurality of fields. The curing agent applied to the two-component waterborne polyurethane is required to have good solubility, miscibility with other resins, enough functionality and reactivity and low toxicity.
The polyisocyanate component can be easily dispersed in the aqueous hydroxyl component by an external emulsification method or an internal emulsification method. The external emulsification method is to add an ionic or nonionic emulsifier into a system to wrap the surface of polyisocyanate to realize water dispersibility, but the method has the defects of coarse particles after dispersion, short adaptation period and poor medium resistance of a coating film. At present, an internal emulsification method is mostly adopted, hydrophilic components are used for chemically modifying polyisocyanate, and after the prepared product is mixed with water, a structure with hydrophilic groups facing to a water phase is formed, so that the structure not only protects isocyanate groups, but also ensures that a polyisocyanate dispersed phase is in a stable state due to mutual repulsion of the hydrophilic groups. At present, non-ionic or anionic hydrophilic monomers are mostly adopted to carry out hydrophilic modification on polyisocyanates.
The non-ionic hydrophilic modified polyisocyanate refers to that the polyisocyanate (such as HDI or IPDI polyisocyanate) is subjected to hydrophilic modification by using polyether polyol, and-OH on a polyether polyol molecular chain is reacted with partial-NCO in the polyisocyanate, so that the polyisocyanate can be easily dispersed in water by manually stirring after modification because epoxy groups in the polyether polyol have hydrophilicity. Commonly used nonionic hydrophilic modifiers include polyethylene glycol, polypropylene glycol, polyethylene glycol monomethyl ether, and copolymers of ethylene oxide and propylene oxide. However, the use of nonionic modified curing agents is inferior in water resistance and tends to crystallize. The invention patents CN105669946A, CN101381443 and the like adopt different types of polyether as hydrophilic modifiers to successfully prepare the waterborne polyurethane curing agent, but the technology introduces a large amount of polyether in the modification process, thereby not only reducing the NCO content of the curing agent, but also greatly increasing the viscosity of the curing agent, further increasing the consumption of the curing agent and the viscosity of a two-component waterborne polyurethane coating during paint preparation, and improving the construction difficulty. In addition, too high polyether segment easily causes the problems of poor stability of the curing agent, low hardness of the paint film, poor water resistance and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide hydroxyl-containing sulfonate which can be used for modifying a polyisocyanate component, improving the water dispersibility of the polyisocyanate component, facilitating the construction of a two-component waterborne polyurethane coating and having excellent film-forming property and a preparation method thereof.
The invention also aims to provide the application of the hydroxyl-containing sulfonate in the waterborne polyurethane curing agent.
The hydroxyl-containing sulfonate is obtained by reacting a mercapto reducing agent with a vinyl sulfonic acid monomer, adding a neutralizing agent for neutralization, and modifying a polyisocyanate component by using the reaction of hydroxyl and NCO, so that the hydrophilic property of the sulfonate enables the polyisocyanate component to be stably dispersed in water. The prepared waterborne polyurethane curing agent has good water dispersibility, low viscosity, high NCO content, excellent stability and excellent waterborne hydroxyl resin matching property. The waterborne polyurethane curing agent and the waterborne hydroxyl resin are compounded to obtain the waterborne polyurethane coating, and the prepared paint film has high hardness and excellent water resistance and chemical resistance, and can be widely applied to the fields of buildings, furniture, terraces and the like as a good crosslinking component.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of hydroxyl-containing sulfonate comprises the following steps:
(1) dissolving a vinyl sulfonic acid monomer in water for dilution, adding a sulfydryl reducing agent, stirring, heating to 40-80 ℃, preserving heat, and reacting for 1-3 hours to obtain a reactant of the vinyl sulfonic acid monomer and the sulfydryl reducing agent; the vinyl sulfonic acid monomer is one or more of sodium vinyl sulfonate, sodium allyl sulfonate, 2-acrylamido-2-methylpropanesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid sodium; the mercapto reducing agent is one or more of mercaptoethanol, mercaptopropanol, mercaptobenzyl alcohol and mercaptobutanol;
(2) adding a neutralizing agent into the reactant obtained in the step (1), preserving the heat at 40-80 ℃, stirring and reacting for 1-3 hours, and removing the unreacted sulfhydryl reducing agent and the neutralizing agent in the reaction system to obtain the hydroxyl-containing sulfonate.
In order to further achieve the object of the present invention, preferably, the amount of water added in step (1) is 80-120% of the mass of the vinylsulfonic acid monomer, and the addition mode is one-time addition.
Preferably, the addition amount of the mercapto group reducing agent in step (1) is 200-300% of the mass of the vinyl sulfonic acid monomer, and the addition manner is one-time addition.
Preferably, the neutralizing agent in the step (2) is one or more of triethylamine, triethanolamine, dimethylethanolamine and diethylethanolamine; the addition amount of the neutralizing agent is 120-150% of the mass of the vinyl sulfonic acid monomer, and the addition mode is one-time addition.
Preferably, the step (2) of removing the unreacted thiol reducing agent and the neutralizing agent in the reaction system is removing by vacuum filtration; and (2) absorbing the redundant waste gas by using an ammonium persulfate solution.
The hydroxyl-containing sulfonate prepared by the preparation method has the chemical formula:
Figure BDA0002376210140000031
wherein M is a cation.
The application of the hydroxyl-containing sulfonate in the waterborne polyurethane curing agent comprises the following steps: under the protection of nitrogen, according to the mass percentage of the raw materials, 1.0-9.0% of hydroxyl-containing sulfonate and 90-96% of polyisocyanate are stirred and reacted for 2-4 hours at the temperature of 60-100 ℃, then 1-3% of neutralizing agent is dripped, the temperature is reduced to 50-80 ℃, the reaction lasts for 30-60 minutes, the reaction is carried out after the temperature is reduced to the room temperature, and the water-based polyurethane curing agent is obtained.
Preferably, the polyisocyanate has an average functionality of at least 1.8 and an NCO content of 20-30% by mass; the polyisocyanate is one or more of Hexamethylene Diisocyanate (HDI) trimer, Toluene Diisocyanate (TDI) trimer, isophorone diisocyanate trimer (IPDI) trimer and hexamethylene diisocyanate trimer; the neutralizing agent is one or more of triethylamine, triethanolamine, N dimethyl cyclohexylamine, dimethyl ethanolamine, N-diethyl methylamine and N, N-dimethyl formamide; the mol ratio of the neutralizing agent to the hydroxyl-containing sulfonate is 1.0-1.5: 1.
Preferably, the solid content of the aqueous polyurethane curing agent is 100 wt%, the NCO mass content is 16-23%, the viscosity at 25 ℃ is 2000-50000mPa & s, and the appearance is colorless transparent or light yellow transparent liquid.
The application of the waterborne polyurethane curing agent in the waterborne polyurethane coating comprises the following steps: the obtained waterborne polyurethane curing agent and the waterborne hydroxyl component are compounded for use, and the molar ratio of NCO/OH is controlled to be 1.2-3.0:1, so that the waterborne polyurethane coating is prepared. Preferably, the hydroxyl component of the waterborne polyurethane comprises Bayer bicomponent hydroxyl acrylic emulsion Bayhydrol a 2546, Bayer bicomponent hydroxyl acrylic emulsion Bayhydrol a 2646, Wanhua bicomponent hydroxyl acrylic emulsion Antkote2033, Wanhua bicomponent hydroxyl acrylic emulsion Antkote2042, and Jia Baoli chemical group Limited company bicomponent hydroxyl acrylic emulsion H2D 012A.
After the hydroxyl-containing sulfonate is used for modifying polyisocyanate by a small amount, the water dispersibility of the polyurethane curing agent can be obviously improved, and the prepared waterborne polyurethane curing agent has low viscosity, high NCO content and excellent physical and chemical properties. The hydroxyl-containing sulfonate and the waterborne polyurethane curing agent have the advantages of cheap preparation raw materials, simple process, mild conditions, convenience and controllability, and contribution to realizing industrialization.
Compared with the prior art, the invention has the following advantages:
(1) the hydrophilic modification monomer containing the hydroxyl sulfonate is an anionic hydrophilic modification monomer containing the hydroxyl sulfonate, the sulfonic acid equivalent of monomer molecules is high, and compared with a sulfonate type anionic modifier which is commercially available for modification, the hydroxyl sulfonate adopted by the hydrophilic modification monomer containing the hydroxyl sulfonate has higher sulfonic acid content, so that the polyisocyanate component can obtain better water dispersibility by only adding a small amount of the hydrophilic modification monomer containing the hydroxyl sulfonate.
(2) According to the invention, the polyisocyanate component can obtain excellent water dispersibility by adding a small amount of hydrophilic modification monomer containing hydroxyl sulfonate, so that the preparation cost is greatly reduced, and the viscosity of the aqueous polyurethane curing agent is greatly reduced due to the low addition amount of the hydrophilic modification monomer, so that the viscosity of the aqueous polyurethane coating prepared by compounding the aqueous polyurethane curing agent and the aqueous hydroxyl resin is reduced, and the construction difficulty is reduced.
(3) In the process of preparing the waterborne polyurethane curing agent, no metal catalyst such as organic tin and the like is added, the waterborne polyurethane curing agent belongs to an environment-friendly coating, and the waterborne polyurethane curing agent does not harm human health and destroy ecological environment before and after the use process.
(4) The waterborne polyurethane curing agent prepared by the invention has good compatibility with hydroxyl resin, different hydroxyl resins are compounded according to different proportions according to the requirements of actual conditions, and the waterborne polyurethane curing agent can be applied to the fields of building interior and exterior walls, terraces, furniture coatings and the like.
(5) According to the preparation method, the hydroxyl-containing sulfonate hydrophilic modified monomer is prepared, no complex equipment is needed in the reaction process of preparing the waterborne polyurethane curing agent, the preparation process steps are simple, the operation is convenient, and the preparation method is suitable for large-scale industrial production.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate, but are not to be construed to limit the scope of the present invention as set forth in the appended claims.
In the following examples, percentages (%) are mass percentages unless otherwise specified. The NCO content was determined by the di-n-butylamine titration method in accordance with GB/T12009-2016; the viscosity was measured according to GB/T12009.3-2009 using a rotational viscometer of model NDJ-1; the solids content was determined according to GB/T2793-1995.
Example 1
A preparation method of hydroxyl-containing sulfonate comprises the following steps:
(1) dissolving 50g of 2-acrylamide-2-methylpropanesulfonic acid in 60g of water, putting the solution into a dry and clean four-neck flask provided with a stirrer and a thermometer, adding 120g of mercaptoethanol into the solution, heating the solution to 60 ℃, keeping the temperature, stirring and reacting for 2 hours to obtain a primary reactant.
(2) And (2) adding 75g of triethylamine into the reactant obtained in the step (1), and carrying out heat preservation and stirring reaction at 60 ℃ for 2 hours to obtain the hydroxyl-containing sulfonate. And removing the excess triethylamine and the oxidized mercaptoethanol by using vacuum filtration and ammonium persulfate washing gas.
(3) The preparation of the waterborne polyurethane curing agent comprises the following raw material components and the using amount of the waterborne polyurethane curing agent as shown in the following table 1:
TABLE 1
Figure BDA0002376210140000051
The preparation process comprises the following steps: under the protection of nitrogen, Hexamethylene Diisocyanate (HDI) trimer and hydroxyl-containing sulfonate are mixed and added into a four-neck round-bottom flask provided with a mechanical stirring pipe, a reflux pipe and a thermometer, the mixture is heated to 80 ℃ and is stirred and reacted for 3 hours under the condition of heat preservation, then triethylamine is added, the temperature is reduced to 60 ℃, the mixture is stirred and reacted for 1 hour under the condition of heat preservation, and the mixture is discharged after the temperature is reduced to the room temperature.
The waterborne polyurethane curing agent prepared by the method has the following properties: the solids content was 100%, the viscosity (25 ℃ C.) was 2200 mPas, the NCO content was 22.4%, the appearance was a colorless transparent liquid, and the average particle size of the dispersion was 132nm after addition of water.
(4) Preparing a two-component waterborne polyurethane coating:
weighing and metering the water-based hydroxyl resin (bi-component hydroxyl acrylic emulsion, Bayer Bayhydrol a 2546), putting the water-based hydroxyl resin into a dispersing barrel, adding 0.2 wt% of defoaming agent (Bick BYK-094), 0.2 wt% of leveling agent (Germany Di high TEGO-450) and 0.5 wt% of substrate wetting agent (Germany Di high TEGO-270), and dispersing for 20min at the rotating speed of 700rpm to obtain the water-based hydroxyl component. According to an NCO/OH molar ratio of 1.6: 1, adding the waterborne polyurethane curing agent prepared by the method into the mixture, and stirring for 3min until the mixture is uniform to obtain a two-component waterborne polyurethane coating, wherein the paint film performance of the two-component waterborne polyurethane coating is shown in the following table 2.
(5) Paint film performance of two-component waterborne polyurethane paint
TABLE 2 film properties of two-component aqueous polyurethane coatings
Figure BDA0002376210140000052
Bayer Bayhydur XP 2487 is a mainstream waterborne polyurethane curing agent in the market, the viscosity of the curing agent is about 5000mPa & s at 25 ℃, the viscosity is high, and the later construction mode is limited to a large extent. From the properties of the prepared waterborne polyurethane curing agent and the paint film properties of the bi-component waterborne polyurethane paint, the waterborne polyurethane curing agent prepared by the embodiment has lower viscosity, and after the waterborne polyurethane curing agent is added into water, the dispersion has smaller particle size and good surface water dispersibility. The paint film prepared from the bi-component waterborne polyurethane coating has better water resistance, luster and hardness, and shows that the paint film has better compatibility with hydroxyl resin and forms a more compact and smooth paint film.
Example 2
A preparation method of hydroxyl-containing sulfonate comprises the following steps:
(1) 50g of sodium vinylsulfonate is dissolved in 50g of water, the solution is put into a dry and clean four-neck flask provided with a stirrer and a thermometer, then 100g of mercaptopropanol is added into the solution, the solution is heated to 50 ℃, and the initial reactant is obtained after the reaction is carried out for 2 hours under the condition of heat preservation and stirring.
(2) Adding 60g of triethanolamine into the reactant obtained in the step (1), heating to 70 ℃, keeping the temperature, stirring and reacting for 1 hour to obtain the hydroxyl-containing sulfonate.
(3) The preparation of the waterborne polyurethane curing agent comprises the following raw material components in percentage by weight:
TABLE 3
Figure BDA0002376210140000061
The preparation process comprises the following steps: under the protection of nitrogen, Toluene Diisocyanate (TDI) trimer and hydroxyl-containing sulfonate are mixed and added into a four-neck round-bottom flask with a mechanical stirring pipe, a reflux pipe and a thermometer, the mixture is heated to 90 ℃ and is stirred and reacted for 4 hours under the condition of heat preservation, then N, N dimethyl cyclohexylamine is added, the mixture is cooled to 60 ℃ and is stirred and reacted for 1 hour under the condition of heat preservation, and the mixture is discharged after the temperature is reduced to the room temperature.
The waterborne polyurethane curing agent prepared by the method has the following properties: the solids content was 100%, the viscosity (25 ℃) was 3100 mPas, the NCO content was 20.3%, the appearance was a colorless transparent liquid, and the average particle size of the dispersion was 140nm after addition of water.
(4) Preparing a two-component waterborne polyurethane coating:
weighing and metering the water-based hydroxyl resin (bi-component hydroxyl acrylic emulsion, Bayer Bayhydrol a 2646), putting the water-based hydroxyl resin into a dispersing barrel, adding 0.2 wt% of defoaming agent (Bike BYK-094), 0.2 wt% of leveling agent (Germany Di high TEGO-450) and 0.5 wt% of substrate wetting agent (Germany Di high TEGO-270), and dispersing for 20min at the rotating speed of 700rpm to obtain the water-based hydroxyl component. According to an NCO/OH molar ratio of 1.6: 1, adding the waterborne polyurethane curing agent prepared by the method into the mixture, and stirring the mixture for 5min to be uniform to obtain a two-component waterborne polyurethane coating, wherein the paint film performance of the two-component waterborne polyurethane coating is shown in the following table 4.
(5) Paint film performance of two-component waterborne polyurethane paint
TABLE 4 film properties of two-component aqueous polyurethane coatings
Figure BDA0002376210140000071
Example 3
A preparation method of hydroxyl-containing sulfonate comprises the following steps:
(1) 60g of sodium allylsulfonate is dissolved in 60g of water, the solution is put into a dry and clean four-neck flask provided with a stirrer and a thermometer, then 150g of mercaptobenzyl alcohol is added into the solution, the solution is heated to 80 ℃, and the reaction is carried out for 3 hours under the condition of heat preservation and stirring, thus obtaining a primary reactant.
(2) And (2) adding 72g of dimethylethanolamine into the reactant obtained in the step (1), cooling to 60 ℃, preserving heat, stirring and reacting for 2 hours to obtain the hydroxyl-containing sulfonate.
(3) The preparation of the waterborne polyurethane curing agent comprises the following raw material components in percentage by weight:
TABLE 5
Figure BDA0002376210140000072
The preparation process comprises the following steps: under the protection of nitrogen, Hexamethylene Diisocyanate (HDI) trimer and hydroxyl-containing sulfonate are mixed and added into a four-neck round-bottom flask provided with a mechanical stirring pipe, a reflux pipe and a thermometer, the mixture is heated to 100 ℃ and is stirred and reacted for 4 hours under the condition of heat preservation, then triethanolamine is added, the temperature is reduced to 80 ℃, the mixture is stirred and reacted for 0.5 hour under the condition of heat preservation, and the mixture is discharged after the temperature is reduced to the room temperature.
The waterborne polyurethane curing agent prepared by the method has the following properties: the solids content was 100%, the viscosity (25 ℃ C.) was 4100 mPas, the NCO content was 20.1%, the appearance was a pale yellow transparent liquid, and the average particle size of the dispersion after addition of water was 148 nm.
(4) Preparing a two-component waterborne polyurethane coating:
weighing and metering the water-based hydroxyl resin (bi-component hydroxyl acrylic emulsion, Wanhua Antkote2033), putting the water-based hydroxyl resin into a dispersing barrel, adding 0.2 wt% of defoaming agent (ByK-094), 0.2 wt% of flatting agent (Germany Digao TEGO-450) and 0.5 wt% of substrate wetting agent (Germany Digao TEGO-270), and dispersing for 20min at the rotating speed of 700rpm to obtain the water-based hydroxyl component. According to an NCO/OH molar ratio of 1.6: 1, adding the waterborne polyurethane curing agent prepared by the method into the mixture, and stirring the mixture for 5min to be uniform to obtain a double-component waterborne polyurethane coating, wherein the paint film property of the double-component waterborne polyurethane coating is shown in the following table 6.
(5) Paint film performance of two-component waterborne polyurethane paint
TABLE 6 film properties of two-component aqueous polyurethane coatings
Figure BDA0002376210140000081
Example 4
A preparation method of hydroxyl-containing sulfonate comprises the following steps:
(1) 80g of 2-acrylamide-2-methyl sodium propanesulfonate is dissolved in 100g of water, the solution is put into a dry and clean four-neck flask provided with a stirrer and a thermometer, 200g of mercaptoethanol is added into the solution, the mixture is heated to 60 ℃, and the mixture is kept warm and stirred to react for 3 hours to obtain a primary reactant.
(2) And (2) adding 110g of diethylethanolamine into the reactant obtained in the step (1), cooling to 50 ℃, preserving heat, stirring, and reacting for 2 hours to obtain the hydroxyl-containing sulfonate.
(3) The preparation of the waterborne polyurethane curing agent comprises the following raw material components in percentage by weight:
TABLE 7
Figure BDA0002376210140000082
The preparation process comprises the following steps: under the protection of nitrogen, Hexamethylene Diisocyanate (HDI) tripolymer, isophorone diisocyanate tripolymer (IPDI) tripolymer and hydroxyl-containing sulfonate are mixed and added into a four-neck round-bottom flask provided with a mechanical stirring pipe, a reflux pipe and a thermometer, the mixture is heated to 80 ℃ and is stirred and reacted for 3 hours under the condition of heat preservation, then N, N-dimethyl methylamine is added, the temperature is reduced to 70 ℃, the mixture is stirred and reacted for 1 hour under the condition of heat preservation, and the mixture is discharged after the temperature is reduced to the room temperature.
The waterborne polyurethane curing agent prepared by the method has the following properties: the solids content was 100%, the viscosity (25 ℃) was 3600 mPas, the NCO content was 21.2%, the appearance was a colorless transparent liquid, and the average particle size of the dispersion after addition of water was 151 nm.
(4) Preparing a two-component waterborne polyurethane coating:
weighing and metering water-based hydroxyl resin (bi-component hydroxyl acrylic emulsion, Wanhua Antkote2042), putting the water-based hydroxyl resin into a dispersing barrel, adding 0.2 wt% of defoaming agent (ByK-094), 0.2 wt% of leveling agent (Germany Digao TEGO-450) and 0.5 wt% of substrate wetting agent (Germany Digao TEGO-270), and dispersing for 20min at the rotating speed of 700rpm to obtain the water-based hydroxyl component. According to an NCO/OH molar ratio of 1.6: 1, adding the waterborne polyurethane curing agent prepared by the method into the mixture, and stirring for 3min until the mixture is uniform to obtain a two-component waterborne polyurethane coating, wherein the paint film properties of the two-component waterborne polyurethane coating are shown in the following table 8.
(5) Paint film performance of two-component waterborne polyurethane paint
TABLE 8 paint film properties of two-component aqueous polyurethane coatings
Figure BDA0002376210140000091
Example 5
A preparation method of hydroxyl-containing sulfonate comprises the following steps:
(1) 50g of 2-acrylamide-2-methylpropanesulfonic acid is dissolved in 50g of water, the solution is put into a dry and clean four-neck flask provided with a stirrer and a thermometer, then 150g of mercaptoethanol is added into the solution, the mixture is heated to 80 ℃, and the mixture is kept warm and stirred for reaction for 3 hours to obtain a primary reactant.
(2) And (2) adding 110g of triethanolamine into the reactant obtained in the step (1), cooling to 60 ℃, preserving heat, stirring, and reacting for 1 hour to obtain the hydroxyl-containing sulfonate.
(3) The preparation of the waterborne polyurethane curing agent comprises the following raw material components and the using amount of the waterborne polyurethane curing agent are shown in the following table 9:
TABLE 9
Figure BDA0002376210140000101
The preparation process comprises the following steps: under the protection of nitrogen, Toluene Diisocyanate (TDI) tripolymer, Hexamethylene Diisocyanate (HDI) tripolymer and hydroxyl-containing sulfonate are mixed and added into a four-neck round-bottom flask provided with a mechanical stirring pipe and a thermometer, the mixture is heated to 90 ℃ and is stirred and reacted for 4 hours under the condition of heat preservation, then N, N-dimethylformamide is added, the temperature is reduced to 70 ℃, the mixture is stirred and reacted for 0.5 hour under the condition of heat preservation, and the mixture is discharged after the temperature is reduced to the room temperature.
The waterborne polyurethane curing agent prepared by the method has the following properties: the solid content was 100%, the viscosity (25 ℃) was 3800 mPas, the NCO content was 21.4%, the appearance was a pale yellow transparent liquid, and the average particle size of the dispersion after addition of water was 146 nm.
(4) Preparing a two-component waterborne polyurethane coating:
weighing and metering the water-based hydroxyl resin (bi-component hydroxyl acrylic emulsion H2D012A, Jia Bao Li chemical group Co., Ltd.), placing the water-based hydroxyl resin into a dispersion barrel, adding 0.2 wt% of defoaming agent (Bike BYK-094), 0.2 wt% of leveling agent (Germany Di gao TEGO-450) and 0.5 wt% of substrate wetting agent (Germany Di gao TEGO-270), and dispersing for 20min at the rotating speed of 700rpm to obtain the water-based hydroxyl component. According to an NCO/OH molar ratio of 1.6: 1, adding the waterborne polyurethane curing agent prepared by the method into the mixture, and stirring for 3min until the mixture is uniform to obtain a two-component waterborne polyurethane coating, wherein the paint film properties of the two-component waterborne polyurethane coating are shown in the following table 10.
(5) Paint film performance of two-component waterborne polyurethane paint
TABLE 10 paint film properties of two-component waterborne polyurethane coatings
Figure BDA0002376210140000102
The above-described embodiments are intended to be illustrative, rather than restrictive, and all such changes, modifications, substitutions, combinations, and simplifications that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (10)

1. A preparation method of hydroxyl-containing sulfonate is characterized by comprising the following steps:
(1) dissolving a vinyl sulfonic acid monomer in water for dilution, adding a sulfydryl reducing agent, stirring, heating to 40-80 ℃, preserving heat, and reacting for 1-3 hours to obtain a reactant of the vinyl sulfonic acid monomer and the sulfydryl reducing agent; the vinyl sulfonic acid monomer is one or more of sodium vinyl sulfonate, sodium allyl sulfonate, 2-acrylamido-2-methylpropanesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid sodium; the mercapto reducing agent is one or more of mercaptoethanol, mercaptopropanol, mercaptobenzyl alcohol and mercaptobutanol;
(2) adding a neutralizing agent into the reactant obtained in the step (1), preserving the heat at 40-80 ℃, stirring and reacting for 1-3 hours, and removing the unreacted sulfhydryl reducing agent and the neutralizing agent in the reaction system to obtain the hydroxyl-containing sulfonate.
2. The method for preparing a hydroxyl-containing sulfonate according to claim 1, characterized in that: the addition amount of the water in the step (1) is 80-120% of the mass of the vinyl sulfonic acid monomer, and the addition mode is one-time addition.
3. The method for preparing a hydroxyl-containing sulfonate according to claim 1, characterized in that: the adding amount of the mercapto reducing agent in the step (1) is 200-300% of the mass of the vinyl sulfonic acid monomer, and the adding mode is one-time adding.
4. The method for preparing a hydroxyl-containing sulfonate according to claim 1, characterized in that: the neutralizing agent in the step (2) is one or more of triethylamine, triethanolamine, dimethylethanolamine and diethylethanolamine; the addition amount of the neutralizing agent is 120-150% of the mass of the vinyl sulfonic acid monomer, and the addition mode is one-time addition.
5. The method for preparing a hydroxyl-containing sulfonate according to claim 1, characterized in that: the step (2) of removing the unreacted sulfhydryl reducing agent and neutralizing agent in the reaction system is removing by vacuum filtration; and (2) absorbing the redundant waste gas by using an ammonium persulfate solution.
6. A hydroxy-containing sulfonate characterized by being produced by the production method according to any one of claims 1 to 5, said hydroxy-containing sulfonate having a chemical formula:
Figure FDA0002376210130000011
wherein M is a cation.
7. The use of the hydroxyl-containing sulfonate of claim 6 in an aqueous polyurethane curing agent, wherein: under the protection of nitrogen, according to the mass percentage of the raw materials, 1.0-9.0% of hydroxyl-containing sulfonate and 90-96% of polyisocyanate are stirred and reacted for 2-4 hours at the temperature of 60-100 ℃, then 1-3% of neutralizing agent is dripped, the temperature is reduced to 50-80 ℃, the reaction lasts for 30-60 minutes, the reaction is carried out after the temperature is reduced to the room temperature, and the water-based polyurethane curing agent is obtained.
8. The use of the hydroxyl-containing sulfonate according to claim 7 in an aqueous polyurethane curing agent, wherein: the average functionality of the polyisocyanate is at least 1.8, and the mass content of NCO is 20-30%; the polyisocyanate is one or a mixture of hexamethylene diisocyanate trimer, toluene diisocyanate trimer, isophorone diisocyanate trimer and hexamethylene diisocyanate trimer; the neutralizing agent is one or more of triethylamine, triethanolamine, N dimethyl cyclohexylamine, dimethyl ethanolamine, N-diethyl methylamine and N, N-dimethyl formamide; the mol ratio of the neutralizing agent to the hydroxyl-containing sulfonate is 1.0-1.5: 1.
9. The use of the hydroxyl-containing sulfonate according to claim 7 in an aqueous polyurethane curing agent, wherein: the solid content of the waterborne polyurethane curing agent is 100 wt%, the NCO mass content is 16-23%, the viscosity at 25 ℃ is 2000-50000mPa & s, and the appearance is colorless transparent or light yellow transparent liquid.
10. The application of the waterborne polyurethane curing agent in the waterborne polyurethane coating is characterized in that: the waterborne polyurethane curing agent obtained in the claim 7 is compounded with waterborne hydroxyl components, and the molar ratio of NCO/OH is controlled to be 1.2-3.0:1, so that the waterborne polyurethane coating is prepared.
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