CN110938230B - Multifunctional foamed natural rubber with high catalytic performance and antibacterial performance and preparation method thereof - Google Patents

Multifunctional foamed natural rubber with high catalytic performance and antibacterial performance and preparation method thereof Download PDF

Info

Publication number
CN110938230B
CN110938230B CN201911266549.4A CN201911266549A CN110938230B CN 110938230 B CN110938230 B CN 110938230B CN 201911266549 A CN201911266549 A CN 201911266549A CN 110938230 B CN110938230 B CN 110938230B
Authority
CN
China
Prior art keywords
natural rubber
aqueous solution
foamed natural
multifunctional
foamed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911266549.4A
Other languages
Chinese (zh)
Other versions
CN110938230A (en
Inventor
陶金龙
李东东
李普旺
赵鹏飞
何东宁
龙华倩
李高荣
廖禄生
彭政
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lingnan Normal University
Agricultural Products Processing Research Institute of CATAS
Original Assignee
Lingnan Normal University
Agricultural Products Processing Research Institute of CATAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lingnan Normal University, Agricultural Products Processing Research Institute of CATAS filed Critical Lingnan Normal University
Priority to CN201911266549.4A priority Critical patent/CN110938230B/en
Publication of CN110938230A publication Critical patent/CN110938230A/en
Application granted granted Critical
Publication of CN110938230B publication Critical patent/CN110938230B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2307/00—Characterised by the use of natural rubber
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Materials Engineering (AREA)
  • Dentistry (AREA)
  • Toxicology (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention provides a multifunctional foamed natural rubber with high catalytic performance and antibacterial performance and a preparation method thereof, belonging to the technical field of functional materials. The preparation method of the multifunctional foamed natural rubber with high catalytic performance and antibacterial performance provided by the invention comprises the following steps: soaking foamed natural rubber in an iron salt aqueous solution, adding a tannic acid aqueous solution for pre-complexing reaction, then adding an alkaline aqueous solution for deep complexing reaction to obtain tannic acid-ferric chloride modified foamed natural rubber; and mixing the tannin-ferric chloride modified foamed natural rubber with a silver salt aqueous solution, and carrying out in-situ reduction reaction to obtain the multifunctional foamed natural rubber. The nano silver in the multifunctional foamed natural rubber obtained by the method is firmly fixed on the surface of the foamed natural rubber, can be recycled, and not only can be used as an antibacterial material, but also can be used as a catalyst.

Description

Multifunctional foamed natural rubber with high catalytic performance and antibacterial performance and preparation method thereof
Technical Field
The invention relates to the technical field of functional materials, in particular to multifunctional foamed natural rubber with high catalytic performance and antibacterial performance and a preparation method thereof.
Background
In recent decades, the pollution of ecological environment of air and water areas is increasingly serious due to the discharge of wastewater and industry generated by human clothes and eating and housing, and the increase of bacterial molecules due to the global temperature rise, so that people pay close attention to the research and development of the field of multifunctional materials with high-efficiency sterilization, deodorization and high catalytic activity.
Researches show that silver atoms have certain bactericidal capacity, and especially after being prepared into nano-scale particles, the specific surface area is greatly improved, the proportion of surface atoms is increased, and the bactericidal activity is correspondingly improved. Due to these characteristics of nano silver, the development of nano silver materials is receiving attention. For example, the nano silver material is attached to cotton yarn fiber to prepare an antibacterial material in Jianghuqing and the like, and the antibacterial material is used for treating burn wounds and bedsores which cannot be cured for a long time and achieves good effects. However, silver in the antibacterial material is easy to fall off and cannot be recycled.
In addition, 4-nitrophenol (4-NP) is considered as a dangerous environmental pollutant in the world, and the catalytic reduction of 4-NP into 4-aminophenol (4-AP) is used as an important intermediate for producing agrochemicals, medicines and pigments, so that the 4-NP can be harmlessly treated while producing a useful substance, 4-AP. Silver is often used as a catalyst for catalytic reduction of 4-NP, but when silver is used as a catalyst, it is generally used in the form of silver nanoparticles, which has a problem of difficulty in recovery, increasing production costs.
Disclosure of Invention
The invention aims to provide multifunctional foamed natural rubber with high catalytic performance and antibacterial performance and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of multifunctional foaming natural rubber with high catalytic performance and antibacterial performance comprises the following steps:
soaking foamed natural rubber in an iron salt aqueous solution, adding a tannic acid aqueous solution for pre-complexing reaction, then adding an alkaline aqueous solution for deep complexing reaction to obtain tannic acid-ferric chloride modified foamed natural rubber;
and mixing the tannin-ferric chloride modified foamed natural rubber with a silver salt aqueous solution, and carrying out in-situ reduction reaction to obtain the multifunctional foamed natural rubber.
Preferably, the concentration of the ferric salt aqueous solution is 4-6 mmol/L, and the dosage ratio of the foamed natural rubber to the ferric salt aqueous solution is 0.05-0.3 g: 15-35 mL.
Preferably, the concentration of the tannic acid aqueous solution is 3.0-3.5 mg/mL, and the dosage ratio of the foamed natural rubber to the tannic acid aqueous solution is 0.05-0.3 g: 15-35 mL.
Preferably, the temperature of the pre-complexation reaction is 10-40 ℃ and the time is 3-10 min.
Preferably, the alkaline aqueous solution is at least one of a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution; the concentration of the alkaline aqueous solution is 0.8-1.2 mol/L; the dosage ratio of the foamed natural rubber to the alkaline aqueous solution is 0.05-0.3 g:600 mu L.
Preferably, the temperature of the deep complexation reaction is 10-40 ℃ and the time is 60-90 min.
Preferably, the concentration of the silver salt aqueous solution is 1.0-12 mmol/L, and the dosage ratio of the foamed natural rubber to the silver salt aqueous solution is 0.05-0.3 g:50 mL.
Preferably, the temperature of the in-situ reduction reaction is 10-40 ℃ and the time is 0.1-24 h.
Preferably, the tannin-ferric chloride modified foamed natural rubber is soaked with water before being mixed with the silver salt aqueous solution.
The invention also provides the multifunctional foamed natural rubber with high catalytic performance and antibacterial performance, and the preparation method is prepared according to the technical scheme.
The invention provides a preparation method of multifunctional foamed natural rubber with high catalytic performance and antibacterial performance, which comprises the following steps: soaking foamed natural rubber in an iron salt aqueous solution, adding a tannic acid aqueous solution for pre-complexing reaction, then adding an alkaline aqueous solution for deep complexing reaction to obtain tannic acid-ferric chloride modified foamed natural rubber; and mixing the tannin-ferric chloride modified foamed natural rubber with a silver salt aqueous solution, and carrying out in-situ reduction reaction to obtain the multifunctional foamed natural rubber. The invention takes nontoxic and harmless high polymer material foamed natural rubber as a carrier, and firstly, introduces an active coating on the surface of the rubber by introducing a tannic acid-ferric chloride complexing system; then reducing Ag in situ through the rubber surface active coating+The nano-silver modified multifunctional foaming natural rubber is obtained, and the composite material can be used as an antibacterial material and a catalyst.
The preparation method provided by the invention is simple and easy to control, and realizes the in-situ controllable preparation of the nano-silver on the surface of the foamed natural rubber.
Drawings
FIG. 1 XPS plots of foamed natural rubber and the multifunctional foamed natural rubber obtained in example 1;
FIG. 2 is an SEM photograph of the multi-functional foamed natural rubber obtained in examples 1 to 3;
FIG. 3 is a diagram showing the results of the bacteriostatic performance test of the multifunctional foamed natural rubber;
FIG. 4 is a diagram of UV spectroscopy monitoring the spectral conversion of 4-nitrophenol to 4-nitroaniline;
FIG. 5 is a graph showing the change in the conversion of 4-NP after 10 cycles of recycling of the multifunctional foamed natural rubber;
Detailed Description
The invention provides a preparation method of multifunctional foamed natural rubber with high catalytic performance and antibacterial performance, which comprises the following steps:
soaking foamed natural rubber in an iron salt aqueous solution, adding a tannic acid aqueous solution for pre-complexing reaction, then adding an alkaline aqueous solution for deep complexing reaction to obtain tannic acid-ferric chloride modified foamed natural rubber;
and mixing the tannin-ferric chloride modified foamed natural rubber with a silver salt aqueous solution, and carrying out in-situ reduction reaction to obtain the multifunctional foamed natural rubber.
According to the invention, foamed natural rubber is soaked in an iron salt aqueous solution, then a tannic acid aqueous solution is added for pre-complexing reaction, and then an alkaline aqueous solution is added for deep complexing reaction, so that the tannic acid-ferric chloride modified foamed natural rubber is obtained.
In the present invention, the foamed natural rubber is preferably first soaked in water for 5min and then soaked in an aqueous solution of an iron salt.
In the invention, the concentration of the ferric salt aqueous solution is preferably 4-6 mmol/L, and more preferably 4.9 mmol/L; the dosage ratio of the foamed natural rubber to the ferric salt aqueous solution is preferably 0.05-0.3 g: 15-35 mL, and more preferably 0.3g: 15-35 mL; the ferric salt in the ferric salt aqueous solution is preferably at least one of ferric chloride, ferric sulfate and ferric nitrate.
In the invention, the dipping temperature is preferably room temperature, and more preferably 10-40 ℃; the time is preferably 2-5 min; during the impregnation, stirring is preferably maintained.
After the impregnation is finished, the invention adds the tannic acid aqueous solution into the mixed solution to carry out pre-complexation reaction. In the invention, after the tannic acid aqueous solution is added, the tannic acid and iron ions distributed in the foamed natural rubber generate a complex reaction to form a coating on the surface of the foamed natural rubber.
In the invention, the concentration of the tannic acid aqueous solution is preferably 3.0-3.5 mg/mL, and more preferably 3.2 mg/mL; the dosage ratio of the foamed natural rubber to the tannic acid aqueous solution is preferably 0.05-0.3 g: 15-35 mL, and more preferably 0.3gL: 15-35 mL; the aqueous tannic acid solution is preferably added in a batch manner, and a person skilled in the art can adjust the specific batch as required. In the invention, the tannic acid aqueous solution is added in batches, which is beneficial to forming a more uniform tannic acid coating on the surface of the foamed natural rubber.
In the invention, the temperature of the pre-complexation reaction is preferably room temperature, more preferably 10-40 ℃, and the time is preferably 3-10 min, more preferably 5 min; the time of the pre-complexing reaction is preferably started when the addition of the aqueous tannic acid solution is completed.
After the pre-complexing reaction is finished, the invention adds alkaline aqueous solution into the reaction liquid obtained by the pre-complexing reaction to carry out deep complexing reaction. In the present invention, the alkaline condition is favorable for the sufficient complexing reaction, thereby forming a more stable coating on the rubber surface.
In the present invention, the alkaline aqueous solution is preferably at least one of an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution; the concentration of the alkaline aqueous solution is preferably 0.8-1.2 mol/L; the preferable dosage ratio of the foamed natural rubber to the alkaline aqueous solution is 0.05-0.3 mg:600 mu L; the addition of the aqueous alkaline solution is preferably dropwise. In the invention, the alkaline aqueous solution is added in a dropwise manner, so that a uniform coating is formed on the surface of the foamed natural rubber.
In the invention, the temperature of the deep complexation reaction is preferably room temperature, more preferably 10-40 ℃, and the time is preferably 60-90 min; the time of the deep complexation reaction is preferably from the time when the addition of the aqueous alkaline solution is complete.
After the deep complexation reaction is completed, the foamed natural rubber obtained by the deep complexation reaction is preferably taken out, cleaned and dried to obtain the foamed natural rubber modified by the tannic acid-ferric chloride.
In the present invention, the washing preferably includes water washing, ethanol washing, and water washing, which are performed in this order. The specific mode of the cleaning is not particularly limited in the present invention, and any conventional washing mode, such as soaking washing, may be used.
In the present invention, the drying is preferably nitrogen blow drying.
After the tannin-ferric chloride modified foamed natural rubber is obtained, the tannin-ferric chloride modified foamed natural rubber is preferably soaked in water, then mixed with silver salt aqueous solution, and subjected to in-situ reduction reaction to obtain the multifunctional foamed natural rubber. In the invention, the foamed natural rubber is soaked by water and then mixed with the silver salt aqueous solution, which is beneficial to obtaining the nano silver with uniform dispersion.
The tannic acid loaded on the surface of the foamed natural rubber can reduce silver ions into silver simple substance.
In the invention, the concentration of the silver salt aqueous solution is preferably 1.0-12 mmol/L, and the dosage ratio of the foamed natural rubber and the silver salt aqueous solution is preferably 0.05-0.3 g:50mL, and more preferably 0.3g:50 mL.
In the invention, the temperature of the in-situ reduction reaction is preferably room temperature, more preferably 10-40 ℃, and the time is preferably 0.1-24 hours, more preferably 2-20 hours, and most preferably 5-15 hours.
After the in-situ reduction reaction is completed, the multifunctional foamed natural rubber obtained by the in-situ reduction reaction is preferably cleaned and dried to obtain the multifunctional foamed natural rubber.
In the present invention, the cleaning and drying of the multifunctional foamed natural rubber obtained by the in-situ reduction reaction is the same as the cleaning and drying of the foamed natural rubber obtained by the deep complexation reaction, and the details are not repeated herein.
The invention also provides the multifunctional foamed natural rubber with high catalytic performance and antibacterial performance, and the preparation method is prepared according to the technical scheme.
In the invention, the loading amount of silver in the multifunctional foamed natural rubber is preferably 0.05-1.3 wt.%; the average particle size of the silver is preferably 19-26 nm.
The multifunctional foamed natural rubber having both high catalytic performance and antibacterial performance and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Soaking 0.3g of foamed natural rubber in water, stirring for 5min, taking out, soaking in 25mL of 0.8mg/mL ferric chloride solution, stirring for 5-10 min, then adding 25mL of 3.2mg/mL tannic acid aqueous solution into the mixed solution in 3 batches, wherein the adding time interval of each batch is 1min, stirring for 2min after the tannic acid aqueous solution is added, then dropwise adding 600 mu L of 1mol/L sodium hydroxide aqueous solution into the mixed solution, continuously stirring for 3h, taking out the foamed natural rubber, sequentially carrying out water washing, ethanol blow-drying washing and water washing, and then carrying out nitrogen to obtain the tannic acid-ferric chloride modified foamed natural rubber;
soaking tannin-ferric chloride modified foamed natural rubber in distilled water, stirring at room temperature (25 deg.C) for 5min, and taking out; and adding 0.03g of silver nitrate into 50mL of deionized water, stirring to completely dissolve, adding the prepared tannin-ferric chloride modified foamed natural rubber, reacting for 8 hours, taking out the obtained foamed natural rubber, and drying by nitrogen to obtain the multifunctional foamed natural rubber.
Example 2
Soaking 0.3g of foamed natural rubber in water, stirring for 5min, taking out, soaking in 35mL of 0.8mg/mL ferric chloride solution, stirring for 5-10 min, then adding 15mL of 3.2mg/mL tannic acid aqueous solution into the mixed solution in 3 batches, wherein the adding time interval of each batch is 1min, stirring for 2min after the tannic acid aqueous solution is added, then dropwise adding 600 mu L of 1mol/L sodium hydroxide aqueous solution into the mixed solution, continuously stirring for 3h, taking out the foamed natural rubber, sequentially carrying out water washing, ethanol blow-drying washing and water washing, and then carrying out nitrogen to obtain the tannic acid-ferric chloride modified foamed natural rubber;
soaking tannin-ferric chloride modified foamed natural rubber in distilled water, stirring at room temperature (25 deg.C) for 5min, and taking out; and adding 0.06g of silver nitrate into 50mL of deionized water, stirring to completely dissolve, adding the prepared tannin-ferric chloride modified foamed natural rubber, reacting for 8 hours, taking out the obtained foamed natural rubber, and drying by nitrogen to obtain the multifunctional foamed natural rubber.
Example 3
Soaking 0.3g of foamed natural rubber in water, stirring for 5min, taking out, soaking in 15mL of 0.8mg/mL ferric chloride solution, stirring for 5-10 min, then adding 35mL of 3.2mg/mL tannic acid aqueous solution into the mixed solution in 3 batches, wherein the adding time interval of each batch is 1min, stirring for 2min after the tannic acid aqueous solution is added, then dropwise adding 900 mu L of 1mol/L sodium hydroxide aqueous solution into the mixed solution, continuously stirring for 3h, taking out the foamed natural rubber, sequentially carrying out water washing, ethanol blow-drying washing and water washing, and then carrying out nitrogen to obtain the tannic acid-ferric chloride modified foamed natural rubber;
soaking tannin-ferric chloride modified foamed natural rubber in distilled water, stirring at room temperature (25 deg.C) for 5min, and taking out; and adding 0.1g of silver nitrate into 50mL of deionized water, stirring to completely dissolve, adding the prepared tannin-ferric chloride modified foam for reaction for 8 hours, taking out the obtained foamed natural rubber, and drying by nitrogen to obtain the multifunctional foamed natural rubber.
XPS characterization was performed on the foamed natural rubber and the multifunctional foamed natural rubber obtained in example 1, and the results are shown in FIG. 1, in which a is an XPS map of a blank foamed natural rubber and b is an XPS map of a multifunctional foamed natural rubber. As can be seen from fig. 1, the characteristic peak of nano silver does not exist in the blank foamed natural rubber, and the characteristic peak of nano silver appears in the multifunctional foamed natural rubber.
The shapes and sizes of the nano silver in the multifunctional foamed natural rubber obtained in examples 1 to 3 were observed by using a scanning electron microscope, as shown in fig. 2. As can be seen from FIG. 2, the surface of the multifunctional foamed natural rubber obtained by the present invention has nano-scale spherical particles, which can be proved to be nano-silver by combining FIG. 1, and the average particle diameters of the nano-silver in the multifunctional foamed natural rubber obtained in examples 1 to 3 are measured to be 19nm, 23.3nm and 26nm in this order.
The antibacterial performance of the multifunctional foaming natural rubber is tested, and the antibacterial performance is as follows:
preparing a bacterial nutrient solution, then carrying out autoclaving, adding agar, pouring the agar into 6 culture dishes to obtain culture media, dividing the culture media into two groups after the culture media are solidified, wherein each group comprises 3 culture media, respectively inoculating 200 mu L of escherichia coli and staphylococcus aureus into the two groups of culture media, respectively placing 0.5g of foamed natural rubber, 0.5g of multifunctional foamed natural rubber obtained in example 2 and 0.25g of multifunctional foamed natural rubber obtained in example 2 into the three culture media of each group, respectively, then culturing in a constant temperature incubator for 24 hours, and observing an inhibition zone. The results are shown in FIG. 3, in which s-C, s-H and s-L are Staphylococcus aureus group, s-C is a medium to which foamed natural rubber was added, s-H is a medium to which 0.5g of the multifunctional foamed natural rubber obtained in example 2 was added, s-L is a medium to which 0.25g of the multifunctional foamed natural rubber obtained in example 2 was added, E-C, E-H and E-L are Escherichia coli group, E-C is a medium to which foamed natural rubber was added, E-H is a medium to which 0.5g of the multifunctional foamed natural rubber obtained in example 2 was added, and E-L is a medium to which 0.25g of the multifunctional foamed natural rubber obtained in example 2 was added. The experimental result shows that the multifunctional foamed natural rubber of the foamed natural rubber has obvious inhibition effect on both escherichia coli and staphylococcus aureus.
The catalytic performance of the multifunctional foaming natural rubber is tested, and the specific test results are as follows:
5mL of NaBH at a concentration of 0.34mol/L4Aqueous solution and 20mL of 5X 10-5After mixing the solution of mol/L4-nitrophenol, 0.03g of the multifunctional foamed natural rubber obtained in example 3 was added, and then every 3min, the ultraviolet absorption spectrum of the reaction solution was recorded and tested for 3 h. The results are shown in fig. 4, and the experimental results show that the multifunctional foamed natural rubber has good capability of converting p-nitrophenol into p-nitroaniline.
The multifunctional foaming natural rubber is circularly catalyzed by the method to obtain the p-nitrophenol, and the conversion rate change chart of the obtained p-nitrophenol is shown in figure 5. As can be seen from FIG. 5, after 10 cycles, the multifunctional foamed natural rubber still has good catalytic activity.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of multifunctional foaming natural rubber with high catalytic performance and antibacterial performance is characterized by comprising the following steps:
soaking foamed natural rubber in an iron salt aqueous solution, adding a tannic acid aqueous solution for pre-complexing reaction, then adding an alkaline aqueous solution for deep complexing reaction to obtain tannic acid-ferric chloride modified foamed natural rubber;
and mixing the tannin-ferric chloride modified foamed natural rubber with a silver salt aqueous solution, and carrying out in-situ reduction reaction to obtain the multifunctional foamed natural rubber.
2. The preparation method of claim 1, wherein the concentration of the ferric salt aqueous solution is 4-6 mmol/L, and the ratio of the foamed natural rubber to the ferric salt aqueous solution is 0.05-0.3 g: 15-35 mL.
3. The method according to claim 1, wherein the concentration of the aqueous solution of tannic acid is 3.0 to 3.5mg/mL, and the ratio of the amount of the foamed natural rubber to the amount of the aqueous solution of tannic acid is 0.05 to 0.3g:15 to 35 mL.
4. The method according to any one of claims 1 to 3, wherein the temperature of the pre-complexation reaction is 10 to 40 ℃ and the time is 3 to 10 min.
5. The production method according to claim 1, wherein the alkaline aqueous solution is at least one of an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution; the concentration of the alkaline aqueous solution is 0.8-1.2 mol/L; the dosage ratio of the foamed natural rubber to the alkaline aqueous solution is 0.05-0.3 g:600 mu L.
6. The preparation method according to claim 1 or 5, wherein the deep complexation reaction is carried out at a temperature of 10-40 ℃ for 60-90 min.
7. The method according to claim 1, wherein the concentration of the silver salt aqueous solution is 1.0 to 12mmol/L, and the ratio of the amount of the foamed natural rubber to the amount of the silver salt aqueous solution is 0.05 to 0.3 g/50 mL.
8. The preparation method according to claim 1 or 7, wherein the temperature of the in-situ reduction reaction is 10-40 ℃ and the time is 0.1-24 h.
9. The method according to claim 1, wherein the tannin-ferric chloride modified foamed natural rubber is soaked with water before the tannin-ferric chloride modified foamed natural rubber is mixed with the silver salt aqueous solution.
10. A multifunctional foamed natural rubber having both high catalytic performance and antibacterial performance, which is obtained by the production method according to any one of claims 1 to 9.
CN201911266549.4A 2019-12-11 2019-12-11 Multifunctional foamed natural rubber with high catalytic performance and antibacterial performance and preparation method thereof Active CN110938230B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911266549.4A CN110938230B (en) 2019-12-11 2019-12-11 Multifunctional foamed natural rubber with high catalytic performance and antibacterial performance and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911266549.4A CN110938230B (en) 2019-12-11 2019-12-11 Multifunctional foamed natural rubber with high catalytic performance and antibacterial performance and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110938230A CN110938230A (en) 2020-03-31
CN110938230B true CN110938230B (en) 2022-03-11

Family

ID=69910440

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911266549.4A Active CN110938230B (en) 2019-12-11 2019-12-11 Multifunctional foamed natural rubber with high catalytic performance and antibacterial performance and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110938230B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112973473B (en) * 2021-03-08 2023-03-24 天津工业大学 Reverse osmosis composite membrane resisting biological pollution and preparation method thereof
CN116832868B (en) * 2023-05-23 2024-05-28 广东省科学院测试分析研究所(中国广州分析测试中心) Preparation method and application of iron nano-enzyme with oxidase-like and peroxidase-like properties

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103589031A (en) * 2013-10-15 2014-02-19 苏州市景荣科技有限公司 Antibacterial foamed rubber sole material
CN106924810A (en) * 2017-02-16 2017-07-07 湖北大学 A kind of nanometer antibacterium coating material based on nano-Ag particles and preparation method thereof
CN108084509A (en) * 2016-11-22 2018-05-29 沈阳赛亚橡胶制品有限公司 A kind of Natural rubber foam material and preparation method thereof
CN108728835A (en) * 2017-04-18 2018-11-02 北京化工大学 A kind of preparation method of electroplate material
CN108816689A (en) * 2018-07-05 2018-11-16 四川大学 A kind of super-hydrophilic coating and preparation method thereof with long acting antibiotic performance

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103589031A (en) * 2013-10-15 2014-02-19 苏州市景荣科技有限公司 Antibacterial foamed rubber sole material
CN108084509A (en) * 2016-11-22 2018-05-29 沈阳赛亚橡胶制品有限公司 A kind of Natural rubber foam material and preparation method thereof
CN106924810A (en) * 2017-02-16 2017-07-07 湖北大学 A kind of nanometer antibacterium coating material based on nano-Ag particles and preparation method thereof
CN108728835A (en) * 2017-04-18 2018-11-02 北京化工大学 A kind of preparation method of electroplate material
CN108816689A (en) * 2018-07-05 2018-11-16 四川大学 A kind of super-hydrophilic coating and preparation method thereof with long acting antibiotic performance

Also Published As

Publication number Publication date
CN110938230A (en) 2020-03-31

Similar Documents

Publication Publication Date Title
Li et al. Er-doped g-C3N4 for photodegradation of tetracycline and tylosin: high photocatalytic activity and low leaching toxicity
Gao et al. A robust superhydrophobic antibacterial Ag–TiO2 composite film immobilized on wood substrate for photodegradation of phenol under visible-light illumination
CN103801284B (en) A kind of preparation method of pucherite-graphene composite photocatalyst
Wang et al. In situ loading of polyurethane/negative ion powder composite film with visible-light-responsive Ag3PO4@ AgBr particles for photocatalytic and antibacterial applications
CN110938230B (en) Multifunctional foamed natural rubber with high catalytic performance and antibacterial performance and preparation method thereof
CN103131030A (en) Cellulose/sliver/silver chloride composite material and preparation method thereof
CN104368325A (en) Preparation method of formaldehyde-photodegrading honeycomb activated carbon
CN111450806A (en) Preparation method of porous adsorption antibacterial composite material based on waste corncobs
Li et al. Preparation and application of silver/chitosan-sepiolite materials with antimicrobial activities and low cytotoxicity
Zhang et al. Extensive solar light utilizing by ternary C-dots/Cu2O/SrTiO3: Highly enhanced photocatalytic degradation of antibiotics and inactivation of E. coli
CN112791729A (en) Sulfhydrylation montmorillonite loaded ZnO-Fe2O3Heterojunction composite material and preparation method
CN113333023A (en) High-adsorption bismuth oxyiodide visible-light-driven photocatalyst and application thereof
CN115652611A (en) Antibacterial medical textile and preparation method thereof
CN108314214B (en) Process for degrading printing and dyeing wastewater through heterogeneous ozone catalysis
CN1217059C (en) Preparing process and use of antibacterial nano silver fabric
Huang et al. Carboxymethyl cellulose gels immobilized Ag/AgCl-ZnO nanoparticles for improving sunlight-catalyzed antibacterial performance
Ikram et al. Facile synthesis of chitosan-grafted polyacrylic acid-doped CaO nanoparticle for catalytic and antimicrobial potential
CN107081148A (en) Prepare the method for material for air purification and by material for air purification made from this method
CN110743591A (en) Preparation method and application of doped composite catalyst
CN114260014A (en) NiCo2O4/CeO2Composite catalyst and preparation method and application thereof
CN107262128A (en) Visible-light response type nitride porous boryl composite photocatalyst material and preparation method
CN108772084B (en) TiO with photocatalytic antibacterial property2/Cu2(OH)2CO3Preparation method and application of composite nano material
KR20030028325A (en) Process for Preparing Activated Carbon Having Nano-structure Photocatalyst
CN114950567B (en) Composite photocatalytic material with hindered Lewis acid-base pair structure and application thereof
CN113152140B (en) Antibacterial paper based on nano-micro heterojunction structure and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant