CN111500217A - Preparation method of multifunctional nano material modified pressure-sensitive adhesive - Google Patents
Preparation method of multifunctional nano material modified pressure-sensitive adhesive Download PDFInfo
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- CN111500217A CN111500217A CN202010262171.7A CN202010262171A CN111500217A CN 111500217 A CN111500217 A CN 111500217A CN 202010262171 A CN202010262171 A CN 202010262171A CN 111500217 A CN111500217 A CN 111500217A
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- sensitive adhesive
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 55
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 31
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 26
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920002907 Guar gum Polymers 0.000 claims abstract description 17
- 229960002154 guar gum Drugs 0.000 claims abstract description 17
- 235000010417 guar gum Nutrition 0.000 claims abstract description 17
- 239000000665 guar gum Substances 0.000 claims abstract description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000010453 quartz Substances 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 24
- 239000007800 oxidant agent Substances 0.000 claims description 18
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 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 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 230000000844 anti-bacterial effect Effects 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 230000001699 photocatalysis Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 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 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 229940096017 silver fluoride Drugs 0.000 claims description 6
- -1 silver ions Chemical class 0.000 claims description 6
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 4
- 230000003115 biocidal effect Effects 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000007540 photo-reduction reaction Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000013082 iron-based metal-organic framework Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
-
- 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
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B01J35/23—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J187/00—Adhesives based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
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- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Catalysts (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a preparation method of a multifunctional nano material modified pressure-sensitive adhesive, which comprises the steps of mixing Fe metal powder and trimesic acid, carrying out hydrothermal reaction with a crystallization reagent, washing, drying and the like, wherein a nano catalytic material (a nano silver metal organic framework compound) is combined with guar gum to prepare the nano material modified pressure-sensitive adhesive, so that the unique advantages of the three materials can be fully combined, the limitation of single function of the conventional pressure-sensitive adhesive is overcome, and the pressure-sensitive adhesive material integrating adsorption-photocatalytic degradation and antibiosis is prepared; compared with the traditional chemical reduction method, the method for preparing the nano silver by adopting the photo-reduction method does not need to add any chemical reducing agent, is cleaner, green and nontoxic, has high reaction efficiency, and can effectively regulate and control the growth and dispersion of the nano silver crystal by means of the porous structure and the high specific surface area of the metal organic framework compound, thereby further improving the reaction activity.
Description
Technical Field
The invention relates to the technical field of pressure-sensitive adhesives, in particular to a preparation method of a multifunctional nano material modified pressure-sensitive adhesive.
Background
Pressure-sensitive adhesives are a class of pressure-sensitive adhesives, which are mainly used for preparing pressure-sensitive adhesive tapes, generally speaking: the pressure-sensitive adhesive is a special adhesive which can be bonded by finger pressure without heating, solvent or other means, generally, the pressure-sensitive adhesive is not directly used for bonding, and can be used only when being coated on a strip-shaped base material to prepare various pressure-sensitive adhesive products, the pressure-sensitive adhesive generally has no phenomena of degumming and the like in the using process, simultaneously has no solvent, no pollution and convenient use, is coated in a melting state, and can play a role in bonding by applying slight finger pressure after being cooled and solidified. It has wide application range, and can be used in diaper, women's product, double-sided adhesive tape, label, package, medical treatment and hygiene, book binding, surface protecting film, wood processing, wallpaper, shoe making, etc. Pressure sensitive adhesives have developed rapidly, but current products still suffer from several disadvantages, thus limiting their range of applications.
Disclosure of Invention
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a preparation method of a multifunctional nano material modified pressure-sensitive adhesive comprises the following steps:
(1) mixing Fe-based metal powder and trimesic acid, adding 10-25 ml of deionized water, stirring, measuring 150-200 mu L hydrofluoric acid and 90-150 mu L nitric acid, dropwise adding into the solution, and magnetically stirring for 15-30 min by using a magnetic stirrer;
(2) transferring the solution prepared in the step (1) into a hydrothermal reaction kettle, adding a crystallization reagent into the hydrothermal reaction kettle, and continuously stirring for 10-20 min; then continuously reacting for 12-24 h at the temperature of 100-150 ℃; naturally cooling to room temperature after the reaction is finished, centrifuging the mixture at 4000rpm for 5min, washing the mixture for 3-6 times by using ethanol, and then performing vacuum drying at 100 ℃ for 12h to obtain a metal organic framework compound product;
(3) adding 0.5-2 g of the metal organic framework compound prepared in the step (2) into 150-300 ml of mixed solution of ethanol and water, adding Ag metal salt into the mixed solution, fully stirring, transferring the mixed solution into a quartz bottle, introducing N2 into the quartz bottle to remove air in the quartz bottle, and irradiating the quartz bottle under an ultraviolet lamp for 20-60 min; finally, washing the obtained substance in the quartz bottle with ethanol for 4-6 times, and then carrying out vacuum drying for 12 hours at 100 ℃ to obtain a final product, namely the nano silver-metal organic framework compound;
(4) and (3) putting 1-3 g of the nano silver-metal organic framework compound prepared in the step (3) into 20-60 ml of deionized water, performing ultrasonic dispersion for 30min, adding 0.33-2 g of guar gum powder, rapidly and mechanically stirring for 6-12 h, adding an oxidant to oxidize the product for self-crosslinking, and standing for 10-30 min to obtain the composite pressure-sensitive adhesive.
Preferably, the Fe-based metal powder in step (1) is a metal salt containing Fe, one of reduced Fe powder, ferric sulfate, ferric nitrate or ferric trichloride is used, and the mixing molar ratio of the Fe-based metal powder to trimesic acid is Fe: h3BTC is 0.5-2.5: 0.67 mol.
Preferably, the crystallization reagent in the step (2) is cetyl trimethyl ammonium bromide, and the molar ratio of the cetyl trimethyl ammonium bromide to the Fe element is 0.3-1.2: 1 mol.
Preferably, in the mixed solution of ethanol and water in the step (3), the volume ratio of ethanol to water is 1: 2; the Ag-series metal salt is a metal salt containing Ag element, one of silver nitrate and silver fluoride is adopted, and after the Ag-series metal salt is added, the concentration of silver ions in the solution is 10-80 mM.
Preferably, the oxidant in the step (4) is sodium periodate NaIO4, and the mass ratio of the oxidant to the guar gum is 0.1-0.5: 1.
preferably, the composite pressure-sensitive adhesive prepared by the preparation method of the multifunctional nano material modified pressure-sensitive adhesive is applied as a photocatalysis, antibacterial and oil-water separating agent.
The invention has the following advantages: according to the invention, a nano catalytic material (nano silver metal organic framework compound) is combined with guar gum to prepare the nano material modified pressure-sensitive adhesive, so that the unique advantages of the three materials can be fully combined, the limitation of single function of the conventional pressure-sensitive adhesive is overcome, and the pressure-sensitive adhesive material integrating adsorption, photocatalytic degradation and antibiosis is prepared; preparing uniformly dispersed nano silver in situ on a Fe-based metal organic framework compound by adopting a green and simple photo-reduction method, and regulating and controlling the growth and dispersion of nano silver crystals by means of the porous structure and the high specific surface area of the metal organic framework compound so as to further improve the reaction activity of the nano silver-metal organic framework compound; the GG porous hydrogel has an enrichment effect on dye pollutants and bacteria, and can well load and disperse the nano-silver-metal organic framework compound nano-catalytic material, so that on one hand, the nano-catalytic material can be effectively prevented from agglomerating to influence the catalytic and antibacterial properties of the nano-catalytic material, and on the other hand, the nano-catalytic material can be dispersed and well immobilized, thereby further promoting the efficient recycling of the pressure-sensitive adhesive; the concrete effects are as follows:
1) the invention integrates photocatalysis and antibacterial technologies into a whole to prepare the nano material modified pressure-sensitive adhesive, and has the advantages of simple preparation method, low cost, high practical value and application prospect.
2) The introduction of the nano silver improves the electron hole separation performance of the metal organic framework compound and promotes the photocatalysis effect of the nano material modified pressure-sensitive adhesive, and the nano silver has a good antibacterial effect and endows the gel material with a good antibacterial effect; the water body is integrated with antibiosis and sterilization, and the bacteriostasis rate is higher than 99 percent.
3) The guar gum can well load and disperse the nano catalytic material, so that the aggregation of the guar gum is avoided from influencing the catalytic and antibacterial properties of the guar gum, and the efficient recycling of the nano powder catalytic material can be promoted.
4) The composite pressure-sensitive adhesive is a natural biodegradable material, has a simple preparation method and low cost, and does not cause secondary pollution to water compared with other metal semiconductor catalytic materials.
5) Compared with the traditional chemical reduction method, the method for preparing the nano silver by adopting the photo-reduction method does not need to add any chemical reducing agent, is cleaner, green and nontoxic, has high reaction efficiency, and can effectively regulate and control the growth and dispersion of the nano silver crystal by means of the porous structure and the high specific surface area of the metal organic framework compound, thereby further improving the reaction activity.
Detailed Description
Example one
A preparation method of a multifunctional nano material modified pressure-sensitive adhesive comprises the following steps:
(1) mixing Fe series metal powder and trimesic acid, adding 10ml deionized water, stirring, measuring 150 mu L hydrofluoric acid and 90 mu L nitric acid, dropwise adding into the solution, and magnetically stirring for 15min by using a magnetic stirrer;
(2) transferring the solution prepared in the step (1) into a hydrothermal reaction kettle, adding a crystallization reagent into the hydrothermal reaction kettle, and continuously stirring for 10 min; then continuously reacting for 12h at the temperature of 100 ℃; naturally cooling to room temperature after the reaction is finished, centrifuging the mixture at 4000rpm for 5min, washing the mixture for 3 times by using ethanol, and then performing vacuum drying at 100 ℃ for 12h to obtain a metal organic framework compound product;
(3) adding 0.5g of the metal organic framework compound prepared in the step (2) into 150ml of mixed solution of ethanol and water, adding Ag series metal salt into the mixed solution, fully stirring, transferring the mixed solution into a quartz bottle, introducing N2 into the quartz bottle to remove air in the quartz bottle, and irradiating the quartz bottle under an ultraviolet lamp for 20 min; finally, washing the obtained substance in the quartz bottle with ethanol for 4 times, and then drying the substance in vacuum at 100 ℃ for 12 hours to obtain a final product, namely the nano silver-metal organic framework compound;
(4) and (3) putting 1g of the nano silver-metal organic framework compound prepared in the step (3) into 20ml of deionized water, performing ultrasonic dispersion for 30min, adding 0.33gg guar gum powder, performing rapid mechanical stirring for 6-12 h, adding an oxidant to oxidize the product for self-crosslinking, and standing for 10min to obtain the composite pressure-sensitive adhesive.
As a preferred embodiment of this embodiment, the Fe-based metal powder in step (1) is an Fe-containing metal salt, and one of reduced Fe powder, ferric sulfate, ferric nitrate or ferric trichloride is used, and the mixing molar ratio of the Fe-based metal powder to trimesic acid is Fe: h3BTC ═ 0.5:0.67 mol.
As a preferred embodiment of this example, the crystallization reagent in step (2) is cetyltrimethylammonium bromide, and the molar ratio of the cetyltrimethylammonium bromide to the Fe element is 0.3:1 mol.
As a preferred embodiment of this example, in the mixed solution of ethanol and water described in the step (3), the volume ratio of ethanol to water is 1: 2; the Ag-series metal salt is a metal salt containing Ag element, one of silver nitrate and silver fluoride is adopted, and after the Ag-series metal salt is added, the concentration of silver ions in the solution is 10 mM.
As a preferred embodiment of this embodiment, the oxidizing agent in step (4) is sodium periodate NaIO4, and the mass ratio of the oxidizing agent to the guar gum is 0.1: 1.
in a preferred embodiment of this embodiment, the composite pressure-sensitive adhesive prepared by the preparation method of the multifunctional nano-material modified pressure-sensitive adhesive is applied as a photocatalytic, antibacterial and oil-water separating agent.
Example two
A preparation method of a multifunctional nano material modified pressure-sensitive adhesive comprises the following steps:
(1) mixing Fe series metal powder and trimesic acid, adding 25ml of deionized water, stirring, measuring 200 mu L hydrofluoric acid and 150 mu L nitric acid, dropwise adding into the solution, and magnetically stirring for 30min by using a magnetic stirrer;
(2) transferring the solution prepared in the step (1) into a hydrothermal reaction kettle, adding a crystallization reagent into the hydrothermal reaction kettle, and continuously stirring for 20 min; then continuously reacting for 24 hours at the temperature of 150 ℃; naturally cooling to room temperature after the reaction is finished, centrifuging the mixture at 4000rpm for 5min, washing the mixture for 6 times by using ethanol, and then performing vacuum drying at 100 ℃ for 12h to obtain a metal organic framework compound product;
(3) adding 2g of the metal organic framework compound prepared in the step (2) into 300ml of mixed solution of ethanol and water, adding Ag metal salt into the mixed solution, fully stirring, transferring the mixed solution into a quartz bottle, introducing N2 into the quartz bottle to remove air in the quartz bottle, and irradiating the quartz bottle under an ultraviolet lamp for 60 min; finally, washing the obtained substance in the quartz bottle with ethanol for 6 times, and then carrying out vacuum drying for 12 hours at 100 ℃ to obtain a final product, namely the nano silver-metal organic framework compound;
(4) and (3) putting 3g of the nano silver-metal organic framework compound prepared in the step (3) into 60ml of deionized water, performing ultrasonic dispersion for 30min, then adding 2g of guar gum powder, performing rapid mechanical stirring for 12h, then adding an oxidant to oxidize the above objects for self-crosslinking, and standing for 30min to obtain the composite pressure-sensitive adhesive.
As a preferred embodiment of this embodiment, the Fe-based metal powder in step (1) is an Fe-containing metal salt, and one of reduced Fe powder, ferric sulfate, ferric nitrate or ferric trichloride is used, and the mixing molar ratio of the Fe-based metal powder to trimesic acid is Fe: h3BTC 2.5:0.67 mol.
As a preferred embodiment of this example, the crystallization reagent in step (2) is cetyltrimethylammonium bromide, and the molar ratio of the cetyltrimethylammonium bromide to the Fe element is 1.2:1 mol.
As a preferred embodiment of this example, in the mixed solution of ethanol and water described in the step (3), the volume ratio of ethanol to water is 1: 2; the Ag-series metal salt is a metal salt containing Ag element, one of silver nitrate and silver fluoride is adopted, and after the Ag-series metal salt is added, the concentration of silver ions in the solution is 80 mM.
As a preferred embodiment of this embodiment, the oxidizing agent in step (4) is sodium periodate NaIO4, and the mass ratio of the oxidizing agent to the guar gum is 0.5: 1.
in a preferred embodiment of this embodiment, the composite pressure-sensitive adhesive prepared by the preparation method of the multifunctional nano-material modified pressure-sensitive adhesive is applied as a photocatalytic, antibacterial and oil-water separating agent.
EXAMPLE III
A preparation method of a multifunctional nano material modified pressure-sensitive adhesive comprises the following steps:
(1) mixing Fe series metal powder and trimesic acid, adding 18ml of deionized water, stirring, measuring 180 mu L hydrofluoric acid and 120 mu L nitric acid, dropwise adding into the solution, and magnetically stirring for 22min by using a magnetic stirrer;
(2) transferring the solution prepared in the step (1) into a hydrothermal reaction kettle, adding a crystallization reagent into the hydrothermal reaction kettle, and continuously stirring for 15 min; then the reaction is continued for 16h at the temperature of 125 ℃; naturally cooling to room temperature after the reaction is finished, centrifuging the mixture at 4000rpm for 5min, washing the mixture for 4 times by using ethanol, and then performing vacuum drying at 100 ℃ for 12h to obtain a metal organic framework compound product;
(3) adding 1.2g of the metal organic framework compound prepared in the step (2) into 150-300 ml of mixed solution of ethanol and water, adding Ag series metal salt into the mixed solution, fully stirring, transferring the mixed solution into a quartz bottle, introducing N2 into the quartz bottle to remove air in the quartz bottle, and irradiating the quartz bottle under an ultraviolet lamp for 40 min; finally, washing the obtained substance in the quartz bottle with ethanol for 5 times, and then drying the substance in vacuum at 100 ℃ for 12 hours to obtain a final product, namely the nano silver-metal organic framework compound;
(4) and (3) placing 2g of the nano silver-metal organic framework compound prepared in the step (3) in 40ml of deionized water, performing ultrasonic dispersion for 30min, then adding 1.4g of guar gum powder, performing rapid mechanical stirring for 9h, then adding an oxidant to oxidize the product for self-crosslinking, and standing for 20min to obtain the composite pressure-sensitive adhesive.
As a preferred embodiment of this embodiment, the Fe-based metal powder in step (1) is an Fe-containing metal salt, and one of reduced Fe powder, ferric sulfate, ferric nitrate or ferric trichloride is used, and the mixing molar ratio of the Fe-based metal powder to trimesic acid is Fe: h3BTC ═ 1.5:0.67 mol.
As a preferred embodiment of this example, the crystallization reagent in step (2) is cetyltrimethylammonium bromide, and the molar ratio of the cetyltrimethylammonium bromide to the Fe element is 0.7:1 mol.
As a preferred embodiment of this example, in the mixed solution of ethanol and water described in the step (3), the volume ratio of ethanol to water is 1: 2; the Ag-series metal salt is a metal salt containing Ag element, one of silver nitrate and silver fluoride is adopted, and after the Ag-series metal salt is added, the concentration of silver ions in the solution is 45 mM.
As a preferred embodiment of this embodiment, the oxidizing agent in step (4) is sodium periodate NaIO4, and the mass ratio of the oxidizing agent to the guar gum is 0.3: 1.
in a preferred embodiment of this embodiment, the composite pressure-sensitive adhesive prepared by the preparation method of the multifunctional nano-material modified pressure-sensitive adhesive is applied as a photocatalytic, antibacterial and oil-water separating agent.
Example four
A preparation method of a multifunctional nano material modified pressure-sensitive adhesive comprises the following steps:
(1) mixing Fe series metal powder and trimesic acid, adding 15ml deionized water, stirring, measuring 160 mu L hydrofluoric acid and 130 mu L nitric acid, dropwise adding into the solution, and magnetically stirring for 20min by using a magnetic stirrer;
(2) transferring the solution prepared in the step (1) into a hydrothermal reaction kettle, adding a crystallization reagent into the hydrothermal reaction kettle, and continuously stirring for 18 min; then continuously reacting for 15h at the temperature of 120 ℃; naturally cooling to room temperature after the reaction is finished, centrifuging the mixture at 4000rpm for 5min, washing the mixture with ethanol for 5 times, and then performing vacuum drying at 100 ℃ for 12h to obtain a metal organic framework compound product;
(3) adding 1g of the metal organic framework compound prepared in the step (2) into 200ml of mixed solution of ethanol and water, adding Ag metal salt into the mixed solution, fully stirring, transferring the mixed solution into a quartz bottle, introducing N2 into the quartz bottle to remove air in the quartz bottle, and irradiating the quartz bottle under an ultraviolet lamp for 50 min; finally, washing the obtained substance in the quartz bottle with ethanol for 6 times, and then carrying out vacuum drying for 12 hours at 100 ℃ to obtain a final product, namely the nano silver-metal organic framework compound;
(4) and (3) putting 3g of the nano silver-metal organic framework compound prepared in the step (3) into 50ml of deionized water, performing ultrasonic dispersion for 30min, then adding 1.7g of guar gum powder, rapidly and mechanically stirring for 10h, then adding an oxidant to oxidize and self-crosslink the articles, and standing for 30min to obtain the composite pressure-sensitive adhesive.
Preferably, the Fe-based metal powder in step (1) is a metal salt containing Fe, one of reduced Fe powder, ferric sulfate, ferric nitrate or ferric trichloride is used, and the mixing molar ratio of the Fe-based metal powder to trimesic acid is Fe: h3BTC ═ 2:0.67 mol.
Preferably, the crystallization reagent in the step (2) is hexadecyl trimethyl ammonium bromide, and the mol ratio of the hexadecyl trimethyl ammonium bromide to the Fe element is 1:1 mol.
Preferably, in the mixed solution of ethanol and water in the step (3), the volume ratio of ethanol to water is 1: 2; the Ag-series metal salt is a metal salt containing Ag element, one of silver nitrate and silver fluoride is adopted, and after the Ag-series metal salt is added, the concentration of silver ions in the solution is 60 mM.
Preferably, the oxidant in the step (4) is sodium periodate NaIO4, and the mass ratio of the oxidant to the guar gum is 0.3: 1.
preferably, the composite pressure-sensitive adhesive prepared by the preparation method of the multifunctional nano material modified pressure-sensitive adhesive is applied as a photocatalysis, antibacterial and oil-water separating agent.
First, performance test results of the adhesive in each embodiment of the invention
Watch 1
Note: in the above table, (1) solid content:
weighing 1g of adhesive sample M according to the GB/T2793-1995 standard, accurately weighing to 0.001g, placing the adhesive sample M in a constant-weight weighed container, placing the container in a 105 ℃ blast constant-temperature oven for heating for 180min, taking out the adhesive sample, placing the adhesive sample in a dryer for cooling to room temperature, weighing the mass M2 g, and obtaining a solid content X according to the following calculation formula:
(2) initial adhesion strength: testing the initial adhesion strength according to the GB/T4852-2002 standard;
(3) and (3) permanent adhesion strength: the permanent bond strength was tested according to standard GB/T4851-1998;
(4) peel strength: according to GB/T2792-1998 standard, an electronic stripping machine is adopted to measure the 180-degree stripping strength;
(5) thermal shear strength: taking the pressure-sensitive adhesive in each embodiment, curing for 2h at 180 ℃, and testing the shear strength at 180 ℃ according to the method of GB 7124-86;
therefore, the pressure-sensitive adhesive prepared by the preparation method of the multifunctional nano material modified pressure-sensitive adhesive has the advantages of high solid content, high viscosity, easy water volatilization, convenient construction, quick solvent volatilization in a drying process and good bonding effect; the peel strength is high, the storage stability is good, and the adhesive performance is still strong after the solid content is reduced; the preparation method is simple, has low cost, and has high practical value and application prospect.
The invention and its embodiments have been described above, without this being limitative. In summary, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. The preparation method of the multifunctional nano material modified pressure-sensitive adhesive is characterized by comprising the following steps:
(1) mixing Fe-based metal powder and trimesic acid, adding 10-25 ml of deionized water, stirring, measuring 150-200 mu L hydrofluoric acid and 90-150 mu L nitric acid, dropwise adding into the solution, and magnetically stirring for 15-30 min by using a magnetic stirrer;
(2) transferring the solution prepared in the step (1) into a hydrothermal reaction kettle, adding a crystallization reagent into the hydrothermal reaction kettle, and continuously stirring for 10-20 min; then continuously reacting for 12-24 h at the temperature of 100-150 ℃; naturally cooling to room temperature after the reaction is finished, centrifuging the mixture at 4000rpm for 5min, washing the mixture for 3-6 times by using ethanol, and then performing vacuum drying at 100 ℃ for 12h to obtain a metal organic framework compound product;
(3) adding 0.5-2 g of the metal organic framework compound prepared in the step (2) into 150-300 ml of mixed solution of ethanol and water, adding Ag metal salt into the mixed solution, fully stirring, transferring the mixed solution into a quartz bottle, introducing N2 into the quartz bottle to remove air in the quartz bottle, and irradiating the quartz bottle under an ultraviolet lamp for 20-60 min; finally, washing the obtained substance in the quartz bottle with ethanol for 4-6 times, and then carrying out vacuum drying for 12 hours at 100 ℃ to obtain a final product, namely the nano silver-metal organic framework compound;
(4) and (3) putting 1-3 g of the nano silver-metal organic framework compound prepared in the step (3) into 20-60 ml of deionized water, performing ultrasonic dispersion for 30min, adding 0.33-2 g of guar gum powder, rapidly and mechanically stirring for 6-12 h, adding an oxidant to oxidize the product for self-crosslinking, and standing for 10-30 min to obtain the composite pressure-sensitive adhesive.
2. The method for preparing the multifunctional nano-material modified pressure-sensitive adhesive according to claim 1, wherein the Fe-based metal powder in the step (1) is Fe-containing metal salt, one of reduced Fe powder, ferric sulfate, ferric nitrate or ferric trichloride is adopted, and the mixing molar ratio of the Fe-based metal powder to trimesic acid is Fe: h3BTC is 0.5-2.5: 0.67 mol.
3. The method for preparing the multifunctional nano material modified pressure-sensitive adhesive according to claim 1, wherein the crystallization reagent in the step (2) is cetyl trimethyl ammonium bromide, and the molar ratio of the cetyl trimethyl ammonium bromide to the Fe element is 0.3-1.2: 1 mol.
4. The method for preparing the multifunctional nano material modified pressure-sensitive adhesive according to claim 1, wherein in the mixed solution of ethanol and water in the step (3), the volume ratio of the ethanol to the water is 1: 2; the Ag-series metal salt is a metal salt containing Ag element, one of silver nitrate and silver fluoride is adopted, and after the Ag-series metal salt is added, the concentration of silver ions in the solution is 10-80 mM.
5. The preparation method of the multifunctional nano-material modified pressure-sensitive adhesive according to claim 1, wherein the oxidant in the step (4) is sodium periodate NaIO4, and the mass ratio of the oxidant to the guar gum is 0.1-0.5: 1.
6. the preparation method of the multifunctional nano-material modified pressure-sensitive adhesive according to claim 1, wherein the composite pressure-sensitive adhesive prepared by the preparation method of the multifunctional nano-material modified pressure-sensitive adhesive is applied as a photocatalytic, antibacterial and oil-water separating agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114806497A (en) * | 2022-05-27 | 2022-07-29 | 湖南省林业科学院 | Soybean-based adhesive and preparation method and application thereof |
| CN114931146A (en) * | 2022-06-30 | 2022-08-23 | 浙江英凡新材料科技有限公司 | MOFs antibacterial material and preparation method thereof |
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| WO2011059123A1 (en) * | 2009-11-11 | 2011-05-19 | 주식회사 메디프렉스 | Heparin compound bound to adhesive material, preparation method thereof, solid surface coating agent containing same as active ingredient, and coating method of solid surface using same |
| CN110433737A (en) * | 2019-09-10 | 2019-11-12 | 陕西科技大学 | A kind of preparation method and applications of multifunctional biomass base composite hydrogel |
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