CN111205628A - Porous carbon modified waterborne polyurethane material and preparation method thereof - Google Patents

Porous carbon modified waterborne polyurethane material and preparation method thereof Download PDF

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CN111205628A
CN111205628A CN202010124582.XA CN202010124582A CN111205628A CN 111205628 A CN111205628 A CN 111205628A CN 202010124582 A CN202010124582 A CN 202010124582A CN 111205628 A CN111205628 A CN 111205628A
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porous carbon
waterborne polyurethane
reaction
diisocyanate
stirring
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赵艳娜
薛瑜瑜
牛育华
林磊
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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Abstract

The invention provides a porous carbon modified waterborne polyurethane material and a preparation method thereof, wherein the preparation method comprises the following steps: s1, preparing a waterborne polyurethane prepolymer: mixing polyglycol, diisocyanate and a hydrophilic chain extender, heating for reaction, then adding a small molecular cross-linking agent for heating for reaction, adding organic base for reaction, and finally adding water for reaction to obtain a waterborne polyurethane prepolymer; s2, preparing oxidized porous carbon: adding organic acid into porous carbon, stirring, adding potassium permanganate in an ice water bath, stirring for oxidation reaction, adjusting the pH to be neutral, and filtering to obtain oxidized porous carbon; s3, preparing a porous carbon modified waterborne polyurethane dispersion liquid: and dispersing the oxidized porous carbon in a solvent, performing ultrasonic treatment, mixing with the waterborne polyurethane prepolymer, stirring, and performing reduced pressure distillation to remove the solvent to obtain the porous carbon modified waterborne polyurethane. The invention improves the thermal stability, mechanical property and adsorption property of the waterborne polyurethane material.

Description

Porous carbon modified waterborne polyurethane material and preparation method thereof
Technical Field
The invention belongs to the field of modified waterborne polyurethane materials, and particularly relates to a porous carbon modified waterborne polyurethane material and a preparation method thereof.
Background
Aqueous polyurethanes are new polyurethane systems in which water is used as the dispersion medium instead of an organic solvent, and are also referred to as water-dispersed polyurethanes, aqueous polyurethanes, or water-based polyurethanes. The high polymer material with the main chain containing the carbamate group has the advantages of no pollution, safety, reliability, excellent mechanical property, good compatibility, easy modification and the like, and is widely applied to a plurality of fields. The waterborne polyurethane material is mainly applied to industries such as light textile, industrial coating, building materials, papermaking, adhesive and the like; are often used in paints, leather coatings, textile coatings, fiber treatments, plastic coatings, floor coatings, coatings of other materials, and the like.
The excellent performance of the waterborne polyurethane is a focus and hot spot of research of people in recent years. With the more intensive research and wider application of the waterborne polyurethane, the performance of the waterborne polyurethane is further required, and the waterborne polyurethane will develop towards high performance, multiple functions and high application direction in the future.
However, the existing unmodified waterborne polyurethane has poor thermal property, mechanical property and adsorption property, and functional modification is needed to expand the application of the existing unmodified waterborne polyurethane.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a porous carbon modified waterborne polyurethane material and a preparation method thereof, which improve the thermal stability, mechanical property and adsorption property of the waterborne polyurethane material.
The invention is realized by the following technical scheme:
a preparation method of a porous carbon modified waterborne polyurethane material comprises the following steps:
s1, preparing a waterborne polyurethane prepolymer: mixing polyglycol, diisocyanate and a hydrophilic chain extender, heating for reaction, then adding a small molecular cross-linking agent for heating for reaction, adding organic base for reaction, and finally adding water for reaction to obtain a waterborne polyurethane prepolymer;
s2, preparing oxidized porous carbon: adding organic acid into porous carbon, stirring, adding potassium permanganate in an ice water bath, stirring for oxidation reaction, adjusting the pH to be neutral, and filtering to obtain oxidized porous carbon;
s3, preparing a porous carbon modified waterborne polyurethane dispersion liquid: and dispersing the oxidized porous carbon in a solvent, performing ultrasonic treatment, mixing with the waterborne polyurethane prepolymer, stirring, and performing reduced pressure distillation to remove the solvent to obtain the porous carbon modified waterborne polyurethane.
Preferably, in S1, the preparation process of the aqueous polyurethane prepolymer is as follows: mixing polyglycol, diisocyanate and hydrophilic chain extender, adding a catalyst, heating to 75-85 ℃, and reacting for 1-3 h; then adding a micromolecular cross-linking agent, and reacting for 1-2 h; reducing the temperature to 35-45 ℃, adding organic base, and reacting for 0.5-1 h; and finally, adding water to obtain the waterborne polyurethane prepolymer.
Preferably, in S1, the polyglycol is polyether diol or polyester diol; the diisocyanate is one or more of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate; the hydrophilic chain extender is dimethylolpropionic acid or dimethylolbutyric acid; the organic base is triethylamine; the catalyst is dibutyltin dilaurate; the micromolecule cross-linking agent is trimethylolpropane.
Preferably, in S1, the molar ratio of diisocyanate to polyglycol is (1.1-1.5): 1, the using amount of the hydrophilic chain extender is 1.5-3% of the total mass of the system, wherein the total mass of the system refers to the total mass of diisocyanate, polyglycol, the hydrophilic chain extender, porous carbon and organic acid.
Preferably, in S2, the amount of porous carbon is 1.0% to 1.5% of the total mass of the system, wherein the total mass of the system refers to the total mass of diisocyanate, polyglycol, hydrophilic chain extender, porous carbon and organic acid.
Preferably, in S2, the organic acid is a mixture of sulfuric acid and phosphoric acid.
Preferably, in S2, the oxidation reaction time is 10-15 h.
Preferably, in S3, the ultrasonic treatment time is 15-45min, and the stirring time is 20-40min after the ultrasonic treatment and the aqueous polyurethane prepolymer are mixed.
A porous carbon modified waterborne polyurethane material is obtained by the preparation method.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the invention, porous carbon is modified to obtain a porous carbon modified waterborne polyurethane material, oxidized porous carbon is used as a modifier and introduced into the polyurethane synthesis process, and the porous carbon is connected with active groups such as carboxyl and hydroxyl through the oxidation process due to the fact that the porous carbon molecular structure is a net structure. Therefore, the oxidized porous carbon serves as a cross-linking agent in the synthesis process of the waterborne polyurethane, the cross-linking degree of a system is increased along with the increase of the using amount of the oxidized porous carbon, and the porous carbon molecules contain rigid structures such as benzene rings and the like, so that the thermal stability and the mechanical property of the waterborne polyurethane material are improved. In addition, the oxidized porous carbon has a highly developed pore structure and a large specific surface area, so that the excellent adsorption performance is the most obvious characteristic of the porous carbon material modified waterborne polyurethane. Compared with unmodified waterborne polyurethane, the porous carbon modified waterborne polyurethane material has better thermal stability and mechanical strength. In conclusion, the comprehensive performance of the waterborne polyurethane can be obviously improved by introducing the oxidized porous carbon, and the application of the waterborne polyurethane in the fields of coating, leather, papermaking and textile is widened.
The porous carbon modified waterborne polyurethane material prepared by the invention has excellent thermal stability, mechanical property and adsorption property, and can be used for adsorptive coatings such as interior wall environment-friendly coatings, paper coating and leather finishing.
Drawings
FIG. 1 is a WPU, porous carbon/WPU thermogram;
FIG. 2 is an infrared spectrum of WPU, porous carbon/WPU;
FIG. 3 is a graph of the mechanical properties of WPU, porous carbon/WPU.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The preparation method of the porous carbon modified waterborne polyurethane material comprises the following steps:
adding polyglycol, diisocyanate, a hydrophilic chain extender and a small amount of catalyst into a 250mL three-neck flask provided with a reflux condenser tube, a thermometer and an electric stirrer;
heating in water bath to 75-85 ℃ for reaction for 1-3 h; then adding a micromolecular cross-linking agent, and reacting for 1-2 h; reducing the temperature of the water bath to 35-45 ℃, adding organic base, and reacting for 0.5-1 h; and finally, adding water, and dispersing the water into the polymer under high-speed stirring for 1h to obtain the waterborne polyurethane prepolymer.
Preparing oxidized porous carbon: adding organic acid into porous carbon, fully stirring, slowly adding potassium permanganate while stirring in an ice water bath, stirring for oxidation reaction, adjusting the pH value to be neutral after 10-15h, filtering after the reaction is finished, and finally freeze-drying to prepare oxidized porous carbon;
preparing a porous carbon modified waterborne polyurethane dispersion liquid: dispersing metered oxidized porous carbon in a solvent, carrying out ultrasonic treatment for 15-45min, then placing the mixture in a waterborne polyurethane prepolymer, finally stirring for 20-40min, carrying out reduced pressure distillation to remove the solvent, and reacting to obtain the porous carbon modified waterborne polyurethane.
The polyglycol is polyether diol or polyester diol; the diisocyanate is one or more of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate; the hydrophilic chain extender is dimethylolpropionic acid or dimethylolbutyric acid; the organic base is triethylamine; the catalyst is dibutyltin dilaurate; the micromolecule cross-linking agent is trimethylolpropane.
The molar ratio of the diisocyanate to the polyglycol is (1.1-1.5): 1, the using amount of the hydrophilic chain extender is 1.5-3% of the total mass of the system, wherein the total mass of the system refers to the total mass of diisocyanate, polyglycol, the hydrophilic chain extender, porous carbon and organic acid.
The dosage of the porous carbon is 1.0-1.5% of the total mass of the system.
The organic acid is a mixture of sulfuric acid and phosphoric acid.
Specific examples are as follows.
Example 1
Adding 15.34g of polycaprolactone diol (PCL2000), 6.25g of isophorone diisocyanate (IPDI) and 1.0g of 2-dihydroxy methyl propionic acid hydrophilic chain extender into a 250mL three-neck flask provided with a reflux condenser tube, a thermometer and an electric stirrer, dissolving in a solvent, adding a small amount of catalyst dibutyltin dilaurate (DBTDL), heating in a water bath to 80 ℃, and reacting for 2 hours; then 0.5g of trimethylolpropane is added, and the reaction time is 1 h; the temperature of the water bath is reduced to 40 ℃, and then 0.8g of triethylamine is added for reaction for 0.7 h; and finally, adding 64.77mL of water, and dispersing into the polymer under high-speed stirring for 1h to obtain the waterborne polyurethane prepolymer (WPU).
Preparing oxidized porous carbon: putting 5g of porous carbon into a beaker, adding 90mL of sulfuric acid and 10mL of phosphoric acid, slowly adding 25g of potassium permanganate while stirring in an ice water bath, and stirring while adding, after the reaction is finished; and stirring for 12h at normal temperature, adjusting the pH value to be neutral until no bubbles are generated, filtering after the reaction is finished, and finally freeze-drying to prepare the oxidized porous carbon.
Preparing a porous carbon modified waterborne polyurethane dispersion liquid: and dispersing metered oxidized porous carbon in a proper amount of acetone, performing ultrasonic treatment for 40min, placing the mixture in a waterborne polyurethane prepolymer, stirring for 30min, performing reduced pressure distillation to remove the acetone, and reacting to obtain the porous carbon modified waterborne polyurethane (porous carbon/WPU).
Example 2
Adding 14.84g of polycaprolactone diol (PCL1000), 6.75g of isophorone diisocyanate (IPDI) and 1.0g of dimethylolpropionic acid hydrophilic chain extender into a 250mL three-neck flask provided with a reflux condenser tube, a thermometer and an electric stirrer, dissolving in a solvent, adding a small amount of catalyst dibutyltin dilaurate (DBTDL), heating in a water bath to 75 ℃ for reaction, wherein the reaction time is 1 h; then 0.5g of trimethylolpropane is added, and the reaction time is 2 hours; the temperature of the water bath is reduced to 40 ℃, and then 0.8g of triethylamine is added for reaction for 0.5 h; and finally, adding 65mL of water, and dispersing the mixture into the polymer under high-speed stirring for 1h to obtain the waterborne polyurethane prepolymer.
Preparing oxidized porous carbon: putting 3g of porous carbon into a beaker, adding 30mL of sulfuric acid and 10mL of phosphoric acid, slowly adding 10g of potassium permanganate while stirring in an ice water bath, and stirring while adding, after the reaction is finished; stirring for 12h at normal temperature, adjusting the pH to be neutral until no bubbles are generated, filtering after the reaction is finished, and finally freeze-drying to prepare oxidized porous carbon;
preparing a porous carbon modified waterborne polyurethane dispersion liquid: and dispersing metered oxidized porous carbon in a proper amount of acetone, carrying out ultrasonic treatment for 30min, then placing the mixture in a waterborne polyurethane prepolymer, finally stirring for 40min, carrying out reduced pressure distillation to remove the acetone, and reacting to obtain the porous carbon modified waterborne polyurethane.
Example 3
Adding 10.8g of diphenylmethane diisocyanate and 17.5g of polycarbonate diol into a 250mL three-neck flask provided with a reflux condenser tube, a thermometer and an electric stirrer, then adding 3.0g of dimethylolbutyric acid hydrophilic chain extender, dissolving in a solvent, adding a small amount of catalyst dibutyltin dilaurate (DBTDL), and heating in a water bath to 85 ℃ for reaction for 3 hours; then 0.5g of trimethylolpropane is added, and the reaction time is 1.5 h; the temperature of the water bath is reduced to 45 ℃, and then 0.86g of triethylamine is added for reaction for 1 hour; and finally, adding 84.9mL of water, and dispersing the water into the polymer under high-speed stirring for 1h to obtain the waterborne polyurethane prepolymer.
Preparing oxidized porous carbon: putting 10g of porous carbon into a beaker, adding 100mL of sulfuric acid and 15mL of phosphoric acid, slowly adding 60g of potassium permanganate while stirring in an ice water bath, and stirring while adding, after the reaction is finished; stirring for 15h at normal temperature, adjusting the pH value to be neutral until no bubbles are generated, filtering after the reaction is finished, and finally freeze-drying to prepare oxidized porous carbon;
preparing a porous carbon modified waterborne polyurethane dispersion liquid: and dispersing metered oxidized porous carbon into a proper amount of acetone, carrying out ultrasonic treatment for 20min, placing the mixture into a waterborne polyurethane prepolymer, stirring the mixture for 30min, carrying out reduced pressure distillation to remove the acetone, and reacting to obtain the porous carbon modified waterborne polyurethane.
Example 4
Adding 8.5g of toluene diisocyanate and 18.4g of polytetrahydrofuran ether glycol into a 250mL three-neck flask provided with a reflux condenser tube, a thermometer and an electric stirrer, then adding 0.8g of dimethylolpropionic acid hydrophilic chain extender, dissolving in a solvent, adding a small amount of catalyst dibutyltin dilaurate (DBTDL), heating in a water bath to 82 ℃ for reaction, wherein the reaction time is 2.5 hours; then 0.5g of trimethylolpropane is added, and the reaction time is 1.2 h; reducing the temperature of the water bath to 35 ℃, adding 0.82g of triethylamine, and reacting for 0.8 h; finally, 63.70mL of water is added, and the mixture is dispersed into the polymer under high-speed stirring, the reaction time is 1h, and finally the waterborne polyurethane prepolymer is obtained.
Preparing oxidized porous carbon: putting 3g of porous carbon into a beaker, adding 60mL of sulfuric acid and 8mL of phosphoric acid, slowly adding 20g of potassium permanganate while stirring in an ice water bath, and stirring while adding, after the reaction is finished; stirring for 11h at normal temperature, adjusting the pH value to be neutral until no bubbles are generated, filtering after the reaction is finished, and finally freeze-drying to prepare oxidized porous carbon;
preparing a porous carbon modified waterborne polyurethane dispersion liquid: dissolving metered oxidized porous carbon in a proper amount of acetone, carrying out ultrasonic treatment for 35min, placing the obtained product in a waterborne polyurethane prepolymer, finally stirring the obtained product for 35min, carrying out reduced pressure distillation to remove the acetone, and reacting to obtain the porous carbon modified waterborne polyurethane.
Example 5
Adding 7.86g of toluene diisocyanate and 14.73g of polytetrahydrofuran ether glycol into a 250mL three-neck flask provided with a reflux condenser tube, a thermometer and an electric stirrer, then adding 1g of dimethylolpropionic acid hydrophilic chain extender, dissolving in a solvent, adding a small amount of catalyst dibutyltin dilaurate (DBTDL), heating in a water bath to 82 ℃ for reaction, wherein the reaction time is 2 hours; then 0.5g of trimethylolpropane is added, and the reaction time is 1 h; the temperature of the water bath is reduced to 36 ℃, and then 0.9g of triethylamine is added for reaction for 0.7 h; and finally adding 67.77mL of water, dispersing the mixture into the polymer under high-speed stirring, and reacting for 40min to finally obtain the waterborne polyurethane prepolymer.
Preparing oxidized porous carbon: putting 6g of porous carbon into a beaker, adding 120mL of sulfuric acid and 20mL of phosphoric acid, slowly adding 30g of potassium permanganate while stirring in an ice water bath, and stirring while adding, after the reaction is finished; stirring for 12h at normal temperature, adjusting the pH to be neutral until no bubbles are generated, filtering after the reaction is finished, and finally freeze-drying to prepare oxidized porous carbon;
preparing a porous carbon modified waterborne polyurethane dispersion liquid: and dispersing metered oxidized porous carbon in a proper amount of acetone, carrying out ultrasonic treatment for 25min, placing the mixture in a waterborne polyurethane prepolymer, stirring for 25min, carrying out reduced pressure distillation to remove the acetone, and reacting to obtain the porous carbon modified waterborne polyurethane.
Example 6
In a 250mL three-necked flask equipped with a reflux condenser, a thermometer and an electric stirrer were charged 11.1g of isophorone diisocyanate (IPDI): hexamethylene diisocyanate (the molar ratio of the hexamethylene diisocyanate to the polyoxypropylene diol is 1: 1) and 16g of polyoxypropylene diol, then 1.0g of 0g of dimethylolpropionic acid hydrophilic chain extender is added to be dissolved in a solvent, a small amount of catalyst dibutyltin dilaurate (DBTDL) is added, the mixture is heated to 85 ℃ in a water bath to react for 2 hours; then 0.5g of trimethylolpropane is added, and the reaction time is 1 h; the temperature of the water bath is reduced to 40 ℃, and then 0.83g of triethylamine is added for reaction for 0.7 h; and finally, adding 81.30mL of water, and dispersing the water into the polymer under high-speed stirring for 1h to obtain the waterborne polyurethane prepolymer.
Preparing oxidized porous carbon: putting 3g of porous carbon into a beaker, adding 70mL of sulfuric acid and 9mL of phosphoric acid, slowly adding 20g of potassium permanganate while stirring in an ice water bath, and stirring while adding, after the reaction is finished; stirring for 10h at normal temperature, adjusting the pH value to be neutral until no bubbles are generated, filtering after the reaction is finished, and finally freeze-drying to prepare oxidized porous carbon;
preparing a porous carbon modified waterborne polyurethane dispersion liquid: and dispersing metered oxidized porous carbon in a proper amount of acetone, performing ultrasonic treatment for 45min, placing the mixture in a waterborne polyurethane prepolymer, stirring for 40min, performing reduced pressure distillation to remove the acetone, and reacting to obtain the porous carbon modified waterborne polyurethane.
Example 7
Adding 13.55g of polycaprolactone diol (PCL2000), 6.44g of isophorone diisocyanate (IPDI) and 1.2g of dimethylolbutyric acid hydrophilic chain extender into a 250mL three-neck flask provided with a reflux condenser tube, a thermometer and an electric stirrer, dissolving in a solvent, adding a small amount of catalyst dibutyltin dilaurate (DBTDL), heating in a water bath to 84 ℃, and reacting for 2 hours; then 0.5g of trimethylolpropane is added, and the reaction time is 1 h; the temperature of the water bath is reduced to 45 ℃, and then 0.86g of triethylamine is added for reaction for 0.7 h; and finally, adding 64.77mL of water, and dispersing the mixture into the polymer under high-speed stirring for 1h to obtain the waterborne polyurethane prepolymer.
Preparing oxidized porous carbon: putting 4g of porous carbon into a beaker, adding 95mL of sulfuric acid and 12mL of phosphoric acid, slowly adding 24g of potassium permanganate while stirring in an ice water bath, and stirring while adding, after the reaction is finished; stirring for 12h at normal temperature, adjusting the pH to be neutral until no bubbles are generated, filtering after the reaction is finished, and finally freeze-drying to prepare oxidized porous carbon;
preparing a porous carbon modified waterborne polyurethane dispersion liquid: and dispersing metered oxidized porous carbon in a proper amount of acetone, performing ultrasonic treatment for 15min, placing the mixture into a waterborne polyurethane prepolymer, stirring for 20min, performing reduced pressure distillation to remove the acetone, and reacting to obtain the porous carbon modified waterborne polyurethane.
Example 8
Adding 14.08g of polycaprolactone diol (PCL1000), 6.44g of isophorone diisocyanate (IPDI) and 1g of dimethylolbutyric acid hydrophilic chain extender into a 250mL three-neck flask provided with a reflux condenser tube, a thermometer and an electric stirrer, dissolving in a solvent, adding a small amount of catalyst dibutyltin dilaurate (DBTDL), heating in a water bath to 80 ℃, and reacting for 2 hours; then 0.5g of trimethylolpropane is added, and the reaction time is 1 h; the temperature of the water bath is reduced to 40 ℃, and then 0.81g of triethylamine is added for reaction for 0.7 h; finally, 61.56mL of water is added, and the mixture is dispersed into the polymer under high-speed stirring, the reaction time is 1h, and finally the waterborne polyurethane prepolymer is obtained.
Preparing oxidized porous carbon: putting 7g of porous carbon into a beaker, adding 135mL of sulfuric acid and 15mL of phosphoric acid, slowly adding 50g of potassium permanganate while stirring in an ice water bath, and stirring while adding, after the reaction is finished; stirring for 12h at normal temperature, adjusting the pH to be neutral until no bubbles are generated, filtering after the reaction is finished, and finally freeze-drying to prepare oxidized porous carbon;
preparing a porous carbon modified waterborne polyurethane dispersion liquid: and dispersing metered oxidized porous carbon into a proper amount of acetone, carrying out ultrasonic treatment for 35min, placing the mixture into a waterborne polyurethane prepolymer, stirring for 35min, carrying out reduced pressure distillation to remove the acetone, and reacting to obtain the porous carbon modified waterborne polyurethane.
Fig. 1 is a thermogravimetric graph of the WPU and the porous carbon/WPU prepared in example 1, and it is obvious from the thermogravimetric graph that the semi-decomposition temperatures of the WPU and the porous carbon/WPU adhesive films are 300 ℃ and 340 ℃, respectively, and the semi-decomposition temperature of the porous carbon/WPU is increased by 13.3% relative to the WPU. This is sufficient to demonstrate that the incorporation of porous carbon provides a very large improvement in the thermal stability of the WPU.
FIG. 2 is an IR spectrum of WPU and porous carbon/WPU prepared in example 1, which shows that the IR spectra of the porous carbon/WPU and WPU are substantially the same and the difference between them is not large.
Fig. 3 is a graph showing the mechanical properties of WPU and porous carbon/WPU prepared in four examples 1, 2, 3 and 5, respectively, and it can be seen from the graph that the tensile strength of the porous carbon/WPU adhesive film shows an increasing trend with increasing amount of the introduced Porous Carbon (PC), and the elongation at break thereof gradually decreases. This is mainly because the porous carbon is used as the inorganic filler, and the structure thereof is mainly a rigid structure, so as to increase the introduced amount, the rigidity of the adhesive film is enhanced, and the corresponding toughness is weakened.
The invention has simple process and convenient operation, and can effectively improve the product performance and reduce the production cost.
The above is a further detailed description of the present invention, and it is not intended that the embodiments of the present invention be limited thereto, and that several experiments can be made by those skilled in the art without departing from the concept of the present invention, and all such experiments should be considered as falling within the scope of the present invention as defined by the appended claims.

Claims (9)

1. A preparation method of a porous carbon modified waterborne polyurethane material is characterized by comprising the following steps:
s1, preparing a waterborne polyurethane prepolymer: mixing polyglycol, diisocyanate and a hydrophilic chain extender, heating for reaction, then adding a small molecular cross-linking agent for heating for reaction, adding organic base for reaction, and finally adding water for reaction to obtain a waterborne polyurethane prepolymer;
s2, preparing oxidized porous carbon: adding organic acid into porous carbon, stirring, adding potassium permanganate in an ice water bath, stirring for oxidation reaction, adjusting the pH to be neutral, and filtering to obtain oxidized porous carbon;
s3, preparing a porous carbon modified waterborne polyurethane dispersion liquid: and dispersing the oxidized porous carbon in a solvent, performing ultrasonic treatment, mixing with the waterborne polyurethane prepolymer, stirring, and performing reduced pressure distillation to remove the solvent to obtain the porous carbon modified waterborne polyurethane.
2. The preparation method of the porous carbon modified waterborne polyurethane material according to claim 1, wherein in S1, the preparation process of the waterborne polyurethane prepolymer is as follows: mixing polyglycol, diisocyanate and hydrophilic chain extender, adding a catalyst, heating to 75-85 ℃, and reacting for 1-3 h; then adding a micromolecular cross-linking agent, and reacting for 1-2 h; reducing the temperature to 35-45 ℃, adding organic base, and reacting for 0.5-1 h; and finally, adding water to obtain the waterborne polyurethane prepolymer.
3. The preparation method of the porous carbon modified waterborne polyurethane material according to claim 1, wherein in S1, the polyglycol is polyether diol or polyester diol; the diisocyanate is one or more of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate; the hydrophilic chain extender is dimethylolpropionic acid or dimethylolbutyric acid; the organic base is triethylamine; the catalyst is dibutyltin dilaurate; the micromolecule cross-linking agent is trimethylolpropane.
4. The preparation method of the porous carbon modified waterborne polyurethane material according to claim 1, wherein in S1, the molar ratio of diisocyanate to polyglycol is (1.1-1.5): 1, the using amount of the hydrophilic chain extender is 1.5-3% of the total mass of the system, wherein the total mass of the system refers to the total mass of diisocyanate, polyglycol, the hydrophilic chain extender, porous carbon and organic acid.
5. The preparation method of the porous carbon modified waterborne polyurethane material according to claim 1, wherein in S2, the usage amount of the porous carbon is 1.0% -1.5% of the total mass of the system, wherein the total mass of the system is the total mass of diisocyanate, polyglycol, hydrophilic chain extender, porous carbon and organic acid.
6. The method for preparing a porous carbon modified waterborne polyurethane material according to claim 1, wherein in S2, the organic acid is a mixture of sulfuric acid and phosphoric acid.
7. The preparation method of the porous carbon modified waterborne polyurethane material as claimed in claim 1, wherein in S2, the oxidation reaction time is 10-15 h.
8. The preparation method of the porous carbon modified waterborne polyurethane material as claimed in claim 1, wherein in S3, the ultrasonic treatment time is 15-45min, and the stirring time is 20-40min after the ultrasonic treatment is mixed with the waterborne polyurethane prepolymer.
9. A porous carbon modified waterborne polyurethane material, which is characterized by being obtained by the preparation method of any one of claims 1 to 8.
CN202010124582.XA 2020-02-27 2020-02-27 Porous carbon modified waterborne polyurethane material and preparation method thereof Pending CN111205628A (en)

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