CN110938230B - A kind of multifunctional foamed natural rubber with both high catalytic performance and antibacterial performance and preparation method thereof - Google Patents
A kind of multifunctional foamed natural rubber with both high catalytic performance and antibacterial performance and preparation method thereof Download PDFInfo
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- 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
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- 244000043261 Hevea brasiliensis Species 0.000 title claims abstract description 124
- 229920003052 natural elastomer Polymers 0.000 title claims abstract description 124
- 229920001194 natural rubber Polymers 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 73
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 30
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 26
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 26
- 229920002258 tannic acid Polymers 0.000 claims abstract description 26
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 26
- 229940033123 tannic acid Drugs 0.000 claims abstract description 26
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 26
- 238000010668 complexation reaction Methods 0.000 claims abstract description 15
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000011065 in-situ storage Methods 0.000 claims abstract description 14
- 238000006722 reduction reaction Methods 0.000 claims abstract description 12
- 150000002505 iron Chemical class 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 229920001971 elastomer Polymers 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000000536 complexating effect Effects 0.000 description 14
- 238000002791 soaking Methods 0.000 description 13
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
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- 150000003839 salts Chemical class 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 238000005187 foaming Methods 0.000 description 5
- 238000000861 blow drying Methods 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
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- 241000191967 Staphylococcus aureus Species 0.000 description 3
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- 239000008367 deionised water Substances 0.000 description 3
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- 239000012153 distilled water Substances 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
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- 230000001580 bacterial effect Effects 0.000 description 2
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- 230000005764 inhibitory process Effects 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 208000004210 Pressure Ulcer Diseases 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- 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
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- 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
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- 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
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- 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
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- C08J2307/00—Characterised by the use of natural rubber
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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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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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
本发明提供了一种兼具高催化性能和抗菌性能的多功能发泡天然橡胶及其制备方法，属于功能材料技术领域。本发明提供的兼具高催化性能和抗菌性能的多功能发泡天然橡胶的制备方法，包括如下步骤：将发泡天然橡胶浸渍于铁盐水溶液中后，加入单宁酸水溶液，进行预络合反应，然后加入碱性水溶液，进行深度络合反应，得到单宁酸‑氯化铁修饰的发泡天然橡胶；将所述单宁酸‑氯化铁修饰的发泡天然橡胶与银盐水溶液混合，进行原位还原反应，得到多功能发泡天然橡胶。采用上述方法得到的多功能发泡天然橡胶中的纳米银被牢固地固定在发泡天然橡胶表面，可循环使用，不仅可作为抗菌材料使用，也可作为催化剂使用。
The invention provides a multifunctional foamed natural rubber with both 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 both high catalytic performance and antibacterial performance provided by the present invention comprises the following steps: after immersing the foamed natural rubber in the iron salt aqueous solution, adding the tannic acid aqueous solution to carry out pre-complexation reaction, then adding an alkaline aqueous solution to carry out a deep complexation reaction to obtain a foamed natural rubber modified by tannic acid-ferric chloride; mixing the foamed natural rubber modified by tannic acid-ferric chloride with an aqueous silver salt solution , carry out in-situ reduction reaction to obtain multifunctional foamed natural rubber. The nano-silver in the multifunctional foamed natural rubber obtained by the above method is firmly fixed on the surface of the foamed natural rubber, can be recycled, and can be used not only as an antibacterial material, but also as a catalyst.
Description
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)
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| CN108728835A (en) * | 2017-04-18 | 2018-11-02 | 北京化工大学 | A kind of preparation method of electroplate material |
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| CN103589031A (en) * | 2013-10-15 | 2014-02-19 | 苏州市景荣科技有限公司 | Antibacterial foamed rubber sole material |
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| 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 |
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