CN111924872A - Method for preparing modified nano zinc oxide by sol-gel process - Google Patents
Method for preparing modified nano zinc oxide by sol-gel process Download PDFInfo
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- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic System; Zincates; Cadmates
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- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
Abstract
The invention provides a method for preparing modified nano zinc oxide by a sol-gel process, which comprises the steps of fully dispersing and dissolving zinc citrate in a solvent, adding polyethylene glycol and thiourea, heating in a water bath at 45-95 ℃ for 16-28h, adding 45-50% of tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution, and then respectively carrying out sol, gelation and high-temperature heat treatment to obtain the modified nano zinc oxide; the invention adopts a sol-gel method and takes thiourea as a modifier, thereby reducing the surface polarity of the nano zinc oxide and improving the dispersibility of the nano zinc oxide and the compatibility between the nano zinc oxide and resin.
Description
Technical Field
The invention relates to the technical field of nano-zinc oxide preparation, in particular to a method for preparing modified nano-zinc oxide by a sol-gel process.
Background
The nano zinc oxide is a multifunctional novel inorganic material, and the particle size of the nano zinc oxide is about 1-100 nm. Due to the fine grain, the surface electronic structure and the crystal structure of the crystal grain are changed, and the characteristics of surface effect, volume effect, quantum size effect, macroscopic tunnel effect, high transparency, high dispersibility and the like which are not possessed by macroscopic objects are generated. In recent years, the zinc oxide has been found to show a plurality of special functions in the aspects of catalysis, optics, magnetism, mechanics and the like, so that the zinc oxide has important application values in a plurality of fields of ceramics, chemical engineering, electronics, optics, biology, medicine and the like, and has specificity and application which can not be compared with common zinc oxide. The nano zinc oxide can be used for ultraviolet light shielding materials, antibacterial agents, fluorescent materials, photocatalytic materials and the like in the fields of textiles, coatings and the like.
The nano zinc oxide has the characteristics of large specific surface area, large specific surface energy and the like, and is easy to agglomerate; on the other hand, the surface polarity of the nano zinc oxide is strong, the nano zinc oxide is not easy to be uniformly dispersed in an organic medium, and the compatibility between the nano zinc oxide and a matrix is poor, so that the exertion of the nano effect is greatly limited.
Disclosure of Invention
Aiming at the problems, the invention provides a method for preparing modified nano zinc oxide by a sol-gel process.
The purpose of the invention is realized by adopting the following technical scheme:
a method for preparing modified nano zinc oxide by a sol-gel process comprises the following steps:
s1, fully dispersing and dissolving zinc citrate in a solvent, wherein the dispersion concentration is 0.1-1mol/L, adding thiourea with the amount of 5-10% of the zinc citrate substance, adding polyethylene glycol with the final concentration of 0.05g/mL, uniformly stirring to obtain a precursor, heating in a water bath at 45-95 ℃ for 16-28h, adding 45-50% of tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution, uniformly mixing, and continuously reacting for 1h, wherein the volume ratio of the tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution to the solvent is 0.1-0.4: 1;
s2, heating the mixed liquid prepared in the S1 to evaporate the solvent to obtain zinc oxide sol, wherein the heating temperature is 50-99 ℃;
s3, heating the zinc oxide sol to the temperature of 120-150 ℃, and quickly evaporating the solvent to obtain zinc oxide gel;
s4, heating the zinc oxide gel to 225-850 ℃, and keeping the temperature for 2-4h to obtain the modified nano zinc oxide powder;
preferably, the solvent is ethanol or an ethanol solution.
Preferably, the method further comprises the steps of:
s5, carrying out heat treatment on the modified nano zinc oxide powder prepared in the S4 in a high-purity nitrogen atmosphere; keeping the atmosphere until the powder is self-cooled to the room temperature; the purity of the high-purity nitrogen is 99.999 percent, wherein O is2≤0.001％；
Further preferably, the temperature of the heat treatment is 180-600 ℃, and the treatment time is 1-3 h;
preferably, the method further comprises surface modification, and the method for surface modification comprises the following steps:
s6, under the stirring condition, adding the modified nano zinc oxide powder prepared by the S4 or the S5 into 1-5% of an anionic or cationic surfactant aqueous solution, wherein the addition liquid-material ratio is 50-100mL/g, adding 10mL/L of glycerol after uniformly mixing, carrying out ultrasonic dispersion uniformly, then carrying out heating reflux for 30-60min, filtering out precipitates, washing with absolute ethyl alcohol and deionized water respectively, and carrying out vacuum drying;
further preferably, the anionic surfactant is sodium dodecyl sulfate, stearic acid or sodium stearate, and the cationic surfactant is a quaternary ammonium salt surfactant.
Another objective of the present invention is to provide an application of the modified nano zinc oxide powder, specifically an application in a high molecular polymer or a textile material, wherein the high molecular polymer includes PE, PP, PET or PA 6; the textile material comprises yarn, fiber, cloth or clothing.
Another object of the present invention is to provide a method for preparing a dispersion liquid containing the modified nano zinc oxide powder, which comprises: and adding the modified nano zinc oxide powder and a dispersing agent into water to prepare a 20% solution, and grinding the solution in a nano sand mill to obtain the dispersion liquid.
The invention has the beneficial effects that:
(1) the invention adopts a sol-gel method and takes thiourea as a modifier to prepare the modified nano zinc oxide, wherein the thiourea is taken as a nitrogen source and a sulfur source, nitrogen and sulfur with larger radius than oxygen atoms are doped into the zinc oxide and replace partial oxygen atoms, the surface polarity is reduced, and the dispersibility of the nano zinc oxide and the compatibility between the nano zinc oxide and resin are improved.
(2) The sol-gel method can disperse the raw materials into the solvent quickly, obtain the uniformity of molecular level in a short time, can easily carry out the uniform doping of elements, and has lower reaction temperature.
Detailed Description
The invention is further described with reference to the following examples.
The embodiment of the application relates to a method for preparing modified nano zinc oxide by a sol-gel process, which comprises the following steps:
s1, fully dispersing and dissolving zinc citrate in a solvent, wherein the dispersion concentration is 0.1-1mol/L, adding thiourea with the amount of 5-10% of the zinc citrate substance, adding polyethylene glycol with the final concentration of 0.05g/mL, uniformly stirring to obtain a precursor, heating in a water bath at 45-95 ℃ for 16-28h, adding 45-50% of tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution, uniformly mixing, and continuously reacting for 1h, wherein the volume ratio of the tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution to the solvent is 0.1-0.4: 1;
s2, heating the mixed liquid prepared in the S1 to evaporate the solvent to obtain zinc oxide sol, wherein the heating temperature is 50-99 ℃;
s3, heating the zinc oxide sol to the temperature of 120-150 ℃, and quickly evaporating the solvent to obtain zinc oxide gel;
s4, heating the zinc oxide gel to 225-850 ℃, and keeping the temperature for 2-4h to obtain the modified nano zinc oxide powder;
the invention takes thiourea as a modifier to prepare the modified nano zinc oxide, improves the dispersibility of the nano zinc oxide and the compatibility between the nano zinc oxide and resin, possibly takes the thiourea as a nitrogen source and a sulfur source, mixes nitrogen and sulfur with larger than oxygen atom radius into the zinc oxide and replaces partial oxygen atoms, reduces the surface polarity, and improves the dispersibility and the compatibility between the zinc oxide and the resin;
the sol-gel method can disperse the raw materials into the solvent, obtain the uniformity of molecular level in a short time, can easily carry out the uniform doping of elements, and has lower reaction temperature;
preferably, the solvent is ethanol or an ethanol solution.
Preferably, the method further comprises the steps of:
s5, carrying out heat treatment on the modified nano zinc oxide powder prepared in the S4 in a high-purity nitrogen atmosphere; keeping the atmosphere until the powder is self-cooled to the room temperature; the purity of the high-purity nitrogen is 99.999 percent, wherein O is2≤0.001％；
Further preferably, the temperature of the heat treatment is 180-600 ℃, and the treatment time is 1-3 h;
the heat treatment of the nano zinc oxide in the high-purity nitrogen atmosphere can further improve the dispersibility and the compatibility of the nano zinc oxide, probably because lattice oxygen is lost under low oxygen partial pressure under the high-purity nitrogen atmosphere and high-temperature condition, partial oxygen defects are introduced into the surface of the nano zinc oxide, the surface polarity of the nano zinc oxide is further reduced, and the improvement of the dispersibility and the compatibility is further obtained;
preferably, the method further comprises surface modification, and the method for surface modification comprises the following steps:
s6, under the stirring condition, adding the modified nano zinc oxide powder prepared by the S4 or the S5 into 1-5% of an anionic or cationic surfactant aqueous solution, wherein the addition liquid-material ratio is 50-100mL/g, adding 10mL/L of glycerol after uniformly mixing, carrying out ultrasonic dispersion uniformly, then carrying out heating reflux for 30-60min, filtering out precipitates, washing with absolute ethyl alcohol and deionized water respectively, and carrying out vacuum drying;
further preferably, the anionic surfactant is sodium dodecyl sulfate, stearic acid or sodium stearate, and the cationic surfactant is a quaternary ammonium salt surfactant;
the anionic or cationic surfactant has hydrophilic anionic/cationic ends and hydrophobic alkyl carbon chain ends, and is used as the surface modifier of nano zinc oxide, the hydrophilic ionic ends are easy to gather near the surface of polar nano zinc oxide, the hydrophobic alkyl carbon chains are outward, the ionic ends enable nano particles to carry the same charge, the electrostatic repulsion enables the nano particles not to easily agglomerate, the dispersibility is good, the nonpolar hydrophobic ends reduce the surface polarity, and the compatibility with resin is improved.
As another alternative, more preferable surface modification method of nano zinc oxide, the surface modification method is as follows:
s7, under the stirring condition, adding the modified nano zinc oxide powder prepared by S4 or S5 into a 4-10% zinc complexing agent aqueous solution, wherein the addition liquid-material ratio is 50-100mL/g, after uniform mixing, dropwise adding 0.01mol/L hydrochloric acid solution until the pH value of the solution is 5.6-5.8, after uniform ultrasonic dispersion, keeping rapid stirring at 1000rpm for 30-60min, filtering out precipitates, washing with deionized water, and drying in vacuum;
the zinc complexing agent is disodium ethylene diamine tetraacetate, sodium phytate or sodium gluconate;
the ionic surfactant has good dispersibility in a low-viscosity solution only by weak intermolecular force formed by polarity, and the surface modifier adsorbed on the surface of the ionic surfactant is easy to desorb in a high-viscosity resin melt.
The modified nano-zinc oxide prepared by the invention is suitable for the synergistic modification of organic high molecular polymer materials, and the prior art shows that the nano-zinc oxide has good photocatalysis, sterilization, ultraviolet resistance and ageing resistance, and can be used as a modifier to be added into the organic high molecular polymer materials, such as polyethylene, polypropylene materials and the like; the modifier can be directly used as a resin modifier to be directly added into a resin melt, and also can be prepared into resin master batches for use, and the specific use method is not limited;
based on good sterilization and ultraviolet resistance of nano zinc oxide, the nano zinc oxide can be added into textiles, such as terylene and nylon, and the nano zinc oxide can be added into the textiles to endow the textiles with functions of sun protection, antibiosis, deodorization and the like, specifically, the nano zinc oxide can be used as an additive to be added into a raw material spinning solution, can also be prepared into resin master batches for use, fibers are prepared through spinning, weaving and cutting, and fibers, cloth or clothes with specific functionality can be obtained through spinning, weaving and cutting; besides being directly used as an additive, the fiber fabric can be prepared into a solution to be used for padding or coating fibers, fabrics or clothes, and the fibers or the fabrics with specific functions can also be obtained;
the embodiment of the invention also discloses a preparation method of the dispersion liquid of the modified nano zinc oxide powder, which comprises the following steps: and adding the modified nano zinc oxide powder and a dispersing agent into water to prepare a 20% solution, and grinding the solution in a nano sand mill to obtain the dispersion liquid.
Example 1
A method for preparing modified nano zinc oxide by a sol-gel process comprises the following steps:
s1, fully dispersing and dissolving zinc citrate in an ethanol solution, wherein the dispersion concentration is 0.4mol/L, adding thiourea with the amount of 7% of that of a zinc citrate substance, adding polyethylene glycol with the final concentration of 0.05g/mL, uniformly stirring to obtain a precursor, heating and refluxing for 24 hours in a water bath at 75 ℃, adding a tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution with the concentration of 45-50%, uniformly mixing, and continuously reacting for 1 hour, wherein the volume ratio of the tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution to the solvent is 0.3: 1;
s2, heating the mixed solution prepared in the S1 to evaporate the solvent to obtain zinc oxide sol, wherein the heating temperature is 50-80 ℃;
s3, heating the zinc oxide sol to the temperature of 120-150 ℃, and quickly evaporating the solvent to obtain zinc oxide gel;
s4, heating the zinc oxide gel to 285-300 ℃, and keeping the temperature for 3-4h to obtain the modified nano zinc oxide powder.
Example 2
A method for preparing modified nano zinc oxide by a sol-gel process comprises the following steps:
s1, fully dispersing and dissolving zinc citrate in an ethanol solution, wherein the dispersion concentration is 0.4mol/L, adding thiourea with the amount of 7% of that of a zinc citrate substance, adding polyethylene glycol with the final concentration of 0.05g/mL, uniformly stirring to obtain a precursor, heating and refluxing for 24 hours in a water bath at 75 ℃, adding a tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution with the concentration of 45-50%, uniformly mixing, and continuously reacting for 1 hour, wherein the volume ratio of the tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution to the solvent is 0.3: 1;
s2, heating the mixed solution prepared in the S1 to evaporate the solvent to obtain zinc oxide sol, wherein the heating temperature is 50-80 ℃;
s3, heating the zinc oxide sol to the temperature of 120-150 ℃, and quickly evaporating the solvent to obtain zinc oxide gel;
s4, heating the zinc oxide gel to 285-300 ℃, and keeping the temperature for 3-4h to obtain the modified nano zinc oxide powder;
s5, carrying out heat treatment on the modified nano zinc oxide powder prepared in the step S4 in a high-purity nitrogen atmosphere, wherein the heat treatment temperature is 386 ℃, the treatment time is 2 hours, and the atmosphere is maintained until the powder is self-cooled to the room temperature; the purity of the high-purity nitrogen is 99.999 percent, wherein O is2≤0.001％。
Example 3
A method for preparing modified nano zinc oxide by a sol-gel process comprises the following steps:
s1, fully dispersing and dissolving zinc citrate in an ethanol solution, wherein the dispersion concentration is 0.4mol/L, adding thiourea with the amount of 7% of that of a zinc citrate substance, adding polyethylene glycol with the final concentration of 0.05g/mL, uniformly stirring to obtain a precursor, heating and refluxing for 24 hours in a water bath at 75 ℃, adding a tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution with the concentration of 45-50%, uniformly mixing, and continuously reacting for 1 hour, wherein the volume ratio of the tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution to the solvent is 0.3: 1;
s2, heating the mixed solution prepared in the S1 to evaporate the solvent to obtain zinc oxide sol, wherein the heating temperature is 50-80 ℃;
s3, heating the zinc oxide sol to the temperature of 120-150 ℃, and quickly evaporating the solvent to obtain zinc oxide gel;
s4, heating the zinc oxide gel to 285-300 ℃, and keeping the temperature for 3-4h to obtain the modified nano zinc oxide powder;
s5, carrying out heat treatment on the modified nano zinc oxide powder prepared in the step S4 in a high-purity nitrogen atmosphere, wherein the heat treatment temperature is 386 ℃, the treatment time is 2 hours, and the atmosphere is maintained until the powder is self-cooled to the room temperature; the purity of the high-purity nitrogen is 99.999 percent, wherein O is2≤0.001％。
S6, adding the modified nano zinc oxide powder prepared in the step S5 into a stearic acid aqueous solution with the concentration of 3% under the stirring condition, wherein the liquid-material ratio of the addition is 80mL/g, adding 10mL/L of glycerol after uniformly mixing, heating and refluxing for 30-60min after uniformly dispersing by ultrasonic waves, filtering out precipitates, washing with absolute ethyl alcohol and deionized water respectively, and drying in vacuum.
Example 4
A method for preparing modified nano zinc oxide by a sol-gel process comprises the following steps:
s1, fully dispersing and dissolving zinc citrate in an ethanol solution, wherein the dispersion concentration is 0.4mol/L, adding thiourea with the amount of 7% of that of a zinc citrate substance, adding polyethylene glycol with the final concentration of 0.05g/mL, uniformly stirring to obtain a precursor, heating and refluxing for 24 hours in a water bath at 75 ℃, adding a tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution with the concentration of 45-50%, uniformly mixing, and continuously reacting for 1 hour, wherein the volume ratio of the tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution to the solvent is 0.3: 1;
s2, heating the mixed solution prepared in the S1 to evaporate the solvent to obtain zinc oxide sol, wherein the heating temperature is 50-80 ℃;
s3, heating the zinc oxide sol to the temperature of 120-150 ℃, and quickly evaporating the solvent to obtain zinc oxide gel;
s4, heating the zinc oxide gel to 285-300 ℃, and keeping the temperature for 3-4h to obtain the modified nano zinc oxide powder;
s5, carrying out heat treatment on the modified nano-zinc oxide powder prepared by the S4 in a high-purity nitrogen atmosphere, and carrying out heat treatmentThe temperature of the treatment is 386 ℃, the treatment time is 2 hours, and the atmosphere is kept until the powder is self-cooled to the room temperature; the purity of the high-purity nitrogen is 99.999 percent, wherein O is2≤0.001％。
S6, adding the modified nano zinc oxide powder prepared in the step S5 into a 3% hexadecyl trimethyl ammonium bromide aqueous solution under the stirring condition, wherein the adding liquid-material ratio is 80mL/g, adding 10mL/L of glycerol after uniformly mixing, heating and refluxing for 30-60min after uniformly dispersing by ultrasonic, filtering out precipitates, washing with absolute ethyl alcohol and deionized water respectively, and drying in vacuum.
Example 5
A method for preparing modified nano zinc oxide by a sol-gel process comprises the following steps:
s1, fully dispersing and dissolving zinc citrate in an ethanol solution, wherein the dispersion concentration is 0.4mol/L, adding thiourea with the amount of 7% of that of a zinc citrate substance, adding polyethylene glycol with the final concentration of 0.05g/mL, uniformly stirring to obtain a precursor, heating and refluxing for 24 hours in a water bath at 75 ℃, adding a tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution with the concentration of 45-50%, uniformly mixing, and continuously reacting for 1 hour, wherein the volume ratio of the tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution to the solvent is 0.3: 1;
s2, heating the mixed solution prepared in the S1 to evaporate the solvent to obtain zinc oxide sol, wherein the heating temperature is 50-80 ℃;
s3, heating the zinc oxide sol to the temperature of 120-150 ℃, and quickly evaporating the solvent to obtain zinc oxide gel;
s4, heating the zinc oxide gel to 285-300 ℃, and keeping the temperature for 3-4h to obtain the modified nano zinc oxide powder;
s5, carrying out heat treatment on the modified nano zinc oxide powder prepared in the step S4 in a high-purity nitrogen atmosphere, wherein the heat treatment temperature is 386 ℃, the treatment time is 2 hours, and the atmosphere is maintained until the powder is self-cooled to the room temperature; the purity of the high-purity nitrogen is 99.999 percent, wherein O is2≤0.001％。
S6, under the stirring condition, adding the modified nano zinc oxide powder prepared by the S4 or the S5 into 8% of disodium ethylene diamine tetraacetate aqueous solution, wherein the adding liquid-material ratio is 80mL/g, after uniformly mixing, dropwise adding 0.01mol/L hydrochloric acid solution until the pH value of the solution is 5.6-5.8, after uniformly dispersing by ultrasonic wave, keeping fast stirring at 700rpm for 45min, filtering out precipitates, washing with deionized water, and drying in vacuum.
Example 6
A method for preparing modified nano zinc oxide by a sol-gel process comprises the following steps:
s1, fully dispersing and dissolving zinc citrate in an ethanol solution, wherein the dispersion concentration is 0.4mol/L, adding thiourea with the amount of 7% of that of a zinc citrate substance, adding polyethylene glycol with the final concentration of 0.05g/mL, uniformly stirring to obtain a precursor, heating and refluxing for 24 hours in a water bath at 75 ℃, adding a tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution with the concentration of 45-50%, uniformly mixing, and continuously reacting for 1 hour, wherein the volume ratio of the tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution to the solvent is 0.3: 1;
s2, heating the mixed solution prepared in the S1 to evaporate the solvent to obtain zinc oxide sol, wherein the heating temperature is 50-80 ℃;
s3, heating the zinc oxide sol to the temperature of 120-150 ℃, and quickly evaporating the solvent to obtain zinc oxide gel;
s4, heating the zinc oxide gel to 285-300 ℃, and keeping the temperature for 3-4h to obtain the modified nano zinc oxide powder;
s5, carrying out heat treatment on the modified nano zinc oxide powder prepared in the step S4 in a high-purity nitrogen atmosphere, wherein the heat treatment temperature is 386 ℃, the treatment time is 2 hours, and the atmosphere is maintained until the powder is self-cooled to the room temperature; the purity of the high-purity nitrogen is 99.999 percent, wherein O is2≤0.001％。
S6, under the stirring condition, adding the modified nano zinc oxide powder prepared by the S4 or the S5 into 8% sodium phytate water solution, wherein the adding liquid-material ratio is 80mL/g, after uniformly mixing, dropwise adding 0.01mol/L hydrochloric acid solution till the pH value of the solution is 5.6-5.8, after uniformly dispersing by ultrasonic, keeping fast stirring at 700rpm for 45min, filtering out precipitates, washing with deionized water, and drying in vacuum.
Application example 1
Mixing nano zinc oxide powder and polyester powder according to a weight ratio of 3:13, performing melt extrusion, cooling, granulating, sieving, mixing and drying to prepare polyester master batch;
drying the polyester master batch and polyester chips, mixing the polyester master batch and the polyester chips according to the weight ratio of 1:9, extruding and melting the polyester master batch and the polyester chips by a screw extruder, controlling the melt temperature to be 280 +/-15 ℃, spinning protofilaments firstly, and then carrying out post-treatment on the protofilaments to obtain the polyester fibers and the fabrics.
Application example 2
Soaking the fabric in 1g/LPDDA solution prepared from 0.5mol/LNaCl solution, washing with deionized water after 10min, uniformly rolling with a padder, and drying, wherein the rolling residual rate is 70%, adding the modified nano zinc oxide powder and the dispersing agent into water to prepare 20% solution, grinding in a nano sand mill to prepare dispersed finishing liquid, soaking the fabric in the finishing liquid, uniformly rolling with the padder after 10min, wherein the rolling residual rate is 70%, drying at 80 ℃, and baking for 5min at 160 ℃.
Examples of the experiments
The ultraviolet resistance of the polyester fabric prepared in application example 1 was tested by using the nano zinc oxides prepared in examples 1 to 6 as additives, the polyester fabric prepared in application example 1 as a test sample, and the nano zinc oxide prepared by a conventional sol-gel method as a reference according to the standard specified in GB/T18830.
| Control | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| UPF value | 30.28 | 37.39 | 39.03 | 45.15 | 44.77 | 50.94 | 51.33 |
| Index of activity | 100％ | 123.5％ | 128.9％ | 149.1％ | 147.9％ | 168.2％ | 169.5％ |
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. A method for preparing modified nano zinc oxide by a sol-gel process is characterized by comprising the following steps:
s1, fully dispersing and dissolving zinc citrate in a solvent, wherein the dispersion concentration is 0.1-1mol/L, adding thiourea with the amount of 5-10% of the zinc citrate substance, adding polyethylene glycol with the final concentration of 0.05g/mL, uniformly stirring to obtain a precursor, heating in a water bath at 45-95 ℃ for 16-28h, adding 45-50% of tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution, uniformly mixing, and continuously reacting for 1h, wherein the volume ratio of the tris- (2-hydroxyethyl) methyl ammonium hydroxide aqueous solution to the solvent is 0.1-0.4: 1;
s2, heating the mixed liquid prepared in the S1 to evaporate the solvent to obtain zinc oxide sol, wherein the heating temperature is 50-99 ℃;
s3, heating the zinc oxide sol to the temperature of 120-150 ℃, and quickly evaporating the solvent to obtain zinc oxide gel;
s4, heating the zinc oxide gel to 225-850 ℃, and keeping the temperature for 2-4h to obtain the modified nano zinc oxide powder.
2. The method for preparing the modified nano zinc oxide by the sol-gel process according to claim 1, wherein the solvent is ethanol or an ethanol solution.
3. The method for preparing modified nano zinc oxide by using the sol-gel process as claimed in claim 1, wherein the method further comprises the following steps:
s5, carrying out heat treatment on the modified nano zinc oxide powder prepared in the S4 in a high-purity nitrogen atmosphere; keeping the atmosphere until the powder is self-cooled to the room temperature; the purity of the high-purity nitrogen is 99.999 percent, wherein O is2≤0.001％。
4. The method for preparing modified nano zinc oxide by using the sol-gel process as claimed in claim 3, wherein the temperature of the heat treatment is 180-600 ℃ and the treatment time is 1-3 h.
5. The method for preparing the modified nano zinc oxide by the sol-gel process according to claim 1 or 3, wherein the method further comprises surface modification, and the method for surface modification comprises the following steps:
s6, under the stirring condition, adding the modified nano zinc oxide powder prepared by the S4 or the S5 into 1-5% of an anionic or cationic surfactant aqueous solution, wherein the addition liquid-material ratio is 50-100mL/g, adding 10mL/L of glycerol after uniformly mixing, carrying out ultrasonic dispersion uniformly, then carrying out heating reflux for 30-60min, filtering out precipitates, washing with absolute ethyl alcohol and deionized water respectively, and carrying out vacuum drying.
6. The method for preparing modified nano zinc oxide by using the sol-gel process as claimed in claim 5, wherein the anionic surfactant is sodium dodecyl sulfate, stearic acid or sodium stearate, and the cationic surfactant is quaternary ammonium salt surfactant.
7. Modified nano zinc oxide prepared by a method for preparing modified nano zinc oxide according to one of claims 1 to 6 by a sol-gel process.
8. The use of the modified nano zinc oxide according to claim 7, characterized in that in high molecular polymers or textile materials, the high molecular polymers comprise PE, PP, PET or PA 6; the textile material comprises yarn, fiber, cloth or clothing.
9. A method for preparing a dispersion liquid containing the modified nano zinc oxide of claim 7, wherein the modified nano zinc oxide and a dispersant are added into water to prepare a 20% solution, and the 20% solution is ground by a nano sand mill to obtain the dispersion liquid.
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