CN117701130B - Wear-resistant antiknock waterborne modified polyurethane matt oil and preparation method thereof - Google Patents
Wear-resistant antiknock waterborne modified polyurethane matt oil and preparation method thereofInfo
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- CN117701130B CN117701130B CN202311751805.5A CN202311751805A CN117701130B CN 117701130 B CN117701130 B CN 117701130B CN 202311751805 A CN202311751805 A CN 202311751805A CN 117701130 B CN117701130 B CN 117701130B
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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
- C08G18/10—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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
- C08G18/3895—Inorganic compounds, e.g. aqueous alkalimetalsilicate solutions; Organic derivatives thereof containing no direct silicon-carbon bonds
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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
- C09D175/02—Polyureas
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及哑油技术领域，且公开了一种耐磨抗爆线水性改性聚氨酯哑油及制备方法，本发明利用γ‑缩水甘油醚氧丙基三甲氧基硅烷依次与二氧化硅、磷酸三丁酯进行反应，得到含硅磷多元醇，再将其与甲苯‑2,4‑二异氰酸酯在二月桂酸二丁基锡的催化反应下，得到含硅磷端异氰酸酯预聚体。先将聚己内酯、二羟甲基丙酸等与含硅磷端异氰酸酯预聚体进行反应得到聚氨酯低聚物，再将其与聚天门冬氨酸酯进行反应，得到水性聚氨酯聚脲乳液，最后将向消泡剂、稀释剂等加入线型水性聚氨酯乳液、水性聚氨酯聚脲乳液，搅拌分散，得到聚氨酯哑油。本发明制备得到的聚氨酯哑油具有优异的耐磨性能、抗爆性能、阻燃性能。
The present invention relates to the technical field of dumb oil, and discloses a kind of wear-resistant and explosion-resistant line water-based modified polyurethane dumb oil and preparation method, the present invention utilizes γ-glycidyl ether oxygen propyl trimethoxy silane to react with silicon dioxide and tributyl phosphate in sequence, obtains silicon-phosphorus-containing polyol, and then reacts it with toluene-2,4-diisocyanate under the catalytic reaction of dibutyltin dilaurate, obtains silicon-phosphorus-terminated isocyanate prepolymer. First, polycaprolactone, dimethylol propionic acid, etc. are reacted with silicon-phosphorus-terminated isocyanate prepolymer to obtain polyurethane oligomer, then reacted with polyaspartic acid ester, obtains water-based polyurethane polyurea emulsion, finally adds linear water-based polyurethane emulsion, water-based polyurethane polyurea emulsion to defoamer, diluent, etc., stir and disperse, obtain polyurethane dumb oil. The polyurethane dumb oil prepared by the present invention has excellent wear resistance, explosion resistance and flame retardant performance.
Description
Technical Field
The invention relates to the technical field of matt oil, in particular to wear-resistant antiknock waterborne modified polyurethane matt oil and a preparation method thereof.
Background
With the improvement of the living standard and aesthetic consciousness of people, the water-based matte paint is popular with people due to the characteristics of being simple, elegant and attractive. Therefore, the research on the water-based matte paint is one of hot spots of research by researchers. The polyurethane material has the characteristics of excellent mechanical property, wear resistance, chemical resistance and the like, and is widely applied to the fields of national defense, textile, medical treatment, traffic and the like.
For example, patent CN105176365B discloses a high-resistance water-based matt surface oil for plastic film and its preparation method, the invention is prepared from water-based matt resin, defoamer, leveling agent, cross-linking agent, etc., and has the advantages of green environmental protection, friction resistance, high viscosity, etc., but does not improve the flame retardant property and antiknock property of the water-based matt surface oil.
The invention discloses a weather-resistant water-based polyurethane matt varnish, which is prepared from PUA emulsion, flame retardant, wetting dispersant and the like, and the prepared polyurethane matt varnish has the characteristics of flame retardance, wear resistance, good flexibility and the like, but the antiknock performance of the polyurethane matt varnish is not improved.
Disclosure of Invention
(One) solving the technical problems
Aiming at the defects of the prior art, the invention provides the wear-resistant antiknock waterborne modified polyurethane matt oil and the preparation method thereof, and the prepared polyurethane matt oil has excellent wear-resistant, antiknock and flame-retardant effects.
(II) technical scheme
The wear-resistant antiknock waterborne modified polyurethane matt oil is prepared from the following raw materials, by weight, 3-6 parts of a defoaming agent, 3-8 parts of a wetting dispersant, 2-6 parts of a surfactant, 1-2 parts of a leveling agent, 8-15 parts of a diluent, 100 parts of a linear waterborne polyurethane emulsion and 60-100 parts of a waterborne polyurethane polyurea emulsion.
Preferably, the preparation method comprises the steps of adding the defoamer, the wetting dispersant, the surfactant, the flatting agent and the diluent into deionized water, stirring and dispersing, adding the linear aqueous polyurethane emulsion and the aqueous polyurethane polyurea emulsion into the mixture, and stirring and dispersing to obtain the polyurethane matt oil.
Preferably, the preparation method of the aqueous polyurethane polyurea emulsion comprises the following steps:
(1) Adding silicon dioxide into a flask filled with an ethyl acetate solvent, stirring and dispersing, adding gamma-glycidoxypropyl trimethoxysilane into the flask, heating to 60-80 ℃, stirring and reacting for 8-15h, filtering, washing with ethyl acetate after the reaction is finished, and drying to obtain an intermediate 1.
(2) Adding tributyl phosphate and phosphoric acid into a flask, controlling the temperature to be 80-90 ℃, stirring uniformly, adding the intermediate 1 into the flask, heating to 95-120 ℃, stirring and reacting for 4-10h, cooling to room temperature after the reaction is finished, washing with acetone, and drying to obtain the silicon-containing phosphorus polyol.
(3) Toluene-2, 4-diisocyanate, silicon-containing phosphorus polyol and dibutyl tin dilaurate are added into a flask filled with an acetone solvent, the temperature is raised to 60-80 ℃, the mixture is stirred and reacted for 5-10 hours, the mixture is cooled to room temperature after the reaction is finished, and the solvent is removed by rotary evaporation, so that the silicon-containing phosphorus-terminated isocyanate prepolymer is obtained.
(4) Adding polycaprolactone, dimethylolpropionic acid and 1, 4-cyclohexanedimethanol into a flask, dehydrating in vacuum, adding silicon-containing phosphorus-terminated isocyanate prepolymer into the flask, stirring and reacting for 2-6 hours at 50-80 ℃, adding polyaspartic acid ester into the flask, continuing to react for 30-80 minutes, adding triethylamine into the flask for neutralization for 30-60 minutes, and expanding chain of the polydiene triamine for 20-50 minutes, thus obtaining the aqueous polyurethane polyurea emulsion after the reaction is finished.
Preferably, in the step (1), the mass ratio of the silicon dioxide to the gamma-glycidoxypropyl trimethoxysilane is 1:8-10.
Preferably, in the step (2), the mass ratio of tributyl phosphate, phosphoric acid and the intermediate 1 is 1:0.2-0.25:0.3-0.42.
Preferably, in the step (3), the ratio of toluene-2, 4-diisocyanate, silicon-containing phosphorus polyol and dibutyltin dilaurate is 0.5-0.8:1:0.003-0.005.
Preferably, in the step (4), the mass ratio of polycaprolactone, dimethylolpropionic acid, 1, 4-cyclohexanedimethanol, silicon-containing phosphorus-terminated isocyanate prepolymer, polyaspartic acid ester, triethylamine and ethylene diamine is 1:0.1-0.18:0.08-0.14:1.2-3.4:0.8-1.6:0.1-0.15:0.02-0.1.
Preferably, in the step (4), the vacuum dehydration temperature is 100-110 ℃, the pressure is-0.08 to-0.05 MPa, and the time is 1-3h.
(III) beneficial technical effects
The invention uses gamma-glycidol ether oxypropyl trimethoxy silane to react with silicon dioxide and tributyl phosphate in sequence to obtain silicon-containing phosphorus polyol, and then the silicon-containing phosphorus polyol reacts with toluene-2, 4-diisocyanate under the catalysis of dibutyl tin dilaurate to obtain silicon-containing phosphorus terminal isocyanate prepolymer. Firstly, reacting polycaprolactone, dimethylolpropionic acid and the like with a silicon-containing phosphorus-terminated isocyanate prepolymer to obtain a polyurethane oligomer, then reacting the polyurethane oligomer with polyaspartic acid ester to obtain a water-based polyurethane polyurea emulsion, and finally adding linear water-based polyurethane emulsion and water-based polyurethane polyurea emulsion into a defoaming agent, a diluting agent and the like, stirring and dispersing to obtain polyurethane matt oil.
The polyurethane matt oil prepared by the invention contains silicon dioxide, the silicon dioxide can be used as a matting agent to reduce the gloss of the polyurethane matt oil, but the silicon dioxide has larger surface energy and is extremely easy to agglomerate, and the polyurethane matt oil can react with organic matters, so that the purpose of dispersing the silicon dioxide can be achieved, and the matting and matt effects can be improved.
The polyurethane matt oil prepared by the invention contains a polyurethane polyurea structure, the polyurethane matt oil has better compatibility with linear polyurethane, urea bonds with stronger acting force exist among polyurea molecules contained in the polyurethane matt oil to form a hard segment chain, the urea bonds are formed by hydrogen bonds, the polyurea molecule chain segments move under the action of external high-frequency impact load, the hydrogen bonds are broken to absorb a large amount of energy, when the impact wave is counteracted, the action among the molecule chain segments stops, new groups of hydrogen bonds are reformed in the polyurethane matt oil, and the polyurea structure can continuously release and absorb energy through the continuous movement, breaking and recombination of the hydrogen bonds, so that the antiknock aim is achieved.
The polyurethane matt oil prepared by the invention contains a polyurethane polyurea structure, wherein the polyurethane structure is a wear-resistant structure, and the siloxane structure and silicon dioxide contained in the polyurethane matt oil have silicon-oxygen bonds with higher bond energy, so that more energy can be absorbed when the polyurethane matt oil is impacted by the outside, and the wear resistance of the polyurethane matt oil is further improved.
The polyurethane matt oil prepared by the invention contains phosphorus element and silicon element, when the material is heated, the phosphorus element contained in the polyurethane matt oil can generate acidic substances such as phosphoric acid, metaphosphoric acid and the like, and the substances have strong dehydration property, can promote the material to dehydrate into carbon, and form a compact carbon layer on the surface of the substrate. When the silicon element contained in the material is heated, a glassy substance can be formed on the surface of the material, and the material is isolated from external substance transmission and energy transmission, so that the flame retardant property of the material is further improved. The polyurethane matt oil prepared by the invention has excellent wear resistance, antiknock performance and flame retardance.
Drawings
FIG. 1 is a route to silicon-containing phosphorus polyol.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
The preparation method of the linear aqueous polyurethane emulsion comprises the steps of taking 5.9g of polycarbonate diol in a flask, dehydrating in vacuum at 120 ℃, adding 1.7g of toluene-2, 4-diisocyanate and 0.007g of dibutyltin dilaurate into the flask, stirring and reacting for 30min at 80 ℃, adding a mixed solution of dimethylolpropionic acid/N-methylpyrrolidone into the flask, continuing to react for 3h, cooling to room temperature, adding 1g of triethylamine into the flask and neutralizing for 30min to obtain the linear aqueous polyurethane emulsion.
Example 1
(1) 3G of silicon dioxide is added into a flask filled with ethyl acetate solvent, stirred and dispersed, 30g of gamma-glycidoxypropyl trimethoxysilane is added into the flask, the temperature is raised to 70 ℃, the reaction is stirred for 12 hours, and after the reaction is finished, the mixture is filtered, washed with ethyl acetate and dried to obtain an intermediate 1.
(2) Adding 20g of tributyl phosphate and 4.2g of phosphoric acid into a flask, controlling the temperature to be 85 ℃, uniformly stirring, adding 8.4g of intermediate 1 into the flask, heating to 110 ℃, stirring for reaction for 8 hours, cooling to room temperature after the reaction is finished, washing with acetone, and drying to obtain the silicon-containing phosphorus polyol.
(3) 15G of toluene-2, 4-diisocyanate, 30g of silicon-containing phosphorus polyol and 0.25g of dibutyltin dilaurate are added into a flask filled with an acetone solvent, the temperature is raised to 70 ℃, the mixture is stirred and reacted for 8 hours, the mixture is cooled to room temperature after the reaction is finished, and the solvent is removed by rotary evaporation, so that the silicon-containing phosphorus-terminated isocyanate prepolymer is obtained.
(4) Adding 40g of polycaprolactone, 5g of dimethylolpropionic acid and 4g of 2-1, 4-cyclohexanedimethanol into a flask, carrying out vacuum dehydration, wherein the vacuum dehydration temperature is 110 ℃, the pressure is-0.05 MPa, the time is 2 hours, then adding 50g of silicon-containing phosphorus-terminated isocyanate prepolymer into the mixture, stirring the mixture at 70 ℃ for reaction for 6 hours, then adding 60g of polyaspartic acid ester into the mixture, continuing the reaction for 60 minutes, then adding 5g of triethylamine into the mixture for neutralization for 40 minutes, and carrying out chain extension for 3.2g of ethylene triamine for 30 minutes, thus obtaining the aqueous polyurethane polyurea emulsion after the reaction is finished.
(5) Adding 4g of defoamer W0506, 5g of wetting dispersant YF-98, 4g of surfactant F-105, 1.5g of flatting agent BYK358 and 12g of 692 active diluent into deionized water, stirring and dispersing, and then adding 100g of linear aqueous polyurethane emulsion and 60g of aqueous polyurethane polyurea emulsion into the mixture, stirring and dispersing to obtain polyurethane matt oil.
Example 2
(1) 3G of silicon dioxide is added into a flask filled with ethyl acetate solvent, stirred and dispersed, 25g of gamma-glycidoxypropyl trimethoxysilane is added into the flask, the temperature is raised to 70 ℃, the reaction is stirred for 10 hours, and after the reaction is finished, the solution is filtered, washed with ethyl acetate and dried to obtain an intermediate 1.
(2) Adding 20g of tributyl phosphate and 4g of phosphoric acid into a flask, controlling the temperature to be 90 ℃, stirring uniformly, adding 8g of intermediate 1 into the flask, heating to 120 ℃, stirring and reacting for 8 hours, cooling to room temperature after the reaction is finished, washing with acetone, and drying to obtain the silicon-containing phosphorus polyol.
(3) 15G of toluene-2, 4-diisocyanate, 30g of silicon-containing phosphorus polyol and 0.15g of dibutyltin dilaurate are added into a flask filled with an acetone solvent, the temperature is raised to 70 ℃, the mixture is stirred and reacted for 5 hours, the mixture is cooled to room temperature after the reaction is finished, and the solvent is removed by rotary evaporation, so that the silicon-containing phosphorus-terminated isocyanate prepolymer is obtained.
(4) Adding 40g of polycaprolactone, 6g of dimethylolpropionic acid and 4g of 2-1, 4-cyclohexanedimethanol into a flask, carrying out vacuum dehydration, wherein the vacuum dehydration temperature is 110 ℃, the pressure is-0.06 MPa, the time is 3 hours, then adding 120g of silicon-containing phosphorus-terminated isocyanate prepolymer into the flask, stirring the mixture at 60 ℃ for reaction for 5 hours, then adding 60g of polyaspartic acid ester into the flask, continuing the reaction for 40 minutes, then adding 5g of triethylamine into the flask for neutralization for 60 minutes, and carrying out chain extension for 3g of ethylene triamine for 50 minutes, thus obtaining the aqueous polyurethane polyurea emulsion after the reaction is finished.
(5) 6G of defoaming agent W0506, 7g of wetting dispersant YF-98, 4g of surfactant F-105, 1.4g of flatting agent BYK358 and 10g of 692 active diluent are added into deionized water, stirred and dispersed, and then 100g of linear aqueous polyurethane emulsion and 70g of aqueous polyurethane polyurea emulsion are added into the mixture, stirred and dispersed, and polyurethane matt oil is obtained.
Example 3
(1) 3G of silicon dioxide is added into a flask filled with ethyl acetate solvent, stirred and dispersed, 28g of gamma-glycidoxypropyl trimethoxysilane is added into the flask, the temperature is raised to 70 ℃, the reaction is stirred for 12 hours, and after the reaction is finished, the mixture is filtered, washed with ethyl acetate and dried to obtain an intermediate 1.
(2) Adding 20g of tributyl phosphate and 4.5g of phosphoric acid into a flask, controlling the temperature to be 80 ℃, uniformly stirring, adding 7g of intermediate 1 into the flask, heating to 100 ℃, stirring and reacting for 10 hours, cooling to room temperature after the reaction is finished, washing with acetone, and drying to obtain the silicon-containing phosphorus polyol.
(3) 15G of toluene-2, 4-diisocyanate, 30g of silicon-containing phosphorus polyol and 0.2g of dibutyltin dilaurate are added into a flask filled with an acetone solvent, the temperature is raised to 70 ℃, the mixture is stirred and reacted for 10 hours, the mixture is cooled to room temperature after the reaction is finished, and the solvent is removed by rotary evaporation, so that the silicon-containing phosphorus-terminated isocyanate prepolymer is obtained.
(4) Adding 40g of polycaprolactone, 6g of dimethylolpropionic acid and 4g of 2-1, 4-cyclohexanedimethanol into a flask, carrying out vacuum dehydration, wherein the vacuum dehydration temperature is 110 ℃, the pressure is-0.05 MPa, the time is 2 hours, then adding 100g of silicon-containing phosphorus-terminated isocyanate prepolymer into the mixture, stirring the mixture at 60 ℃ for reaction for 6 hours, then adding 50g of polyaspartic acid ester into the mixture, continuing the reaction for 80 minutes, then adding 4g of triethylamine into the mixture for neutralization for 60 minutes, and carrying out chain extension for 40 minutes by 0.8g of ethylene triamine, thus obtaining the aqueous polyurethane polyurea emulsion after the reaction is finished.
(5) 3G of defoamer W0506, 7g of wetting dispersant YF-98, 5g of surfactant F-105, 1.5g of flatting agent BYK358 and 12g of 692 active diluent are added into deionized water, stirred and dispersed, and then 100g of linear aqueous polyurethane emulsion and 80g of aqueous polyurethane polyurea emulsion are added into the mixture, stirred and dispersed, and polyurethane matt oil is obtained.
Example 4
(1) 3G of silicon dioxide is added into a flask filled with ethyl acetate solvent, stirred and dispersed, 30g of gamma-glycidoxypropyl trimethoxysilane is added into the flask, the temperature is raised to 70 ℃, the reaction is stirred for 12 hours, and after the reaction is finished, the mixture is filtered, washed with ethyl acetate and dried to obtain an intermediate 1.
(2) Adding 20g of tributyl phosphate and 4.5g of phosphoric acid into a flask, controlling the temperature to be 80 ℃, uniformly stirring, adding 8g of intermediate 1 into the flask, heating to 100 ℃, stirring and reacting for 10 hours, cooling to room temperature after the reaction is finished, washing with acetone, and drying to obtain the silicon-containing phosphorus polyol.
(3) 24G of toluene-2, 4-diisocyanate, 30g of silicon-containing phosphorus polyol and 0.13g of dibutyltin dilaurate are added into a flask filled with an acetone solvent, the temperature is raised to 80 ℃, the mixture is stirred and reacted for 7 hours, the mixture is cooled to room temperature after the reaction is finished, and the solvent is removed by rotary evaporation, so that the silicon-containing phosphorus-terminated isocyanate prepolymer is obtained.
(4) Adding 40g of polycaprolactone, 4g of dimethylolpropionic acid and 5g of 2-1, 4-cyclohexanedimethanol into a flask, carrying out vacuum dehydration, wherein the vacuum dehydration temperature is 100 ℃, the pressure is-0.07 MPa, the time is 2 hours, adding 120g of silicon-containing phosphorus-terminated isocyanate prepolymer into the mixture, stirring the mixture at 70 ℃ for reaction for 5 hours, adding 50g of polyaspartic acid ester into the mixture, continuing the reaction for 80 minutes, adding 4g of triethylamine into the mixture for neutralization for 40 minutes, and adding 2g of ethylene triamine into the mixture for chain extension for 40 minutes, thus obtaining the aqueous polyurethane polyurea emulsion after the reaction is finished.
(5) 5G of defoaming agent W0506, 7g of wetting dispersant YF-98, g of surfactant F-105, 2g of flatting agent BYK358 and 12g of 692 active diluent are added into deionized water, stirred and dispersed, and then 100g of linear aqueous polyurethane emulsion and 90g of aqueous polyurethane polyurea emulsion are added into the mixture, stirred and dispersed, and polyurethane matt oil is obtained.
Example 5
(1) 3G of silicon dioxide is added into a flask filled with ethyl acetate solvent, stirred and dispersed, 25g of gamma-glycidoxypropyl trimethoxysilane is added into the flask, the temperature is raised to 70 ℃, the reaction is stirred for 14 hours, and after the reaction is finished, the mixture is filtered, washed with ethyl acetate and dried to obtain an intermediate 1.
(2) Adding 20g of tributyl phosphate and 4.2g of phosphoric acid into a flask, controlling the temperature to be 80 ℃, uniformly stirring, adding 7g of intermediate 1 into the flask, heating to 110 ℃, stirring for reaction for 8 hours, cooling to room temperature after the reaction is finished, washing with acetone, and drying to obtain the silicon-containing phosphorus polyol.
(3) 20G of toluene-2, 4-diisocyanate, 30g of silicon-containing phosphorus polyol and 0.15g of dibutyltin dilaurate are added into a flask filled with an acetone solvent, the temperature is raised to 70 ℃, the mixture is stirred and reacted for 8 hours, the mixture is cooled to room temperature after the reaction is finished, and the solvent is removed by rotary evaporation, so that the silicon-containing phosphorus-terminated isocyanate prepolymer is obtained.
(4) Adding 40g of polycaprolactone, 7g of dimethylolpropionic acid and 4g of 2-1, 4-cyclohexanedimethanol into a flask, carrying out vacuum dehydration, wherein the vacuum dehydration temperature is 110 ℃, the pressure is-0.08 MPa, the time is 2.4h, adding 120g of silicon-containing phosphorus-terminated isocyanate prepolymer into the flask, stirring the mixture at 50 ℃ for reaction for 3h, adding 60g of polyaspartic acid ester into the mixture, continuing the reaction for 80min, adding 4g of triethylamine into the mixture for neutralization 40min, and carrying out chain extension on 3g of ethandienetriamine for 20-50min, thus obtaining the aqueous polyurethane polyurea emulsion after the reaction is finished.
(5) 6G of defoaming agent W0506, 3g of wetting dispersant YF-98, 5g of surfactant F-105, 1.5g of flatting agent BYK358 and 10g of 692 active diluent are added into deionized water, stirred and dispersed, and then 100g of linear aqueous polyurethane emulsion and 100g of aqueous polyurethane polyurea emulsion are added into the mixture, stirred and dispersed, and polyurethane matt oil is obtained.
Comparative example 1
Adding 4g of defoamer W0506, 5g of wetting dispersant YF-98, 4g of surfactant F-105, 1.5g of flatting agent BYK358 and 12g of 692 active diluent into deionized water, stirring and dispersing, and then adding 100g of linear aqueous polyurethane emulsion into the mixture, stirring and dispersing to obtain polyurethane matt oil.
Adding a nitrogen-pyridine cross-linking agent into the polyurethane matt oil, uniformly mixing, coating the mixture on the surface of black paint leather, drying the mixture in an oven at room temperature for 24 hours and at 100 ℃ for 10 hours, and testing.
And (3) performing low-temperature bending test, namely placing the material at a temperature of-20 ℃ and repeatedly bending for 30000 times, and observing whether the coating cracks or not.
Scratch resistance test, namely rubbing the surface of the coating layer with cotton cloth for 30 times, and observing the change of the coating layer.
| Low temperature resistant flex | Scratch resistance | |
| Example 1 | Slight cracking | Excellent (excellent) |
| Example 2 | No cracking | Excellent (excellent) |
| Example 3 | No cracking | Excellent (excellent) |
| Example 4 | No cracking | Excellent (excellent) |
| Example 5 | No cracking | Excellent (excellent) |
| Comparative example 1 | Cracking of | Difference of difference |
As can be seen from the table, the low temperature flexibility and scratch resistance of examples 1 to 5 are better than those of comparative example 1, and therefore, the polyurethane matt oil prepared by the invention has excellent wear resistance.
The limiting oxygen index of the material was tested using a limiting oxygen index tester.
The hardness of the material was tested using a shore durometer.
| Oxygen index (%) | Hardness (HA) | |
| Example 1 | 24.9 | 21 |
| Example 2 | 26.8 | 29 |
| Example 3 | 29.1 | 34 |
| Example 4 | 30.2 | 45 |
| Example 5 | 31.4 | 42 |
| Comparative example 1 | 21.4 | 15 |
As shown in the table, the oxygen index of examples 1-5 is larger than that of comparative example 1, and the flame retardant effect is better than that of comparative example 1, so that the polyurethane matt oil prepared by the invention has better flame retardant property. The higher the hardness is, the stronger the deformation resistance caused by external pressure is, and the higher the antiknock capability is, so that the polyurethane matt oil prepared by the invention has better antiknock capability.
The foregoing description illustrates the major features, principles, and advantages of the invention. It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments or examples, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The foregoing implementations or examples should be regarded as illustrative rather than limiting. The scope of the invention is indicated by the appended claims rather than by the foregoing description, and all changes that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (7)
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| CN107345106A (en) * | 2017-06-27 | 2017-11-14 | 天长市巨龙车船涂料有限公司 | A kind of anti-corrosion heat-resisting modified coating |
| CN108047904A (en) * | 2017-11-15 | 2018-05-18 | 张军志 | A kind of preparation method of the polyureas wear-resistant paint based on the double modifications of organic and inorganic |
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| CN108047904A (en) * | 2017-11-15 | 2018-05-18 | 张军志 | A kind of preparation method of the polyureas wear-resistant paint based on the double modifications of organic and inorganic |
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