CN112194772B - High-solid self-repairing type waterborne polyurethane acrylate and preparation method thereof - Google Patents
High-solid self-repairing type waterborne polyurethane acrylate and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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Abstract
The invention relates to the technical field of coating materials, and provides a preparation method of a high-solid-content aqueous polyurethane acrylate dispersion, which comprises the following steps: reacting diisocyanate with polyester polyol or polyether polyol to obtain a polyurethane prepolymer; mixing and reacting the polyurethane prepolymer with a viscosity-reducing solvent, a hydrophilic chain extender and a dihydric alcohol chain extender containing a disulfide bond to obtain a first mixed solution; mixing the first mixed solution and hydroxyl-containing acrylate monomers for reaction to obtain a double-bond-terminated polyurethane prepolymer; adding water into the double-bond-terminated polyurethane prepolymer for emulsification, removing the solvent to obtain a second mixed solution, mixing and emulsifying the second mixed solution and the acrylate monomer, and mixing and reacting the second mixed solution and the initiator solution. A high-solid aqueous polyurethane acrylate dispersion is prepared by the method, and when the high-solid aqueous polyurethane acrylate dispersion is used as a coating film, a coating material with self-repairing performance is prepared by the method. The coating material has good self-repairing performance under irradiation of visible light and ultraviolet light and at a proper temperature.
Description
Technical Field
The invention relates to the technical field of waterborne polyurethane, in particular to a high-solid waterborne polyurethane acrylate dispersion, a preparation method thereof and a coating material with self-repairing performance.
Background
The waterborne polyurethane has good ageing resistance and wear resistance, does not release organic solvent, but has poor mechanical property, poor water resistance, lower solid content and narrow applicability. The acrylate modified water-based polyurethane is a common effective method, the acrylate is added into the water-based polyurethane emulsion, the initiator promotes the free radical emulsion to polymerize so as to form the composite emulsion, a core-shell structure type is formed, the polyurethane acrylate composite emulsion can obtain a coating with high toughness, high hardness and high elasticity by adjusting the formula in a large range, different requirements can be met, the crosslinking degree after the water-based polyurethane acrylate is formed into a film can exceed 90%, an interpenetrating network is successfully constructed, the organic solvent resistance and the mechanical property of the water-based polyurethane are obviously improved, and the defect that the solid content of a single polyurethane system is too low can be overcome.
In the process of using the polyurethane acrylate as a coating, a coating film is inevitably subjected to microscopic or macroscopic damage to a material due to the comprehensive influence of internal and external factors in the processes of processing, transporting, storing and using, so that the mechanical property of the material is reduced, in order to eliminate the micro damage in the material, avoid the expansion of the damage, increase the safety and durability of the material and prolong the service life of the material, the damage-self-repair is realized by introducing reversible covalent bonds into the material, and the polyurethane has a micro-phase separation structure so that the mechanical property, particularly the tensile strength, the tear strength and the flexibility of the polyurethane material are high, so that the polyurethane becomes a research hotspot from repairing materials in recent years. This material has many advantages: such as polymerization initiated by cracks, strong pertinence, high efficiency, no need of artificial observation and the like.
Disclosure of Invention
The invention aims to provide a high-solid aqueous polyurethane acrylate dispersion and a preparation method thereof. Aims to provide the high-solid-content aqueous polyurethane acrylate dispersoid which has the function of automatically repairing cracks and scratches under the irradiation of ultraviolet light after being mixed with a photoinitiator for use.
The invention also provides a coating material with self-repairing performance, which is coated on the surface of an article and has the performance of automatically repairing cracks under the condition of ultraviolet illumination.
The invention is realized by the following steps:
a preparation method of a high-solid aqueous polyurethane acrylate dispersion comprises the following steps:
preparing a polyurethane prepolymer: reacting diisocyanate with polyester polyol or polyether polyol to obtain a polyurethane prepolymer, wherein the ratio of the amount of isocyanate groups in the diisocyanate to the amount of hydroxyl groups in the polyester polyol or the polyether polyol is (2.5-4): 1.
preparation of a first mixed solution: dropwise adding a small amount of catalyst, and mixing and reacting the polyurethane prepolymer, a viscosity-reducing solvent, a hydrophilic chain extender and a dihydric alcohol chain extender containing a disulfide bond to obtain a first mixed solution, wherein the first mixed solution contains a prepolymer terminated by isocyanate containing a disulfide bond, the dosage of the viscosity-reducing solvent accounts for 3-10% of the mass of reaction monomers in the first mixed solution, the reaction monomers comprise the polyurethane prepolymer, the hydrophilic chain extender and the dihydric alcohol chain extender containing a disulfide bond, the dosage of the hydrophilic chain extender accounts for 3-6% of the mass of the monomers in the first mixed solution, and the dosage of the chain extender containing a disulfide bond accounts for 5-10% of the mass of the monomers in the first mixed solution.
Preparing a double-bond end-capped polyurethane prepolymer: and measuring the content of isocyanate groups in the first mixed solution, and mixing a hydroxyl-containing acrylate monomer (first acrylate monomer) which accounts for 5-10% of the mass of the monomers in the first mixed solution with the first mixed solution for reaction to obtain the double-bond-terminated polyurethane prepolymer.
Preparation of an emulsion: and adding water into the double-bond-terminated polyurethane prepolymer for emulsification, removing the solvent to obtain a terminal double-bond-containing aqueous polyurethane dispersion with the solid content of 30%, wherein the terminal double-bond-containing aqueous polyurethane dispersion is a second mixed solution, and mixing and emulsifying the second mixed solution and an acrylate monomer (a second acrylate monomer) to obtain an emulsion, wherein the mass of the acrylate monomer is 30-50% of that of the second mixed solution.
Preparation of final product: and mixing the emulsion and an initiator solution for reaction to obtain the aqueous polyurethane acrylate dispersion containing the reversible dynamic covalent disulfide bond, wherein the initiator in the initiator solution accounts for 0.8-1.5% of the total amount of the hydroxyl-containing acrylate monomer and the acrylate monomer.
The high-solid aqueous polyurethane acrylate dispersoid is prepared by the preparation method.
The coating material with the self-repairing performance comprises a photoinitiator and the high-solid aqueous polyurethane acrylate dispersoid, wherein the dosage of the photoinitiator accounts for 1-3% of the mass of the high-solid aqueous polyurethane acrylate.
The invention has the following advantages:
according to the high-solid-content aqueous polyurethane acrylate dispersion and the preparation method thereof, due to the adoption of a reasonable preparation method and the proportion of the polyurethane dispersion and the acrylic resin, the dispersion and the photoinitiator have the following advantages in mixed use:
1. the aqueous polyurethane acrylate dispersion with high solid content can be prepared by compounding the proper polyurethane dispersion and the acrylic resin in proportion, so that the defect of low solid content of a single polyurethane system is overcome, and the surface drying speed in the liquid film forming process, the mechanical property of the formed film and the water and solvent resistance are effectively improved.
2. Disulfide bonds with dynamic reversibility under the action of ultraviolet light are bonded into the high-solid aqueous polyurethane acrylate dispersion containing main chain and/or side group hydrogen bonds, and the strong dynamic reversibility of the disulfide bonds and the non-dynamic covalent reversibility of the hydrogen bonds under the action of light are utilized, so that the function of automatically repairing cracks and scratches under the stimulation of light is obtained. The crack self-repairing material contains two reversible elements (disulfide bond and hydrogen bond), can play a role in superposing reversibility, has better dynamic performance than single dynamic reversibility, can obtain a more excellent self-repairing effect, and can realize multiple-cycle damage-self-repairing of cracks under the synergistic action of reversible covalent bonds, thereby realizing economic recycling.
Drawings
FIG. 1 is an infrared spectrum of a synthetic high solid polyurethane acrylate aqueous dispersion. According to the infrared spectrum, WPU and AWPUA are in 2268cm-1The characteristic peak at NCO disappeared at 1533cm-1The characteristic peak of amino ester group (COONH) appears, and the crosslinking monomer hydroxyethyl acrylate (HEA) is at 1640cm-1Has a clearly visible double bond peak, and the synthesized AWPUA composite material is 1640cm-1The peak of C = C bond disappears, which shows that the C = C double bond participates in the polymerization, and the polyurethane acrylate composite material is successfully prepared.
FIG. 2 is a diagram of the disulfide bond repair mechanism. The covalent bond of the disulfide bond is easy to break and is recombined with other sulfur atoms to achieve damage-self repair, and due to the good low-temperature, light and heat reversible repair characteristics of the disulfide bond, the film can be repaired under mild conditions and can be repaired for many times.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below.
The invention relates to a preparation method of a high-solid aqueous polyurethane acrylate dispersion, which comprises the following steps:
the method comprises the following steps: adding diisocyanate and polyester polyol or diisocyanate and polyether polyol into a four-neck flask provided with standard synthetic reaction equipment (a thermometer, a condenser and a mechanical stirring device), wherein the ratio of the amount of isocyanate groups to the amount of hydroxyl substances in the added diisocyanate and polyester polyol is 2.5-4: 1, the ratio of the amount of isocyanate groups to the amount of hydroxyl substances in the added diisocyanate and polyether polyol is 2.5-4: 1, heating to 70-90 ℃, and reacting for 1-3 hours to obtain the polyurethane prepolymer.
Step two: adding a catalyst, wherein the dosage of the catalyst is 1-2 drops. Adding a viscosity reduction solvent, a hydrophilic chain extender and a chain extender containing disulfide bonds, mixing and reacting to obtain a first mixed solution, wherein the first mixed solution comprises isocyanate-terminated prepolymer containing disulfide bonds, the solvent accounts for 3-10% of the monomer of the first mixed solution, the hydrophilic chain extender accounts for 3-6% of the monomer of the first mixed solution, the chain extender containing disulfide bonds accounts for 5-10% of the monomer of the first mixed solution, the temperature is adjusted to 55-85 ℃, and reacting for 1-3 hours.
Step three: and measuring the content of isocyanate groups in the first mixed solution, adding a hydroxyl-containing acrylate monomer accounting for 5-10% of the mass of the monomers in the first mixed solution, adjusting the temperature to 50-60 ℃, and reacting for 1-2 hours to obtain the double-bond-terminated polyurethane prepolymer.
Step four: cooling to 25-40 ℃, adding water into the double-bond-terminated polyurethane prepolymer for emulsification, removing the solvent to obtain a terminal double-bond-containing aqueous polyurethane dispersion with a solid content of 30%, wherein the terminal double-bond-containing aqueous polyurethane dispersion is a second mixed solution, mixing and emulsifying the second mixed solution and an acrylate monomer to obtain an emulsion, the acrylate monomer accounts for 30-50% of the second mixed solution, and the ratio of the acrylate soft monomer to the acrylate hard monomer is 1: 1.5 to 2.5.
Step five: heating to 40-60 ℃, adding an anionic emulsifier and a nonionic emulsifier, wherein the anionic emulsifier and the nonionic emulsifier are in a ratio of 2: 1, the amount of the emulsifier accounts for 1.8-2.2% of the total amount of the hydroxyl-containing acrylate monomer and the acrylate monomer, and the reaction lasts for 0.5-1 h.
Step six: adjusting the temperature to be 60-70 ℃, dropwise adding an inorganic peroxide initiator to initiate reaction, wherein the dropwise adding time is 2-4 h, so that the high-solid-content aqueous polyurethane acrylate dispersion containing reversible dynamic covalent disulfide bonds is obtained, and the initiator accounts for 0.8-1.5% of the total amount of the hydroxyl-containing acrylate monomer and the acrylate monomer.
In the first step, the diisocyanate compound is selected from isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate.
In the second step, the catalyst is selected from dibutyltin dilaurate, stannous octoate and dioctyltin dilaurate; the viscosity reducing solvent is selected from acetone and butanone; the hydrophilic chain extender is selected from the group consisting of bis (hydroxymethyl) propionic acid, bis (hydroxymethyl) butyric acid, sodium ethylene diamine sulfonate, sodium 1, 2-propanediol-3-sulfonate and sodium 1, 4-butanediol-2-sulfonate; the chain extender containing disulfide bonds is selected from thiuram disulfide glycol (TDS) and 2, 2-dithiodiethanol.
In the third step, the acrylate monomer containing hydroxyl is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.
In the fourth step, the acrylate monomer is selected from methyl acrylate, butyl acrylate and methyl methacrylate.
In the fifth step, the anionic emulsifier is selected from dodecyl sulfonic acid, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium didodecyl phenyl ether disulfonate; the nonionic emulsifier is selected from fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, and polyoxyethylene alkylolamide.
In the sixth step, the inorganic peroxide initiator is selected from hydrogen peroxide, ammonium persulfate and potassium persulfate.
The high-solid aqueous polyurethane acrylate dispersoid is prepared by the preparation method.
The high-solid aqueous polyurethane acrylate dispersion prepared by the method is mixed with a photoinitiator for coating on the surface of an object, and the high-solid aqueous polyurethane acrylate dispersion adopts a reasonable preparation method and preparation raw materials, so that the coating material has the function of automatically repairing fine cracks and scratches under the ultraviolet light or heating condition.
Example 1:
the method comprises the following steps: adding 5.55g of isophorone diisocyanate and 20g of polyester polyol into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, adjusting the temperature of the magnetic stirrer to 80 ℃, and the stirring speed to 300rpm, and fully reacting for 1 h.
Step two: adding 1-2 drops of dibutyltin dilaurate, adding 0.7665g of acetone into the reaction, and sequentially adding 0.7665g of bis (hydroxymethyl) propionic acid and 1.2775g of 2, 2-dithiodiethanol. The temperature of the reactants is adjusted to 75 ℃ and the reaction lasts for 3 hours.
Step three: the temperature is reduced to 50 ℃, 1.2775g of hydroxyethyl acrylate is added, and the reaction is carried out for 1 hour.
Step four: cooling to 30 ℃, adding 0.5777g of triethylamine for neutralization, wherein the neutralization time is 30min, then adding 70.3g of water, adjusting the stirring speed to 1500rpm, and reacting for 30 min.
Step five: heating to 50 ℃, adding 18g of methyl methacrylate and 12g of butyl acrylate, adding 0.3753g of sodium dodecyl sulfate and 0.1877g of fatty alcohol-polyoxyethylene ether, adjusting the stirring speed to 600rpm, and emulsifying for 1 h.
Step six: adjusting the stirring speed to 300rpm, heating to 75 ℃, weighing 0.2502g of ammonium persulfate, dissolving with 10g of water, and finishing the dropwise addition within 3 hours.
Step seven: and (3) plugging the bottle mouth, and carrying out heat preservation reaction for 1h to obtain the high-solid aqueous polyurethane acrylate emulsion containing the disulfide bond.
The coating material with self-repairing performance comprises the high-solid aqueous polyurethane acrylate dispersion containing disulfide bonds provided in the embodiment and a photoinitiator accounting for 1% of the mass of the acrylate monomer of the system, wherein the photoinitiator is 2-hydroxy-2-methyl-1-phenyl ketone.
Example 2:
the method comprises the following steps: adding 6.66g of isophorone diisocyanate and 20g of polyether polyol into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, adjusting the temperature of the magnetic stirrer to be 70 ℃, and the stirring speed to be 300rpm, and fully reacting for 2 hours.
Step two: adding 1-2 drops of dioctyltin dilaurate, adding 1.0664g of butanone into the reaction, and sequentially adding 1.0664g of bis (hydroxymethyl) butyric acid and 1.5996g of TDS. The temperature of the reactants is adjusted to 80 ℃ and the reaction lasts for 3 hours.
Step three: the temperature is reduced to 60 ℃, 1.8662g of hydroxyethyl methacrylate is added, and the reaction is carried out for 1 hour.
Step four: cooling to 30 ℃, adding 0.8038g of triethylamine for neutralization, wherein the neutralization time is 40min, then adding 77.8g of water, adjusting the stirring speed to 1500rpm, and reacting for 40 min.
Step five: heating to 50 ℃, adding 25.92g of methyl acrylate and 12.96g of butyl acrylate, adding 0.5433g of lauryl sodium sulfate and 0.2716g of fatty alcohol-polyoxyethylene ether, adjusting the stirring speed to 600rpm, and emulsifying for 1 h.
Step six: the stirring speed is adjusted to 300rpm, the temperature is raised to 80 ℃, 0.4075g of potassium persulfate is weighed and dissolved by 10g of water, and the dropwise addition is finished within 2.5 h.
Step seven: and (3) plugging the bottle mouth, and carrying out heat preservation reaction for 1h to obtain the high-solid aqueous polyurethane acrylate emulsion containing the disulfide bond.
The coating material with self-repairing performance comprises the high-solid aqueous polyurethane acrylate dispersion containing disulfide bonds provided by the embodiment and a photoinitiator accounting for 1.5 percent of the mass of the acrylate monomer of the system, wherein the photoinitiator is 1-hydroxycyclohexyl phenyl ketone.
Example 3:
the method comprises the following steps: adding 7.77g of hexamethylene diisocyanate and 20g of polyester polyol into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, adjusting the temperature of the magnetic stirrer to 70 ℃, and the stirring speed to 300rpm, and fully reacting for 1.5 h.
Step two: adding 1-2 drops of stannous octoate, adding 1.3885g of acetone in the reaction, and sequentially adding 1.1108g of ethylenediamine sodium sulfonate and 1.6662g of 2, 2-dithiodiethanol. The temperature of the reactants is adjusted to 80 ℃ and the reaction lasts for 3 hours.
Step three: the temperature is reduced to 55 ℃, 1.6662g of hydroxypropyl methacrylate is added, and the reaction is carried out for 1.5 h.
Step four: the temperature is reduced to 25 ℃, 78.4g of water is added, the stirring speed is adjusted to 1500rpm, and the reaction is carried out for 30 min.
Step five: heating to 40 ℃, adding 24.0012g of methyl methacrylate and 9.6004g of butyl acrylate, adding 0.4702g of dodecyl sulfonic acid and 0.2351g of alkylphenol polyoxyethylene, adjusting the stirring speed to 600rpm, and emulsifying for 2 h.
Step six: adjusting the stirring speed to 300rpm, heating to 80 ℃, weighing 0.5290g of ammonium persulfate, dissolving with 10g of water, and finishing the dropwise addition within 2 hours.
Step seven: and (3) plugging the bottle mouth, and carrying out heat preservation reaction for 1h to obtain the high-solid aqueous polyurethane acrylate emulsion containing the disulfide bond.
The coating material with self-repairing performance comprises the high-solid aqueous polyurethane acrylate dispersion containing disulfide bonds provided in the embodiment and a photoinitiator accounting for 2% of the mass of the acrylate monomer of the system, wherein the photoinitiator is 2-hydroxy-2-methyl-1-phenyl ketone.
Example 4:
the method comprises the following steps: 6.66g of toluene diisocyanate and 20g of polyester polyol are added into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, the mixture is uniformly mixed, the temperature of a magnetic stirrer is adjusted to be 75 ℃, the stirring speed is 300rpm, and the mixture is fully reacted for 1.5 h.
Step two: adding 1-2 drops of dibutyltin dilaurate, adding 1.333g of butanone into the reaction, and sequentially adding 1.5996g of bis (hydroxymethyl) butyric acid and 2.1328g of TDS. The temperature of the reactants is adjusted to 80 ℃ and the reaction lasts for 2.5 h.
Step three: the temperature is reduced to 60 ℃, 2.1328g of hydroxyethyl acrylate is added, and the reaction is carried out for 2 h.
Step four: cooling to 30 ℃, adding 1.2057g of triethylamine for neutralization, wherein the neutralization time is 40min, then adding 81.8g of water, adjusting the stirring speed to 1500rpm, and reacting for 30 min.
Step five: heating to 45 ℃, adding 31.3333g of methyl acrylate, 15.6667g of butyl acrylate, 0.7206g of didodecyl phenyl ether disulfonate and 0.3603g of polyoxyethylene fatty acid ester, adjusting the stirring speed to 600rpm, and emulsifying for 2 hours.
Step six: the stirring speed is adjusted to 300rpm, the temperature is raised to 80 ℃, 0.5896g of potassium persulfate is weighed and dissolved by 10g of water, and the dropwise addition is finished within 2.5 h.
Step seven: and (3) plugging the bottle mouth, and carrying out heat preservation reaction for 1h to obtain the high-solid aqueous polyurethane acrylate emulsion containing the disulfide bond.
The coating material with self-repairing performance comprises the high-solid-content water-based polyurethane acrylate dispersion containing the disulfide bond provided by the embodiment and a photoinitiator accounting for 1% of the mass of the acrylate monomer of the system, wherein the photoinitiator is 2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide.
Example 5:
the method comprises the following steps: adding 7.56g of diphenylmethane diisocyanate and 20g of polyether polyol into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, adjusting the temperature of the magnetic stirrer to be 90 ℃, and the stirring speed to be 300rpm, and fully reacting for 2 hours.
Step two: adding 1-2 drops of stannous octoate, adding 2.756g of acetone into the reaction, and sequentially adding 1.6536g of hydroxymethyl propionic acid and 2.4804g of TDS. The temperature of the reactants is adjusted to 80 ℃ and the reaction lasts for 3 hours.
Step three: the temperature is reduced to 55 ℃, 2.4804g of hydroxypropyl methacrylate is added, and the reaction is carried out for 1.5 h.
Step four: cooling to 40 ℃, adding 1.2463g of triethylamine for neutralization, wherein the neutralization time is 30min, then adding 89.1g of water, adjusting the stirring speed to 2000rpm, and reacting for 30 min.
Step five: heating to 50 ℃, adding 38.1767g of methyl methacrylate, 25.4511g of butyl acrylate, 0.8484g of sodium dodecyl sulfate and 0.4241g of polyoxyethylene alkyl alcohol amide, adjusting the stirring speed to 600rpm, and emulsifying for 2 hours.
Step six: adjusting the stirring speed to 300rpm, heating to 75 ℃, weighing 0.8594g of ammonium persulfate, dissolving with 10g of water, and finishing the dropwise addition within 2 hours.
Step seven: and (3) plugging the bottle mouth, and carrying out heat preservation reaction for 1h to obtain the high-solid aqueous polyurethane acrylate emulsion containing the disulfide bond.
The coating material with self-repairing performance comprises the high-solid aqueous polyurethane acrylate dispersion containing disulfide bonds provided by the embodiment and a photoinitiator accounting for 3% of the mass of the acrylate monomer of the system, wherein the photoinitiator is 1-hydroxycyclohexyl phenyl ketone.
Comparative example 1:
the method comprises the following steps: adding 5.55g of isophorone diisocyanate and 20g of polyester polyol into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, adjusting the temperature of the magnetic stirrer to 80 ℃, and the stirring speed to 300rpm, and fully reacting for 1 h.
Step two: adding 1-2 drops of dibutyltin dilaurate, adding 0.7665g of acetone into the reaction, and sequentially adding 0.7665g of bis (hydroxymethyl) propionic acid and 1.486g of 1, 4-butanediol. The temperature of the reactants is adjusted to 75 ℃ and the reaction lasts for 3 hours.
Step three: cooling to 30 ℃, adding 0.5777g of triethylamine for neutralization for 30min, adding 72.5g of water, adjusting the stirring speed to 1500rpm, and reacting for 30 min. Obtaining the aqueous polyurethane emulsion.
Comparative example 2:
the method comprises the following steps: adding 5.55g of isophorone diisocyanate and 20g of polyester polyol into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, adjusting the temperature of the magnetic stirrer to 80 ℃, and the stirring speed to 300rpm, and fully reacting for 1 h.
Step two: adding 1-2 drops of dibutyltin dilaurate, adding 0.7665g of acetone into the reaction, and sequentially adding 0.7665g of bis (hydroxymethyl) propionic acid and 1.486g of 1, 4-butanediol. The temperature of the reactants is adjusted to 75 ℃ and the reaction lasts for 3 hours.
Step three: the temperature is reduced to 50 ℃, 1.2775g of hydroxyethyl acrylate is added, and the reaction is carried out for 1 hour.
Step four: cooling to 30 ℃, adding 0.5777g of triethylamine for neutralization, wherein the neutralization time is 30min, then adding 70.3g of water, adjusting the stirring speed to 1500rpm, and reacting for 30 min.
Step five: heating to 50 ℃, adding 18g of methyl methacrylate and 12g of butyl acrylate, adding 0.3753g of sodium dodecyl sulfate and 0.1877g of fatty alcohol-polyoxyethylene ether, adjusting the stirring speed to 600rpm, and emulsifying for 1 h.
Step six: adjusting the stirring speed to 300rpm, heating to 75 ℃, weighing 0.2502g of ammonium persulfate, dissolving with 10g of water, and finishing the dropwise addition within 3 hours.
Step seven: and (3) plugging the bottle mouth, and carrying out heat preservation reaction for 1h to obtain the high-solid waterborne polyurethane acrylate emulsion.
Control evaluation
Table 1 shows the physical and chemical properties of aqueous polyurethane (WPU), high-solid aqueous urethane acrylate (AWPUA) and urethane acrylate containing disulfide bond (AWPUAS) emulsion. Wherein the AWPUAS2 was evaluated on the sample of example 2; WPU was prepared according to the sample method of comparative example 1, AWPUA was prepared according to the sample method of comparative example 2,
as can be seen from table 1, the solid content of the AWPUAS emulsion is significantly increased compared to the solid content of the WPU and AWPUA emulsions, and after introduction of the disulfide bond, the solid content of the AWPUAS can reach 52.7%, which emulsion is stable.
Table 1 shows the film properties of Waterborne Polyurethanes (WPU), high-solid waterborne urethane acrylates (AWPUA) and urethane acrylates containing disulfide bonds (AWPUAS). WPU was prepared according to the sample method of comparative example 1, AWPUA was prepared according to the sample method of comparative example 2, AWPUAS1, 2, 3 were prepared according to examples 1, 2, 4.
As can be seen from the coating properties in Table 2, the water absorption of AWPUA is lower than that of WPU, indicating that the hydrolysis resistance is effectively improved and that a crosslinking reaction occurs, so that the structure of the film is dense. The water and solvent resistance of AWPUAS1, 2, 3 was also significantly improved with increasing disulfide bond content compared to WPU and AWPUAS, and it was found that the stress strain increased with increasing disulfide bond content compared to their mechanical properties, because the number of hard segments increased with increasing disulfide content, the hard segments acting as physical cross-linking and reinforcing elements. Therefore, the modulus and the rigidity can also be increased along with the increase of the content of the disulfide, so the introduction of the disulfide bond can effectively improve the mechanical performance of the film formation, but the content of the disulfide bond is too large, so the proportion of soft satin in a molecular chain segment is reduced, the ductility of the film is reduced, the elongation at break of the film is reduced, and the proper content of the disulfide bond can endow the film with self-repairing performance while the film has better performance.
Claims (8)
1. The preparation method of the aqueous polyurethane acrylate dispersion is characterized by comprising the following steps:
reacting diisocyanate with polyester polyol or polyether polyol to obtain a polyurethane prepolymer, wherein the mass ratio of isocyanate groups to hydroxyl groups is (2.5-4): 1;
adding a viscosity-reducing solvent, a hydrophilic chain extender and a chain extender containing disulfide bonds, wherein the chain extender contains 5-10% of the total mass of diisocyanate, polyester polyol and polyether polyol, and reacting to obtain a first mixed solution;
adding a first acrylate monomer accounting for 5-10% of the total mass of diisocyanate, polyester polyol and polyether polyol into the first mixed solution, and reacting to obtain a double-bond-terminated polyurethane prepolymer;
adding water into the double-bond end-capped polyurethane prepolymer for emulsification, removing the solvent to prepare a second mixed solution, adding a second acrylate monomer, and adding an anionic emulsifier and a nonionic emulsifier for reaction; then adding an inorganic peroxide initiator to initiate free radical polymerization reaction, and completely reacting to obtain the aqueous polyurethane acrylate dispersoid;
the anionic emulsifier is dodecyl sulfonic acid, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate or sodium didodecyl phenyl ether disulfonate; the nonionic emulsifier is fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester or polyoxyethylene alkylolamide.
2. The method of claim 1, wherein the viscosity-reducing solvent is at least one of acetone and butanone; the dosage of the viscosity reducing solvent is 3-10% of the total mass of the diisocyanate, the polyester polyol and the polyether polyol; the hydrophilic chain extender is at least one of bis-hydroxymethyl propionic acid, bis-hydroxymethyl butyric acid, ethylene diamine sodium sulfonate, 1, 2-propylene glycol-3-sodium sulfonate and 1, 4-butanediol-2-sodium sulfonate; the using amount of the hydrophilic chain extender is 3-6% of the total mass of the diisocyanate, the polyester polyol and the polyether polyol; the first acrylate monomer is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; the chain extender containing disulfide bonds is at least one of thiuram disulfide glycol and 2, 2-dithiodiethanol.
3. The method of claim 1, wherein the reaction temperature of the diisocyanate and the polyester polyol or polyether polyol is 70 to 90 ℃ and the reaction time is 1 to 3 hours; in the preparation process of the first mixed solution, the reaction temperature is 55-85 ℃, and the reaction time is 1-3 h; the reaction temperature after the first acrylate monomer is added is 50-60 ℃, and the reaction time is 1-2 h.
4. The method of claim 1, wherein the second acrylate monomer is at least one of methyl acrylate, butyl acrylate, methyl methacrylate; the amount of the second acrylic ester monomer is 30-50% of the total mass of the second mixed solution.
5. The method of claim 1, wherein the inorganic peroxide initiator is at least one of hydrogen peroxide, ammonium persulfate, and potassium persulfate; the dosage of the inorganic peroxide initiator is 0.8-1.5% of the total mass of the first acrylate monomer and the second acrylate monomer.
6. An aqueous polyurethane acrylate dispersion obtainable by the process according to any one of claims 1 to 5.
7. A coating composition with self-repairing performance is characterized by comprising the aqueous polyurethane acrylate dispersion disclosed by claim 6 and a photoinitiator accounting for 1-3% of the total mass of the first acrylate monomer and the second acrylate monomer in the dispersion.
8. The composition of claim 7, wherein the photoinitiator is one or more of 2-hydroxy-2-methyl-1-phenyl methanone, 1-hydroxycyclohexyl phenyl methanone, 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide.
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