CN108034349B - Preparation method of octanitrosilsesquioxane modified bi-component waterborne polyurethane emulsion - Google Patents
Preparation method of octanitrosilsesquioxane modified bi-component waterborne polyurethane emulsion Download PDFInfo
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- CN108034349B CN108034349B CN201810060743.6A CN201810060743A CN108034349B CN 108034349 B CN108034349 B CN 108034349B CN 201810060743 A CN201810060743 A CN 201810060743A CN 108034349 B CN108034349 B CN 108034349B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/837—Chemically modified polymers by silicon containing compounds
Abstract
The invention discloses a preparation method of octa-nitro silsesquioxane modified bi-component waterborne polyurethane emulsion. The method comprises the steps of mixing oligomer polyol and diisocyanate for reaction, adding a chain extender for reaction to obtain a polyurethane polyol prepolymer, adding a cross-linking agent and a neutralizing agent, carrying out high-speed shearing, emulsifying and dispersing to obtain a water-based polyurethane polyol dispersoid, adding octanitrosilsesquioxane to obtain an octanitrosilsesquioxane modified water-based polyurethane polyol dispersoid, and finally mixing the octanitrosilsesquioxane modified water-based polyurethane polyol dispersoid with a polyisocyanate curing agent to obtain the octanitrosilsesquioxane modified two-component water-based polyurethane emulsion. The method is simple, the octanitrosilsesquioxane is adopted to modify the bi-component waterborne polyurethane, the water resistance, the transparency and the mechanical property of the waterborne polyurethane are improved, and the stability is better.
Description
Technical Field
The invention belongs to the technical field of aqueous polyurethane emulsion, relates to a two-component aqueous polyurethane emulsion, and particularly relates to a preparation method of an octa-nitro silsesquioxane modified two-component aqueous polyurethane emulsion.
Background
The waterborne polyurethane takes water as a dispersion medium, has the advantages of no pollution, environmental friendliness, safe storage and transportation, no fire-fighting hidden danger, resource saving and the like, and is widely applied to the fields of fabric coatings, leather edge oil, adhesives and the like. The two-component waterborne polyurethane has the excellent performances of low film-forming temperature, high hardness, good wear resistance and the like, the content of Volatile Organic Compounds (VOC) and Harmful Air Pollutants (HAP) is greatly reduced compared with that of solvent-based polyurethane, and the performance is superior to that of solvent-based polyurethane. However, two-component aqueous polyurethanes also have certain problems. The aqueous polyurethane polyol dispersoid is directly mixed with polyisocyanate to hardly obtain a uniform system, and directly influences film formation, thereby influencing the water resistance, transparency, mechanical property and the like of the aqueous polyurethane. Ge and the like modify two-component waterborne polyurethane with bis-hydroxybutyl polydimethylsiloxane, it is difficult to obtain a uniform system, and the transparency is poor (Z. Ge, Y. Luo. Synthesis and characterization of silicon-modified two-component waterborne polyurethane, 2013,76(11): 1522-. Guo et al directly modify two-component waterborne polyurethane with rosin, the A component and the B component cannot be completely dissolved, and the water resistance and mechanical properties are poor (W.J. Guo, et al. Water polyurethane added modified by rosin for coated packaging Engineering,2007,28(1): 33-48).
Disclosure of Invention
Aiming at the defects of uneven mixing, poor water resistance, poor mechanical property, poor film forming property and the like of the existing A component and B component of the double-component waterborne polyurethane, the invention provides a preparation method of octa-nitro silsesquioxane modified double-component waterborne polyurethane emulsion.
The technical scheme of the invention is as follows:
the preparation method of the octa-nitro silsesquioxane modified bi-component waterborne polyurethane emulsion comprises the following specific steps:
step 1, preparation of octanitrosilsesquioxane: under ice water bath, stirring and dissolving the oligomeric silsesquioxane in 85-90% concentrated nitric acid, stirring and reacting at 15-25 ℃, adding water after the reaction is finished, separating out light yellow precipitate, performing suction filtration, washing the precipitate with an alkaline solution to be neutral, and drying to obtain octa-nitro silsesquioxane;
step 2, synthesizing the octanitrosilsesquioxane modified aqueous polyurethane polyol dispersion: mixing oligomer polyol and diisocyanate according to the weight ratio of 1000-2400: 1500-4000 parts by weight, uniformly mixing, dropwise adding a catalyst, reacting at 80-90 ℃ for 1-2 hours to obtain a polyurethane prepolymer, cooling to 60-70 ℃, adding polyhydroxycarboxylic acid for reacting for 2-3 hours, heating to 70-80 ℃, adding a small molecular diol monomer, reacting for 0.5-1 hour, adding an organic solvent to reduce the viscosity until the solution is colorless, reacting for 1-1.5 hours, adding a cross-linking agent for reacting for 2-3 hours, cooling to 20-30 ℃, adding a neutralizing agent for neutralizing for 0.5-1 hour, adding octanitrosilsesquioxane according to the mass ratio of the octanitrosilsesquioxane to the total amount of 4-10: 100, stirring for 1-2 hours, shearing and emulsifying, reacting for 0.5-1 hour, removing the organic solvent by rotary evaporation, obtaining octa-nitro silsesquioxane modified aqueous polyurethane polyol dispersoid;
step 3, preparing the octa-nitro silsesquioxane modified bi-component aqueous polyurethane emulsion:
adding a defoaming agent and a flatting agent into the octa-nitro silsesquioxane modified waterborne polyurethane polyol dispersoid, and mixing the octa-nitro silsesquioxane modified waterborne polyurethane polyol dispersoid with a polyisocyanate curing agent to obtain the octa-nitro silsesquioxane modified bi-component waterborne polyurethane emulsion.
In step 1, the alkaline solution is selected from one of sodium carbonate solution, sodium bicarbonate solution and sodium hydroxide solution.
In the step 1, the mass ratio of the oligomeric silsesquioxane to the concentrated nitric acid is 10-20: 100 to 150.
In the step 1, the stirring reaction time is 15-20 h.
Preferably, in the step 2, the mass ratio of the oligomer polyol to the diisocyanate is 1200-2000: 1600-3000.
In step 2, the oligomer polyol is selected from polyester polyol or polyether polyol.
The polyester polyol is selected from polyethylene glycol adipate glycol, 1, 4-butanediol adipate glycol, polyethylene glycol adipate glycol, polycarbonate glycol or polycaprolactone glycol.
The polyether polyol is selected from polyoxypropylene diol, polyoxypropylene triol, polytetrahydrofuran diol or tetrahydrofuran-propylene oxide copolymerized diol.
In the step 2, the polyisocyanate is selected from one or more of lysine diisocyanate, dimethyl diphenyl diisocyanate, naphthalene diisocyanate, diphenylmethane-4, 4' -diisocyanate, tetramethyl m-xylylene diisocyanate and 2-methylpentane diisocyanate.
In the step 2, the polyhydroxy carboxylic acid is selected from dimethylol acetic acid, dimethylol propionic acid or dimethylol butyric acid, preferably dimethylol propionic acid; the small molecular diol monomer is selected from one or more of 2-ethyl-1, 3-hexanediol, 1, 3-propanediol, trimethylpentanediol, methylpropanediol, 1, 6-hexanediol or neopentyl glycol, and is preferably trimethylpentanediol; the cross-linking agent is selected from trimethylolpropane, pentaerythritol or glycerol, preferably glycerol; the neutralizing agent is selected from triethylamine, sodium hydroxide or ammonia water, and preferably the ammonia water.
In the step 2, the neutralization degree of the neutralization reaction is 75-115%, and preferably 100%.
In step 2, the shear rate is controlled at 1700 r/min.
In the step 3, the leveling agent is an acetylene glycol leveling agent, can be a leveling agent with the model of SAN1 or SAN2, and is preferably SAN 1; the defoaming agent is a silicone oil defoaming agent, can be a defoaming agent with the type of ATF-1 or ATF-2, and is preferably ATF-1; the polyisocyanate curing agent may be a polyisocyanate curing agent of type PUDS80, PUDS81, PUDS 82.
Compared with the prior art, the invention has the following advantages:
the octanitrosilsesquioxane modified two-component waterborne polyurethane emulsion prepared by modifying two-component waterborne polyurethane through octanitrosilsesquioxane has good stability, can be stably stored for more than 8 months, has improved film forming property, and can obviously improve water resistance, thermal stability and mechanical property.
Detailed Description
In order to better understand the present invention, the following embodiments are further described in detail. The scope of the invention is not limited to the embodiments shown.
Comparative example 1: one-component waterborne polyurethane
Synthesizing a single-component aqueous polyurethane emulsion:
raw materials:
21.59g polycarbonate diol 2000
9.54g 2-methylpentane diisocyanate (MPDI)
10.82g Lysine Diisocyanate (LDI)
0.4g of dibutyltin dilaurate
3g Dimethylolpropionic acid (DMPA)
3.05g of trimethylpentanediol
2g of Glycerol
0.78g of Ammonia water (neutralization degree: 100%)
150g deionized water
The preparation method comprises the following steps: adding polycarbonate diol 2000, 2-methylpentane diisocyanate, lysine diisocyanate and dibutyltin dilaurate into a three-neck flask, reacting for 1.5h at 85 ℃ to obtain a polyurethane prepolymer, cooling to 65 ℃, adding dimethylolpropionic acid for reacting for 2.5h, heating to 75 ℃, adding trimethylpentanediol for reacting for 1.5h, adding glycerol for reacting for 2.5h, cooling to 25 ℃, adding ammonia water for neutralizing reaction for 0.5h, adding octanitrosilsesquioxane, stirring for 2h, adding deionized water for high-speed shearing and emulsifying, reacting for 0.5h, and removing an organic solvent by rotary evaporation to obtain the single-component waterborne polyurethane emulsion.
Comparative example 2: octa-nitro silsesquioxane modified single-component waterborne polyurethane
(1) Preparation of octanitrosilsesquioxane: 6mL of deionized water is added into a beaker, 85mL of concentrated nitric acid is slowly added while stirring, and 100mL of nitric acid with the mass fraction of 85% is prepared for standby. In an ice-water bath, 84mL of prepared nitric acid having a mass fraction of 85% was added to a 500mL three-necked flask equipped with an electric stirrer and a thermometer. Stirring until the system temperature reached 2 ℃. 13g of the oligomeric silsesquioxane was weighed and added to the flask over 40min to allow uniform dissolution. After the addition was complete, stirring was continued for 30min in an ice-water bath and then at room temperature (20 ℃ C.) for 16 h. After the reaction was completed, the reaction mixture was poured into 175g of deionized water, and a pale yellow precipitate appeared immediately. And (4) carrying out suction filtration, washing the precipitate to be neutral by using an alkaline solution with the mass fraction of 6%, and washing the precipitate for three times by using ethanol. Vacuum drying at 60 ℃ to obtain a light yellow sample, namely the octa-nitro silsesquioxane.
(2) Synthesizing octa-nitro silsesquioxane modified single-component aqueous polyurethane emulsion:
raw materials:
19.67g of polycarbonate diol 2000
18.52g 2-methylpentane diisocyanate (MPDI)
3.47g Lysine Diisocyanate (LDI)
0.4g of dibutyltin dilaurate
3g Dimethylolpropionic acid (DMPA)
3.34g trimethylpentanediol
2g of Glycerol
0.78g of Ammonia water (neutralization degree: 100%)
2g octanitrosilsesquioxane
150g deionized water
The preparation method comprises the following steps: adding polycarbonate diol 2000, 2-methylpentane diisocyanate, lysine diisocyanate and dibutyltin dilaurate into a three-neck flask, reacting for 1.5h at 85 ℃ to obtain a polyurethane prepolymer, cooling to 65 ℃, adding dimethylolpropionic acid for reacting for 2.5h, heating to 75 ℃, adding trimethylpentanediol for reacting for 1.5h, adding glycerol for reacting for 2.5h, cooling to 25 ℃, adding ammonia water for neutralizing reaction for 0.5h, adding octanitrosilsesquioxane, stirring for 2h, adding deionized water for high-speed shearing and emulsifying, reacting for 0.5h, and removing an organic solvent by rotary evaporation to obtain the octanitrosilsesquioxane modified single-component waterborne polyurethane emulsion.
Comparative example 3: unmodified two-component waterborne polyurethanes
(1) Synthesis of aqueous polyurethane polyol dispersion:
raw materials:
21.59g polycarbonate diol 2000
9.54g 2-methylpentane diisocyanate (MPDI)
10.82g Lysine Diisocyanate (LDI)
0.4g of dibutyltin dilaurate
3g Dimethylolpropionic acid (DMPA)
3.05g of trimethylpentanediol
2g of Glycerol
0.78g of Ammonia water (neutralization degree: 100%)
150g deionized water
The preparation method comprises the following steps: adding polycarbonate diol 2000, 2-methylpentane diisocyanate, lysine diisocyanate and dibutyltin dilaurate into a three-neck flask, reacting for 1.5h at 85 ℃ to obtain a polyurethane prepolymer, cooling to 65 ℃, adding dimethylolpropionic acid for reacting for 2.5h, heating to 75 ℃, adding trimethylpentanediol for reacting for 1.5h, adding glycerol for reacting for 2.5h, cooling to 25 ℃, adding ammonia water for neutralizing reaction, neutralizing for 0.5h, adding octanitrosilsesquioxane, stirring for 2h, adding deionized water for high-speed shearing and emulsifying, reacting for 0.5h, and removing an organic solvent by rotary evaporation to obtain the aqueous polyurethane polyol dispersoid.
(2) Preparing a two-component aqueous polyurethane emulsion: and (2) adding 1g of a leveling agent SAN1 and 0.5g of a defoaming agent ATF-1 into 100g of the prepared aqueous polyurethane polyol dispersoid, mixing with 1g of a curing agent PUDS80, and uniformly stirring to obtain the unmodified two-component aqueous polyurethane emulsion.
Comparative example 4: octanitrosilsesquioxane modified two-component waterborne polyurethane (the mass ratio of octanitrosilsesquioxane to the total mass is 2:100)
(1) Preparation of octanitrosilsesquioxane: 6mL of deionized water is added into a beaker, 85mL of concentrated nitric acid is slowly added while stirring, and 100mL of nitric acid with the mass fraction of 85% is prepared for standby. In an ice-water bath, 84mL of prepared nitric acid having a mass fraction of 85% was added to a 500mL three-necked flask equipped with an electric stirrer and a thermometer. Stirring until the system temperature reached 2 ℃. 13g of the oligomeric silsesquioxane was weighed and added to the flask over 40min to allow uniform dissolution. After the addition was complete, stirring was continued for 30min in an ice-water bath and then at room temperature (20 ℃ C.) for 16 h. After the reaction was completed, the reaction mixture was poured into 175g of deionized water, and a pale yellow precipitate appeared immediately. And (4) carrying out suction filtration, washing the precipitate to be neutral by using an alkaline solution with the mass fraction of 6%, and washing the precipitate for three times by using ethanol. Vacuum drying at 60 ℃ to obtain a light yellow sample, namely the octa-nitro silsesquioxane.
(2) Synthesis of octanitrosilsesquioxane modified aqueous polyurethane polyol dispersion:
raw materials:
19.67g of polycarbonate diol 2000
18.52g 2-methylpentane diisocyanate (MPDI)
3.47g Lysine Diisocyanate (LDI)
0.4g of dibutyltin dilaurate
3g Dimethylolpropionic acid (DMPA)
3.34g trimethylpentanediol
2g of Glycerol
0.78g of Ammonia water (neutralization degree: 100%)
1g octanitrosilsesquioxane
150g deionized water
The preparation method comprises the following steps: adding polycarbonate diol 2000, 2-methylpentane diisocyanate, lysine diisocyanate and dibutyltin dilaurate into a three-neck flask, reacting for 1.5h at 85 ℃ to obtain a polyurethane prepolymer, cooling to 65 ℃, adding dimethylolpropionic acid for reacting for 2.5h, heating to 75 ℃, adding trimethylpentanediol for reacting for 1.5h, adding glycerol for reacting for 2.5h, cooling to 25 ℃, adding ammonia water for neutralizing reaction for 0.5h, adding octanitrosilsesquioxane, stirring for 2h, adding deionized water for high-speed shearing and emulsifying, reacting for 0.5h, and removing an organic solvent by rotary evaporation to obtain the octanitrosilsesquioxane modified aqueous polyurethane polyol dispersion.
(3) Preparing octa-nitro silsesquioxane modified bi-component waterborne polyurethane emulsion: and adding 1g of a leveling agent SAN1 and 0.5g of a defoaming agent ATF-1 into 100g of the octanitrosilsesquioxane modified waterborne polyurethane polyol dispersoid, mixing with 1g of a curing agent PUDS80, and uniformly stirring to obtain the octanitrosilsesquioxane modified two-component waterborne polyurethane emulsion.
Comparative example 5: octanitrosilsesquioxane modified two-component waterborne polyurethane (the mass ratio of octanitrosilsesquioxane to the total amount is 12:100)
(1) Preparation of octanitrosilsesquioxane: 6mL of deionized water is added into a beaker, 85mL of concentrated nitric acid is slowly added while stirring, and 100mL of nitric acid with the mass fraction of 85% is prepared for standby. In an ice-water bath, 84mL of prepared nitric acid having a mass fraction of 85% was added to a 500mL three-necked flask equipped with an electric stirrer and a thermometer. Stirring until the system temperature reached 2 ℃. 13g of the oligomeric silsesquioxane was weighed and added to the flask over 40min to allow uniform dissolution. After the addition was complete, stirring was continued for 30min in an ice-water bath and then at room temperature (20 ℃ C.) for 16 h. After the reaction was completed, the reaction mixture was poured into 175g of deionized water, and a pale yellow precipitate appeared immediately. And (4) carrying out suction filtration, washing the precipitate to be neutral by using an alkaline solution with the mass fraction of 6%, and washing the precipitate for three times by using ethanol. Vacuum drying at 60 ℃ to obtain a light yellow sample, namely the octa-nitro silsesquioxane.
(2) Synthesis of octanitrosilsesquioxane modified aqueous polyurethane polyol dispersion:
raw materials:
19.67g of polycarbonate diol 2000
18.52g 2-methylpentane diisocyanate (MPDI)
3.47g Lysine Diisocyanate (LDI)
0.4g of dibutyltin dilaurate
3g Dimethylolpropionic acid (DMPA)
3.34g trimethylpentanediol
2g of Glycerol
0.78g of Ammonia water (neutralization degree: 100%)
6g octanitrosilsesquioxane
150g deionized water
The preparation method comprises the following steps: adding polycarbonate diol 2000, 2-methylpentane diisocyanate, lysine diisocyanate and dibutyltin dilaurate into a three-neck flask, reacting for 1.5h at 85 ℃ to obtain a polyurethane prepolymer, cooling to 65 ℃, adding dimethylolpropionic acid for reacting for 2.5h, heating to 75 ℃, adding trimethylpentanediol for reacting for 1.5h, adding glycerol for reacting for 2.5h, cooling to 25 ℃, adding ammonia water for neutralizing reaction for 0.5h, adding octanitrosilsesquioxane, stirring for 2h, adding deionized water for high-speed shearing and emulsifying, reacting for 0.5h, and removing an organic solvent by rotary evaporation to obtain the octanitrosilsesquioxane modified aqueous polyurethane polyol dispersion.
(3) Preparing octa-nitro silsesquioxane modified bi-component waterborne polyurethane emulsion: and adding 1g of a leveling agent SAN1 and 0.5g of a defoaming agent ATF-1 into 100g of the octanitrosilsesquioxane modified waterborne polyurethane polyol dispersoid, mixing with 1g of a curing agent PUDS80, and uniformly stirring to obtain the octanitrosilsesquioxane modified two-component waterborne polyurethane emulsion.
Example 1: octanitrosilsesquioxane modified two-component waterborne polyurethane (the mass ratio of octanitrosilsesquioxane to the total mass is 4:100)
(1) Preparation of octanitrosilsesquioxane: 6mL of deionized water is added into a beaker, 85mL of concentrated nitric acid is slowly added while stirring, and 100mL of nitric acid with the mass fraction of 85% is prepared for standby. In an ice-water bath, 84mL of prepared nitric acid having a mass fraction of 85% was added to a 500mL three-necked flask equipped with an electric stirrer and a thermometer. Stirring until the system temperature reached 2 ℃. 13g of the oligomeric silsesquioxane was weighed and added to the flask over 40min to allow uniform dissolution. After the addition was complete, stirring was continued for 30min in an ice-water bath and then at room temperature (20 ℃ C.) for 16 h. After the reaction was completed, the reaction mixture was poured into 175g of deionized water, and a pale yellow precipitate appeared immediately. And (4) carrying out suction filtration, washing the precipitate to be neutral by using an alkaline solution with the mass fraction of 6%, and washing the precipitate for three times by using ethanol. Vacuum drying at 60 ℃ to obtain a light yellow sample, namely the octa-nitro silsesquioxane.
(2) Synthesis of octanitrosilsesquioxane modified aqueous polyurethane polyol dispersion:
raw materials:
19.67g of polycarbonate diol 2000
18.52g 2-methylpentane diisocyanate (MPDI)
3.47g Lysine Diisocyanate (LDI)
0.4g of dibutyltin dilaurate
3g Dimethylolpropionic acid (DMPA)
3.34g trimethylpentanediol
2g of Glycerol
0.78g of Ammonia water (neutralization degree: 100%)
2g octanitrosilsesquioxane
150g deionized water
The preparation method comprises the following steps: adding polycarbonate diol 2000, 2-methylpentane diisocyanate, lysine diisocyanate and dibutyltin dilaurate into a three-neck flask, reacting for 1.5h at 85 ℃ to obtain a polyurethane prepolymer, cooling to 65 ℃, adding dimethylolpropionic acid for reacting for 2.5h, heating to 75 ℃, adding trimethylpentanediol for reacting for 1.5h, adding glycerol for reacting for 2.5h, cooling to 25 ℃, adding ammonia water for neutralizing reaction for 0.5h, adding octanitrosilsesquioxane, stirring for 2h, adding deionized water for high-speed shearing and emulsifying, reacting for 0.5h, and removing an organic solvent by rotary evaporation to obtain the octanitrosilsesquioxane modified aqueous polyurethane polyol dispersion.
(3) Preparing octa-nitro silsesquioxane modified bi-component waterborne polyurethane emulsion: and adding 1g of a leveling agent SAN1 and 0.5g of a defoaming agent ATF-1 into 100g of the octanitrosilsesquioxane modified waterborne polyurethane polyol dispersoid, mixing with 1g of a curing agent PUDS80, and uniformly stirring to obtain the octanitrosilsesquioxane modified two-component waterborne polyurethane emulsion.
Example 2: octanitrosilsesquioxane modified two-component waterborne polyurethane (the mass ratio of octanitrosilsesquioxane to the total mass is 6:100)
(1) Preparation of octanitrosilsesquioxane: 6mL of deionized water is added into a beaker, 85mL of concentrated nitric acid is slowly added while stirring, and 100mL of nitric acid with the mass fraction of 85% is prepared for standby. In an ice-water bath, 84mL of prepared nitric acid having a mass fraction of 85% was added to a 500mL three-necked flask equipped with an electric stirrer and a thermometer. Stirring until the system temperature reached 2 ℃. 13g of the oligomeric silsesquioxane was weighed and added to the flask over 40min to allow uniform dissolution. After the addition was complete, stirring was continued for 30min in an ice-water bath and then at room temperature (20 ℃ C.) for 16 h. After the reaction was completed, the reaction mixture was poured into 175g of deionized water, and a pale yellow precipitate appeared immediately. And (4) carrying out suction filtration, washing the precipitate to be neutral by using an alkaline solution with the mass fraction of 6%, and washing the precipitate for three times by using ethanol. Vacuum drying at 60 ℃ to obtain a light yellow sample, namely the octa-nitro silsesquioxane.
(2) Synthesis of octanitrosilsesquioxane modified aqueous polyurethane polyol dispersion:
raw materials:
19.67g of polycarbonate diol 2000
18.52g 2-methylpentane diisocyanate (MPDI)
3.47g Lysine Diisocyanate (LDI)
0.4g of dibutyltin dilaurate
3g Dimethylolpropionic acid (DMPA)
3.34g trimethylpentanediol
2g of Glycerol
0.78g of Ammonia water (neutralization degree: 100%)
3g octanitrosilsesquioxane
150g deionized water
The preparation method comprises the following steps: adding polycarbonate diol 2000, 2-methylpentane diisocyanate, lysine diisocyanate and dibutyltin dilaurate into a three-neck flask, reacting for 1.5h at 85 ℃ to obtain a polyurethane prepolymer, cooling to 65 ℃, adding dimethylolpropionic acid for reacting for 2.5h, heating to 75 ℃, adding trimethylpentanediol for reacting for 1.5h, adding glycerol for reacting for 2.5h, cooling to 25 ℃, adding ammonia water for neutralizing reaction for 0.5h, adding octanitrosilsesquioxane, stirring for 2h, adding deionized water for high-speed shearing and emulsifying, reacting for 0.5h, and removing an organic solvent by rotary evaporation to obtain the octanitrosilsesquioxane modified aqueous polyurethane polyol dispersion.
(3) Preparing octa-nitro silsesquioxane modified bi-component waterborne polyurethane emulsion: and adding 1g of a leveling agent SAN1 and 0.5g of a defoaming agent ATF-1 into 100g of the octanitrosilsesquioxane modified waterborne polyurethane polyol dispersoid, mixing with 1g of a curing agent PUDS80, and uniformly stirring to obtain the octanitrosilsesquioxane modified two-component waterborne polyurethane emulsion.
Example 3: octanitrosilsesquioxane modified two-component waterborne polyurethane (the mass ratio of octanitrosilsesquioxane to the total mass is 8:100)
(1) Preparation of octanitrosilsesquioxane: 6mL of deionized water is added into a beaker, 85mL of concentrated nitric acid is slowly added while stirring, and 100mL of nitric acid with the mass fraction of 85% is prepared for standby. In an ice-water bath, 84mL of prepared nitric acid having a mass fraction of 85% was added to a 500mL three-necked flask equipped with an electric stirrer and a thermometer. Stirring until the system temperature reached 2 ℃. 13g of the oligomeric silsesquioxane was weighed and added to the flask over 40min to allow uniform dissolution. After the addition was complete, stirring was continued for 30min in an ice-water bath and then at room temperature (20 ℃ C.) for 16 h. After the reaction was completed, the reaction mixture was poured into 175g of deionized water, and a pale yellow precipitate appeared immediately. And (4) carrying out suction filtration, washing the precipitate to be neutral by using an alkaline solution with the mass fraction of 6%, and washing the precipitate for three times by using ethanol. Vacuum drying at 60 ℃ to obtain a light yellow sample, namely the octa-nitro silsesquioxane.
(2) Synthesis of octanitrosilsesquioxane modified aqueous polyurethane polyol dispersion:
raw materials:
19.67g of polycarbonate diol 2000
18.52g 2-methylpentane diisocyanate (MPDI)
3.47g Lysine Diisocyanate (LDI)
0.4g of dibutyltin dilaurate
3g Dimethylolpropionic acid (DMPA)
3.34g trimethylpentanediol
2g of Glycerol
0.78g of Ammonia water (neutralization degree: 100%)
4g octanitrosilsesquioxane
150g deionized water
The preparation method comprises the following steps: adding polycarbonate diol 2000, 2-methylpentane diisocyanate, lysine diisocyanate and dibutyltin dilaurate into a three-neck flask, reacting for 1.5h at 85 ℃ to obtain a polyurethane prepolymer, cooling to 65 ℃, adding dimethylolpropionic acid for reacting for 2.5h, heating to 75 ℃, adding trimethylpentanediol for reacting for 1.5h, adding glycerol for reacting for 2.5h, cooling to 25 ℃, adding ammonia water for neutralizing reaction for 0.5h, adding octanitrosilsesquioxane, stirring for 2h, adding deionized water for high-speed shearing and emulsifying, reacting for 0.5h, and removing an organic solvent by rotary evaporation to obtain the octanitrosilsesquioxane modified aqueous polyurethane polyol dispersion.
(3) Preparing octa-nitro silsesquioxane modified bi-component waterborne polyurethane emulsion: and adding 1g of a leveling agent SAN1 and 0.5g of a defoaming agent ATF-1 into 100g of the octanitrosilsesquioxane modified waterborne polyurethane polyol dispersoid, mixing with 1g of a curing agent PUDS80, and uniformly stirring to obtain the octanitrosilsesquioxane modified two-component waterborne polyurethane emulsion.
Example 4: octanitrosilsesquioxane modified two-component waterborne polyurethane (the mass ratio of octanitrosilsesquioxane to the total amount is 10:100)
(1) Preparation of octanitrosilsesquioxane: 6mL of deionized water is added into a beaker, 85mL of concentrated nitric acid is slowly added while stirring, and 100mL of nitric acid with the mass fraction of 85% is prepared for standby. In an ice-water bath, 84mL of prepared nitric acid having a mass fraction of 85% was added to a 500mL three-necked flask equipped with an electric stirrer and a thermometer. Stirring until the system temperature reached 2 ℃. 13g of the oligomeric silsesquioxane was weighed and added to the flask over 40min to allow uniform dissolution. After the addition was complete, stirring was continued for 30min in an ice-water bath and then at room temperature (20 ℃ C.) for 16 h. After the reaction was completed, the reaction mixture was poured into 175g of deionized water, and a pale yellow precipitate appeared immediately. And (4) carrying out suction filtration, washing the precipitate to be neutral by using an alkaline solution with the mass fraction of 6%, and washing the precipitate for three times by using ethanol. Vacuum drying at 60 ℃ to obtain a light yellow sample, namely the octa-nitro silsesquioxane.
(2) Synthesis of octanitrosilsesquioxane modified aqueous polyurethane polyol dispersion:
raw materials:
19.67g of polycarbonate diol 2000
18.52g 2-methylpentane diisocyanate (MPDI)
3.47g Lysine Diisocyanate (LDI)
0.4g of dibutyltin dilaurate
3g Dimethylolpropionic acid (DMPA)
3.34g trimethylpentanediol
2g of Glycerol
0.78g of Ammonia water (neutralization degree: 100%)
5g octanitrosilsesquioxane
150g deionized water
The preparation method comprises the steps of adding polycarbonate diol 2000, 2-methylpentane diisocyanate, lysine diisocyanate and dibutyltin dilaurate into a three-neck flask, reacting for 1.5h at 85 ℃ to obtain a polyurethane prepolymer, cooling to 65 ℃, adding dimethylolpropionic acid, reacting for 2.5h, heating to 75 ℃, adding trimethylpentanediol, reacting for 1.5h, adding glycerol, reacting for 2.5h, cooling to 25 ℃, adding ammonia water for neutralization, neutralizing for 0.5h, adding octanitrosilsesquioxane, stirring for 2h, adding deionized water for high-speed shearing emulsification, reacting for 0.5h, and removing an organic solvent by rotary evaporation to obtain the octanitrosilsesquioxane modified aqueous polyurethane polyol dispersoid.
The properties of the aqueous polyurethane emulsions obtained in the above examples are shown in the following table. Tensile strength, elongation at break and contact angle are measured after a certain amount of emulsion is formed on a polytetrafluoroethylene plate, and the appearance of the emulsion is the measured value of the aqueous polyurethane emulsion in the table.
Table 1: performance test Table for each comparative example and example
As can be seen from the above table, the appearance of the octanitrosilsesquioxane bi-component modified waterborne polyurethane emulsion is transparent, and the octanitrosilsesquioxane bi-component modified waterborne polyurethane emulsion can be stably stored for more than 8 months, which indicates that the component A and the component B are uniformly mixed after the octanitrosilsesquioxane is modified. Moreover, the octanitrosilsesquioxane bi-component modified waterborne polyurethane emulsion has the advantages of optimal performance after coating, good mechanical property, large tensile strength which can reach 50.73MPa, elongation at break which can reach 850 percent, relatively maximum contact angle which can reach 105.2 degrees, and good water resistance.
Claims (10)
1. The preparation method of the octa-nitro silsesquioxane modified bi-component waterborne polyurethane emulsion is characterized by comprising the following specific steps:
step 1, preparation of octanitrosilsesquioxane: under ice water bath, stirring and dissolving the oligomeric silsesquioxane in concentrated nitric acid with the mass fraction of 85-90%, stirring and reacting at 15-25 ℃, adding water after the reaction is finished, separating out light yellow precipitate, performing suction filtration, washing the precipitate with alkaline solution to be neutral, and drying to obtain octa-nitro silsesquioxane;
step 2, synthesizing the octanitrosilsesquioxane modified aqueous polyurethane polyol dispersion: mixing oligomer polyol and diisocyanate according to the weight ratio of 1000-2400: 1500-4000 parts by weight, uniformly mixing, dropwise adding a catalyst, reacting at 80-90 ℃ for 1-2 hours to obtain a polyurethane prepolymer, cooling to 60-70 ℃, adding polyhydroxycarboxylic acid for reacting for 2-3 hours, heating to 70-80 ℃, adding a small molecular diol monomer, reacting for 0.5-1 hour, adding an organic solvent to reduce the viscosity until the solution is colorless, reacting for 1-1.5 hours, adding a cross-linking agent for reacting for 2-3 hours, cooling to 20-30 ℃, adding a neutralizing agent for neutralizing for 0.5-1 hour, adding octanitrosilsesquioxane according to the mass ratio of the octanitrosilsesquioxane to the total amount of 4-10: 100, stirring for 1-2 hours, shearing and emulsifying, reacting for 0.5-1 hour, removing the organic solvent by rotary evaporation, obtaining octa-nitro silsesquioxane modified aqueous polyurethane polyol dispersoid;
step 3, preparing the octa-nitro silsesquioxane modified bi-component aqueous polyurethane emulsion:
adding a defoaming agent and a flatting agent into the octa-nitro silsesquioxane modified waterborne polyurethane polyol dispersoid, and mixing the octa-nitro silsesquioxane modified waterborne polyurethane polyol dispersoid with a polyisocyanate curing agent to obtain the octa-nitro silsesquioxane modified bi-component waterborne polyurethane emulsion.
2. The method according to claim 1, wherein in step 1, the alkaline solution is selected from one of sodium carbonate solution, sodium bicarbonate solution and sodium hydroxide solution.
3. The preparation method according to claim 1, wherein in the step 1, the mass ratio of the oligomeric silsesquioxane to the concentrated nitric acid is 10-20: 100-150, and the stirring reaction time is 15-20 h.
4. The preparation method according to claim 1, wherein in the step 2, the mass ratio of the oligomer polyol to the diisocyanate is 1200-2000: 1600-3000, wherein the oligomer polyol is selected from polyester polyol or polyether polyol.
5. The method according to claim 4, wherein the polyester polyol is selected from the group consisting of polyethylene adipate glycol, polyethylene glycol adipate glycol, 1, 4-butanediol adipate glycol, polycarbonate glycol and polycaprolactone glycol; the polyether polyol is selected from polyoxypropylene diol, polyoxypropylene triol, polytetrahydrofuran diol or tetrahydrofuran-propylene oxide copolymerized diol.
6. The method according to claim 1, wherein in step 2, the diisocyanate is selected from one or more of lysine diisocyanate, dimethyl diphenyl diisocyanate, naphthalene diisocyanate, diphenylmethane-4, 4' -diisocyanate, tetramethyl m-xylylene diisocyanate, and 2-methylpentane diisocyanate.
7. The method according to claim 1, wherein in step 2, the polyhydroxycarboxylic acid is selected from the group consisting of dimethylolacetic acid, dimethylolpropionic acid and dimethylolbutyric acid; the small molecular diol monomer is selected from one or more of 2-ethyl-1, 3-hexanediol, 1, 3-propanediol, trimethylpentanediol, methylpropanediol, 1, 6-hexanediol or neopentyl glycol; the cross-linking agent is selected from trimethylolpropane, pentaerythritol or glycerol; the neutralizing agent is selected from triethylamine, sodium hydroxide or ammonia water.
8. The preparation method according to claim 1, wherein in the step 2, the neutralization degree of the neutralization reaction is 75-115%, and the shear rate is controlled at 1700 r/min.
9. The method according to claim 8, wherein the neutralization reaction is performed at a neutralization degree of 100%.
10. The production method according to claim 1, wherein in step 3, the leveling agent is an acetylene glycol-based leveling agent; the defoaming agent is a silicone oil defoaming agent.
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| CN109535372B (en) * | 2018-10-31 | 2021-08-27 | 优美特（北京）环境材料科技股份公司 | Waterborne polyurethane and preparation method thereof |
| US11407904B2 (en) | 2019-02-11 | 2022-08-09 | King Fahd University Of Petroleum And Minerals | Waterborne polyurethane containing polyhedral oligomeric silsesquioxane |
| CN110527417A (en) * | 2019-07-26 | 2019-12-03 | 罗苗苗 | A kind of high attachment water resistant coating of insulating tape |
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