CN113278096B - White carbon black with surface grafted with poly Schiff base ionic liquid and preparation method thereof - Google Patents
White carbon black with surface grafted with poly Schiff base ionic liquid and preparation method thereof Download PDFInfo
- Publication number
- CN113278096B CN113278096B CN202110563470.9A CN202110563470A CN113278096B CN 113278096 B CN113278096 B CN 113278096B CN 202110563470 A CN202110563470 A CN 202110563470A CN 113278096 B CN113278096 B CN 113278096B
- Authority
- CN
- China
- Prior art keywords
- carbon black
- white carbon
- mass
- schiff base
- ionic liquid
- 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
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses white carbon black of a surface grafted poly-Schiff base ionic liquid and a preparation method thereof, which comprises the steps of grafting a polymer with a side chain containing a tertiary amine group on the surface of a material by a reversible addition-fragmentation chain transfer (RAFT) polymerization method, introducing a quaternary ammonium group and salicylaldehyde on the chain structure of the polymer through the quaternization reaction of the polymer and 5-chloromethyl salicylaldehyde, and finally performing a condensation reaction of an aldehyde group and an aromatic amine compound to prepare the white carbon black of the surface grafted Schiff base functionalized poly-quaternary amine base ionic liquid; the polymer/white carbon black nano composite material provided by the invention can be used for detection, identification, solid-phase extraction and enrichment separation of heavy metal ions in water.
Description
Technical Field
The invention relates to the field of high-molecular modification of inorganic nano material surfaces, in particular to white carbon black with a surface grafted with poly Schiff base ionic liquid and a preparation method thereof, and the white carbon black can be used for detection, identification, solid-phase extraction and enrichment separation of heavy metal ions in a water body.
Background
With the development of economy and industry, heavy metal wastewater is increasing day by day, causing great harm to environmental safety and human health. The adsorption method has certain advantages in the field of heavy metal wastewater treatment, and becomes the key point of water treatment research. The nano material has large specific surface area, so that the surface energy and activity of the nano material are increased, and the nano material has good adsorption performance on a plurality of inorganic pollutants in water, and therefore, the nano heavy metal adsorbent receives more and more attention. The organic chelating group with strong coordination with heavy metal ions can be further modified by utilizing the reaction sites on the surface of the nano material, and the method can further improve the adsorption performance of the nano material.
Compared with the traditional free radical polymerization, the living free radical polymerization can better realize the control of molecular structure, and is an important means for realizing molecular design and synthesizing polymers with specific structures and performances. The reversible addition-fragmentation chain transfer (RAFT) polymerization has the advantage of being capable of polymerizing monomers containing special functional groups such as carboxyl, hydroxyl and the like, and meanwhile, the RAFT polymerization temperature is low, the molecular weight distribution of the polymer is narrow, and the method is suitable for polymer grafting modification on the surface of an inorganic nano material.
The white carbon black is porous material, and its composition can be SiO2·nH2O represents, wherein nH2O exists in the form of surface hydroxyl, is high temperature resistant, non-combustible, tasteless and has good electrical insulation. The fumed silica is nano-sized silicon dioxide, the primary particle size can reach 7nm, and the fumed silica can be used as an environment-friendly, low-cost and excellent-performance auxiliary agent and is mainly used in the fields of rubber products, textiles, papermaking, pesticides and food additives. Because the action of hydroxyl on the surface of the white carbon black and heavy metal ions is weaker, if the material is used in the field of water treatment, new organic chelating groups are required to be introduced into the surface of the white carbon black to improve the adsorption capacity of the heavy metal ions.
According to the invention, a polymer containing a chelating group is grafted by adopting a RAFT polymerization method initiated by the surface of the nano white carbon black, and the polymer chain structure grafted on the surface contains a quaternary amino group and a Schiff base type chelating group. The quaternary ammonium group has strong hydrophilicity, can obviously improve the dispersibility of the nano composite material in water, and avoids the material from generating sedimentation in the water treatment process to influence the adsorption effect. The grafted Schiff base has strong chelating capacity to metal ions such as Cu (II), Co (II), Cr (III), Fe (III) and the like, generates different color or fluorescence changes while having coordination effect, and can be used for detection, identification, solid phase extraction and enrichment separation of target ions.
Disclosure of Invention
The invention provides a white carbon black nano composite material with a surface grafted with poly Schiff base ionic liquid, wherein the polymer chain structure grafted on the surface contains quaternary amino and Schiff base type chelating groups, and the general structural formula is as follows:
wherein the content of the first and second substances,
the nano-particle is white carbon black nano-particle, n is the average polymerization degree of the grafting monomer, Y is selected from O, NH, R is selected from methyl and ethyl, and Q is selected from 2-hydroxyphenyl, 2-carboxyl phenyl and 2-pyridyl.
The invention further provides a preparation method of the white carbon black nano composite material with the surface grafted with the poly Schiff base ionic liquid, which comprises the following steps:
step one, dispersing acidified fumed silica in an anhydrous organic solvent, adding S-methoxycarbonylphenyl methyl S' -trimethoxysilylpropyl trithiocarbonate, refluxing for 12 hours under the protection of nitrogen, cooling, performing suction filtration, washing with acetone, and performing vacuum drying to obtain the silica (Si-MPTT) with the surface modified chain transfer agent, wherein the reaction formula of the synthesis steps is expressed as follows:
step two, adding the Si-MPTT in the step one into an organic solvent, adding a monomer, an azodiisobutyronitrile initiator and a small amount of S-methoxycarbonylphenyl methyl S' -propyl trithiocarbonate as a micromolecular RAFT reagent to improve the polymerization controllability, vacuumizing, introducing high-purity nitrogen, repeating the operation for 3 times, controlling the temperature to be 70 ℃, heating for 24 hours, cooling by air in an open contact reaction bottle to terminate the reaction, performing suction filtration, washing by tetrahydrofuran, and performing vacuum drying to obtain the white carbon black (Si-DA) with the surface modified polymer containing the tertiary amine group, wherein the reaction formula in the synthesis step is expressed as follows:
step three, adding the Si-DA obtained in the step two into acetonitrile, adding 5-chloromethyl salicylaldehyde, stirring at room temperature for reaction for 24 hours, then performing suction filtration, washing with acetone, and performing vacuum drying to obtain the white carbon black (Si-CAS) with the surface modified polyquaternary amino groups and salicylaldehyde, wherein the reaction formula in the synthesis steps is expressed as follows:
step four, adding Si-CAS in the step three into ethanol, adding an aromatic amine compound, controlling the temperature to be 50 ℃, stirring to react for 12 hours, then performing suction filtration, washing with acetone, and performing vacuum drying to obtain the white carbon black (Si-AA) with the surface modified with polyquaternary amino and Schiff base, wherein the reaction formula in the synthesis steps is expressed as follows:
further, the organic solvent in the first step is selected from any one of acetone, ethanol, toluene, tetrahydrofuran, dioxane, acetonitrile and N, N-dimethylformamide, the volume consumption of the organic solvent is 10-50 times of the mass of the white carbon black, and the mass of the S-methoxycarbonylphenyl methyl S' -trimethoxysilylpropyl trithiocarbonate is 0.5-2 times of the mass of the white carbon black.
Further, the organic solvent in the second step is selected from any one of acetone, ethanol, toluene, tetrahydrofuran, dioxane, acetonitrile and N, N-dimethylformamide, the monomer is one of dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, N- (2-dimethylamino) -2-methacrylamide and N- (2-diethylamino) -2-methacrylamide, the volume consumption of the organic solvent is 20-40 times of the mass of the Si-MPTT, the volume of the monomer is 5-10 times of the mass of Si-MPTT, the mass of the azodiisobutyronitrile initiator is 1-3% of the mass of Si-MPTT, and the mass of the S-methoxycarbonylphenyl methyl S' -propyl trithiocarbonate is 4-8 times of the mass of the azodiisobutyronitrile initiator.
Furthermore, the volume usage amount of acetonitrile in the third step is 10-50 times of the mass of Si-DA, and the mass of 5-chloromethyl salicylaldehyde is 0.5-2 times of the mass of Si-DA.
Further, the organic solvent in the fourth step is selected from any one of acetone, ethanol, toluene, tetrahydrofuran, dioxane, acetonitrile and N, N-dimethylformamide, the aromatic amine compound is selected from any one of 2-aminophenol, 2-aminopyridine and 2-aminobenzoic acid, the volume consumption of the organic solvent is 10-50 times of the mass of the Si-CAS, and the mass of the aromatic amine compound is 0.5-2 times of the mass of the Si-CAS.
The invention has the beneficial effects that:
1. the method has the advantages that the polymer containing the chelating group is grafted by the RAFT polymerization method initiated by the surface of the nano particles, the method is simple to operate, the one-time preparation amount is relatively large, the grafting density of the surface of the polymer is high, and the adsorption performance of the white carbon black material on heavy metal ions can be remarkably improved;
2. the quaternary amine group contained in the graft polymer chain structure has strong hydrophilicity, can obviously improve the dispersibility of the nano composite material in water, and avoids the sedimentation of the material in the water treatment process to influence the adsorption effect. The grafted Schiff base has stronger chelating capacity to metal ions such as Cu (II), Co (II), Cr (III), Fe (III) and the like, generates different color or fluorescence changes while having coordination effect, and can be used for detection, identification, solid phase extraction and enrichment separation of target heavy metal ions;
3. after the white carbon black/polymer nano composite material is used, the white carbon black/polymer nano composite material can be separated and recovered in a filtering or centrifuging mode, and after metal ion desorption treatment, the regeneration and reutilization of the material can be realized, and the use cost of the material is reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a Fourier transform infrared spectrum of Si-AA1 and its intermediate product prepared in example 1.
Detailed Description
To further disclose the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
dispersing 2.0g of acidified fumed silica in 100mL of anhydrous toluene, adding 4.0g of S-methoxycarbonylphenylmethyl S' -trimethoxysilylpropyl trithiocarbonate, refluxing for 12 hours under the protection of nitrogen, cooling, performing suction filtration, washing with acetone, and performing vacuum drying to obtain the surface-modified chain transfer agent of silica Si-MPTT 1.
And (II) adding 2.0g of Si-MPTT1 in the step (I) into 80mL of N, N-dimethylformamide, adding 20mL of monomer diethylaminoethyl methacrylate, 0.020g of azodiisobutyronitrile initiator and 0.160g of S-methoxycarbonylphenyl methyl S' -propyl trithiocarbonate, vacuumizing, introducing high-purity nitrogen, repeating the operation for 3 times, controlling the temperature to heat at 70 ℃ for 24 hours, cooling by contacting air in a reaction bottle to stop the reaction, performing suction filtration, washing with tetrahydrofuran, and performing vacuum drying to obtain the white carbon black Si-DA1 with the surface modified tertiary amine group-containing polymer.
And (III) adding 2.0g of Si-DA1 obtained in the step (II) into 100mL of acetonitrile, adding 4.0g of 5-chloromethyl salicylaldehyde, stirring at room temperature, reacting for 24 hours, performing suction filtration, washing with acetone, and performing vacuum drying to obtain the white carbon black Si-CAS1 with the surface modified polyquaternary ammonium group and salicylaldehyde.
And (IV) adding 2.0g of Si-CAS1 obtained in the step (III) into 100mL of ethanol, adding 4.0g of 2-aminophenol, controlling the temperature to be 50 ℃, stirring and reacting for 12 hours, then carrying out suction filtration, washing with acetone, and carrying out vacuum drying to obtain the white carbon black Si-AA1 with the surface modified polyquaternary ammonium group and Schiff base, wherein the structural formula is as follows:
example 2:
dispersing 2.0g of acidified fumed silica in 20mL of absolute ethanol, adding 1.0g of S-methoxycarbonylphenyl methyl S' -trimethoxysilylpropyl trithiocarbonate, refluxing for 12 hours under the protection of nitrogen, cooling, performing suction filtration, washing with acetone, and performing vacuum drying to obtain the surface-modified chain transfer agent silica Si-MPTT 2.
And (II) adding 2.0g of Si-MPTT2 in the step (I) into 40mL of dioxane, adding 10mL of monomer dimethylaminoethyl methacrylate, 0.040g of azodiisobutyronitrile initiator and 0.160g of S-methoxycarbonylphenyl methyl S' -propyl trithiocarbonate, vacuumizing, introducing high-purity nitrogen, repeating the operation for 3 times, controlling the temperature to be 70 ℃ and heating for 24 hours, then cooling by contacting air in an open reaction bottle to stop the reaction, carrying out suction filtration, washing with tetrahydrofuran, and carrying out vacuum drying to obtain the white carbon black Si-DA2 with the surface modified tertiary amine group-containing polymer.
And (III) adding 2.0g of Si-DA2 obtained in the step (II) into 20mL of acetonitrile, adding 1.0g of 5-chloromethyl salicylaldehyde, stirring at room temperature for reaction for 24 hours, then carrying out suction filtration, washing with acetone, and carrying out vacuum drying to obtain the white carbon black Si-CAS2 with the surface modified polyquaternary ammonium group and salicylaldehyde.
And (IV) adding 2.0g of Si-CAS obtained in the step (III) into 20mL of ethanol, adding 1.0g of 2-aminopyridine, controlling the temperature to be 50 ℃, stirring, reacting for 12 hours, then performing suction filtration, washing with acetone, and performing vacuum drying to obtain the white carbon black Si-AA2 with the surface modified polyquaternary ammonium and Schiff base, wherein the structural formula is as follows:
example 3:
dispersing 2.0g of acidified fumed silica in 40mL of anhydrous acetonitrile, adding 2.0g of S-methoxycarbonylphenylmethyl S' -trimethoxysilylpropyl trithiocarbonate, refluxing for 12 hours under the protection of nitrogen, cooling, performing suction filtration, washing with acetone, and performing vacuum drying to obtain the surface-modified chain transfer agent of silica Si-MPTT 3.
And (II) adding 2.0g of Si-MPTT3 in the step (I) into 60mL of toluene, adding 15mL of monomer N- (2-dimethylamino) -2-methacrylamide, 0.030g of azodiisobutyronitrile initiator and 0.180g of S-methoxycarbonylphenyl methyl S-propyl trithiocarbonate, vacuumizing, introducing high-purity nitrogen, repeating the operation for 3 times, controlling the temperature to be 70 ℃ and heating for 24 hours, then cooling by contacting the open of a reaction bottle with air to stop the reaction, carrying out suction filtration, washing with tetrahydrofuran, and carrying out vacuum drying to obtain the white carbon black Si-DA3 with the surface modified with the tertiary amine group polymer.
And (III) adding 2.0g of Si-DA3 obtained in the step (II) into 50mL of acetonitrile, adding 2.0g of 5-chloromethyl salicylaldehyde, stirring at room temperature for reaction for 24 hours, then carrying out suction filtration, washing with acetone, and carrying out vacuum drying to obtain the white carbon black Si-CAS3 with the surface modified polyquaternary ammonium group and salicylaldehyde.
And (IV) adding 2.0g of Si-CAS3 obtained in the step (III) into 35mL of ethanol, adding 2.0g of 2-aminobenzoic acid, controlling the temperature to be 50 ℃, stirring for reaction for 12 hours, then carrying out suction filtration, washing with acetone, and carrying out vacuum drying to obtain the white carbon black Si-AA3 with the surface modified polyquaternary ammonium group and Schiff base, wherein the structural formula is as follows:
example 4:
Si-AA1 of example 1 and virgin white carbon SiO2In contrast (shown in FIG. 1), 2927 and 2852cm were observed in the Si-MPTT1 IR spectrum-1The wide band observed nearby belongs to the tensile vibration peak of the introduced RAFT agent and the C-H bond in the attached carbon chain. After grafting of Polydimethylaminoethyl methacrylate onto the surface of the Material Using surface initiated RAFT polymerisation, the Si-DA IR spectrum was 1731cm-1A strong stretching vibration peak of the monomeric ester carbonyl group appears. Quaternization with 5-chloromethyl salicylaldehyde to 1659cm-1A new peak appears nearby due to stretching vibration of the introduced aldehyde group. When reacted with aminophenol, at 1659cm-1The peak at 1625cm disappeared-1A new peak appeared due to the tensile vibration of the formed schiff base imine bond, and from these results, it can be concluded that the white carbon black Si-AA1 of example 1, on which the poly schiff base ionic liquid was surface-grafted, was successfully prepared.
Example 5:
the Si-AA1 multifunctional nanocomposite prepared in example 1 was used as an experimental sample to study the influence of the pH of different heavy metal ion solutions on the adsorption capacity of the Si-AA1 multifunctional nanocomposite.
400.00mg/L of aqueous solution of copper sulfate, cobalt nitrate and chromium nitrate is prepared, and the pH value of the solution is adjusted to 2.0, 3.0, 4.0, 5.0 and 6.0 for standby by respectively using 20 mass percent of nitric acid and 30 mass percent of sodium acetate aqueous solution. Since ferric nitrate is susceptible to hydrolysis under non-strong acid conditions, the pH of 400.00mg/L ferric nitrate solution was adjusted to 3.0 for use. 0.0500g of a plurality of parts of Si-AA1 are accurately weighed and placed in a 250mL conical flask, 50mL of metal ion solutions with different pH values and the concentration of 400mg/L are respectively added, the sample is oscillated for 2 hours under the conditions of constant temperature of 25 ℃ and oscillation speed of 120rpm, the concentration of the metal ions in the dispersion liquid is detected, the adsorption capacity is calculated, and the result is shown in Table 1.
TABLE 1 relationship between pH and metal ion adsorption capacity of Si-AA1 multifunctional nanocomposite
Preparing 20.00mg/L aqueous solution of copper sulfate, cobalt nitrate and chromium nitrate, and adjusting the pH value of the solution to 6.0 for later use. Preparing 20.00mg/L ferric nitrate solution, and only adjusting the pH value to 3.0 for later use. 5.0mL of an aqueous dispersion of Si-AA1 having a mass concentration of 4.0mg/L was mixed with 5.0mL of the previously prepared metal ion solution, and the mixture was ultrasonically treated for 1 minute to complete adsorption and coordination, and the change in color and fluorescence was observed, and the results are shown in Table 2.
TABLE 2 color and fluorescence change of Si-AA1 multifunctional nanocomposites with metal ions
The result shows that the Si-AA1 multifunctional nano composite material can be used for heavy metal ion detection, identification, solid phase extraction and enrichment separation in water.
Claims (6)
1. The surface grafted white carbon black with poly Schiff base ionic liquid has polymer chain structure comprising quaternary amino group and Schiff base type chelating group and general structural formula:
wherein the content of the first and second substances,
refers to white carbon black nano particles, n is the average polymerization degree of the grafting monomer,y is any one of O, NH, R is any one of methyl and ethyl, and Q is any one of 2-hydroxyphenyl, 2-carboxyphenyl and 2-pyridyl.
2. The preparation method of the white carbon black with the surface grafted with the poly-schiff base ionic liquid according to claim 1, which is characterized by comprising the following specific preparation steps:
step one, dispersing acidified fumed silica in an anhydrous organic solvent, adding S-methoxycarbonylphenyl methyl-S' -trimethoxysilylpropyl trithiocarbonate, refluxing for 12 hours under the protection of nitrogen, cooling, performing suction filtration, washing with acetone, and performing vacuum drying to obtain the silica with the surface modified chain transfer agent, which is named as Si-MPTT, wherein the reaction formula of the synthesis steps is expressed as follows:
step two, adding the Si-MPTT in the step one into an organic solvent, adding a monomer, an azodiisobutyronitrile initiator and a small amount of S-methoxycarbonylphenyl methyl-S' -propyl trithiocarbonate as a micromolecular RAFT reagent to improve the polymerization controllability, vacuumizing, introducing high-purity nitrogen, repeating the operation for 3 times, controlling the temperature to be 70 ℃, heating for 24 hours, cooling by air in an open contact reaction bottle to terminate the reaction, performing suction filtration, washing by tetrahydrofuran, and performing vacuum drying to obtain the white carbon black with the surface modified polymer containing the tertiary amine group, wherein the reaction formula in the synthesis step is expressed as follows:
step three, adding the Si-DA in the step two into acetonitrile, adding 5-chloromethyl salicylaldehyde, stirring at room temperature, reacting for 24 hours, performing suction filtration, washing with acetone, and performing vacuum drying to obtain the white carbon black with the surface modified with quaternary ammonium and salicylaldehyde, which is named as Si-CAS, wherein the reaction formula in the synthesis step is expressed as follows:
step four, adding Si-CAS in the step three into ethanol, adding an amine compound, wherein the amine compound is selected from any one of 2-aminophenol, 2-aminopyridine and 2-aminobenzoic acid, controlling the temperature to be 50 ℃, stirring for reaction for 12 hours, then performing suction filtration, washing with acetone, and performing vacuum drying to obtain white carbon black with a surface modified with a quaternary ammonium group and Schiff base, which is named as Si-AA, and the reaction formula in the synthesis step is expressed as follows:
3. the preparation method of the white carbon black with the surface grafted with the poly-schiff base ionic liquid according to claim 2, which is characterized by comprising the following steps: the organic solvent in the first step is selected from any one of acetone, ethanol, toluene, tetrahydrofuran, dioxane, acetonitrile and N, N-dimethylformamide, the volume consumption of the organic solvent is 10-50 times of the mass of the white carbon black, and the mass of the S-methoxycarbonylphenyl methyl-S' -trimethoxysilylpropyl trithiocarbonate is 0.5-2 times of the mass of the white carbon black.
4. The preparation method of the white carbon black with the surface grafted with the poly-schiff base ionic liquid according to claim 2, which is characterized by comprising the following steps: the organic solvent in the second step is selected from any one of acetone, ethanol, toluene, tetrahydrofuran, dioxane, acetonitrile and N, N-dimethylformamide, the monomer is any one of dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, N- (2-dimethylamino) -2-methacrylamide and N- (2-diethylamino) -2-methacrylamide, the volume consumption of the organic solvent is 20-40 times of the mass of the Si-MPTT, the volume of the monomer is 5-10 times of the mass of Si-MPTT, the mass of the azodiisobutyronitrile initiator is 1-3% of the mass of Si-MPTT, and the mass of the S-methoxycarbonylphenyl methyl-S' -propyl trithiocarbonate is 4-8 times of the mass of the azodiisobutyronitrile initiator.
5. The preparation method of the white carbon black with the surface grafted with the poly-schiff base ionic liquid according to claim 2, which is characterized by comprising the following steps: the volume usage amount of acetonitrile in the third step is 10-50 times of the mass of Si-DA, and the mass of 5-chloromethyl salicylaldehyde is 0.5-2 times of the mass of Si-DA.
6. The preparation method of the white carbon black with the surface grafted with the poly-schiff base ionic liquid according to claim 2, which is characterized by comprising the following steps: the volume consumption of the ethanol is 10-50 times of the mass of the Si-CAS, and the mass of the amine compound is 0.5-2 times of the mass of the Si-CAS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110563470.9A CN113278096B (en) | 2021-05-24 | 2021-05-24 | White carbon black with surface grafted with poly Schiff base ionic liquid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110563470.9A CN113278096B (en) | 2021-05-24 | 2021-05-24 | White carbon black with surface grafted with poly Schiff base ionic liquid and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113278096A CN113278096A (en) | 2021-08-20 |
| CN113278096B true CN113278096B (en) | 2022-06-03 |
Family
ID=77280963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110563470.9A Active CN113278096B (en) | 2021-05-24 | 2021-05-24 | White carbon black with surface grafted with poly Schiff base ionic liquid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113278096B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114574004B (en) * | 2022-01-22 | 2022-12-27 | 德欣精细化工(深圳)有限公司 | Preparation method of carbon black nano material |
| CN115672261B (en) * | 2022-10-31 | 2024-02-20 | 江苏海洋大学 | Sulfhydryl Schiff base side group-containing polymer modified attapulgite and preparation method thereof |
| CN115725122B (en) * | 2023-01-05 | 2024-04-19 | 浙江工业大学 | Carbon black rubber composite material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417559A (en) * | 2011-09-07 | 2012-04-18 | 淮海工学院 | Acrylic acid ester copolymer porous resin ball containing quaternary ammonium group and salicylaldehyde and preparation method thereof |
| CN102504061A (en) * | 2011-10-14 | 2012-06-20 | 淮海工学院 | Super chelating ion exchange resin |
| CN109589418A (en) * | 2018-12-14 | 2019-04-09 | 华南理工大学 | A kind of mesoporous silicon oxide medicine-carried nano particles and its preparation method and application of the schiff bases copolymer cladding with pH responsiveness |
| CN111285897A (en) * | 2020-03-03 | 2020-06-16 | 江苏海洋大学 | Mesoporous silicon fluorescent probe for copper ion detection and separation and preparation method thereof |
-
2021
- 2021-05-24 CN CN202110563470.9A patent/CN113278096B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417559A (en) * | 2011-09-07 | 2012-04-18 | 淮海工学院 | Acrylic acid ester copolymer porous resin ball containing quaternary ammonium group and salicylaldehyde and preparation method thereof |
| CN102504061A (en) * | 2011-10-14 | 2012-06-20 | 淮海工学院 | Super chelating ion exchange resin |
| CN109589418A (en) * | 2018-12-14 | 2019-04-09 | 华南理工大学 | A kind of mesoporous silicon oxide medicine-carried nano particles and its preparation method and application of the schiff bases copolymer cladding with pH responsiveness |
| CN111285897A (en) * | 2020-03-03 | 2020-06-16 | 江苏海洋大学 | Mesoporous silicon fluorescent probe for copper ion detection and separation and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Liping Luan等.Removal of aqueous Zn(II) and Ni(II) by Schiff base functionalized PAMAM dendrimer/silica hybrid materials.《Journal of Molecular Liquids》.2021,第1-9页. * |
| M.A. Betiha等.Polyvinylpyrrolidone-Aminopropyl-SBA-15 schiff Base hybrid for efficient removal of divalent heavy metal cations from wastewater.《Journal of Hazardous Materials》.2020,第1-13页. * |
| Tengteng Hou等.Synthesis of well-defined polymers grafted onto fumed silica by chain exchange reaction and highly pure block copolymers thereby.《Chem. Commun.》.2010,第7397-7399页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113278096A (en) | 2021-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113278096B (en) | White carbon black with surface grafted with poly Schiff base ionic liquid and preparation method thereof | |
| Sruthi et al. | An overview of synthetic modification of nitrile group in polymers and applications | |
| Chauhan et al. | Synthesis, characterization and metal ion sorption studies of graft copolymers of cellulose with glycidyl methacrylate and some comonomers | |
| GB2590792A (en) | Method for preparing amidoxime functionalized hollow porous polymer microsphere by using CO2 as emulsion template | |
| CA3082668C (en) | Plant fiber-based intelligent adsorptive material with multi-adsorption sites and preparation method and use thereof | |
| CN111573802B (en) | Hydrophobic modified organic/inorganic composite flocculant and preparation method and application thereof | |
| CN112760086B (en) | Modified filtrate reducer for petroleum drilling fluid | |
| CN112774641A (en) | Preparation method of carboxyl modified magnetic starch-based adsorption material | |
| Su et al. | Separation of bovine hemoglobin using novel magnetic molecular imprinted nanoparticles | |
| Feng et al. | The investigation of the specific behavior of a cationic block structure and its excellent flocculation performance in high-turbidity water treatment | |
| CN111514867A (en) | Polyethyleneimine grafted nano Fe3O4-graphene adsorption material and preparation method thereof | |
| Mohamadnia et al. | Preparation of smart brush-type cation-exchange adsorbents grafted nanosurface via SI-ATRP for dye removal | |
| CN107555569B (en) | Preparation method and application of multi-group magnetic coagulant | |
| Hosseinzadeh et al. | Fast and enhanced removal of mercury from aqueous solutions by magnetic starch-g-poly (acryl amide)/graphene oxide nanocomposite superabsorbents | |
| Liu et al. | Post-synthetic functionalization of UiO-66-NH2 by polyacrylamide and polyvinylimidazolium salt brushes via ATRP and adsorption behavior | |
| CN110982022B (en) | Magnetic capsaicin molecularly imprinted polymer and preparation method thereof | |
| CN109650602B (en) | Method for removing antimony ions in water body by using magnetic adsorption material | |
| CN109999677B (en) | Gradient functional organic-inorganic hybrid membrane for deep water treatment and preparation method thereof | |
| Adeyi et al. | Hydrophilic thiourea-modified poly (acrylonitrile-co-acrylic acid) adsorbent: preparation, characterization, and dye removal performance | |
| CN110683567A (en) | Preparation method of submicron magnesium hydroxide | |
| Lin et al. | Cellulose functionalization via ATRP grafting of glycidyl methacrylate for Cr (VI) adsorption | |
| Salih et al. | Removal of cadmium (11) ions by using Alkali Blue 6B attached poly (EGDMA-HEMA) microspheres | |
| CN109201015B (en) | Surface imprinting Fe3+ potassium tetratitanate whisker adsorbent and preparation method thereof | |
| CN113145077A (en) | Epoxy modified starch baseFe3O4Method for preparing adsorbent material | |
| CN114130364A (en) | Efficient and safe method for adsorbing and degrading tetracycline by using mixed metal organic framework material |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221104 Address after: 223800 West of 1st Floor, Building 4, New Materials Science and Technology City, Suqian Hi tech Industrial Development Zone, Suqian, Jiangsu Province Patentee after: SUQIAN LEILI ENVIRONMENTAL PROTECTION TECHNOLOGY CO.,LTD. Address before: No.59 Cangwu Road, Haizhou District, Lianyungang City, Jiangsu Province 222000 Patentee before: Jiangsu Ocean University |
|
| TR01 | Transfer of patent right |