CN109666124A - A kind of polystyrene microsphere modified polyurethane water-base resin and preparation method - Google Patents
A kind of polystyrene microsphere modified polyurethane water-base resin and preparation method Download PDFInfo
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- CN109666124A CN109666124A CN201811520428.3A CN201811520428A CN109666124A CN 109666124 A CN109666124 A CN 109666124A CN 201811520428 A CN201811520428 A CN 201811520428A CN 109666124 A CN109666124 A CN 109666124A
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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
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/6283—Polymers of nitrogen containing compounds having carbon-to-carbon double bonds
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/30—Low-molecular-weight compounds
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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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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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The present invention relates to a kind of polystyrene microsphere modified polyurethane water-base resins, prepolymer is aggregated by amine Modified polystyrene spheres, oligomer polyol, isocyanates and hydrophilic agent, alcohol chain extension is carried out under catalyst, is then carried out chain extension with amine again after amine, water emulsification and is made；The amine Modified polystyrene spheres pass through chloromethylation by polystyrene crosslinked microsphere, then react and be made with amine modifying agent.The present invention provides a kind of preparation method of polystyrene microsphere modified polyurethane water-base resin；Polystyrene microsphere modified polyurethane water-base resin produced by the present invention, with high rigidity and storage stability, its coating has excellent adhesive force, wearability, hot water resistance, temperature tolerance, resistance to ag(e)ing, stain resistance, crack resistance and corrosion resistance, both can be used alone can also be blended with other water-base resins, be used for water-borne wood coating, aqueous floor coatings, aqueous steel structure coating, aqueous engineering coating, Water-based thermal insulation coating and water-based anticorrosive paint.
Description
Technical field
The present invention relates to a kind of modified polyurethane water-base resin more particularly to a kind of polystyrene microsphere modified polyurethanes
Water-base resin belongs to water-base resin technical field.
Technical background
Both at home and abroad formulated severe environmental regulation in succession limit volatile organic compounds (VOC) to atmosphere discharge,
High-performance, environmental protection have become the direction of paint development.The synthesis of polyurethane resin is by traditional solvent type hydrotropism's polyurethane
Transformation, aqueous polyurethane coating take water as a solvent, and with pollution-free, safe and reliable, good mechanical performance, compatibility is good, is easy to
It is the advantages that modified, famous with its durability and chemical resistance, in woodcare paint field with car paint field since its is excellent
Performance, the favor by user.
But that there are solid contents is smaller for polyaminoester emulsion, film formation time is long, coating can the disadvantages such as burning point is low, in patent and article
It is delivered in the presence of a large amount of related modified aqueous polyurethane researchs with what is applied.
Chinese patent CN105461863A discloses a kind of acrylic ester modified water-soluble polyurethane lotion and preparation method thereof,
Aqueous polyurethane is modified using acrylate, the polyurethane material of excellent combination property is obtained, is joined using acrylate
Double bond is introduced into polyurethane backbone with reacting, then causes the polymerization of acrylic monomers, is capable of forming complicated reticular structure,
For the traditional waterborne polyurethane that compares, water resistance, heat resistance, mechanical property are significantly improved.
Polystyrene microsphere can prepare ion exchange resin, chelating resin and absorption resin；It can synthesis catalytic agent carrier use
In organic synthesis and combinatorial chemistry system；It can also prepare micro- for the functional polymer of large biological molecule immobilization, separation, purifying
Ball and chromatographic stationary phases.But polystyrene microsphere is for the modification of waterborne polyurethane resin that there is not yet reported.
Summary of the invention
The present invention provides a kind of polystyrene microsphere modified polyurethane water-base resin and preparation method thereof.
At present to Surfaces of Polystyrene Microparticles introduce functional group have carboxyl, amino, aldehyde radical, ketone group, ester group, sulfonic group,
Chloromethyl, halogen, acid chloride group, sulfuryl chlorio etc. give microballoon more new functions；The present invention is micro- using amine modified polystyrene
Ball, then by polymerization reaction, introduces polystyrene microsphere in polyurethane molecular structure, can effectively improve as function monomer
Hardness, drawing crack, temperature tolerance, wearability, water resistance and the corrosion resistance of coating.
In order to solve the technical problem, the present invention takes following technical scheme, a kind of polystyrene microsphere
Modified polyurethane water-base resin, according to parts by weight, ingredient are as follows: 8.0~16.0 parts of amine Modified polystyrene spheres, 15.0~
25.0 parts of oligomer polyols, 10.0~25.0 parts of diisocyanate, 3.0~6.0 parts of hydrophilic modifiers, 10.0~25.0 parts it is molten
Agent A, 0.03~0.4 part of catalyst, 3.0~8.0 parts of small molecular alcohol chain extenders, 2.0~5.0 parts of triethylamines, 0.8~2.0 part have
Machine amine chainextender, 100.0~160.0 parts of deionized waters.
Wherein, the amine Modified polystyrene spheres, preparation step are as follows:
A), polystyrene crosslinked microsphere and solvent B, stirring are added in the four-hole boiling flask equipped with blender and thermometer makes
Microballoon is sufficiently swollen, and Isosorbide-5-Nitrae-dichloro methyl butyl ether and SnCl is added4, control temperature is in 25 DEG C or less 5~8h of reaction, reaction knot
Shu Houyong sufficiently washes away the SnCl of attachment with dilute hydrochloric acid4, filter；It is washed with Isosorbide-5-Nitrae-dioxane to remove remaining solvent B,
Distilled water and ethanol washing are used again, and lower 60 DEG C of vacuum dry 12h obtain the chloromethylated polystyrene microballoon；
According to parts by weight, each primary raw material ingredient are as follows: 3.0~5.0 parts of polystyrene crosslinked microsphere, solvent A 30.0~
50.0 parts, Isosorbide-5-Nitrae -15.0~25.0 parts of dichloro methyl butyl ether, SnCl43.5~6.0 parts；
B), chloromethylated polystyrene microballoon and solvent C are added in the four-hole boiling flask equipped with blender and thermometer, stirs
It mixes to abundant swelling, adds di-primary amine and triethylamine, 4~8h of reaction is stirred at room temperature, steams under reduced pressure after reaction
Solvent C is gone, solid is dissolved in methylene chloride, successively washs 3~5 with 3% sodium bicarbonate solution and 3% acetic acid solution
Secondary, anhydrous magnesium sulfate is dry, depressurizes lower steaming vibrating dichloromethane, then twice with petroleum ether recrystallization, lower 60 DEG C of vacuum dry 12h,
Obtain the amine Modified polystyrene spheres；
According to parts by weight, each primary raw material ingredient are as follows: 3.0~6.0 parts of chloromethylated polystyrene microballoon, di-primary amine
0.3~1.0 part, 15.0~30.0 parts of solvent B, 0.5~1.5 part of triethylamine, 15.0~30.0 parts of methylene chloride.
The polystyrene crosslinked microsphere is the polystyrene-divinylbenzene crosslinked microsphere of the degree of cross linking 4~8%, micro-
0.5~5 μm of spherolite diameter.
The di-primary amine be ethylenediamine, 1,3- propane diamine, 1,4- butanediamine, 1,5- pentanediamine or 1,6- hexamethylene diamine in extremely
Few one kind.
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 methylene chloride, chloroform, carbon tetrachloride, tetrachloroethanes.
The solvent C is at least one of isopropyl alkane, toluene, dimethylbenzene, methyl ethyl ketone, ethyl acetate, butyl acetate.
The oligomer polyol is polyester polyol or polyether polyol；The polyester polyol is polyadipate fourth two
At least one of alcohol ester dihydric alcohol, polycarbonate glycol or polycaprolactone diols, number-average molecular weight Mn be 1000~
3000；The polyether polyol is in polytetrahydrofuran ether glycol, polytetramethylene ether diol or polyoxypropylene glycol
At least one, number-average molecular weight Mn are 1000~3000.
The diisocyanate is at least one of HDI, MDI, IPDI or HMDI.
The hydrophilic modifier be 2 hydroxy propanoic acid, 2-Pyrrolidone, 3- hydracrylic acid or 2- hydroxybutyric acid at least
It is a kind of.
The catalyst is alkalinous metal carboxylate, organo-metallic compound, phosphorus-containing compound or amine compounds；Further
, preferably dibutyl tin dilaurate, lithium acetate, three normal-butyl phosphorus, stannous octoate, aphthenic acids tin, lead naphthenate, aphthenic acids
At least one of cobalt, dibutyitin maleate or dibutyltin diacetate.
The small molecular alcohol chain extender is ethylene glycol, 1,2- propylene glycol, 1,4- butanediol, 1,6-HD, 1,5- penta 2
At least one of alcohol, trimethylolpropane, neopentyl glycol or diethylene glycol (DEG).
Organic amine chainextender is at least one of ethylenediamine, diethylenetriamine, hexamethylene diamine or piperazine.
The present invention provides a kind of preparation method of polystyrene microsphere modified polyurethane water-base resin, and its step are as follows:
A), by weight, in the four-hole boiling flask equipped with blender and thermometer, in N2Under protection and stirring, successively
Diisocyanate, amine Modified polystyrene spheres, oligomer polyol and hydrophilic modifier is added, at 75~95 DEG C of temperature of control
React 1~3h, sample detection, when measured-nco value reaches the theoretical value of defined, be cooled to 60~70 DEG C stop it is anti-
It answers；
B), solvent A regulation system viscosity is added, is that 500~600rpm is added with stirring small molecular alcohol chain extender in revolving speed
And catalyst, start sample detection after 1h, when measured-nco value reaches the theoretical value of defined, be down to room temperature stop it is anti-
It answers, obtains modified polyurethane prepolymer；
C), 10~20% deionized water is added to organic amine chainextender to be in advance configured to organic amine chainextender water-soluble
Liquid；
D), in the case where being kept stirring revolving speed, triethylamine is added, reacts 10~20min；Then remaining deionized water is added,
It improves revolving speed and emulsifies 10~30min to 1000~1500rpm；Reducing mixing speed is that organic amine is added dropwise under 500~600rpm to expand
Chain agent aqueous solution, is added dropwise in 15~30min, keeps reacting 1~2h at room temperature；It is evaporated under reduced pressure out solvent A, is obtained described
Polystyrene microsphere modified polyurethane water-base resin.
A kind of polystyrene microsphere modified polyurethane water-base resin produced by the present invention has high transparency, high glaze, height
Hardness and storage stability, manufactured film have excellent adhesive force, wearability, hot water resistance, temperature tolerance, resistance to ag(e)ing,
Stain resistance, crack resistance and corrosion resistance, both can be used alone can also be blended with other water-base resins, apply for aqueous wooden ware
Material, aqueous floor coatings, aqueous steel structure coating, aqueous engineering coating, Water-based thermal insulation coating and water-based anticorrosive paint.
Specific embodiment
A kind of polystyrene microsphere modified polyurethane water-base resin of the invention is done further below with reference to embodiment
Description.It is understood that specific embodiment described herein is used only for explaining related invention, rather than to the limit of the invention
It is fixed.
Embodiment 1
A kind of amine Modified polystyrene spheres X, preparation step are as follows:
A), the preparation of chloromethylated polystyrene crosslinked microsphere: by weight, in four equipped with blender and thermometer
3 parts and 30 parts of methylene chloride of polystyrene crosslinked microsphere of 5% degree of cross linking are added in mouth flask, stirring is swollen microballoon sufficiently,
15.6 parts of 1,4- dichloro methyl butyl ether and SnCl is added43.5 parts, control temperature reacts 5h at 22 DEG C, uses after reaction
The catalyst of attachment is sufficiently washed away with dilute hydrochloric acid, is filtered；It is washed with Isosorbide-5-Nitrae-dioxane to remove remaining solvent, then with steaming
Distilled water and ethanol washing, it is dry under vacuum, obtain the chloromethylated polystyrene microballoon；
B), the polystyrene microsphere of 3.0 parts of chloromethylations is dissolved in 15.0 parts of methyl ethyl ketone, stirring to abundant swelling,
0.4 part of 1,6- hexamethylene diamine and 0.5 part of triethylamine are added, reaction 5h is stirred at room temperature, boils off under reduced pressure after reaction
Solid is dissolved in 20.0 parts of methylene chloride, successively washs 4 with 3% sodium bicarbonate solution and 3% acetic acid solution by methyl ethyl ketone
Secondary, anhydrous magnesium sulfate is dry, depressurizes lower steaming vibrating dichloromethane, then twice with petroleum ether recrystallization, lower 60 DEG C of vacuum dry 12h,
Obtain the amine Modified polystyrene spheres X.
Embodiment 2
A kind of amine Modified polystyrene spheres Y, preparation step are as follows:
A), the polystyrene of 6% degree of cross linking by weight, is added in the four-hole boiling flask equipped with blender and thermometer
4.5 parts of crosslinked microsphere and 45 parts of methylene chloride, stirring is swollen microballoon sufficiently, be added Isosorbide-5-Nitrae -22.8 parts of dichloro methyl butyl ether and
SnCl45.2 parts, control temperature reacts 8h at 25 DEG C, after reaction with the catalysis for sufficiently washing away attachment with dilute hydrochloric acid
Agent filters；It is washed with Isosorbide-5-Nitrae-dioxane to remove remaining solvent, then with distilled water and ethanol washing, it is dry under vacuum, it obtains
The chloromethylated polystyrene microballoon；
B), 6.0 parts of chloromethylated polystyrene microballoons are added to the mixed solvent of 20.0 parts of methyl ethyl ketone and butyl acetate
In, stirring to abundant swelling adds 0.8 part of 1,3- propane diamine and 1.0 parts of triethylamines, reaction 8h, reaction is stirred at room temperature
After boil off solvent under reduced pressure, solid is dissolved in 30.0 parts of methylene chloride, successively with 3% sodium bicarbonate solution and
3% acetic acid solution washs 5 times, and anhydrous magnesium sulfate is dry, depressurizes lower steaming vibrating dichloromethane, then twice with petroleum ether recrystallization,
Lower 60 DEG C of vacuum dry 12h obtain the amine Modified polystyrene spheres Y.
Embodiment 3
A kind of amine Modified polystyrene spheres Z, preparation step are as follows:
A), the polystyrene of 8% degree of cross linking by weight, is added in the four-hole boiling flask equipped with blender and thermometer
4.0 parts and 42 parts of methylene chloride of crosslinked microsphere, stirring is swollen microballoon sufficiently, and Isosorbide-5-Nitrae -21 parts of dichloro methyl butyl ether is added and urges
Agent SnCl44.8 parts, control temperature 6h is reacted at 25 DEG C, after reaction with dilute hydrochloric acid sufficiently to wash away urging for attachment
Agent filters；It is washed with Isosorbide-5-Nitrae-dioxane to remove remaining solvent, then with distilled water and ethanol washing, it is dry under vacuum,
Obtain the chloromethylated polystyrene microballoon；
B), 5.0 parts of chloromethylated polystyrene microballoons are added in 18.0 parts of methyl ethyl ketone, stirring to abundant swelling, then
0.6 part of ethylenediamine and 0.6 part of triethylamine is added, reaction 6h is stirred at room temperature, boils off methyl ethyl ketone under reduced pressure after reaction,
Solid is dissolved in 25.0 parts of methylene chloride, is successively washed 5 times with 3% sodium bicarbonate solution and 3% acetic acid solution, it is anhydrous
Magnesium sulfate is dry, depressurizes lower steaming vibrating dichloromethane, then twice with petroleum ether recrystallization, lower 60 DEG C of vacuum dry 12h, obtain described in
Amine Modified polystyrene spheres Z.
Embodiment 4
A kind of polystyrene microsphere modified polyurethane water-base resin A, according to parts by weight, each material composition are as follows: 10.0 parts
Amine Modified polystyrene spheres X, 25.0 parts of poly adipate succinic acid ester dihydric alcohols (Mn 2000), 18.0 parts of HDI, 3.0 parts of 2-
Hydracrylic acid, 12.0 parts, 0.08 part dibutyl tin dilaurate of N-Methyl pyrrolidone, 2.0 parts of ethylene glycol, 2.0 parts of triethylamines,
0.8 part of hexamethylene diamine, 120.0 parts of deionized waters；
The polystyrene microsphere modified polyurethane water-base resin A, preparation step are as follows:
A), in the four-hole boiling flask equipped with blender and thermometer, in N2Under protection and stirring, HDI is sequentially added, amine changes
Property polystyrene microsphere X, poly adipate succinic acid ester dihydric alcohol and Lactic acid control and react 3h at 80 DEG C of temperature, sample
Detection is cooled to 60 DEG C of stopping and reacts when measured-nco value reaches the theoretical value of defined；
B), N-Methyl pyrrolidone regulation system viscosity is added, is that 500~600rpm is added with stirring ethylene glycol in revolving speed
And dibutyl tin dilaurate, start sample detection after 1h, when measured-nco value reaches the theoretical value of defined, is down to
Room temperature stops reaction, obtains modified polyurethane prepolymer；
C), 12.0 parts of deionized waters are added in 0.8 part of hexamethylene diamine and are configured to hexamethylene diamine aqueous solution；
D), in the case where being kept stirring revolving speed, triethylamine is added, reacts 15min；Then 108.0 parts of deionized waters are added, improve
Revolving speed emulsifies 20min to 1200rpm；Reducing mixing speed is that hexamethylene diamine aqueous solution is added dropwise under 500~600rpm, in 30min
It is added dropwise, 1.5h is reacted in holding at room temperature；It is evaporated under reduced pressure out N-Methyl pyrrolidone, it is modified to obtain the polystyrene microsphere
Polyurethane aqueous Resin A.
Embodiment 5
A kind of polystyrene microsphere modified polyurethane water-base resin B, according to parts by weight, ingredient are as follows: 15.0 parts of amine change
Property polystyrene microsphere Y, 25.0 parts of polytetrahydrofuran ether glycol (Mn 1500), 25.0 parts of IPDI, 4.0 parts of 3- hydracrylic acids,
15.0 parts of 2-Pyrrolidones, 0.2 part of stannous octoate, 3.0 parts of 1,6-HDs, 4.0 parts of triethylamines, 1.0 parts of ethylenediamines, 145.0
Part deionized water；
The polystyrene microsphere modified polyurethane water-base resin B, preparation step are as follows:
A), in the four-hole boiling flask equipped with blender and thermometer, in N2Under protection and stirring, IPDI, amine are sequentially added
Modified polystyrene spheres Y, polytetrahydrofuran ether glycol and 3- hydracrylic acid control and react 2h at 85 DEG C of temperature, sample detection,
When measured-nco value reaches the theoretical value of defined, it is cooled to 70 DEG C of stoppings reactions；
B), 2-Pyrrolidone regulation system viscosity is added, is that 500~600rpm is added with stirring 1,6- hexylene glycol in revolving speed
And stannous octoate, start sample detection after 1h, when measured-nco value reaches the theoretical value of defined, is down to room temperature stopping
Reaction, obtains modified polyurethane prepolymer；
C), 15.0 parts of deionized waters are added in 1.0 parts of ethylenediamines and are configured to ethylenediamine solution；
D), in the case where being kept stirring revolving speed, triethylamine is added, reacts 15min；Then 130.0 parts of deionized waters are added, improve
Revolving speed emulsifies 15min to 1300rpm；Reducing mixing speed is that ethylenediamine solution is added dropwise under 500~600rpm, in 30min
It is added dropwise, 1h is reacted in holding at room temperature；It is evaporated under reduced pressure out 2-Pyrrolidone, obtains the polystyrene microsphere modified polyurethane
Water-base resin B.
Embodiment 6
A kind of polystyrene microsphere modified polyurethane water-base resin C, according to parts by weight, ingredient are as follows: 20.0 parts of amine change
Property polystyrene microsphere Z, 20.0 parts of polytetramethylene ether diols (Mn 3000), 25.0 parts of HDI, 6.0 parts of 2- hydroxybutyric acids, third
15.0 parts, 0.3 part dibutyitin maleate of ketone, 4.0 parts of 1,6-HDs, 4.0 parts of triethylamines, 2.0 parts of diethylenetriamines,
160.0 parts of deionized waters；
The polystyrene microsphere modified polyurethane water-base resin C, preparation step are as follows:
A), in the four-hole boiling flask equipped with blender and thermometer, in N2Under protection and stirring, HDI is sequentially added, amine changes
Property polystyrene microsphere Z, polytetramethylene ether diol and 2- hydroxybutyric acid, react 2.5h at 90 DEG C of temperature of control, sample detection,
When measured-nco value reaches the theoretical value of defined, it is cooled to 70 DEG C of stoppings reactions；
B), acetone regulation system viscosity is added, is that 500~600rpm is added with stirring 1,6- hexylene glycol and Malaysia in revolving speed
Sour dibutyl tin starts sample detection after 1h, when measured-nco value reaches the theoretical value of defined, is down to room temperature stopping
Reaction, obtains modified polyurethane prepolymer；
C), 16.0 parts of deionized waters are added in 2.0 parts of diethylenetriamines and are configured to diethylenetriamine aqueous solution；
D), in the case where being kept stirring revolving speed, triethylamine is added, reacts 20min；Then 130.0 parts of deionized waters are added, improve
Revolving speed emulsifies 20min to 1300rpm；Reducing mixing speed is that diethylenetriamine aqueous solution is added dropwise under 500~600rpm,
It is added dropwise in 25min, 2h is reacted in holding at room temperature；It is evaporated under reduced pressure out acetone, obtains the modified poly- ammonia of the polystyrene microsphere
Ester water-base resin C.
By the polystyrene microsphere modified polyurethane water-base resin in the embodiment of the present invention be configured to aqueous industrial coating with
Aqueous polyurethane industrial coating (comparative example) on the market carries out performance contrast test under the same conditions, according to relevant criterion into
Row detection, test data are as shown in table 1:
1 polystyrene microsphere modified polyurethane water paint performance technologies index of table
Although the present invention has been explained in detail and has referred to embodiment, for those of ordinary skill in the art, show
Various schemes, modification and the change that can so make as specified above, should be construed as being included within the scope of the claims.
Claims (10)
1. a kind of preparation method of polystyrene microsphere modified polyurethane water-base resin, it is characterised in that: the preparation method,
Steps are as follows:
A), in the four-hole boiling flask equipped with blender and thermometer, in N2Under protection and stirring, diisocyanate, amine are sequentially added
Modified polystyrene spheres, oligomer polyol and hydrophilic modifier react 1~3h, sampling inspection at 75~95 DEG C of temperature of control
It surveys, when measured-nco value reaches the theoretical value of defined, is cooled to 60~70 DEG C of stopping and reacts；
B), solvent A regulation system viscosity is added, is that 500~600rpm is added with stirring small molecular alcohol chain extender and urges in revolving speed
Agent starts sample detection after 1h, when measured-nco value reaches the theoretical value of defined, is down to room temperature and stops reaction,
Obtain modified polyurethane prepolymer；
C), 10~20% deionized water is added to organic amine chainextender in advance and is configured to organic amine chainextender aqueous solution；
D), in the case where being kept stirring revolving speed, triethylamine is added, reacts 10~20min；Then remaining deionized water is added, improves
Revolving speed emulsifies 10~30min to 1000~1500rpm；Reducing mixing speed is that organic amine chainextender is added dropwise under 500~600rpm
Aqueous solution is added dropwise in 15~30min, keeps reacting 1~2h at room temperature；It is evaporated under reduced pressure out solvent A, obtains the polyphenyl
The microsphere modified polyurethane aqueous resin of ethylene；
According to parts by weight, each material composition are as follows:
8.0~16.0 parts of amine Modified polystyrene spheres
15.0~25.0 parts of oligomer polyol
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 part of organic amine chainextender
100.0~160.0 parts of deionized water；
Wherein, the amine Modified polystyrene spheres, preparation step are as follows:
A), polystyrene crosslinked microsphere and solvent B are added in the four-hole boiling flask equipped with blender and thermometer, stirring makes microballoon
Isosorbide-5-Nitrae-dichloro methyl butyl ether and SnCl is added in sufficiently swelling4, control temperature in 25 DEG C or less 5~8h of reaction, after reaction
With the SnCl for sufficiently washing away attachment with dilute hydrochloric acid4, filter；It is washed with Isosorbide-5-Nitrae-dioxane to remove remaining solvent B, then used
Distilled water and ethanol washing, lower 60 DEG C of vacuum dry 12h obtain the chloromethylated polystyrene microballoon；
According to parts by weight, each primary raw material ingredient are as follows: 3.0~5.0 parts of polystyrene crosslinked microsphere, solvent B30.0~50.0
Part, Isosorbide-5-Nitrae -15.0~25.0 parts of dichloro methyl butyl ether, SnCl43.5~6.0 parts；
B), chloromethylated polystyrene microballoon and solvent C are added in the four-hole boiling flask equipped with blender and thermometer, stirring is extremely
Sufficiently swelling, adds di-primary amine and triethylamine, 4~8h of reaction is stirred at room temperature, boil off under reduced pressure after reaction molten
Agent C, solid is dissolved in methylene chloride, successively washs 3~5 times with 3% sodium bicarbonate solution and 3% acetic acid solution, nothing
Water magnesium sulfate is dry, depressurizes lower steaming vibrating dichloromethane, then twice with petroleum ether recrystallization, lower 60 DEG C of vacuum dry 12h are obtained described
Amine Modified polystyrene spheres；
According to parts by weight, each primary raw material ingredient are as follows: 3.0~6.0 parts of chloromethylated polystyrene microballoon, di-primary amine 0.3~
1.0 parts, 15.0~30.0 parts of solvent B, 0.5~1.5 part of triethylamine, 15.0~30.0 parts of methylene chloride.
2. preparation method according to claim 1, it is characterised in that: the oligomer polyol be polyester polyol or
Polyether polyol；The polyester polyol is poly adipate succinic acid ester dihydric alcohol, polycarbonate glycol or polycaprolactone
At least one of dihydric alcohol, number-average molecular weight Mn are 1000~3000；The polyether polyol is polytetrahydrofuran ether
At least one of glycol, polytetramethylene ether diol or polyoxypropylene glycol, number-average molecular weight Mn be 1000~
3000。
3. preparation method according to claim 1, it is characterised in that: the diisocyanate be HDI, MDI, IPDI or
At least one of HMDI.
4. preparation method according to claim 1, it is characterised in that: the hydrophilic modifier is 2 hydroxy propanoic acid, 2-
At least one of pyrrolidones, 3- hydracrylic acid or 2- hydroxybutyric acid；The catalyst is alkalinous metal carboxylate, organic
Metallic compound, phosphorus-containing compound or amine compounds.
5. preparation method according to claim 1, it is characterised in that: the catalyst be dibutyl tin dilaurate,
Lithium acetate, three normal-butyl phosphorus, stannous octoate, aphthenic acids tin, lead naphthenate, cobalt naphthenate, dibutyitin maleate or oxalic acid
At least one of dibutyl tin.
6. preparation method according to claim 1, it is characterised in that: the solvent A be acetone, butanone, ethyl acetate,
At least one of cyclohexanone or N-Methyl pyrrolidone；The solvent B is methylene chloride, chloroform, carbon tetrachloride, four chloroethenes
At least one of alkane；The solvent C be isopropyl alkane, toluene, dimethylbenzene, methyl ethyl ketone, ethyl acetate, in butyl acetate extremely
Few one kind.
7. preparation method according to claim 1, it is characterised in that: the small molecular alcohol chain extender be ethylene glycol, 1,
2- propylene glycol, 1,4- butanediol, 1,6-HD, 1,5- pentanediol, trimethylolpropane, neopentyl glycol or diethylene glycol (DEG) are at least
It is a kind of.
8. preparation method according to claim 1, it is characterised in that: organic amine chainextender is ethylenediamine, diethyl
At least one of alkene triamine, hexamethylene diamine or piperazine.
9. preparation method according to claim 1, it is characterised in that: the di-primary amine be ethylenediamine, 1,3- propane diamine,
At least one of 1,4- butanediamine, 1,5- pentanediamine or 1,6- hexamethylene diamine.
10. preparation method according to claim 1, it is characterised in that: the polystyrene crosslinked microsphere is the degree of cross linking 4
~8% polystyrene-divinylbenzene crosslinked microsphere, 0.5~5 μm of microspherulite diameter.
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| CN112625532A (en) * | 2021-01-21 | 2021-04-09 | 山东益利油漆有限公司 | Efficient anticorrosive water-based acrylic coating and preparation method thereof |
| CN115159479A (en) * | 2022-08-11 | 2022-10-11 | 衢州市九洲化工有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
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| CN115159479B (en) * | 2022-08-11 | 2024-01-30 | 衢州市九洲化工有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
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