WO2018192239A1 - 一种改性棉纤维及制备方法与应用 - Google Patents
一种改性棉纤维及制备方法与应用 Download PDFInfo
- Publication number
- WO2018192239A1 WO2018192239A1 PCT/CN2017/115318 CN2017115318W WO2018192239A1 WO 2018192239 A1 WO2018192239 A1 WO 2018192239A1 CN 2017115318 W CN2017115318 W CN 2017115318W WO 2018192239 A1 WO2018192239 A1 WO 2018192239A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cotton fiber
- pgma
- psmp
- reaction
- deta
- Prior art date
Links
Images
Classifications
-
- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/332—Di- or polyamines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
- D06M14/04—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Definitions
- the invention relates to the field of water treatment materials, in particular to a modified cotton fiber and a preparation method and application thereof.
- Heavy metals are difficult to degrade and have enrichment. Heavy metal pollutants emitted in production activities such as mining and smelting enter the atmosphere and water resources, causing atmospheric and water pollution, and entering the human body through the food chain, in some organs of the human body. Enrichment can cause acute or chronic poisoning in humans, and it is carcinogenic, teratogenic and mutagenic.
- cadmium As one of the heavy metals, cadmium accumulates in the human body, causing damage to important organs such as kidney, bone, liver, central and lung. Since the discovery of cadmium in the early 20th century, the production of cadmium has increased year by year. Cadmium is widely used in the electroplating industry, chemical industry, electronics industry and nuclear industry. Cadmium is a by-product of the zinc smelting industry and is mainly used in batteries, dyes or plastic stabilizers. It is more easily adsorbed by crops than other heavy metals. A considerable amount of cadmium is discharged into the environment through waste gas, waste water and waste residue, causing pollution. Therefore, the removal of heavy metal cadmium ions is very necessary.
- Methods for detecting cadmium ions in a solution include visible spectrophotometry, atomic absorption spectrometry, electrochemical analysis, fluorescence spectroscopy, and inductively coupled plasma mass spectrometry.
- visible spectrophotometry atomic absorption spectrometry
- electrochemical analysis fluorescence spectroscopy
- inductively coupled plasma mass spectrometry a method for detecting cadmium ions in a solution.
- most of these methods require a complicated sample preparation process, and the equipment has a large footprint and high detection cost, which is not suitable for on-site inspection.
- Cadmium-containing wastewater is a kind of wastewater that is very polluting to the environment and is very harmful to human health.
- treatment methods for cadmium-containing wastewater such as neutralization precipitation method, sulfide precipitation method, adsorption method, membrane separation method, electrolysis method, etc., but the treatment cost is high, the control conditions are many, the actual operation is difficult, and it will be produced. Secondary pollution.
- the “13th Five-Year Plan” eco-environment planning clearly pointed out that strengthening green technology innovation leads the way, promotes the deep integration of greenization and innovation, and implements water environment quality target management based on control units.
- New wastewater treatment methods that are cheap, efficient, stable, and free of secondary pollution have gradually attracted people's attention.
- the new material adsorption method retains the physical properties of raw materials, and is coated by chemical modification methods such as coating and grafting polymer chains. By giving it more features and making the material multifunctional, it is considered to be a promising alternative.
- the natural polymer and its derivative adsorbent have the advantages of economical, wide source, easy biodegradation, easy recycling, and easy preparation, and thus have attracted much attention and application.
- cellulose is a natural polymer material with high utilization rate.
- Cellulose is the most abundant polymer material. Cotton, wood, straw, bamboo, etc. are all sources of cellulosic materials.
- cellulose is a polysaccharide formed by linking ( ⁇ )- ⁇ -glycosidic bonds between ⁇ -D-glucopyranose.
- ⁇ - ⁇ -glycosidic bonds between ⁇ -D-glucopyranose There are a large number of hydroxyl groups, and various chemical reactions, including grafting and esterification, can occur. , oxidation and other reactions, through which the cellulose can be chemically modified to add corresponding functional groups.
- the natural product cotton fiber contains a large number of groups such as hydroxyl groups and oxime bonds, which can undergo degradation, esterification, etherification and other reactions, and produce many valuable cotton fiber derivatives.
- the cotton fiber is functionalized by chemical modification and applied to the adsorption and detection of water weight metal.
- the aminated modified cotton fiber adsorbs Cd 2+ and creates a spectrometer Cd 2+ concentration detection method through color reaction. No relevant reports have been reported.
- the object of the present invention is to provide an aminated modified cotton fiber to adsorb Cd 2+ and to create a spectrometer Cd 2+ concentration detection method by color reaction, so as to solve the existing detection methods, most of which require a complicated sample preparation process, equipment and equipment. It has a large area and high testing cost, and is not suitable for on-site inspection.
- the existing treatment methods have high processing costs, many control conditions, practical operation difficulties, and secondary pollution problems.
- the object of the present invention is to provide a modified cotton fiber, a preparation method and an application thereof, and aim to solve the problem that most of the existing detection methods require a complicated sample preparation process, and the equipment has a large area and a detection cost.
- High, not suitable for on-site inspection; and existing treatment methods have high processing costs, many control conditions, practical operation difficulties, and secondary pollution problems.
- a method for preparing a modified cotton fiber which comprises:
- Step A cotton fiber and 2-bromoisobutyryl bromide are reacted at room temperature for 12-48 h to obtain brominated cotton;
- Step B bromide cotton and GMA are reacted at 40-50 ° C for 1-4 h to obtain cotton fiber-PGMA (cotton fiber grafted with PGMA);
- Step C cotton fiber-PGMA and SMP are reacted in an inert atmosphere for 6-24h to obtain cotton fiber-PGMA-PSMP (cotton fiber grafted with PGMA and PSMP in sequence);
- Step D cotton fiber-PGMA-PSMP and DETA are reacted at room temperature for 12-48h to obtain cotton fiber-PGMA(DETA)-PSMP (sequentially grafted aminated PGMA polymer chain and PSMP cotton fiber);
- Step E Cotton fiber-PGMA (DETA)-PSMP and TMPyP are reacted at room temperature for 6-24h to obtain cotton fiber-PGMA(DETA)-PSMP-TMPyP (sequentially grafted aminated PGMA polymer chain and porphyrinated PSMP high) Molecular chain of cotton fiber).
- the preparation method of the modified cotton fiber wherein the reaction solvent of the step A is dichloromethane, and the reaction catalyst is pyridine.
- the method for preparing the modified cotton fiber wherein the reaction condition of the step A further comprises: sealing and placing the reaction under magnetic stirring.
- the preparation method of the modified cotton fiber wherein the reaction solvent of the step B is a mixture of deionized water and dimethylformamide, and the reaction catalyst is 2,2-bipyridine (Bpy), CuBr and CuBr. 2 .
- the method for preparing a modified cotton fiber wherein the mass ratio of the CuBr to CuBr 2 is 1-5:1.
- reaction solvent of the step C is a mixed solution of deionized water and methanol, and the reaction catalyst is CuBr and Bpy.
- the method for preparing a modified cotton fiber wherein the reaction solvent of the step D is tetrahydrofuran.
- the method for preparing a modified cotton fiber wherein in the step E, the mass ratio of the cotton fiber-PGMA (DETA)-PSMP and TMPyP is 1-5:1.
- the invention has the beneficial effects that the cotton fiber of the raw material of the invention is cheap and easy to obtain, and a large amount of hydroxyl groups are present on the surface, and various chemical reactions can occur, which is convenient for modification.
- chemical modification method Through chemical modification method, the multi-functionalization of cotton fiber is realized, and its detection and adsorption performance are imparted.
- the chemical modification of cotton fiber by SI-ATRP method and acyclic polyamine amination is simple and easy to control.
- the CPDPT material prepared by the invention has short response time to cadmium ions, and the color change is fast and obvious, and can be used for rapid detection of cadmium ions; after block polymerization, the PGMA segment is introduced.
- the amine group increases the adsorption of cadmium ions by CPDPT materials.
- Figure 1 is a schematic view showing the preparation process of the modified cotton fiber of the present invention.
- Example 2 is a graph showing the results of adsorption test of the modified cotton fiber material prepared in Example 1 of the present invention.
- the present invention provides a modified cotton fiber, a preparation method and an application thereof, and the present invention will be further described in detail below in order to make the objects, technical solutions and effects of the present invention more clear and clear. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
- a method for preparing a modified cotton fiber of the present invention comprises:
- Step A cotton fiber and 2-bromoisobutyryl bromide are reacted at room temperature for 12-48 h to obtain brominated cotton.
- the step A is specifically as follows:
- the cotton fiber of the raw material selected by the invention is cheap and easy to obtain, and a large amount of hydroxyl groups are present on the surface, and various chemical reactions can occur, which is convenient for modification.
- cotton fiber with rich content and easy modification is used as the adsorbent matrix, and substituted with 2-bromoisobutyryl bromide (BIBB) to obtain brominated cotton (cotton fiber-Br).
- BIBB 2-bromoisobutyryl bromide
- Step B brominated cotton and GMA are reacted at 40-50 ° C for 1-4 h to obtain cotton fiber-PGMA.
- the step B is specifically as follows:
- SI-ATRP reaction Place cotton fiber-Br in a container, then add 1-15 mL of deionized water, 5-20 mL of dimethylformamide (DMF), 10-30 mL of glycidyl methacrylate (GMA), 0.1 -1.0 g of 2,2-bipyridyl (Bpy), CuBr and CuBr 2 , wherein the mass ratio of CuBr to CuBr 2 is 1-5:1 (eg 1:1, 2:1 or 5:1), under magnetic stirring, The stirring speed is 150 rpm, and the reaction is carried out at 40-50 ° C (such as 45 ° C) and argon atmosphere for 1-4 h. After the reaction is completed, cotton fiber-PGMA is obtained, and then washed with tetrahydrofuran (THF), acetone and deionized water, and dried. Dry spare.
- DMF dimethylformamide
- GMA glycidyl methacrylate
- Bpy 2,2-bipyridyl
- Deionized water and dimethylformamide in the above steps are used as a reaction solvent, and Bpy, CuBr and CuBr 2 are used as reaction catalysts, and the reaction catalyst is advantageous for increasing the reaction rate.
- the surface-initiated-atomic transfer radical polymerization (SI-ATRP) method is used to graft the PGMA polymer segment, which is simple and easy, requires less monomer, allows certain oxygen and impurities to exist during the reaction, and can control the activity.
- SI-ATRP surface-initiated-atomic transfer radical polymerization
- the molecular weight of the polymerization and its distribution coefficient do not destroy the skeletal structure of the cellulose.
- Step C cotton fiber-PGMA and SMP were reacted in an inert atmosphere for 6-24 h to obtain cotton fiber-PGMA-PSMP.
- the step C is specifically as follows:
- SI-ATRP reaction dissolve 0.01-0.10g cotton fiber-PGMA, 0.05-0.2g Bpy, 0.01-0.20g CuBr and 1-5g 3-sulfonic acid propyl methacrylate potassium salt (SMP) in 1-5mL In a mixed solution of ionized water and 4-45 mL of methanol, and stirring under magnetic stirring, the stirring speed was 150 rpm, and the reaction was carried out for 6-24 hours in an argon atmosphere. After completion of the reaction, cotton fiber-PGMA-PSMP was obtained. The product was repeatedly washed with an excess of 0.05-0.2 mol/L EDTA (ethylenediaminetetraacetic acid) solution, deionized water, and air-dried for use.
- EDTA ethylenediaminetetraacetic acid
- the PSMP segment helps to further introduce TMPyP and increase the number of TMPyP imports. Thereby increasing the complexation with Cd 2+ to adsorb and remove Cd 2+ from the sewage.
- the catalyst system used in this step is Bpy and CuBr, which can control the reaction rate well.
- this step is also grafted by the SI-ATRP method, and the advantages are not described again.
- Step D cotton fiber-PGMA-PSMP and DETA were reacted at room temperature for 12-48 h to obtain cotton fiber-PGMA(DETA)-PSMP.
- the step D is specifically as follows:
- Amination reaction Take cotton fiber-PGMA-PSMP in a test tube, add 1-15 mL of tetrahydrofuran (THF) and 1-15 mL of diethylenetriamine (DETA), stir using a magnetic stirrer, rotate at 150 rpm, and react at room temperature. After -48 h, cotton fiber-PGMA (DETA)-PSMP was obtained, and cotton fiber-PGMA (DETA)-PSMP was taken out, washed with acetone and deionized water, and air-dried for use.
- THF tetrahydrofuran
- DETA diethylenetriamine
- DETA is grafted onto PGMA by ring-opening reaction, which greatly increases the adsorption amount of Cd 2+ on the final modified cotton fiber.
- DETA is introduced by a ring opening reaction of an amine group with an epoxy group on cotton fiber-PGMA.
- the chemical modification of cotton fibers can be carried out by replacing the acyclic polyamine compound, such as ethylenediamine, triethylenetetramine, tetraethylenepentamine or other polyethene polyamine compounds. Sex, from A similar aminated cotton material was prepared.
- Step E Cotton fiber-PGMA (DETA)-PSMP and TMPyP were reacted at room temperature for 6-24 h to obtain cotton fiber-PGMA(DETA)-PSMP-TMPyP.
- the step E is specifically as follows:
- Electrostatic composite reaction immerse cotton fiber-PGMA(DETA)-PSMP in 10-20mg/L 5,10,15,20-four (1-A) by mass ratio of 1-5:1
- TMPyP 4-pyridyl)porphyrin tetrakis(p-toluenesulfonate)
- CPDPT modified cotton fiber cotton fiber-PGMA (DETA)-PSMP-TMPyP
- TMPyP 5,10,15,20-tetrakis(1-methyl-4-pyridyl)porphyrin tetra(p-toluenesulfonate)
- TMPyP 5,10,15,20-tetrakis(1-methyl-4-pyridyl)porphyrin tetra(p-toluenesulfonate)
- a cotton fiber-PGMA (DETA)-PSMP-TMPyP modified cotton fiber material was obtained.
- TMPyP can adsorb cadmium ions in a large amount, and the color gradually becomes shallower and deeper. Therefore, TMPyP has both cadmium ion detection and adsorption.
- This step introduces TMPyP on the surface of the material by electrostatic interaction of the positively charged TMPyP with the negatively charged PSMP.
- TMPyP other porphyrins such as 5,10,15,20-tetrakis(3,5-dimethoxyphenyl)porphyrin, 5,10,15,20-tetrakis(4-amino) can be introduced. Phenyl)porphyrins, etc., are modified to produce similar aminated cotton materials.
- the prepared modified cotton fiber CPDPT material was subjected to adsorption experiment.
- the method for measuring the adsorption amount was as follows: 50 mg of modified cotton fiber CPDPT was added to 50 ml of 4 mmol/l Cd(NO 3 ) 2 solution, and protected from light at room temperature. After shaking to the adsorption equilibrium, the concentration of cadmium ions in the solution was measured and the color development of the material was observed. Calculate the amount of adsorption of CPDPT material according to the following formula:
- C 0 and C e are the original solution concentration and adsorption equilibrium concentration (mmol/L) of cadmium ions
- V is the volume (L) of the adsorption solution
- m is the mass of the adsorbent CPDPT.
- the invention utilizes cotton fiber with rich content and easy modification as the adsorbent matrix, and replaces with 2-bromoisobutyryl bromide (BIBB) to obtain brominated cotton (Coton-Br), and then utilizes convenient and controllable surface initiation- Atomic Transfer Radical Polymerization (SI-ATRP) technology grafted polyglycidyl methacrylate (PGMA) polymer brush on the surface of brominated cotton material, and continued to use G-ATRP technology to graft a bunch of polymer behind PGMA polymer brush.
- SI-ATRP surface initiation- Atomic Transfer Radical Polymerization
- PGMA polyglycidyl methacrylate
- PSMP 3-sulfonic acid propyl methacrylate potassium salt
- DETA diethylenetriamine
- TMPyP Adsorbed 5,10,15,20-tetrakis(1-methyl-4-pyridyl)porphyrin tetra(p-toluenesulfonate)
- the modified cotton fiber material obtained by the invention adsorbs Cd 2+ color reaction to establish a linear relationship between Cd 2+ concentration and color development absorbance, and the amine group introduced on the PGMA segment increases the adsorption of cadmium ions by CPDPT material.
- the amount of CPDPT can be successfully applied to the detection and adsorption of Cd 2+ in water.
- the present invention has the following advantages:
- the surface of cotton fiber is rich in hydroxyl, easy to modify graft
- CPDPT material has a short response time to cadmium ions, color change is fast and obvious, and can be used for rapid detection of cadmium ions;
- the amine group introduced on the PGMA segment increases the adsorption amount of CPDPT material to cadmium ions.
- bromination reaction Take 1g cotton fiber and 30mL DCM into the container, then place the container in the ice water bath, then take 10mL BIBB into the container, then slowly add 1mL of pyridine, seal the container after the addition, and set In a magnetic stirrer, the stirring speed is 150 rpm, and the reaction is carried out at room temperature for 20 hours. After the reaction is completed, the cotton fiber-Br is obtained, the cotton fiber-Br is taken out, repeatedly washed with acetone and deionized water, finally dried, and stored in a drying oven. ,spare.
- SI-ATRP reaction take 0.05g cotton fiber-PGMA, 0.1g Bpy, 0.05g CuBr and 1g SMP dissolved in the mixed solution (2mL deionized water and 8mL methanol), magnetic stirring, stirring speed is 150rpm After reacting for 12 hours, the cotton fiber-PGMA-PSMP was obtained after the reaction was completed, and repeatedly washed with an excess of 0.1 mol/L EDTA (ethylenediaminetetraacetic acid) solution, deionized water, and dried for use.
- EDTA ethylenediaminetetraacetic acid
- the prepared modified cotton fiber material (CPDPT) was used as the adsorption experiment.
- the method for measuring the adsorption amount was as follows: 50 mg of CPDPT was added to 50 ml of 4 mmol/L Cd(NO 3 ) 2 solution, and shaken at room temperature until adsorption. After equilibration, the concentration of cadmium ions in the solution was measured and the color development of the material was observed. Calculate the amount of adsorption (q) of CPDPT material according to the following formula:
- C 0 and C e are the original solution concentration and adsorption equilibrium concentration (mmol/L) of cadmium ion, respectively;
- V is the volume (L) of the adsorption solution
- m is the mass of the adsorbent CPDPT.
- the CPDPT material prepared by the method has a cadmium ion adsorption capacity of 141.12 mg/g, which is very suitable for treating sewage containing cadmium ions.
- bromination reaction take 0.8g cotton fiber and 20mL DCM into the container, then place the container in the ice water bath, then take 8mL BIBB into the container, then slowly add 0.8mL of pyridine, after sealing, seal the container The mixture was placed in a magnetic stirrer at a stirring speed of 150 rpm and reacted at room temperature for 20 hours. After completion of the reaction, cotton fiber-Br was obtained, cotton fiber-Br was taken out, repeatedly washed with acetone and deionized water, finally dried, and stored in Dry box, spare.
- SI-ATRP reaction Take 0.05g cotton fiber-PGMA, 0.08g Bpy, 0.08g CuBr and 1.5g SMP dissolved in mixed solution (2mL deionized water and 10mL methanol), stir under magnetic stirring After 150 rpm, the reaction was carried out for 10 h. After completion of the reaction, cotton fiber-PGMA-PSMP was obtained, which was repeatedly washed with an excess of 0.1 mol/L EDTA (ethylenediaminetetraacetic acid) solution, deionized water, and dried for use.
- EDTA ethylenediaminetetraacetic acid
- the present invention provides a modified cotton fiber, a preparation method and application thereof, and the invention utilizes a cotton fiber with rich content and easy modification as a adsorbent matrix, and occurs with 2-bromoisobutyryl bromide (BIBB).
- BIBB 2-bromoisobutyryl bromide
- Substitution reaction to obtain brominated cotton (cotton fiber-Br) and then grafting polyglycidyl methacrylate (PGMA) on the surface of brominated cotton material by a convenient and controllable surface initiation-atomic transfer radical polymerization (SI-ATRP) technique.
- SI-ATRP surface initiation-atomic transfer radical polymerization
- the modified cotton fiber material obtained by the invention exhibits rapid color development for Cd 2+ and can reach 90% of saturated adsorption amount within 10 min, which is suitable for on-site detection; the adsorption capacity of Cd 2+ reaches 141.12 mg/g, adsorption High efficiency, simple operation, suitable for treating cadmium-containing sewage; and the raw material cotton fiber used is cheap and easy to obtain, and the SI-ATRP method adopted by the invention is simple and easy to control, and the obtained product is clean and pollution-free, and the prior art is solved.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
Claims (10)
- 一种改性棉纤维的制备方法,其特征在于,包括:步骤A、棉纤维和2-溴异丁酰溴室温下反应12-48h,得到溴化棉;步骤B、溴化棉和GMA在40-50℃下反应1-4h,得到棉纤维-PGMA;步骤C、棉纤维-PGMA和SMP惰性气氛下反应6-24h,得到棉纤维-PGMA-PSMP;步骤D、棉纤维-PGMA-PSMP和DETA室温下反应12-48h,得到棉纤维-PGMA(DETA)-PSMP;步骤E、将棉纤维-PGMA(DETA)-PSMP和TMPyP室温下反应6-24h,得到棉纤维-PGMA(DETA)-PSMP-TMPyP。
- 根据权利要求1所述的改性棉纤维的制备方法,其特征在于,所述步骤A的反应溶剂为二氯甲烷,反应催化剂为吡啶。
- 根据权利要求1所述的改性棉纤维的制备方法,其特征在于,所述步骤A的反应条件还包括:密闭,并置于磁力搅拌下进行反应。
- 根据权利要求1所述的改性棉纤维的制备方法,其特征在于,所述步骤B的反应溶剂为去离子水和二甲基甲酰胺的混合液,反应催化剂为2,2-联吡啶、CuBr和CuBr2。
- 根据权利要求4所述的改性棉纤维的制备方法,其特征在于,所述CuBr和CuBr2的质量比为1-5:1。
- 根据权利要求1所述的改性棉纤维的制备方法,其特征在于,所述步骤C的反应溶剂为去离子水和甲醇的混合液,反应催化剂为CuBr和Bpy。
- 根据权利要求1所述的改性棉纤维的制备方法,其特征在于,所述步骤D的反应溶剂为四氢呋喃。
- 根据权利要求1所述的改性棉纤维的制备方法,其特征在于,所述步骤E中,所述棉纤维-PGMA(DETA)-PSMP和TMPyP的质量比为1-5:1。
- 一种改性棉纤维,其特征在于,采用如权利要求1~8任一所述的制备方法制备而成。
- 一种改性棉纤维的应用,其特征在于,将如权利要求9所述的改性棉纤维应用于检测和吸附镉离子。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710249925.3 | 2017-04-17 | ||
CN201710249925.3A CN107099999B (zh) | 2017-04-17 | 2017-04-17 | 一种改性棉纤维及制备方法与应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018192239A1 true WO2018192239A1 (zh) | 2018-10-25 |
Family
ID=59656288
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2017/115318 WO2018192239A1 (zh) | 2017-04-17 | 2017-12-08 | 一种改性棉纤维及制备方法与应用 |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN107099999B (zh) |
WO (1) | WO2018192239A1 (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107099999B (zh) * | 2017-04-17 | 2019-10-25 | 深圳大学 | 一种改性棉纤维及制备方法与应用 |
CN109912046A (zh) * | 2019-03-30 | 2019-06-21 | 杨晓飞 | 一种农业污水处理剂及其制备方法 |
CN110124623A (zh) * | 2019-05-21 | 2019-08-16 | 南昌大学 | 一种改性玉米秸秆纤维素吸附剂、制备方法及用途 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1970876A (zh) * | 2006-12-01 | 2007-05-30 | 陕西师范大学 | 一种制备具有亲水或疏水性纤维的方法 |
CN103706334A (zh) * | 2014-01-07 | 2014-04-09 | 福州大学 | 一种结构可控的纤维素吸附剂及其制备方法 |
CN104345043A (zh) * | 2014-07-16 | 2015-02-11 | 天津工业大学 | 一种适用于重金属离子检测的卟啉光学传感功能膜及其制备方法 |
CN104667891A (zh) * | 2015-02-09 | 2015-06-03 | 南京工业大学 | 一种吸附水中重金属螯合纤维材料的制备方法 |
CN107099999A (zh) * | 2017-04-17 | 2017-08-29 | 深圳大学 | 一种改性棉纤维及制备方法与应用 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103709340B (zh) * | 2013-12-29 | 2016-03-09 | 哈尔滨工业大学 | 粉末活性炭表面接枝聚(n-异丙基丙烯酰胺)的方法 |
-
2017
- 2017-04-17 CN CN201710249925.3A patent/CN107099999B/zh active Active
- 2017-12-08 WO PCT/CN2017/115318 patent/WO2018192239A1/zh active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1970876A (zh) * | 2006-12-01 | 2007-05-30 | 陕西师范大学 | 一种制备具有亲水或疏水性纤维的方法 |
CN103706334A (zh) * | 2014-01-07 | 2014-04-09 | 福州大学 | 一种结构可控的纤维素吸附剂及其制备方法 |
CN104345043A (zh) * | 2014-07-16 | 2015-02-11 | 天津工业大学 | 一种适用于重金属离子检测的卟啉光学传感功能膜及其制备方法 |
CN104667891A (zh) * | 2015-02-09 | 2015-06-03 | 南京工业大学 | 一种吸附水中重金属螯合纤维材料的制备方法 |
CN107099999A (zh) * | 2017-04-17 | 2017-08-29 | 深圳大学 | 一种改性棉纤维及制备方法与应用 |
Non-Patent Citations (2)
Title |
---|
LIU, C.K. ET AL.: "Preparation of the Porphyrin-Functionalized Cotton Fiber for the Chromogenic Detection and Efficient Adsorption of Cd 2+ Ions", JOURNAL OF COLLOID AND INTERFACE SCIENCE, vol. 488, 4 November 2016 (2016-11-04), XP029825093 * |
LIU, C.K. ET AL.: "Visible Sequestration of Cu2+ Ions Using Amino-Functionalized Cotton Fiber", RSC ADVANCES, 2 February 2017 (2017-02-02), pages 9744 - 9752, XP055550367 * |
Also Published As
Publication number | Publication date |
---|---|
CN107099999A (zh) | 2017-08-29 |
CN107099999B (zh) | 2019-10-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Wang et al. | A marine‐inspired hybrid sponge for highly efficient uranium extraction from seawater | |
CN109092265B (zh) | 一种聚咪唑离子液体改性的纤维素基吸附剂及其制备方法和应用 | |
WO2018192239A1 (zh) | 一种改性棉纤维及制备方法与应用 | |
CN107321319B (zh) | 多孔纳米纤维膜的制备及其在重金属离子吸附应用 | |
Zhao et al. | α-ketoglutaric acid modified chitosan/polyacrylamide semi-interpenetrating polymer network hydrogel for removal of heavy metal ions | |
Zhang et al. | Homochiral fluorescence responsive molecularly imprinted polymer: Highly chiral enantiomer resolution and quantitative detection of L-penicillamine | |
CN106076279A (zh) | 一种重金属离子吸附剂及其制备方法和应用 | |
Jia et al. | Double functional polymer brush-grafted cotton fiber for the fast visual detection and efficient adsorption of cadmium ions | |
CN110918067B (zh) | 一种接枝纤维素吸附剂及其制备方法和应用 | |
CN104525129A (zh) | 一种用于重金属废水处理的改性活性炭的制备方法 | |
CN104923176B (zh) | 一种树枝状高密度固态胺纤维材料及其制备方法 | |
Chai et al. | In-suit ion-imprinted bio-sorbent with superior adsorption performance for gallium (III) capture | |
CN111636145A (zh) | 一种吸附重金属的聚酯纤维膜及其制备方法 | |
CN113648984A (zh) | 一种温度-pH响应分子印迹纤维膜及其制备方法 | |
KR101987667B1 (ko) | 금속이온 흡착막, 이의 제조방법 및 이의 응용 | |
CN110090627A (zh) | 一种钙离子印迹壳聚糖吸附剂及其制备方法与应用 | |
CN108126678B (zh) | 一种可再生的纳米碳材料涂覆纤维吸附剂及其制备方法 | |
CN105833846B (zh) | 一种汞离子吸附螯合纤维的制备方法 | |
WO2018121165A1 (zh) | 选择性吸附金离子的中空纤维膜及其制备方法与应用 | |
CN107115846A (zh) | 一种冠醚固载化玻璃纤维材料及其制备方法 | |
CN109810266B (zh) | 一种用于吸附重金属离子的羟乙基纤维素水凝胶及其制备方法、应用 | |
CN113145077A (zh) | 一种环氧改性淀粉基Fe3O4吸附剂材料的制备方法 | |
CN106492768A (zh) | 一种离子选择性纤维素基吸附剂的制备方法及应用 | |
Wolman et al. | Peptide imprinted polymer synthesized by radiation-induced graft polymerization | |
CN109666101A (zh) | 一种邻菲罗啉改性淀粉螯合剂及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17906213 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17906213 Country of ref document: EP Kind code of ref document: A1 |
|
32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205 DATED 04/08/2020) |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17906213 Country of ref document: EP Kind code of ref document: A1 |