CN108610721B - Flame-retardant modified polyurethane curing agent, preparation method thereof and two-component polyurethane coating - Google Patents
Flame-retardant modified polyurethane curing agent, preparation method thereof and two-component polyurethane coating Download PDFInfo
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Abstract
The invention relates to the technical field of polyurethane curing agents, in particular to a flame-retardant modified polyurethane curing agent, a preparation method thereof and a two-component polyurethane coating, wherein the preparation method of the curing agent comprises the following steps: (1) preparing microcrystalline cellulose solution; (2) mixing the microcrystalline cellulose solution with nano magnesium hydroxide; (3) electrostatic spraying to obtain composite microsphere; (4) mixing and modifying 4, 4-diphenylmethane diisocyanate and composite microspheres to obtain a modified isocyanate solution; (5) and preparing the polyurethane curing agent. According to the invention, the nano magnesium hydroxide coated in the microcrystalline cellulose is added into the cross-linked structure of the curing agent, so that the hardness promotion property and the flame retardance of the curing agent to a paint film are improved. In addition, the invention also leads the curing agent to form a stable three-dimensional cross-linked structure by strictly controlling reaction conditions, improves the bonding degree of isocyanate and hydroxyl resin to the surface of microcrystalline cellulose, and endows the coating with lower viscosity and curing time.
Description
Technical Field
The invention relates to the technical field of polyurethane curing agents, in particular to a flame-retardant modified polyurethane curing agent, a preparation method and a two-component polyurethane coating.
Background
Polyurethane is a high molecular material containing repeated carbamate structural units, and organic solvents contained in the traditional solvent type polyurethane are inflammable, explosive and toxic, and have adverse effects on human bodies and the environment. With the enhancement of environmental awareness of people, the water-based polyurethane material is gradually paid attention.
The waterborne polyurethane takes water as a dispersion medium, has the advantages of environmental protection, no toxicity, safety and the like, and is widely applied to the fields of coatings, adhesives, synthetic leather, elastomers, building materials, fabric finishing, high molecular surfactants and the like. The waterborne polyurethane comprises single-component waterborne polyurethane and double-component waterborne polyurethane.
The single-component waterborne polyurethane can obtain the required service performance without adding a cross-linking agent, but has certain defects in the aspects of hardness, water resistance, solvent resistance and the like due to the linear structure, low cross-linking degree and hydrophilic groups in molecules, so that the application range is limited; the two-component waterborne polyurethane has high crosslinking density, excellent mechanical properties such as high coating hardness, good wear resistance, strong adhesive force and the like, and chemical properties such as water resistance, solvent resistance and the like, makes up for the defects of single-component waterborne polyurethane to a certain extent, can be used as high-grade materials, and is a trend for developing waterborne polyurethane.
The two-component waterborne polyurethane is mainly composed of a hydroxyl-containing polyol component and an isocyanate group (NCO) -containing waterborne curing agent component. The water-based isocyanate component is used as an important component of the water-based polyurethane, and the composition and the structure of the water-based isocyanate component determine the physical and mechanical properties, weather resistance, medium resistance and other chemical properties of the water-based polyurethane, so the research on the water-based polyurethane curing agent is the key of the water-based polyurethane entering the substantial application stage.
In view of industrial sources of raw materials, economic efficiency, physical properties of products, and the like, aromatic polyisocyanates which are currently in practical use in the polyurethane industry are mainly TDI, MDI, and IPDI. MDI has excellent performances of small toxicity, low cost, strong corrosion resistance, good flexibility and the like in an isocyanate family, but MDI lags behind the application of TDI on coating because of insufficient hardness and poor performance of a paint film existing in a molecular structure.
In addition, in order to make the two-component waterborne polyurethane have flame retardant property, a mechanical blending method is generally adopted to add the flame retardant in the process of preparing the coating, but the flame retardant is dispersed unevenly in the method, so that the demand on the quantity of the flame retardant is high, and the mechanical property of the coating is easily reduced.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a polyurethane curing agent, and a two-component polyurethane coating prepared by using the curing agent has the characteristics of high hardness, good flexibility, strong impact resistance, flame retardance and the like.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a flame-retardant modified polyurethane curing agent comprises the following steps:
(1) dissolving microcrystalline cellulose in a chlorinated 1-methyl-3-butylimidazolium salt ionic liquid at a mass ratio of 4-10:100 at 70-90 ℃ to form a microcrystalline cellulose solution;
(2) adding nano magnesium hydroxide into the microcrystalline cellulose solution obtained in the step (1), and uniformly stirring to obtain a suspension, wherein the nano magnesium hydroxide accounts for 2-6wt% of the suspension;
(3) performing electrostatic spraying on the suspension obtained in the step (2) to obtain composite microspheres;
(4) dissolving 4, 4-diphenylmethane diisocyanate in an organic solvent to obtain a mixed solution, adding the composite microspheres obtained in the step (3) into the mixed solution, performing ultrasonic dispersion, heating to 60-70 ℃, and keeping the temperature for 3-6 hours to obtain a modified isocyanate solution, wherein the mass ratio of the composite microspheres to the mixed solution is 2-3: 10;
(5) adding polyalcohol and catalyst into the modified isocyanate solution, heating to 70-80 ℃, preserving heat for 2-4h, adding polymerization inhibitor, cooling to 40-50 ℃, and preserving heat for 1-2h to obtain the flame-retardant modified polyurethane curing agent, wherein the molar ratio of the polyalcohol to the 4, 4-diphenylmethane diisocyanate is 0.07-0.12:1, the amount of the catalyst is 0.1-0.8wt% of the modified isocyanate solution, and the amount of the polymerization inhibitor is 0.1-0.6wt% of the modified isocyanate solution.
According to the invention, active hydroxyl on microcrystalline cellulose reacts with-NCO of 4, 4-diphenylmethane diisocyanate, so that nano magnesium hydroxide coated in microcrystalline cellulose is added into a cross-linking structure of a curing agent, the hardness promotion property and flame retardance of the curing agent to a paint film are improved, and the problem that nano magnesium hydroxide is easy to agglomerate is solved. In addition, the invention also leads the curing agent to form a stable three-dimensional cross-linked structure by strictly controlling reaction conditions, improves the bonding degree of isocyanate and hydroxyl resin to the surface of microcrystalline cellulose, and endows the coating with lower viscosity and curing time.
Wherein in the step (3), the spraying voltage of electrostatic spraying is 20-40kV, and the spraying temperature is 20-30 ℃. By controlling the spraying voltage and the spraying temperature, the surface appearance of the composite microsphere can be adjusted, so that the composite microsphere has good coating property on the nano magnesium hydroxide, has larger specific surface area and is beneficial to the improvement of the number of surface active hydroxyl groups.
Wherein the particle size of the nano magnesium hydroxide is 23-47nm, the particle size of the composite microsphere is 13.7-16.4 mu m, and the BET specific surface area of the composite microsphere is 26.3-54.4m2(ii) in terms of/g. The particle size of the nano magnesium hydroxide can influence the size and the shape of the composite microsphere, the particle size and the specific surface area of the composite microsphere have great influence on the stability of the composite microsphere in a cross-linked structure, when the particle size of the nano magnesium hydroxide is 23-47nm, the particle size of the composite microsphere is 13.7-16.4 mu m, and the BET specific surface area of the composite microsphere is 26.3-54.4m2The curing agent has stable three-dimensional cross-linked structure, the hardness improvement and storage property of the curing agent on a paint film are greatly improved, and the storage time at normal temperature can reach more than 5 months (the storage time refers to the time required for preventing the curing agent at normal temperature until the viscosity is more than 50 s).
In the step (4), the organic solvent is ethyl acetate and/or xylene, and the mass ratio of the 4, 4-diphenylmethane diisocyanate to the organic solvent is 0.4-0.6: 1. The solvent type has a large influence on the viscosity and tolerance of the product, and ethyl acetate and xylene have lower viscosity and larger tolerance compared with other conventional solvents (such as acetone) of 4, 4-diphenylmethane diisocyanate, and generally speaking, the viscosity can be reduced by 1-3s, and the tolerance can be improved by 0.1-0.2. More preferably, the organic solvent consists of ethyl acetate and xylene according to the weight ratio of 2:3, under the same condition, the viscosity can be reduced by 3s and the tolerance can be improved by 0.2 compared with pure acetone.
Wherein the polyol is at least one of ethylene glycol, polyethylene glycol, trimethylolpropane, pentaerythritol, polyether polyol and polyester polyol. The polyol improves the performance of the curing agent through a grafting reaction, and different alcohols improve the viscosity of the curing agent, the hardness improvement performance and the tolerance of a paint film and the like to different degrees.
Further, the-NCO content of the 4, 4-diphenylmethane diisocyanate is 20% -28%, the polyol is a mixture of polyethylene glycol and polytetrahydrofuran ether glycol according to the mass ratio of 1-3:1, the molecular weight of the polyethylene glycol is 2000-3000, and the molecular weight of the polytetrahydrofuran ether glycol is 1000-1400. The linear cross-linked structure is generated by controlling the-NCO content of the 4, 4-diphenylmethane diisocyanate and the type and molecular weight of the polyol, the composite microspheres are stabilized in the cross-linked structure, the tensile strength and strength of a paint film can be increased, and the excessive viscosity of the curing agent is avoided.
Wherein, in the step (5), the catalyst is at least one of dibutyltin dilaurate, alkyl titanate and triethylenediamine. The selection of the catalyst has great influence on the intensity of the reaction, the reduction degree of-NCO content, the viscosity of the curing agent and the like, and compared with other types of catalysts, the dibutyltin dilaurate, the alkyl titanate and the triethylene diamine have stable catalysis, the reduction of NCO value is stable, and the reaction is easy to control. Preferably, the catalyst consists of dibutyltin dilaurate, alkyl titanate and triethylenediamine in a weight ratio of 1-3:1-2: 1.
Wherein the polymerization inhibitor is at least one of phosphoric acid, sulfuric acid and benzoyl chloride. The polymerization inhibitor may be a catalyst which deactivates and terminates the reaction. The kind of the polymerization inhibitor has a large influence on the appearance and storage stability of the curing agent, and in order to provide a curing agent with lower chroma and longer-lasting storage stability, the polymerization inhibitor of the present invention is preferably composed of sulfuric acid and benzoyl chloride in a weight ratio of 1: 1-2.
A flame-retardant modified polyurethane curing agent: the flame-retardant modified polyurethane curing agent is prepared by the preparation method, the-NCO content of the flame-retardant modified polyurethane curing agent is 8.47-9.36 wt%, the content of free MDI is 0.4-0.6 wt%, the conditional viscosity at 25 ℃ measured by a coating-4 cup method is 4.3-10.1s, and the xylene tolerance is 2.1-2.6.
A two-component polyurethane coating: the flame-retardant modified polyurethane curing agent is prepared by mixing the flame-retardant modified polyurethane curing agent, hydroxyl resin and an auxiliary agent, wherein the molar ratio of-NCO of the flame-retardant modified polyurethane curing agent to-OH of the hydroxyl resin is 1.0-1.2: 1. The auxiliaries may include, but are not limited to: the coating comprises a dispersing agent, a leveling agent and a defoaming agent, wherein the using amounts of the dispersing agent, the leveling agent and the defoaming agent are respectively 1 wt% -3 wt%, 0.1 wt% -0.3 wt% and 0.1 wt% -0.4 wt% of the coating, the dispersing agent is preferably composed of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium polyacrylate according to the weight ratio of 1-3:1-3:1, the leveling agent is preferably an acrylate leveling agent, and the defoaming agent is preferably dimethyl hexynol. The stability of the coating material and the strength after forming a coating film can be further enhanced by the combination of the preferred auxiliaries.
The invention has the beneficial effects that: according to the invention, active hydroxyl on microcrystalline cellulose reacts with-NCO of 4, 4-diphenylmethane diisocyanate, so that nano magnesium hydroxide coated in microcrystalline cellulose is added into a cross-linking structure of a curing agent, the hardness promotion property and flame retardance of the curing agent to a paint film are improved, and the problem that nano magnesium hydroxide is easy to agglomerate is solved. In addition, the invention also leads the curing agent to form a stable three-dimensional cross-linked structure by strictly controlling reaction conditions, improves the bonding degree of isocyanate and hydroxyl resin to the surface of microcrystalline cellulose, and endows the coating with lower viscosity and curing time.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A preparation method of a flame-retardant modified polyurethane curing agent comprises the following steps:
(1) dissolving microcrystalline cellulose in chlorinated 1-methyl-3-butylimidazolium salt ionic liquid according to the mass ratio of 7:100 at the temperature of 80 ℃ to form a microcrystalline cellulose solution;
(2) adding nano magnesium hydroxide into the microcrystalline cellulose solution obtained in the step (1), and uniformly stirring to obtain a suspension, wherein the nano magnesium hydroxide accounts for 4wt% of the suspension;
(3) performing electrostatic spraying on the suspension obtained in the step (2) to obtain composite microspheres;
(4) dissolving 4, 4-diphenylmethane diisocyanate in an organic solvent to obtain a mixed solution, adding the composite microspheres obtained in the step (3) into the mixed solution, performing ultrasonic dispersion, heating to 65 ℃, and keeping the temperature for 4.5 hours to obtain a modified isocyanate solution, wherein the mass ratio of the composite microspheres to the mixed solution is 2.5: 10;
(5) adding polyalcohol and a catalyst into the modified isocyanate solution, heating to 75 ℃, keeping the temperature for 3h, adding a polymerization inhibitor, cooling to 45 ℃, and keeping the temperature for 1.5h to obtain the flame-retardant modified polyurethane curing agent, wherein the molar ratio of the polyalcohol to the 4, 4-diphenylmethane diisocyanate is 0.1:1, the dosage of the catalyst is 0.4wt% of the modified isocyanate solution, and the dosage of the polymerization inhibitor is 0.3 wt% of the modified isocyanate solution.
Wherein in the step (3), the spraying voltage of electrostatic spraying is 30kV, and the spraying temperature is 25 ℃.
Wherein the particle size of the nano magnesium hydroxide is 34nm, the particle size of the composite microsphere is 14.4 mu m, and the BET specific surface area of the composite microsphere is 50.3m2/g。
In the step (4), the mass ratio of the 4, 4-diphenylmethane diisocyanate to the organic solvent is 0.5:1, and the organic solvent is composed of ethyl acetate and xylene according to the weight ratio of 2: 3.
Further, the-NCO content of the 4, 4-diphenylmethane diisocyanate is 24%, the polyol is a mixture of polyethylene glycol and polytetrahydrofuran ether glycol according to the mass ratio of 2:1, the molecular weight of the polyethylene glycol is 2500, and the molecular weight of the polytetrahydrofuran ether glycol is 1200.
Wherein, in the step (5), the catalyst consists of dibutyltin dilaurate, alkyl titanate and triethylenediamine according to the weight ratio of 2:1.5: 1.
The polymerization inhibitor of the invention preferably comprises sulfuric acid and benzoyl chloride in a weight ratio of 1: 1.5.
A flame-retardant modified polyurethane curing agent: the flame-retardant modified polyurethane curing agent is prepared by the preparation method, the-NCO content of the flame-retardant modified polyurethane curing agent is 8.66 wt%, the content of free MDI is 0.4wt%, the conditional viscosity at 25 ℃ measured by a coating-4 cup method is 4.3s, and the xylene tolerance is 2.6.
Example 2
A preparation method of a flame-retardant modified polyurethane curing agent comprises the following steps:
(1) dissolving microcrystalline cellulose in chlorinated 1-methyl-3-butylimidazolium salt ionic liquid according to the mass ratio of 4:100 at the temperature of 70 ℃ to form a microcrystalline cellulose solution;
(2) adding nano magnesium hydroxide into the microcrystalline cellulose solution obtained in the step (1), and uniformly stirring to obtain a suspension, wherein the nano magnesium hydroxide accounts for 2 wt% of the suspension;
(3) performing electrostatic spraying on the suspension obtained in the step (2) to obtain composite microspheres;
(4) dissolving 4, 4-diphenylmethane diisocyanate in an organic solvent to obtain a mixed solution, adding the composite microspheres obtained in the step (3) into the mixed solution, performing ultrasonic dispersion, heating to 60 ℃, and keeping the temperature for 3 hours to obtain a modified isocyanate solution, wherein the mass ratio of the composite microspheres to the mixed solution is 2: 10;
(5) adding polyalcohol and a catalyst into the modified isocyanate solution, heating to 70 ℃, keeping the temperature for 2h, adding a polymerization inhibitor, cooling to 40 ℃, and keeping the temperature for 1h to obtain the flame-retardant modified polyurethane curing agent, wherein the molar ratio of the polyalcohol to the 4, 4-diphenylmethane diisocyanate is 0.07:1, the dosage of the catalyst is 0.1 wt% of the modified isocyanate solution, and the dosage of the polymerization inhibitor is 0.1 wt% of the modified isocyanate solution.
Wherein in the step (3), the spraying voltage of electrostatic spraying is 20kV, and the spraying temperature is 20 ℃.
Wherein the particle size of the nano magnesium hydroxide is 23nm, the particle size of the composite microsphere is 15.3 mu m, and the BET specific surface area of the composite microsphere is 33.1m2/g。
In the step (4), the mass ratio of the 4, 4-diphenylmethane diisocyanate to the organic solvent is 0.4:1, and the organic solvent is composed of ethyl acetate and xylene according to the weight ratio of 1:1.
Further, the-NCO content of the 4, 4-diphenylmethane diisocyanate is 20%, the polyol is a mixture of polyethylene glycol and polytetrahydrofuran ether glycol according to the mass ratio of 1:1, the molecular weight of the polyethylene glycol is 2000, and the molecular weight of the polytetrahydrofuran ether glycol is 1000.
Wherein, in the step (5), the catalyst consists of dibutyltin dilaurate, alkyl titanate and triethylenediamine according to the weight ratio of 1:1: 1.
Among them, the polymerization inhibitor of the present invention is preferably composed of sulfuric acid and benzoyl chloride in a weight ratio of 1:1.
A flame-retardant modified polyurethane curing agent: the flame-retardant modified polyurethane curing agent is prepared by the preparation method, the-NCO content of the flame-retardant modified polyurethane curing agent is 9.02 wt%, the content of free MDI is 0.5 wt%, the conditional viscosity at 25 ℃ measured by a coating-4 cup method is 7.4s, and the xylene tolerance is 2.2.
Example 3
A preparation method of a flame-retardant modified polyurethane curing agent comprises the following steps:
(1) dissolving microcrystalline cellulose in chlorinated 1-methyl-3-butylimidazolium salt ionic liquid according to the mass ratio of 10:100 at the temperature of 90 ℃ to form a microcrystalline cellulose solution;
(2) adding nano magnesium hydroxide into the microcrystalline cellulose solution obtained in the step (1), and uniformly stirring to obtain a suspension, wherein the nano magnesium hydroxide accounts for 6wt% of the suspension;
(3) performing electrostatic spraying on the suspension obtained in the step (2) to obtain composite microspheres;
(4) dissolving 4, 4-diphenylmethane diisocyanate in an organic solvent to obtain a mixed solution, adding the composite microspheres obtained in the step (3) into the mixed solution, performing ultrasonic dispersion, heating to 70 ℃, and keeping the temperature for 6 hours to obtain a modified isocyanate solution, wherein the mass ratio of the composite microspheres to the mixed solution is 3: 10;
(5) adding polyalcohol and a catalyst into the modified isocyanate solution, heating to 80 ℃, keeping the temperature for 4h, adding a polymerization inhibitor, cooling to 50 ℃, and keeping the temperature for 2h to obtain the flame-retardant modified polyurethane curing agent, wherein the molar ratio of the polyalcohol to the 4, 4-diphenylmethane diisocyanate is 0.12:1, the dosage of the catalyst is 0.8wt% of the modified isocyanate solution, and the dosage of the polymerization inhibitor is 0.6wt% of the modified isocyanate solution.
Wherein in the step (3), the spraying voltage of electrostatic spraying is 40kV, and the spraying temperature is 30 ℃.
Wherein the particle size of the nano magnesium hydroxide is 47nm, the particle size of the composite microsphere is 15.5 mu m, and the BET specific surface area of the composite microsphere is 47.1m2/g。
In the step (4), the mass ratio of the 4, 4-diphenylmethane diisocyanate to the organic solvent is 0.6:1, and the organic solvent is composed of ethyl acetate and xylene according to the weight ratio of 2:1.
Further, the-NCO content of the 4, 4-diphenylmethane diisocyanate is 28%, the polyol is a mixture of polyethylene glycol and polytetrahydrofuran ether glycol according to the mass ratio of 3:1, the molecular weight of the polyethylene glycol is 3000, and the molecular weight of the polytetrahydrofuran ether glycol is 1400.
Wherein, in the step (5), the catalyst consists of dibutyltin dilaurate, alkyl titanate and triethylenediamine according to the weight ratio of 3:2: 1.
Among them, the polymerization inhibitor of the present invention is preferably composed of sulfuric acid and benzoyl chloride in a weight ratio of 1: 2.
A flame-retardant modified polyurethane curing agent: the flame-retardant modified polyurethane curing agent is prepared by the preparation method, the-NCO content of the flame-retardant modified polyurethane curing agent is 8.47wt%, the content of free MDI is 0.5 wt%, the conditional viscosity at 25 ℃ measured by a coating-4 cup method is 6.3s, and the xylene tolerance is 2.1.
Example 4
This example differs from example 1 in that:
wherein, in the step (4), the organic solvent is acetone.
The prepared flame-retardant modified polyurethane curing agent has the-NCO content of 9.36 percent, the free MDI content of 0.6 percent, the conditional viscosity at 25 ℃ measured by a coating-4 cup method of 7.3s and the xylene tolerance of 2.4.
Example 5
This example differs from example 1 in that:
the polyol is trimethylolpropane.
The step (5): adding polyalcohol and a catalyst into the modified isocyanate solution, heating to 75 ℃, preserving heat for 2.5h, adding a polymerization inhibitor, cooling to 45 ℃, and preserving heat for 1.5h to obtain the flame-retardant modified polyurethane curing agent, wherein the molar ratio of the polyalcohol to the 4, 4-diphenylmethane diisocyanate is 0.1: 1.
The prepared flame-retardant modified polyurethane curing agent has 8.63 wt% of-NCO, 0.6wt% of free MDI, 6.2s of conditional viscosity at 25 ℃ measured by a coating-4 cup method and 2.3 of xylene tolerance.
Example 6
This example differs from example 1 in that:
wherein, in the step (5), the catalyst is dibutyltin dilaurate. The step (5): adding polyalcohol and a catalyst into the modified isocyanate solution, heating to 75 ℃, preserving heat for 4h, adding a polymerization inhibitor, cooling to 45 ℃, and preserving heat for 1.5h to obtain the flame-retardant modified polyurethane curing agent, wherein the molar ratio of the polyalcohol to the 4, 4-diphenylmethane diisocyanate is 0.1: 1.
A flame-retardant modified polyurethane curing agent: the flame-retardant modified polyurethane curing agent is prepared by the preparation method, the-NCO content of the flame-retardant modified polyurethane curing agent is 9.36wt%, the content of free MDI is 0.5 wt%, the conditional viscosity at 25 ℃ measured by a coating-4 cup method is 8.2s, and the xylene tolerance is 2.4.
Comparative example 1
The preparation method of the curing agent of the comparative example is mainly different from that of the example 1 in that: the composite microspheres are not added for modification.
The preparation method comprises the following steps:
a preparation method of a curing agent comprises the following steps:
dissolving 4, 4-diphenylmethane diisocyanate in an organic solvent to obtain a mixed solution, adding polyol and a catalyst into the mixed solution, heating to 75 ℃, preserving heat for 3 hours, adding a polymerization inhibitor, cooling to 45 ℃, and preserving heat for 1.5 hours to obtain the curing agent of the comparative example, wherein the molar ratio of the polyol to the 4, 4-diphenylmethane diisocyanate is 0.1: 1.
The mass ratio of the 4, 4-diphenylmethane diisocyanate to the organic solvent is 0.5:1, and the organic solvent is composed of ethyl acetate and xylene according to the weight ratio of 2: 3.
The 4, 4-diphenylmethane diisocyanate is characterized in that the-NCO content of the 4, 4-diphenylmethane diisocyanate is 24%, the polyol is a mixture of polyethylene glycol and polytetrahydrofuran ether glycol according to the mass ratio of 2:1, the molecular weight of the polyethylene glycol is 2500, and the molecular weight of the polytetrahydrofuran ether glycol is 1200.
The catalyst comprises dibutyltin dilaurate, alkyl titanate and triethylenediamine according to the weight ratio of 2:1.5: 1.
The polymerization inhibitor of the invention preferably comprises sulfuric acid and benzoyl chloride in a weight ratio of 1: 1.5.
The curing agent of this comparative example had an-NCO content of 9.02% by weight, a free MDI content of 0.6% by weight, a conditional viscosity at 25 ℃ of 4.7s as measured by the paint-4 cup method, and a xylene tolerance of 2.8.
Comparative example 2
This comparative example differs from example 1 in that: replacing the composite microspheres with magnesium hydroxide particles of equal mass, wherein the particle size of the magnesium hydroxide is 36 nm.
The curing agent of this comparative example had an-NCO content of 8.83%, a free MDI content of 0.7%, a conditional viscosity at 25 ℃ of 6.5s as measured by the paint-4 cup method, and a xylene tolerance of 2.0.
Comparative example 3
This comparative example differs from example 1 in that: the composite microspheres are replaced by microcrystalline cellulose microspheres with equal mass, the particle size of the prepared microcrystalline cellulose microspheres is 10.4 mu m, and the BET specific surface area is 57.4m2The preparation method of the microcrystalline cellulose microspheres comprises the following steps:
(1) dissolving microcrystalline cellulose in chlorinated 1-methyl-3-butylimidazolium salt ionic liquid according to the mass ratio of 7:100 at the temperature of 80 ℃ to form a microcrystalline cellulose solution;
(2) and (2) performing electrostatic spraying on the suspension obtained in the step (1) to obtain microcrystalline cellulose microspheres, wherein the spraying voltage of the electrostatic spraying is 30kV, and the spraying temperature is 25 ℃.
The curing agent of this comparative example had an-NCO content of 8.47% by weight, a free MDI content of 0.7% by weight, a conditional viscosity at 25 ℃ of 4.6s as measured by the paint-4 cup method, and a xylene tolerance of 2.5.
EXAMPLE 7 stability testing of curing Agents
The curing agents of examples 1 to 6 and comparative examples 1 to 3 were placed in an ambient temperature environment, and the-NCO content and viscosity of the curing agents were measured every 1 month for 6 months continuously, with the following results:
as is apparent from the data of examples 1 to 6, the curing agent of the present application has excellent storage stability and satisfies the industrial production and marketing requirements; as can be seen from the example 1 and the comparative example 1, the curing agent of the comparative example 1 is not added with the composite microspheres with hydroxyl groups, so that the initial-NCO content is higher than that of the example 1, the composite microspheres are not involved, and the crosslinking structure formed by the curing agent has more branched chains, so that the viscosity is increased, and the participation of the composite microspheres in the invention is beneficial to the generation of a straight-chain crosslinking structure, thereby having the effect of reducing the viscosity; as is clear from a comparison between example 1 and comparative example 2, since magnesium hydroxide fine particles have few reactive hydroxyl groups relative to microcrystalline cellulose and thus are poor in crosslinkability with isocyanate, the curing agent forms a crosslinked structure having more branches, resulting in an increase in the-NCO content and an increase in viscosity of the curing agent of comparative example 2; as is clear from comparison between example 1 and comparative example 3, the viscosity and-NCO content are both relatively close to each other because whether microcrystalline cellulose is coated with magnesium hydroxide does not greatly affect the crosslinking structure of the curing agent.
Example 8 preparation and testing of two-component polyurethane coating films
The curing agents of examples 1-6 and comparative examples 1-3 were mixed with bayhydrol @ XP2470 hydroxy acrylic resin respectively according to a molar ratio of-NCO to-OH of 1.1:1, water equal in mass to the curing agent was added, paint was then sprayed on a copper plate, and curing was performed at 70 ℃ to obtain a two-component polyurethane coating film.
Paint film hardness, paint film adhesion, paint film flexibility, paint film impact resistance and flame retardance were tested according to GB/T6739-2006, GB/T1720-1979, GB/T1731-1993, GB/T1732-1993 and GB/T2406.2-2009, respectively, and the results are as follows:
from the results, the acrylic paint film formed by crosslinking the curing agent has the characteristics of good hardness, strong adhesive force, strong flexibility, good impact resistance and good flame retardance, and the comparison between the example 1 and the comparative example 1 shows that the composite microspheres have good modification effect, so that the curing agent and the hydroxyl resin have more physical crosslinking points, and the crosslinking density is increased; from the comparison between example 1 and comparative example 2, it is understood that magnesium hydroxide is the substance that mainly contributes to the improvement of flame retardancy, but since magnesium hydroxide is not subjected to coating treatment, the crosslinking property with resin is poor, and the formed paint film is also inferior in properties; as can be seen from the examples 1, the comparative examples 2 and the comparative examples 3, the magnesium hydroxide and the microcrystalline cellulose can improve the mechanical property of the paint film, and the microcrystalline cellulose has good crosslinking property with resin, so the mechanical property of the paint film is improved to a better extent than that of the magnesium hydroxide, but the problem of poor crosslinking property can be solved by coating the magnesium hydroxide with the microcrystalline cellulose; it is understood from the comparison of example 1, comparative example 1 and comparative example 3 that the addition of microcrystalline cellulose also provides a lower degree of improvement in flame retardancy, because microcrystalline cellulose is rich in carbon and can serve as a carbon source, but the improvement is not significant without the addition of an acid source.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (7)
1. A two-component polyurethane coating is characterized in that: the flame-retardant modified polyurethane curing agent is prepared by mixing a flame-retardant modified polyurethane curing agent, hydroxyl resin and an auxiliary agent, wherein the molar ratio of-NCO of the flame-retardant modified polyurethane curing agent to-OH of the hydroxyl resin is 1.0-1.2:1, and the preparation method of the flame-retardant modified polyurethane curing agent comprises the following steps:
(1) dissolving microcrystalline cellulose in a chlorinated 1-methyl-3-butylimidazolium salt ionic liquid at a mass ratio of 4-10:100 at 70-90 ℃ to form a microcrystalline cellulose solution;
(2) adding nano magnesium hydroxide into the microcrystalline cellulose solution obtained in the step (1), and uniformly stirring to obtain a suspension, wherein the nano magnesium hydroxide accounts for 2-6wt% of the suspension;
(3) performing electrostatic spraying on the suspension obtained in the step (2) to obtain composite microspheres;
(4) dissolving 4, 4-diphenylmethane diisocyanate in an organic solvent to obtain a mixed solution, adding the composite microspheres obtained in the step (3) into the mixed solution, performing ultrasonic dispersion, heating to 60-70 ℃, and keeping the temperature for 3-6 hours to obtain a modified isocyanate solution, wherein the mass ratio of the composite microspheres to the mixed solution is 2-3: 10;
(5) adding polyalcohol and a catalyst into the modified isocyanate solution, heating to 70-80 ℃, preserving heat for 2-4h, adding a polymerization inhibitor, cooling to 40-50 ℃, and preserving heat for 1-2h to obtain the flame-retardant modified polyurethane curing agent, wherein the molar ratio of the polyalcohol to the 4, 4-diphenylmethane diisocyanate is 0.07-0.12:1, the amount of the catalyst is 0.1-0.8wt% of the modified isocyanate solution, and the amount of the polymerization inhibitor is 0.1-0.6wt% of the modified isocyanate solution;
the polyalcohol is a mixture of polyethylene glycol and polytetrahydrofuran ether glycol according to the mass ratio of 1-3:1, the molecular weight of the polyethylene glycol is 2000-3000, and the molecular weight of the polytetrahydrofuran ether glycol is 1000-1400.
2. The two-component polyurethane coating of claim 1, wherein: in the step (3), the spraying voltage of electrostatic spraying is 20-40kV, and the spraying temperature is 20-30 ℃.
3. The two-component polyurethane coating of claim 1, wherein: the particle size of the nano magnesium hydroxide is 23-47nm, the particle size of the composite microsphere is 13.7-16.4 mu m, and the BET specific surface area of the composite microsphere is 26.3-54.4m2/g。
4. The two-component polyurethane coating of claim 1, wherein: in the step (4), the organic solvent is ethyl acetate and/or xylene, and the mass ratio of the 4, 4-diphenylmethane diisocyanate to the organic solvent is 0.4-0.6: 1.
5. The two-component polyurethane coating of claim 1, wherein: in the step (5), the catalyst is at least one of dibutyltin dilaurate, alkyl titanate and triethylenediamine.
6. The two-component polyurethane coating of claim 1, wherein: the polymerization inhibitor is at least one of phosphoric acid, sulfuric acid and benzoyl chloride.
7. The two-component polyurethane coating of claim 1, wherein: the flame-retardant modified polyurethane curing agent has 8.47-9.36 wt% of-NCO, 0.4-0.6 wt% of free MDI, 6.3-8.1s of conditional viscosity at 25 ℃ measured by a coating-4 cup method and 2.1-2.3 of xylene tolerance.
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