CN109666124B - Polystyrene microsphere modified polyurethane waterborne resin and preparation method thereof - Google Patents
Polystyrene microsphere modified polyurethane waterborne resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polystyrene microsphere modified polyurethane waterborne resin, which is prepared by polymerizing amine modified polystyrene microspheres, oligomer polyol, isocyanate and a hydrophilic agent into a prepolymer, carrying out alcohol chain extension under a catalyst, emulsifying amine and water, and then carrying out chain extension with amine; the amine modified polystyrene microsphere is prepared by performing chloromethylation reaction on a polystyrene crosslinking microsphere and then reacting with an amine modifier. The invention provides a preparation method of polystyrene microsphere modified polyurethane waterborne resin; the polystyrene microsphere modified polyurethane aqueous resin prepared by the invention has high hardness and storage stability, and the coating has excellent adhesive force, wear resistance, hot water resistance, temperature resistance, aging resistance, stain resistance, crack resistance and corrosion resistance, can be used alone or blended with other aqueous resins, and is used for aqueous wood coatings, aqueous terrace coatings, aqueous steel coatings, aqueous engineering coatings, aqueous heat insulation coatings and aqueous anticorrosive coatings.
Description
Technical Field
The invention relates to a modified polyurethane waterborne resin, in particular to a polystyrene microsphere modified polyurethane waterborne resin, belonging to the technical field of waterborne resins.
Technical Field
Strict environmental regulations are successively made at home and abroad to limit the emission of Volatile Organic Compounds (VOC) to the atmosphere, and high-performance and environmental protection become the development direction of coatings. The synthesis of polyurethane resin is changed from the traditional solvent type to the waterborne polyurethane, the waterborne polyurethane coating takes water as a solvent, has the advantages of no pollution, safety, reliability, excellent mechanical property, good compatibility, easy modification and the like, is famous for durability and chemical resistance, and is favored by users in the fields of wood lacquer and automobile coating due to excellent performance.
However, polyurethane emulsion has the disadvantages of small solid content, long film forming time, low coating flammability point and the like, and a great deal of research and application of modified waterborne polyurethane exists in patents and articles.
Chinese patent CN105461863A discloses an acrylate modified waterborne polyurethane emulsion and a preparation method thereof, wherein acrylate is used for modifying waterborne polyurethane to obtain a polyurethane material with excellent comprehensive performance, acrylate is used for participating in reaction to introduce double bonds into a polyurethane main chain, and then polymerization of acrylic monomers is initiated to form a complex network structure.
The polystyrene microspheres can be used for preparing ion exchange resin, chelating resin and adsorption resin; the synthesizable catalyst carrier is used for organic synthesis and combined chemical systems; also can be used for preparing functional polymer microspheres for immobilization, separation and purification of biological macromolecules and chromatographic stationary phases. However, the modification of the polystyrene microspheres for the waterborne polyurethane resin has not been reported.
Disclosure of Invention
The invention provides a polystyrene microsphere modified polyurethane waterborne resin and a preparation method thereof.
Functional groups introduced into the surface of the polystyrene microsphere at present comprise carboxyl, amino, aldehyde group, ketone group, ester group, sulfonic group, chloromethyl, halogen, acyl chloride group, sulfonyl chloride group and the like, so that more new functions are provided for the microsphere; according to the invention, the amine modified polystyrene microspheres are used as functional monomers, and then the polystyrene microspheres are introduced into the molecular structure of polyurethane through a polymerization reaction, so that the hardness, the crack resistance, the temperature resistance, the wear resistance, the water resistance and the corrosion resistance of the coating can be effectively improved.
In order to solve the technical problem, the invention adopts the following technical scheme that the polystyrene microsphere modified polyurethane waterborne resin comprises the following components in parts by weight: 8.0-16.0 parts of amine modified polystyrene microspheres, 15.0-25.0 parts of oligomer polyhydric alcohol, 10.0-25.0 parts of diisocyanate, 3.0-6.0 parts of hydrophilic modifier, 10.0-25.0 parts of solvent A, 0.03-0.4 part of catalyst, 3.0-8.0 parts of small molecular alcohol chain extender, 2.0-5.0 parts of triethylamine, 0.8-2.0 parts of organic amine chain extender and 100.0-160.0 parts of deionized water.
The preparation method of the amine modified polystyrene microsphere comprises the following steps:
a) adding the polystyrene crosslinked microspheres and the solvent B into a four-neck flask provided with a stirrer and a thermometer, stirring to fully swell the microspheres, adding 1, 4-dichloromethoxybutane and SnCl4Controlling the temperature below 25 ℃ for reaction for 5-8 h, and using dilute hydrochloric acid to sufficiently wash off attached SnCl after the reaction is finished4Carrying out suction filtration; washing with 1, 4-dioxane to remove residual solvent B, washing with distilled water and ethanol, and drying at 60 deg.C under vacuum for 12 hr to obtain chloromethylated polystyrene microsphere;
the main raw materials comprise the following components in parts by weight: 3.0-5.0 parts of polystyrene crosslinked microspheres, 30.0-50.0 parts of solvent A, 15.0-25.0 parts of 1, 4-dichloromethoxybutane, and SnCl43.5-6.0 parts;
b) adding chloromethylated polystyrene microspheres and a solvent C into a four-neck flask provided with a stirrer and a thermometer, stirring until the materials are fully swelled, adding primary diamine and triethylamine, stirring at room temperature for reaction for 4-8 h, evaporating the solvent C under reduced pressure after the reaction is finished, dissolving a solid in dichloromethane, washing 3-5 times with a 3% sodium bicarbonate solution and a 3% acetic acid solution in sequence, drying with anhydrous magnesium sulfate, evaporating dichloromethane under reduced pressure, recrystallizing with petroleum ether twice, and drying at 60 ℃ for 12h under vacuum to obtain the amine modified polystyrene microspheres;
the main raw materials comprise the following components in parts by weight: 3.0-6.0 parts of chloromethylated polystyrene microspheres, 0.3-1.0 part of diprimary amine, 15.0-30.0 parts of solvent B, 0.5-1.5 parts of triethylamine and 15.0-30.0 parts of dichloromethane.
The polystyrene crosslinked microspheres are polystyrene-divinylbenzene crosslinked microspheres with the crosslinking degree of 4-8%, and the particle size of the microspheres is 0.5-5 mu m.
The diprimary amine is at least one of ethylenediamine, 1, 3-propanediamine, 1, 4-butanediamine, 1, 5-pentanediamine or 1, 6-hexanediamine.
The solvent A is at least one of acetone, butanone, ethyl acetate, cyclohexanone or N-methyl pyrrolidone.
The solvent B is at least one of dichloromethane, chloroform, carbon tetrachloride and tetrachloroethane.
The solvent C is at least one of isopropyl alcohol, toluene, xylene, methyl ethyl ketone, ethyl acetate and butyl acetate.
The oligomer polyol is polyester polyol or polyether polyol; the polyester polyol is at least one of polybutylene adipate diol, polycarbonate diol or polycaprolactone diol, and the number average molecular weight Mn of the polyester polyol is 1000-3000; the polyether polyol is at least one of polytetrahydrofuran ether glycol, polytetramethylene ether glycol or polypropylene oxide ether glycol, and the number average molecular weight Mn of the polyether polyol is 1000-3000.
The diisocyanate is at least one of HDI, MDI, IPDI or HMDI.
The hydrophilic modifier is at least one of 2-hydroxypropionic acid, 2-pyrrolidone, 3-hydroxypropionic acid or 2-hydroxybutyric acid.
The catalyst is alkali metal carboxylate, organic metal compound, phosphorus-containing compound or amine compound; further, at least one of dibutyltin dilaurate, lithium acetate, tri-n-butylphosphor, stannous octoate, tin naphthenate, lead naphthenate, cobalt naphthenate, dibutyltin maleate, and dibutyltin diacetate is preferable.
The chain extender of the micromolecule alcohol is at least one of ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 5-pentanediol, trimethylolpropane, neopentyl glycol or diethylene glycol.
The organic amine chain extender is at least one of ethylenediamine, diethylenetriamine, hexamethylenediamine or piperazine.
The invention provides a preparation method of polystyrene microsphere modified polyurethane waterborne resin, which comprises the following steps:
a) in a four-necked flask equipped with a stirrer and a thermometer in parts by weight, in the presence of N2Under protection and stirring, sequentially adding diisocyanate, amine modified polystyrene microspheres, oligomer polyol and a hydrophilic modifier, controlling the temperature to be 75-95 ℃ for reaction for 1-3 hours, sampling and detecting, and cooling to 60-70 ℃ to stop the reaction when the measured-NCO value reaches a specified theoretical value;
b) adding a solvent A to adjust the viscosity of the system, adding a small molecular alcohol chain extender and a catalyst under the stirring of the rotation speed of 500-600 rpm, starting sampling and detecting after 1h, and cooling to room temperature to stop the reaction when the measured-NCO value reaches a specified theoretical value to obtain a modified polyurethane prepolymer;
c) adding 10-20% of deionized water into an organic amine chain extender in advance to prepare an organic amine chain extender aqueous solution;
d) adding triethylamine under the condition of keeping stirring speed, and reacting for 10-20 min; adding the rest deionized water, and increasing the rotating speed to 1000-1500 rpm for emulsification for 10-30 min; dropping an organic amine chain extender aqueous solution at a reduced stirring speed of 500-600 rpm, keeping the reaction at room temperature for 1-2 h after dropping within 15-30 min; and distilling the solvent A under reduced pressure to obtain the polystyrene microsphere modified polyurethane waterborne resin.
The polystyrene microsphere modified polyurethane aqueous resin prepared by the invention has high transparency, high gloss, high hardness and storage stability, and the prepared coating has excellent adhesion, wear resistance, hot water resistance, temperature resistance, aging resistance, stain resistance, crack resistance and corrosion resistance, can be used alone or blended with other aqueous resins, and is used for aqueous wood coatings, aqueous floor coatings, aqueous steel structure coatings, aqueous engineering coatings, aqueous heat insulation coatings and aqueous anticorrosive coatings.
Detailed Description
The polystyrene microsphere modified polyurethane waterborne resin of the invention is further described with reference to the following examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1
An amine modified polystyrene microsphere X is prepared by the following steps:
a) and preparing chloromethylated polystyrene crosslinked microspheres: adding 3 parts by weight of polystyrene crosslinked microspheres with the crosslinking degree of 5 percent and 30 parts by weight of dichloromethane into a four-neck flask provided with a stirrer and a thermometer, stirring to fully swell the microspheres, adding 15.6 parts by weight of 1, 4-dichloromethoxybutane and SnCl43.5 parts of the mixture is reacted for 5 hours at the temperature of 22 ℃, and after the reaction is finished, diluted hydrochloric acid is used for fully washing off the attached catalyst, and the filtration is carried out; washing with 1, 4-dioxane to remove residual solvent, washing with distilled water and ethanol, and vacuum drying to obtain chloromethylated polystyrene microsphere;
b) dissolving 3.0 parts of chloromethylated polystyrene microspheres in 15.0 parts of methyl ethyl ketone, stirring until the microspheres are fully swelled, adding 0.4 part of 1, 6-hexanediamine and 0.5 part of triethylamine, stirring at room temperature for reaction for 5 hours, evaporating the methyl ethyl ketone under reduced pressure after the reaction is finished, dissolving the solid in 20.0 parts of dichloromethane, washing with 3% sodium bicarbonate solution and 3% acetic acid solution for 4 times, drying with anhydrous magnesium sulfate, evaporating the dichloromethane under reduced pressure, recrystallizing with petroleum ether twice, and drying at 60 ℃ for 12 hours under vacuum to obtain the amine modified polystyrene microspheres X.
Example 2
An amine modified polystyrene microsphere Y is prepared by the following steps:
a) adding 4.5 parts by weight of polystyrene crosslinked microspheres with the crosslinking degree of 6% and 45 parts by weight of dichloromethane into a four-neck flask provided with a stirrer and a thermometer, stirring to fully swell the microspheres, adding 22.8 parts by weight of 1, 4-dichloromethoxybutane and SnCl45.2 parts of the catalyst, controlling the temperature to react for 8 hours at 25 ℃, using dilute hydrochloric acid to fully wash off the attached catalyst after the reaction is finished, and performing suction filtration; washing with 1, 4-dioxane to remove residual solvent, washing with distilled water and ethanol, and vacuum drying to obtain chloromethylated polystyrene microsphere;
b) adding 6.0 parts of chloromethylated polystyrene microspheres into 20.0 parts of a mixed solvent of methyl ethyl ketone and butyl acetate, stirring until the mixture is fully swelled, adding 0.8 part of 1, 3-propane diamine and 1.0 part of triethylamine, stirring at room temperature for reaction for 8 hours, evaporating the solvent under reduced pressure after the reaction is finished, dissolving the solid in 30.0 parts of dichloromethane, washing with 3% sodium bicarbonate solution and 3% acetic acid solution for 5 times, drying with anhydrous magnesium sulfate, evaporating dichloromethane under reduced pressure, recrystallizing with petroleum ether twice, and drying at 60 ℃ for 12 hours under vacuum to obtain the amine modified polystyrene microspheres Y.
Example 3
An amine modified polystyrene microsphere Z is prepared by the following steps:
a) adding 4.0 parts by weight of polystyrene crosslinked microspheres with the crosslinking degree of 8% and 42 parts by weight of dichloromethane into a four-neck flask provided with a stirrer and a thermometer, stirring to fully swell the microspheres, adding 21 parts by weight of 1, 4-dichloromethoxybutane and a catalyst SnCl44.8 parts of the catalyst, controlling the temperature to react for 6 hours at 25 ℃, using dilute hydrochloric acid to fully wash off the attached catalyst after the reaction is finished, and performing suction filtration; washing with 1, 4-dioxane to remove residual solvent, washing with distilled water and ethanol, and vacuum drying to obtain chloromethylated polystyrene microsphere;
b) adding 5.0 parts of chloromethylated polystyrene microspheres into 18.0 parts of methyl ethyl ketone, stirring until the chloromethylated polystyrene microspheres are fully swelled, adding 0.6 part of ethylenediamine and 0.6 part of triethylamine, stirring at room temperature for reaction for 6 hours, evaporating the methyl ethyl ketone under reduced pressure after the reaction is finished, dissolving a solid in 25.0 parts of dichloromethane, washing with 3% sodium bicarbonate solution and 3% acetic acid solution for 5 times in sequence, drying with anhydrous magnesium sulfate, evaporating the dichloromethane under reduced pressure, recrystallizing with petroleum ether twice, and drying at 60 ℃ for 12 hours under vacuum to obtain the amine modified polystyrene microspheres Z.
Example 4
The polystyrene microsphere modified polyurethane waterborne resin A comprises the following raw materials in parts by weight: 10.0 parts of amine modified polystyrene microsphere X, 25.0 parts of polybutylene adipate glycol (Mn is 2000), 18.0 parts of HDI, 3.0 parts of 2-hydroxypropionic acid, 12.0 parts of N-methylpyrrolidone, 0.08 part of dibutyltin dilaurate, 2.0 parts of ethylene glycol, 2.0 parts of triethylamine, 0.8 part of hexamethylenediamine and 120.0 parts of deionized water;
the preparation method of the polystyrene microsphere modified polyurethane waterborne resin A comprises the following steps:
a) in a four-necked flask equipped with a stirrer and a thermometer, under N2Under protection and stirring, sequentially adding HDI, amine modified polystyrene microsphere X, polybutylene adipate glycol and 2-hydroxypropionic acid, controlling the temperature to be 80 ℃, reacting for 3 hours, sampling and detecting, and cooling to 60 ℃ to stop the reaction when the measured-NCO value reaches the specified theoretical value;
b) adding N-methyl pyrrolidone to adjust the viscosity of the system, adding ethylene glycol and dibutyltin dilaurate while stirring at the rotating speed of 500-600 rpm, starting sampling and detecting after 1h, and cooling to room temperature to stop the reaction when the measured-NCO value reaches a specified theoretical value to obtain a modified polyurethane prepolymer;
c) adding 12.0 parts of deionized water into 0.8 part of hexamethylene diamine to prepare a hexamethylene diamine aqueous solution;
d) adding triethylamine under the condition of keeping stirring speed, and reacting for 15 min; then 108.0 parts of deionized water is added, and the rotating speed is increased to 1200rpm for emulsification for 20 min; dropping a hexamethylenediamine aqueous solution at a reduced stirring speed of 500-600 rpm, finishing dropping within 30min, and keeping the reaction at room temperature for 1.5 h; and distilling the N-methyl pyrrolidone under reduced pressure to obtain the polystyrene microsphere modified polyurethane waterborne resin A.
Example 5
A polystyrene microsphere modified polyurethane waterborne resin B comprises the following components in parts by weight: 15.0 parts of amine modified polystyrene microsphere Y, 25.0 parts of polytetrahydrofuran ether glycol (Mn is 1500), 25.0 parts of IPDI, 4.0 parts of 3-hydroxypropionic acid, 15.0 parts of 2-pyrrolidone, 0.2 part of stannous octoate, 3.0 parts of 1, 6-hexanediol, 4.0 parts of triethylamine, 1.0 part of ethylenediamine and 145.0 parts of deionized water;
the preparation method of the polystyrene microsphere modified polyurethane waterborne resin B comprises the following steps:
a) in a four-necked flask equipped with a stirrer and a thermometer, under N2Under protection and stirring, sequentially adding IPDI, amine modified polystyrene microsphere Y, polytetrahydrofuran ether glycol and 3-hydroxypropionic acid, controlling the temperature to 85 ℃ for reaction for 2h, sampling and detecting, and when the measured-NCO value reaches a specified theoretical value, cooling to 70 ℃ to stop the reaction;
b) adding 2-pyrrolidone to adjust the viscosity of the system, adding 1, 6-hexanediol and stannous octoate under stirring at the rotating speed of 500-600 rpm, starting sampling and detecting after 1h, and cooling to room temperature to stop reaction when the measured-NCO value reaches a specified theoretical value to obtain a modified polyurethane prepolymer;
c) adding 15.0 parts of deionized water into 1.0 part of ethylenediamine to prepare an ethylenediamine aqueous solution;
d) adding triethylamine under the condition of keeping stirring speed, and reacting for 15 min; then 130.0 parts of deionized water is added, and the rotating speed is increased to 1300rpm for emulsification for 15 min; dropping an ethylenediamine aqueous solution at a reduced stirring speed of 500-600 rpm, finishing dropping within 30min, and keeping reacting at room temperature for 1 h; and distilling the 2-pyrrolidone under reduced pressure to obtain the polystyrene microsphere modified polyurethane waterborne resin B.
Example 6
The polystyrene microsphere modified polyurethane waterborne resin C comprises the following components in parts by weight: 20.0 parts of amine modified polystyrene microsphere Z, 20.0 parts of polytetramethylene ether glycol (Mn is 3000), 25.0 parts of HDI, 6.0 parts of 2-hydroxybutyric acid, 15.0 parts of acetone, 0.3 part of dibutyltin maleate, 4.0 parts of 1, 6-hexanediol, 4.0 parts of triethylamine, 2.0 parts of diethylenetriamine and 160.0 parts of deionized water;
the preparation method of the polystyrene microsphere modified polyurethane waterborne resin C comprises the following steps:
a) in a four-necked flask equipped with a stirrer and a thermometer, under N2Under protection and stirring, sequentially adding HDI, amine modified polystyrene microspheres Z, polytetramethylene ether glycol and 2-hydroxybutyric acid, controlling the temperature to 90 ℃ for reacting for 2.5h, sampling and detecting, and cooling to 70 ℃ to stop the reaction when the measured-NCO value reaches the specified theoretical value;
b) adding acetone to adjust the viscosity of the system, adding 1, 6-hexanediol and dibutyltin maleate under stirring at the rotating speed of 500-600 rpm, starting sampling and detecting after 1h, and cooling to room temperature to stop reaction when the measured-NCO value reaches a specified theoretical value to obtain a modified polyurethane prepolymer;
c) adding 16.0 parts of deionized water into 2.0 parts of diethylenetriamine to prepare a diethylenetriamine aqueous solution;
d) adding triethylamine under the condition of keeping stirring speed, and reacting for 20 min; then 130.0 parts of deionized water is added, and the rotating speed is increased to 1300rpm for emulsification for 20 min; dropping a diethylenetriamine aqueous solution at a reduced stirring speed of 500-600 rpm, finishing dropping within 25min, and keeping reacting for 2h at room temperature; and distilling the acetone under reduced pressure to obtain the polystyrene microsphere modified polyurethane waterborne resin C.
The polystyrene microsphere modified polyurethane aqueous resin in the embodiment of the invention is prepared into an aqueous industrial coating, and the aqueous industrial coating and the commercial aqueous polyurethane industrial coating (comparative example) are subjected to performance comparison test under the same condition, and the test data is shown in table 1:
TABLE 1 technical indexes of performance of polystyrene microsphere modified polyurethane waterborne coating
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the following claims.
Claims (10)
1. A preparation method of polystyrene microsphere modified polyurethane waterborne resin is characterized by comprising the following steps: the preparation method comprises the following steps:
a) in a four-necked flask equipped with a stirrer and a thermometer, under N2Under protection and stirring, sequentially adding diisocyanate, amine modified polystyrene microspheres, oligomer polyol and a hydrophilic modifier, controlling the temperature to be 75-95 ℃ for reaction for 1-3 hours, sampling and detecting, and cooling to 60-70 ℃ to stop the reaction when the measured-NCO value reaches a specified theoretical value;
b) adding a solvent A to adjust the viscosity of the system, adding a small molecular alcohol chain extender and a catalyst under the stirring of the rotation speed of 500-600 rpm, starting sampling and detecting after 1h, and cooling to room temperature to stop the reaction when the measured-NCO value reaches a specified theoretical value to obtain a modified polyurethane prepolymer;
c) adding 10-20% of deionized water into an organic amine chain extender in advance to prepare an organic amine chain extender aqueous solution;
d) adding triethylamine under the condition of keeping stirring speed, and reacting for 10-20 min; adding the rest deionized water, and increasing the rotating speed to 1000-1500 rpm for emulsification for 10-30 min; dropping an organic amine chain extender aqueous solution at a reduced stirring speed of 500-600 rpm, keeping the reaction at room temperature for 1-2 h after dropping within 15-30 min; distilling the solvent A under reduced pressure to obtain the polystyrene microsphere modified polyurethane waterborne resin;
the raw materials comprise the following components in parts by weight:
8.0-16.0 parts of amine modified polystyrene microsphere
Oligomer polyol 15.0-25.0 parts
10.0 to 25.0 parts of diisocyanate
3.0-6.0 parts of hydrophilic modifier
10.0-25.0 parts of solvent A
0.03-0.4 part of catalyst
3.0-8.0 parts of micromolecular alcohol chain extender
2.0 to 5.0 portions of triethylamine
0.8-2.0 parts of organic amine chain extender
100.0-160.0 parts of deionized water;
the preparation method of the amine modified polystyrene microsphere comprises the following steps:
a) adding the polystyrene crosslinked microspheres and the solvent B into a four-neck flask provided with a stirrer and a thermometer, stirring to fully swell the microspheres, adding 1, 4-dichloromethoxybutane and SnCl4Controlling the temperature below 25 ℃ for reaction for 5-8 h, and using dilute hydrochloric acid to fully wash off attached SnCl after the reaction is finished4Carrying out suction filtration; washing with 1, 4-dioxane to remove residual solvent B, washing with distilled water and ethanol, and vacuum drying at 60 deg.C for 12 hr to obtain chloromethylated polystyrene microsphere;
the main raw materials comprise the following components in parts by weight: 3.0-5.0 parts of polystyrene crosslinked microspheres, 30.0-50.0 parts of solvent B, 15.0-25.0 parts of 1, 4-dichloromethoxybutane, and SnCl43.5-6.0 parts;
b) adding chloromethylated polystyrene microspheres and a solvent C into a four-neck flask provided with a stirrer and a thermometer, stirring until the materials are fully swelled, adding primary diamine and triethylamine, stirring at room temperature for reaction for 4-8 h, evaporating the solvent C under reduced pressure after the reaction is finished, dissolving a solid in dichloromethane, washing 3-5 times with a 3% sodium bicarbonate solution and a 3% acetic acid solution in sequence, drying with anhydrous magnesium sulfate, evaporating dichloromethane under reduced pressure, recrystallizing with petroleum ether twice, and drying at 60 ℃ for 12h under vacuum to obtain the amine modified polystyrene microspheres;
the main raw materials comprise the following components in parts by weight: 3.0-6.0 parts of chloromethylated polystyrene microspheres, 0.3-1.0 part of diprimary amine, 15.0-30.0 parts of solvent B, 0.5-1.5 parts of triethylamine and 15.0-30.0 parts of dichloromethane.
2. The method of claim 1, wherein: the oligomer polyol is polyester polyol or polyether polyol; the polyester polyol is at least one of polybutylene adipate dihydric alcohol, polycarbonate dihydric alcohol or polycaprolactone dihydric alcohol, and the number average molecular weight Mn of the polyester polyol is 1000-3000; the polyether polyol is at least one of polytetrahydrofuran ether glycol and polypropylene oxide ether glycol, and the number average molecular weight Mn of the polyether polyol is 1000-3000.
3. The method of claim 1, wherein: the diisocyanate is at least one of HDI, MDI, IPDI or HMDI.
4. The method of claim 1, wherein: the hydrophilic modifier is at least one of 2-hydroxypropionic acid, 2-pyrrolidone, 3-hydroxypropionic acid or 2-hydroxybutyric acid; the catalyst is alkali metal carboxylate, phosphorus-containing compound or amine compound.
5. The method of claim 1, wherein: the catalyst is at least one of dibutyltin dilaurate, lithium acetate, tri-n-butyl phosphorus, stannous octoate, tin naphthenate, lead naphthenate, cobalt naphthenate, dibutyltin maleate or dibutyltin diacetate.
6. The method of claim 1, wherein: the solvent A is at least one of acetone, butanone, ethyl acetate, cyclohexanone or N-methyl pyrrolidone; the solvent B is at least one of dichloromethane, chloroform, carbon tetrachloride and tetrachloroethane; the solvent C is at least one of isopropyl, toluene, xylene, methyl ethyl ketone, ethyl acetate and butyl acetate.
7. The method of claim 1, wherein: the chain extender of the micromolecule alcohol is at least one of ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 5-pentanediol, trimethylolpropane, neopentyl glycol or diethylene glycol.
8. The method of claim 1, wherein: the organic amine chain extender is at least one of ethylenediamine, diethylenetriamine, hexamethylenediamine or piperazine.
9. The method of claim 1, wherein: the diprimary amine is at least one of ethylenediamine, 1, 3-propanediamine, 1, 4-butanediamine, 1, 5-pentanediamine or 1, 6-hexanediamine.
10. The method of claim 1, wherein: the polystyrene crosslinked microspheres are polystyrene-divinylbenzene crosslinked microspheres with the crosslinking degree of 4-8%, and the particle size of the microspheres is 0.5-5 mu m.
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| CN106589414A (en) * | 2016-12-30 | 2017-04-26 | 合众（佛山）化工有限公司 | Compound magnetic microsphere hydrogel prepared through waterborne ATRP polymerization method |
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| US5334650A (en) * | 1992-09-29 | 1994-08-02 | Basf Corporation | Polyurethane coating composition derived from long-chain aliphatic polyol |
| US6465566B2 (en) * | 2000-07-06 | 2002-10-15 | Omnova Solutions Inc. | Anionic waterborne polyurethane dispersions containing polyfluorooxetanes |
| CN101250374B (en) * | 2008-04-03 | 2011-07-27 | 同济大学 | Nano hollow silica dioxide micro-sphere/polyurethane composite aqueous paint and preparation method thereof |
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| US8354151B1 (en) * | 2011-07-06 | 2013-01-15 | Bayer Materialscience Llc | Waterborne polyurethane coating compositions |
| CN105080604B (en) * | 2014-05-16 | 2017-09-05 | 中北大学 | A kind of crosslinked polystyrene microsphere surface synthesis and the preparation method of immobilized N hydroxyphthalimides catalyst |
| CN105732940A (en) * | 2016-05-11 | 2016-07-06 | 江南大学 | Preparation method of waterborne polyurethane-silicon dioxide nano composite emulsion |
| CN106750155A (en) * | 2016-12-23 | 2017-05-31 | 浙江工业大学 | A kind of preparation method of aqueous polyurethane/fluorine-containing polyphosphazene microspheres composite |
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