CN112574621B - Preparation method and application of carboxylated graphene/chitosan composite coating agent - Google Patents
Preparation method and application of carboxylated graphene/chitosan composite coating agent Download PDFInfo
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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
- C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
- C09D105/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
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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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses a preparation method and application of a carboxylated graphene/chitosan composite coating agent, which comprises the following steps: the method comprises the following steps: preparing carboxylated graphene powder; step two: preparing a chitosan solution; step three: taking carboxylated graphene powder, and mixing the carboxylated graphene powder with water to obtain a carboxylated graphene solution; step four: preparing a carboxylated graphene/chitosan composite finishing agent: adding 1-10 parts of carboxylated graphene solution into 1000 parts of chitosan solution, uniformly mixing, adding 1-5 parts of activating agent, reacting for a period of time, adding 1-5 parts of cross-linking agent, reacting for a period of time, and finally adding 0-3 parts of nano metal material to obtain a carboxylated graphene/chitosan composite coating agent; the formaldehyde removal rate of the composite finishing agent is more than or equal to 95 percent, and the composite finishing agent is used in the finishing procedure of leather making, so that the obtained finished leather product is less than or equal to 20ppm and meets the use standard of most industries.
Description
Technical Field
The invention relates to the technical field of tanning chemistry and tanning engineering, in particular to a preparation method and application of a carboxylated graphene/chitosan composite finishing agent.
Background
In the process of processing and manufacturing leather, chemicals such as modified aldehyde, oxazolidine, amino resin, organic phosphine, modified protein and the like are synthesized by taking formaldehyde as a precursor, the chemicals contain a certain amount of formaldehyde, and the formaldehyde is brought into finished leather through tanning, retanning, filling, finishing and the like and is slowly released in the process of long-term use. In recent years, green consumption is gradually becoming a consumption trend at home and abroad, strict limits are provided on formaldehyde control, European Union is clearly specified in European Union chemical registration, evaluation, authorization and restriction regulations, and the formaldehyde content of leather and products thereof is not higher than 150 mg/kg. The national mandatory standards also specify: the formaldehyde content of the infant product is not higher than 20mg/kg, the formaldehyde content of a direct contact product is not higher than 75mg/kg, and the formaldehyde content of a non-direct contact product is not higher than 300 mg/kg. Therefore, the control and elimination of formaldehyde in leather products are of great significance to the sustainable development of the tanning industry and to the health of consumers.
At present, the main components of the formaldehyde scavenger and formaldehyde scavenger in leather chemicals at home and abroad comprise proteins, amino and the like. Wherein, the adsorption capacity of the protein formaldehyde is limited, and when the consumption is excessive, the finished leather board is hard and is easy to nourish bacteria to mildew; the ammonia chemicals have strong formaldehyde adsorption capacity, but the ammonia substances are limited by the synthesis process, and the materials carry a certain amount of formaldehyde, so that the formaldehyde is easily and slowly released in subsequent use, the health of a user is influenced, and an ideal effect cannot be achieved.
Disclosure of Invention
The embodiment of the application provides a preparation method and application of a carboxylated graphene/chitosan composite coating agent, so that the technical problem that the coating agent for leather products in the prior art does not have a formaldehyde adsorption effect or has a poor adsorption effect is solved, the formaldehyde removal rate of the composite coating agent is more than or equal to 95%, and meanwhile, when the composite coating agent is used in a coating procedure of leather making, the obtained finished leather product is less than or equal to 20ppm and meets the use standards of most industries.
The embodiment of the application provides a preparation method of a carboxylated graphene/chitosan composite finishing agent, which comprises the following steps:
the method comprises the following steps: preparing carboxylated graphene powder;
step two: preparing a chitosan solution;
step three: taking carboxylated graphene powder, and mixing the carboxylated graphene powder with water to obtain a carboxylated graphene solution;
step four: preparing a carboxylated graphene/chitosan composite coating agent: adding 1-10 parts of carboxylated graphene solution into 1000 parts of chitosan solution, uniformly mixing, adding 1-5 parts of activating agent, reacting for a period of time, adding 1-5 parts of cross-linking agent, reacting for a period of time, and finally adding 0-3 parts of nano metal material to obtain the carboxylated graphene/chitosan composite coating agent.
Further, the preparation method of the carboxylated graphene powder comprises the following specific steps:
1) adding 1-10 parts of graphene oxide into 1000 parts of deionized water, performing ultrasonic dispersion for 60-90 minutes, then adding 10-100 parts of alkaline solution, performing ultrasonic dispersion for 30-60 minutes, then adding 10-400 parts of active micromolecules, performing ultrasonic dispersion for 30-60 minutes, finally adjusting the reaction temperature to 30-50 ℃, and reacting for 3-12 hours to obtain a carboxylated graphene dispersion liquid;
2) alternately washing the carboxylated graphene dispersion liquid for 6-10 times by using an acid solution and deionized water, and finally washing for 3-5 times by using absolute ethyl alcohol;
3) and (3) drying the product obtained in the last step in vacuum to obtain the carboxylated graphene powder.
Further, the specific steps for preparing the chitosan solution are as follows:
dissolving 3-5 parts of acid solution in 100 parts of deionized water, then adding 1-5 parts of chitosan, and adjusting the pH value of the solution to 3.0-4.0 to obtain a chitosan solution.
Further, the third step comprises the following specific steps:
adding 1-5 parts of carboxylated graphene into 100 parts of deionized water, performing ultrasonic dispersion for 5-15 minutes, and adjusting the pH value of the solution to 4.5-5.5 to obtain a carboxylated graphene solution.
Further, the third step comprises the following specific steps:
adding 1-10 parts of carboxylated graphene solution into 1000 parts of chitosan solution, uniformly mixing, adjusting the pH value of the solution to 3.0-3.5, reacting at 30-45 ℃ for 1-3h, then adding 1-5 parts of activating agent, reacting at 35-50 ℃ for 1-3h, then adding 1-5 parts of cross-linking agent, reacting at 40-55 ℃ for 1-3h, finally adding 0-3 parts of nano metal material, and reacting at 40-55 ℃ for 1h to obtain the carboxylated graphene/chitosan composite coating agent.
Further, the activating agent is selected from at least one of pyruvic acid, beta-hydroxy pyruvic acid, alpha-ketoglutaric acid and 2-carbonyl propionic acid;
the cross-linking agent is selected from at least one of ethylenediamine, diethylenetriamine, triethylene tetramine and tetraethylene pentamine;
the nano metal material is selected from at least one of nano titanium dioxide, nano manganese dioxide, nano silicon dioxide, nano zinc oxide, nano iron oxide and nano silver.
Further, the alkaline solution is selected from any one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, triethylamine and ammonia water.
Further, the active small molecule is selected from any one of alpha-bromoacetic acid, alpha-chloroacetic acid and azodibutyrronitrile.
Further, the acidic solution is selected from any one of formic acid, acetic acid, hydrochloric acid and sulfuric acid.
A finished leather comprising a finishing step, wherein the carboxylated graphene/chitosan composite finishing agent according to claim 1 is used as a finishing agent in the finishing step.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
n
1. pi on graphene oxide lamellaenThe lamellar structure has certain adsorption performance and can adsorb formaldehyde with a free electronic structure, particularly unsaturated double bonds. The chitosan is a chain natural polymer containing a large amount of amino and hydroxyl, and the amino has certain formaldehyde adsorption performance. The nano metal material has long-term lasting formaldehyde removing effect, oxygen atoms and metal ions in a molecular structure can be combined with a small amount of (OH-) in water to improve the water solubility of the nano metal material, and the nano metal material can also be bonded with a high polymer material through an ionic bond.
2. The carboxyl content of the graphene sheet layer is increased by the carboxylated graphene oxide, active small molecules mainly react with (-O-) in the sheet layer, 2 carboxyl groups can be grafted at most by 1 epoxy group, and the increase of the number of oxygen-containing functional groups is beneficial to destroying the pi-pi action between the graphene sheet layer and the sheet layer, promotes the stripping of the graphene sheet layer and improves the formaldehyde adsorption capacity. Meanwhile, the increase of the number of oxygen-containing functional groups is also helpful to increase the oxidation capacity of the graphene sheet layer to formaldehyde, and the generated graphene is nontoxic and non-toxicNoxious CO2. In addition, the increase of the carboxyl content is beneficial to improving the reaction capability with the amino group of the chitosan, thereby improving the compatibility of the composite material, promoting the uniform film formation of the composite material and being beneficial to improving the physical and mechanical properties of the coating.
3. The activating agent mainly reacts with hydroxyl in chitosan to generate carboxyl chitosan, the carboxyl chitosan and carboxyl functionalized graphene can react with polyamine materials to enhance the interface interaction of the graphene and the chitosan, and meanwhile, residual amino can adsorb free formaldehyde.
Detailed Description
In order to better understand the technical solutions, the technical solutions will be described in detail with reference to the description and the specific embodiments.
Example 1:
a preparation method of a carboxylated graphene/chitosan composite finishing agent comprises the following steps:
step one, preparing carboxylated graphene powder
Adding 1 part of graphene oxide into 1000 parts of deionized water, performing ultrasonic dispersion for 60 minutes, then adding 10 parts of sodium hydroxide, performing ultrasonic dispersion for 30 minutes, then adding 20 parts of alpha-bromoacetic acid, performing ultrasonic dispersion for 30 minutes, finally adjusting the reaction temperature to 30 ℃, performing reaction for 6 hours to obtain a carboxylated graphene dispersion liquid, alternately washing the obtained product with acetic acid and deionized water for 6 times, finally washing the product with absolute ethyl alcohol for 3 times, and performing vacuum drying on the product to obtain carboxylated graphene powder;
step two, preparing chitosan solution
Dissolving 5 parts of acetic acid in 100 parts of deionized water, then adding 2.5 parts of chitosan, and adjusting the pH value of the solution to 3.5 to obtain a chitosan solution;
step three, preparing a carboxylated graphene solution:
adding 2.5 parts of carboxylated graphene powder into 100 parts of deionized water, performing ultrasonic dispersion for 5 minutes, and adjusting the pH value of the solution to 4.5 to obtain a carboxylated graphene solution;
step four, preparing the carboxylated graphene/chitosan composite finishing agent
Adding 5 parts of carboxylated graphene solution into 1000 parts of chitosan solution, uniformly mixing, adjusting the pH value of the solution to 3.5, reacting for 3 hours at 30 ℃, then adding 2.5 parts of pyruvic acid, reacting for 3 hours at 35 ℃, then adding 2.5 parts of triethylene tetramine, reacting for 3 hours at 40 ℃, finally adding 1 part of nano titanium dioxide, and reacting for 1 hour at 40 ℃ to obtain the carboxylated graphene/chitosan composite coating agent.
Example 2
A finished leather comprises the steps of applying a carboxylated graphene/chitosan composite finishing agent to a leather-making finishing working section, adjusting the solid content of the carboxylated graphene/chitosan finishing agent to be 5%, and adopting a spraying finishing method, wherein the coating amount is 20g/sf 2; the coating operation flow sequentially comprises: semi-finished leather to be finished → spraying of topping finish → ironing → standing → vibration staking → ironing → finished leather, wherein ironing temperature is 130 ℃, pressure is 30kgf, vibration staking strength is grade 6.
The experimental tests on the finished leather obtained in this example 1 gave the experimental data shown in table 1, and the experimental tests on the finished leather obtained in example 2 gave the experimental data shown in table 2:
TABLE 1
TABLE 2
It should be understood that the above description is only an example of the technical disclosure, and any modifications and variations made by those skilled in the art can be covered by the present disclosure, and not limited by the embodiments disclosed in the present disclosure.
Claims (8)
1. A preparation method of a carboxylated graphene/chitosan composite finishing agent is characterized by comprising the following steps:
the method comprises the following steps: preparing carboxylated graphene powder;
step two: preparing a chitosan solution;
step three: taking carboxylated graphene powder, and mixing the carboxylated graphene powder with water to obtain a carboxylated graphene solution;
step four: preparing a carboxylated graphene/chitosan composite finishing agent: adding 1-10 parts of carboxylated graphene solution into 1000 parts of chitosan solution, uniformly mixing, adjusting the pH value of the solution to 3.0-3.5, reacting at 30-45 ℃ for 1-3h, then adding 1-5 parts of activating agent, reacting at 35-50 ℃ for 1-3h, then adding 1-5 parts of cross-linking agent, reacting at 40-55 ℃ for 1-3h, finally adding 0-3 parts of nano metal material, and reacting at 40-55 ℃ for 1h to obtain a carboxylated graphene/chitosan composite coating agent;
the activating agent is selected from at least one of pyruvic acid, beta-hydroxy pyruvic acid, alpha-ketoglutaric acid and 2-carbonyl propionic acid;
the cross-linking agent is selected from at least one of ethylenediamine, diethylenetriamine, triethylene tetramine and tetraethylene pentamine;
the nano metal material is selected from at least one of nano titanium dioxide, nano manganese dioxide, nano silicon dioxide, nano zinc oxide, nano iron oxide and nano silver.
2. The preparation method of the carboxylated graphene/chitosan composite coating agent according to claim 1, wherein the preparation method of the carboxylated graphene powder comprises the following specific steps:
1) adding 1-10 parts of graphene oxide into 1000 parts of deionized water, performing ultrasonic dispersion for 60-90 minutes, then adding 10-100 parts of alkaline solution, performing ultrasonic dispersion for 30-60 minutes, then adding 10-400 parts of active micromolecules, performing ultrasonic dispersion for 30-60 minutes, finally adjusting the reaction temperature to 30-50 ℃, and reacting for 3-12 hours to obtain a carboxylated graphene dispersion liquid;
2) alternately washing the carboxylated graphene dispersion liquid for 6-10 times by using an acid solution and deionized water, and finally washing for 3-5 times by using absolute ethyl alcohol;
3) and (3) drying the product obtained in the last step in vacuum to obtain the carboxylated graphene powder.
3. The preparation method of the carboxylated graphene/chitosan composite finishing agent according to claim 1, wherein the preparation method of the chitosan solution comprises the following specific steps:
dissolving 3-5 parts of acid solution in 100 parts of deionized water, then adding 1-5 parts of chitosan, and adjusting the pH value of the solution to 3.0-4.0 to obtain a chitosan solution.
4. The preparation method of the carboxylated graphene/chitosan composite coating agent according to claim 1, wherein the specific steps of the third step are as follows:
adding 1-5 parts of carboxylated graphene into 100 parts of deionized water, performing ultrasonic dispersion for 5-15 minutes, and adjusting the pH value of the solution to 4.5-5.5 to obtain a carboxylated graphene solution.
5. The method for preparing a carboxylated graphene/chitosan composite finishing agent according to claim 2, wherein the alkaline solution is selected from any one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, triethylamine and ammonia water.
6. The preparation method of the carboxylated graphene/chitosan composite finishing agent according to claim 2, wherein the active small molecule is selected from any one of α -bromoacetic acid, α -chloroacetic acid and azodibutyrronitrile.
7. The method for preparing a carboxylated graphene/chitosan composite finishing agent according to claim 2 or 3, wherein the acidic solution is selected from any one of formic acid, acetic acid, hydrochloric acid and sulfuric acid.
8. Finished leather comprising a finishing step, wherein the carboxylated graphene/chitosan composite finishing agent of claim 1 is used as a finishing agent in the finishing step.
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| CN114836078B (en) * | 2022-04-28 | 2023-04-14 | 山东华冠智能卡有限公司 | Anti-aging graphene conductive paste for gravure printing and preparation method thereof |
| CN114932601B (en) * | 2022-05-27 | 2023-04-11 | 江苏零界科技集团有限公司 | Environment-friendly moisture-proof solid wood board and preparation process thereof |
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